Elucidating the Role of Reduction Kinetics in the Phase-Controlled Growth on Preformed Nanocrystal Seeds: A Case Study of RuClick to copy article linkArticle link copied!
- Quynh N. NguyenQuynh N. NguyenSchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesMore by Quynh N. Nguyen
- Eun Mi KimEun Mi KimDepartment of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16803, United StatesMore by Eun Mi Kim
- Yong DingYong DingSchool of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesMore by Yong Ding
- Annemieke JanssenAnnemieke JanssenSchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesMore by Annemieke Janssen
- Chenxiao WangChenxiao WangSchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesMore by Chenxiao Wang
- Kei Kwan LiKei Kwan LiSchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesMore by Kei Kwan Li
- Junseok KimJunseok KimDepartment of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16803, United StatesMore by Junseok Kim
- Kristen A. Fichthorn*Kristen A. Fichthorn*Email: [email protected]Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16803, United StatesMore by Kristen A. Fichthorn
- Younan Xia*Younan Xia*Email: [email protected]School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United StatesThe Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta, Georgia 30332, United StatesMore by Younan Xia
Abstract
This study demonstrates the crucial role of reduction kinetics in phase-controlled synthesis of noble-metal nanocrystals using Ru nanocrystals as a case study. We found that the reduction kinetics played a more important role than the templating effect from the preformed seed in dictating the crystal structure of the deposited overlayers despite their intertwined effects on successful epitaxial growth. By employing two different polyols, a series of Ru nanocrystals with tunable sizes of 3–7 nm and distinct patterns of crystal phase were synthesized by incorporating different types of Ru seeds. Notably, the use of ethylene glycol and triethylene glycol consistently resulted in the formation of Ru shell in natural hexagonal close-packed (hcp) and metastable face-centered cubic (fcc) phases, respectively, regardless of the size and phase of the seed. Quantitative measurements and theoretical calculations suggested that this trend was a manifestation of the different reduction kinetics associated with the precursor and the chosen polyol, which, in turn, affected the reduction pathway (solution versus surface) and packing sequence of the deposited Ru atoms. This work not only underscores the essential role of reduction kinetics in controlling the packing of atoms and thus the phase taken by Ru nanocrystals but also suggests a potential extension to other noble-metal systems.
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Introduction
Results and Discussion
Selection and Rationale of a Model System
Synthesis and Characterizations of the hcp-Ru Seeds
Growth of Ru Overlayers on Ru Seeds in Different Polyols
Quantitative Analysis of the Reduction Kinetics and Pathways Involved
Mechanistic Investigation by First-Principles DFT Calculations
Conclusion
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.4c01725.
Descriptions of synthetic protocols, computational details, additional TEM and HRTEM images, and XRD patterns of the initial Ru seeds and samples prepared under different conditions, as well as results from additional computational analyses (PDF)
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Acknowledgments
This work was supported in part by a grant from the National Science Foundation (CHE-2105602) and start-up funds from the Georgia Institute of Technology. Q.N.N. acknowledges the support from the National Science Foundation Graduate Research Fellowship under Grant No. DGE-2039655. TEM imaging was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (ECCS-2025462). The theoretical work was funded by the Department of Energy, Office of Basic Energy Sciences, Materials Science Division, Grant DE-FG02-07ER46414 (EK, JK, and KF). This work used Bridges-2 at the Pittsburgh Supercomputing Center through allocation DMR110061 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by National Science Foundation grants #2138259, #2138286, #2138307, #2137603, and #2138296.
References
This article references 60 other publications.
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- 4Li, J.; Sun, S. Intermetallic nanoparticles: synthetic control and their enhanced electrocatalysis. Acc. Chem. Res. 2019, 52, 2015– 2025, DOI: 10.1021/acs.accounts.9b00172Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1Kis7zK&md5=132569abe7c3cc95c0ac8e279812c575Intermetallic Nanoparticles: Synthetic Control and Their Enhanced ElectrocatalysisLi, Junrui; Sun, ShouhengAccounts of Chemical Research (2019), 52 (7), 2015-2025CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Intermetallic nanoparticles (NPs) described in this Account are a class of metallic alloy NPs within which metal atoms are bonded via strong d-orbital interaction and ordered anisotropically in a specific crystallog. direction. Compared to the common metallic alloy NPs with solid soln. structure, intermetallic NPs are generally more stable against chem. oxidn. and etching. The strict stoichiometry requirement, well-defined atom binding environment and layered at. arrangement also make intermetallic NPs an ideal model for understanding their phys. and catalytic properties. This account summarizes the synthetic principles and strategies developed to obtain monodisperse intermetallic NPs, esp. tetragonal L10-NPs. The thermodn. and kinetics involved in the conversion between disordered and ordered structures are briefly discussed. The synthetic methods are grouped into two slightly different categories: soln.-phase synthesis followed by solid state annealing and direct soln.-phase synthesis. In the former method, high-surface-area supports are often needed to disperse NPs and to prevent them from aggregation, while in the latter method such supports are not required since the structure conversion temp. is lowered to a level that the conversion can proceed in the soln. reaction condition. In any of these two synthetic approaches, various factors influencing intermetallic structure formation should be carefully controlled to ensure more complete structural transition within NPs. Using representative synthetic examples, we highlight the strategies explored to facilitate the formation of intermetallic structure, including the introduction of vacancies/defects within NP structures and the control of atom addn. rate/seed-mediated diffusion to lower the energy barrier. These strategies illustrate how the concept of thermodn. and kinetics can be used to design the synthesis of intermetallic NPs. Addnl., to correlate NP structure and catalysis, we introduce briefly the d-band theory to explain how the electronic, strain and ensemble effects can be used to tune NP catalysis. We focus specifically on Pt-, Pd-, and Au-based L10-NPs and demonstrate how these L10-NPs could be prepd. to show much enhanced catalysis for electrochem. reactions, including oxygen redn. reaction (ORR), hydrogen evolution reaction (HER), formic acid oxidn. reaction (FAOR), and thermo-oxidn. reaction of CO. Due to the enhanced metal atom stability in the "sandwich"-type structure, the roles of the first-row transition metal atoms in catalysis are better understood to achieve catalysis optimization. This concept can be extended to other alloy NPs, demonstrating great potentials in using intermetallic structures to control NP redn. and oxidn. catalysis for important chem. and energy applications.
- 5Chen, Y.; Lai, Z.; Zhang, X.; Fan, Z.; He, Q.; Tan, C.; Zhang, H. Phase engineering of nanomaterials. Nat. Rev. Chem. 2020, 4, 243– 256, DOI: 10.1038/s41570-020-0173-4Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmtFynsb0%253D&md5=45377e0eb0774ed5c9ef5bd96be8c551Phase engineering of nanomaterialsChen, Ye; Lai, Zhuangchai; Zhang, Xiao; Fan, Zhanxi; He, Qiyuan; Tan, Chaoliang; Zhang, HuaNature Reviews Chemistry (2020), 4 (5), 243-256CODEN: NRCAF7; ISSN:2397-3358. (Nature Research)A review. Abstr.: Phase has emerged as an important structural parameter - in addn. to compn., morphol., architecture, facet, size and dimensionality - that dets. the properties and functionalities of nanomaterials. In particular, unconventional phases in nanomaterials that are unattainable in the bulk state can potentially endow nanomaterials with intriguing properties and innovative applications. Great progress has been made in the phase engineering of nanomaterials (PEN), including synthesis of nanomaterials with unconventional phases and phase transformation of nanomaterials. This Review provides an overview on the recent progress in PEN. We discuss various strategies used to synthesize nanomaterials with unconventional phases and induce phase transformation of nanomaterials, by taking noble metals and layered transition metal dichalcogenides as typical examples. Moreover, we also highlight recent advances in the prepn. of amorphous nanomaterials, amorphous-cryst. and crystal phase-based hetero-nanostructures. We also provide personal perspectives on challenges and opportunities in this emerging field, including exploration of phase-dependent properties and applications, rational design of phase-based heterostructures and extension of the concept of phase engineering to a wider range of materials.
- 6Yao, Q.; Yu, Z.; Li, L.; Huang, X. Strain and surface engineering of multicomponent metallic nanomaterials with unconventional phases. Chem. Rev. 2023, 123, 9676– 9717, DOI: 10.1021/acs.chemrev.3c00252Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsVamsLzE&md5=2187e8afcdadc710f98f5602609bf442Strain and Surface Engineering of Multicomponent Metallic Nanomaterials with Unconventional PhasesYao, Qing; Yu, Zhiyong; Li, Leigang; Huang, XiaoqingChemical Reviews (Washington, DC, United States) (2023), 123 (15), 9676-9717CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Multicomponent metallic nanomaterials with unconventional phases show great prospects in electrochem. energy storage and conversion, owing to unique crystal structures and abundant structural effects. In this review, we emphasize the progress in the strain and surface engineering of these novel nanomaterials. We start with a brief introduction of the structural configurations of these materials, based on the interaction types between the components. Next, the fundamentals of strain, strain effect in relevant metallic nanomaterials with unconventional phases, and their formation mechanisms are discussed. Then the progress in surface engineering of these multicomponent metallic nanomaterials is demonstrated from the aspects of morphol. control, crystallinity control, surface modification, and surface reconstruction. Moreover, the applications of the strain- and surface-engineered unconventional nanomaterials mainly in electrocatalysis are also introduced, where in addtion to the catalytic performance, the structure-performance correlations are highlighted. Finally, the challenges and opportunities in this promising field are prospected.
- 7Zhao, M.; Xia, Y. Crystal-phase and surface-structure engineering of ruthenium nanocrystals. Nat. Rev. Mater. 2020, 5, 440– 459, DOI: 10.1038/s41578-020-0183-3Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlslGgsLk%253D&md5=7ffb8f8b136f97ed3f2325cfb3606d89Crystal-phase and surface-structure engineering of ruthenium nanocrystalsZhao, Ming; Xia, YounanNature Reviews Materials (2020), 5 (6), 440-459CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Metal nanocrystals with controlled shapes or surface structures have received increasing attention, owing to their desirable properties for applications ranging from catalysis to photonics, energy and biomedicine. Most studies, however, have been limited to nanocrystals with the same crystal phase as the bulk material. Engineering the phase of metal nanocrystals while simultaneously attaining shape-controlled synthesis has recently emerged as a new frontier of research. Here, we use Ru as an example to evaluate recent progress in the synthesis of metal nanocrystals featuring different crystal phases and well-controlled shapes. We first discuss synthetic strategies for controlling the crystal phase and shape of Ru nanocrystals, with a focus on new mechanistic insights. We then highlight the major factors that affect the packing of Ru atoms and, thus, the crystal phase, followed by an examn. of the thermal stability of Ru nanocrystals in terms of both crystal phase and shape. Next, we showcase the successful implementation of these Ru nanocrystals in various catalytic applications. Finally, we end with a discussion of the challenges and opportunities in the field, including leveraging the lessons learned from Ru to engineer the crystal phase and surface structure of other metals.
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- 11Ge, Y.; Huang, Z.; Ling, C.; Chen, B.; Liu, G.; Zhou, M.; Liu, J.; Zhang, X.; Cheng, H.; Liu, G. Phase-selective epitaxial growth of heterophase nanostructures on unconventional 2H-Pd nanoparticles. J. Am. Chem. Soc. 2020, 142, 18971– 18980, DOI: 10.1021/jacs.0c09461Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitV2qtrrO&md5=330aa30ecd6c39378a71aa1b3efaec7aPhase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd NanoparticlesGe, Yiyao; Huang, Zhiqi; Ling, Chongyi; Chen, Bo; Liu, Guigao; Zhou, Ming; Liu, Jiawei; Zhang, Xiao; Cheng, Hongfei; Liu, Guanghua; Du, Yonghua; Sun, Cheng-Jun; Tan, Chaoliang; Huang, Jingtao; Yin, Pengfei; Fan, Zhanxi; Chen, Ye; Yang, Nailiang; Zhang, HuaJournal of the American Chemical Society (2020), 142 (44), 18971-18980CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the prepn. of Pd nanoparticles with an unconventional hcp. (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepd. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochem. carbon dioxide redn. reaction (CO2RR) for prodn. of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (vs. the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochem. cells.
- 12Zhou, X.; Ma, Y.; Ge, Y.; Zhu, S.; Cui, Y.; Chen, B.; Liao, L.; Yun, Q.; He, Z.; Long, H. Preparation of Au@Pd core-shell nanorods with fcc-2H-fcc heterophase for highly efficient electrocatalytic alcohol oxidation. J. Am. Chem. Soc. 2022, 144, 547– 555, DOI: 10.1021/jacs.1c11313Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXislyht7%252FO&md5=86a946cf219a55e6aeac513a2366aaa8Preparation of Au@Pd Core-Shell Nanorods with fcc-2H-fcc. Heterophase for Highly Efficient Electrocatalytic Alcohol OxidationZhou, Xichen; Ma, Yangbo; Ge, Yiyao; Zhu, Shangqian; Cui, Yu; Chen, Bo; Liao, Lingwen; Yun, Qinbai; He, Zhen; Long, Huiwu; Li, Lujiang; Huang, Biao; Luo, Qinxin; Zhai, Li; Wang, Xixi; Bai, Licheng; Wang, Gang; Guan, Zhiqiang; Chen, Ye; Lee, Chun-Sing; Wang, Jinlan; Ling, Chongyi; Shao, Minhua; Fan, Zhanxi; Zhang, HuaJournal of the American Chemical Society (2022), 144 (1), 547-555CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and studying the structure-dependent catalytic performance. Here, a wet-chem. synthesis method was used to prep. Au@Pd core-shell nanorods with a unique fcc.-2H-fcc. heterophase (fcc.: fcc.; 2H: hcp. with a stacking sequence of AB). The obtained fcc.-2H-fcc. heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic EtOH oxidn. performance with a mass activity ≤6.82 A mgPd-1, which is 2.44, 6.96, and 6.43 times those of 2H-Pd nanoparticles, fcc.-Pd nanoparticles, and com. Pd/C, resp. The operando IR reflection absorption spectroscopy reveals a C2 pathway with fast reaction kinetics for the EtOH oxidn. on the prepd. heterophase Au@Pd nanorods. The authors' exptl. results together with d. functional theory calcns. indicate that the enhanced performance of heterophase Au@Pd nanorods can be attributed to the unconventional 2H phase, the 2H/fcc. phase boundary, and the lattice expansion of the Pd shell. Also, the heterophase Au@Pd nanorods can also serve as an efficient catalyst for the electrochem. oxidn. of MeOH, ethylene glycol, and glycerol. The authors' work in the area of phase engineering of nanomaterials (PENs) opens the way for developing high-performance electrocatalysts toward future practical applications.
- 13Tan, X.; Geng, S.; Ji, Y.; Shao, Q.; Zhu, T.; Wang, P.; Li, Y.; Huang, X. Closest packing polymorphism interfaced metastable transition metal for efficient hydrogen evolution. Adv. Mater. 2020, 32, 2002857 DOI: 10.1002/adma.202002857Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhslWqur7J&md5=6a07d2671678fddbe2b58c40626c6f36Closest Packing Polymorphism Interfaced Metastable Transition Metal for Efficient Hydrogen EvolutionTan, Xinyue; Geng, Shize; Ji, Yujin; Shao, Qi; Zhu, Ting; Wang, Pengtang; Li, Youyong; Huang, XiaoqingAdvanced Materials (Weinheim, Germany) (2020), 32 (40), 2002857CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Metastable materials are promising because of their catalytic properties, high-energy structure, and unique electronic environment. However, the unstable nature inherited from the metastability hinders further performance improvement and practical applications of these materials. Herein, this limitation is successfully addressed by constructing an in situ polymorphism interface (inf) between the metastable hexagonal-close-packed (hcp) phase and its stable counterpart (face-centered cubic, fcc) in cobalt-nickel (CoNi) alloy. Calcns. reveal that the interfacial synergism derived from the hcp and fcc phases lowers the formation energy and enhances stability. Consequently, the optimized CoNi-inf exhibits an exceptionally low potential of 72 mV at 10 mA cm-2 and a Tafel slope of 57 mV dec-1 for the hydrogen evolution reaction (HER) in 1.0 M KOH. Furthermore, it is superior to most state-of-the-art non-noble-metal-based HER catalysts. No noticeable activity decay or structural changes are obsd. even over 14 h of catalysis. The computational simulation further rationalizes that the interface of CoNi-inf with a suitable d-band center provides uniform sites for hydrogen adsorption, leading to a distinguished HER catalytic activity. This work, therefore, presents a new route for designing metastable catalysts for potential energy conversion.
- 14Xia, Y.; Gilroy, K. D.; Peng, H. C.; Xia, X. Seed-mediated growth of colloidal metal nanocrystals. Angew. Chem., Int. Ed. 2017, 56, 60– 95, DOI: 10.1002/anie.201604731Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitV2mtLzO&md5=3a4a218eb28c15ac3691bb5822262b16Seed-Mediated Growth of Colloidal Metal NanocrystalsXia, Younan; Gilroy, Kyle D.; Peng, Hsin-Chieh; Xia, XiaohuAngewandte Chemie, International Edition (2017), 56 (1), 60-95CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Seed-mediated growth is a powerful and versatile approach for the synthesis of colloidal metal nanocrystals. The vast allure of this approach mainly stems from the staggering degree of control one can achieve over the size, shape, compn., and structure of nanocrystals. These parameters not only control the properties of nanocrystals but also det. their relevance to, and performance in, various applications. The ingenuity and artistry inherent to seed-mediated growth offer extensive promise, enhancing a no. of existing applications and opening the door to new developments. This Review demonstrates how the diversity of metal nanocrystals can be expanded with endless opportunities by using seeds with well-defined and controllable internal structures in conjunction with a proper combination of capping agent and redn. kinetics. New capabilities and future directions are also highlighted.
- 15Gilroy, K. D.; Yang, X.; Xie, S.; Zhao, M.; Qin, D.; Xia, Y. Shape-controlled synthesis of colloidal metal nanocrystals by replicating the surface atomic structure on the seed. Adv. Mater. 2018, 30, 1706312 DOI: 10.1002/adma.201706312Google ScholarThere is no corresponding record for this reference.
- 16Zhao, M.; Xu, L.; Vara, M.; Elnabawy, A. O.; Gilroy, K. D.; Hood, Z. D.; Zhou, S.; Figueroa-Cosme, L.; Chi, M.; Mavrikakis, M.; Xia, Y. Synthesis of Ru icosahedral nanocages with a face-centered-cubic structure and evaluation of their catalytic properties. ACS Catal. 2018, 8, 6948– 6960, DOI: 10.1021/acscatal.8b00910Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVagsrnP&md5=bdf4a3093dc2e2feedf622514e501ff2Synthesis of Ru Icosahedral Nanocages with a Face-Centered-Cubic Structure and Evaluation of Their Catalytic PropertiesZhao, Ming; Xu, Lang; Vara, Madeline; Elnabawy, Ahmed O.; Gilroy, Kyle D.; Hood, Zachary D.; Zhou, Shan; Figueroa-Cosme, Legna; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanACS Catalysis (2018), 8 (8), 6948-6960CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Owing to the presence of {111} facets, twin boundaries, and strain fields on the surface, noble-metal nanocrystals with an icosahedral shape have been reported with stellar performance toward an array of catalytic reactions. Here, we report the successful synthesis of Ru icosahedral nanocages with a face-centered cubic (fcc) structure by conformally coating Pd icosahedral seeds with ultrathin Ru shells, followed by selective removal of the Pd cores via chem. etching. We discovered that the presence of bromide ions was crit. to the layer-by-layer deposition of Ru atoms. According to in situ XRD, the fcc structure in the Ru nanocages could be retained up to 300 °C before it was transformed into the conventional hcp. (hcp) structure. Addnl., the icosahedral shape of the Ru nanocages could be largely preserved up to 300 °C. The Ru icosahedral nanocages with twin boundaries on the surface exhibited greatly enhanced activities toward both the redn. of 4-nitrophenol and decompn. of hydrazine than their cubic and octahedral counterparts. When benchmarked against the parental Pd@Ru core-shell nanocrystals, all the Ru nanocages displayed superior catalytic activities. First-principles d. functional theory calcns. also suggest that the fcc-Ru icosahedral nanocages contg. residual Pd atoms are more promising than the conventional hcp-Ru solid nanoparticles in catalyzing nitrogen redn. for ammonia synthesis. With the subsurface impurities of Pd, the twin boundary regions of the icosahedral nanocages are able to stabilize the N2 dissocn. transition state, reducing the overall reaction barrier and promoting the competition with the N2 desorption process.
- 17Zhao, M.; Figueroa-Cosme, L.; Elnabawy, A. O.; Vara, M.; Yang, X.; Roling, L. T.; Chi, M.; Mavrikakis, M.; Xia, Y. Synthesis and characterization of Ru cubic nanocages with a face-centered cubic structure by templating with Pd nanocubes. Nano Lett. 2016, 16, 5310– 5317, DOI: 10.1021/acs.nanolett.6b02795Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1Ggtr3E&md5=d343198af41c4dde7d954e17ab8601c3Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd NanocubesZhao, Ming; Figueroa-Cosme, Legna; Elnabawy, Ahmed O.; Vara, Madeline; Yang, Xuan; Roling, Luke T.; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanNano Letters (2016), 16 (8), 5310-5317CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Ru cubic nanocages with ultrathin walls, in which the atoms are crystd. in fcc. rather than hcp. structure, have been prepd. The key to the success of this synthesis was to ensure layer-by-layer deposition of Ru atoms on the surface of Pd cubic seeds by controlling the reaction temp. and the injection rate of a Ru(III) precursor. By selectively etching away the Pd from the Pd@Ru core-shell nanocubes, the authors obtained Ru nanocages with an av. wall thickness of 1.1 nm or about six at. layers. The Ru nanocages adopted an fcc. crystal structure rather than the hcp. structure obsd. in bulk Ru. The synthesis was applied to Pd cubic seeds with different edge lengths in the range of 6-18 nm, with smaller seeds being more favorable for the formation of Ru shells with a flat, smooth surface due to shorter distance for the surface diffusion of the Ru adatoms. Self-consistent d. functional theory calcns. indicated that these unique fcc.-structured Ru nanocages might possess promising catalytic properties for ammonia synthesis compared to hcp. Ru(0001), on the basis of strengthened binding of at. N and substantially reduced activation energies for N2 dissocn., which is the rate-detg. step for ammonia synthesis on hcp. Ru catalysts.
- 18Gu, J.; Guo, Y.; Jiang, Y.-Y.; Zhu, W.; Xu, Y.-S.; Zhao, Z.-Q.; Liu, J.-X.; Li, W.-X.; Jin, C.-H.; Yan, C.-H.; Zhang, Y. W. Robust phase control through hetero-seeded epitaxial growth for face-centered cubic Pt@Ru nanotetrahedrons with superior hydrogen electro-oxidation activity. J. Phys. Chem. C 2015, 119, 17697– 17706, DOI: 10.1021/acs.jpcc.5b04587Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1Sgs7bE&md5=43459bdacdb1a28d51f3b245262737cfRobust Phase Control through Hetero-Seeded Epitaxial Growth for Face-Centered Cubic Pt@Ru Nanotetrahedrons with Superior Hydrogen Electro-Oxidation ActivityGu, Jun; Guo, Yu; Jiang, Ying-Ying; Zhu, Wei; Xu, Yan-Shuang; Zhao, Ze-Qiong; Liu, Jin-Xun; Li, Wei-Xue; Jin, Chuan-Hong; Yan, Chun-Hua; Zhang, Ya-WenJournal of Physical Chemistry C (2015), 119 (31), 17697-17706CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Controllable synthesis of metallic nanocrystals (NCs) with tunable phase, uniform shape, and size is of multidisciplinary interests but has still remained challenging. Herein, a robust phase control strategy is developed, in which seeds with a given phase are added to guide the epitaxial growth of the target metal to inherit the seeds' phase. Through this strategy, M@Ru (M = Pt, Pd) NCs in the fcc. phase, a metastable phase for Ru under ambient conditions, were synthesized with the hydrothermal method. The Pt@Ru NCs showed not only the pure fcc. phase but also high morphol. selectivity to tetrahedrons surrounded by {111} facets. As revealed by d. function theory (DFT) calcns., the preferentially epitaxial growth of Ru atom layers on the nonclosest-packed facets of hetero fcc. metal seeds gave fcc. Ru shells. Also, the fcc. Pt@Ru tetrahedrons/C showed electrocatalytic activity enhancement with more than an order of magnitude toward H oxidn. reaction (HOR) in acidic electrolyte compared with hydrothermally synthesized Ru/C. Electrochem. measurement combined with DFT calcns. revealed that the optimum HOR activity should be achieved on well-crystd. fcc. Ru catalysts exposing max. {111} facets.
- 19Janssen, A.; Lyu, Z.; Figueras-Valls, M.; Chao, H.-Y.; Shi, Y.; Pawlik, V.; Chi, M.; Mavrikakis, M.; Xia, Y. Phase-controlled synthesis of Ru nanocrystals via template-directed growth: surface energy versus bulk energy. Nano Lett. 2022, 22, 3591– 3597, DOI: 10.1021/acs.nanolett.1c05009Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhtVaqurbF&md5=4fd2b4cffaf9664ac87b8f3467ac15d1Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk EnergyJanssen, Annemieke; Lyu, Zhiheng; Figueras-Valls, Marc; Chao, Hsin-Yun; Shi, Yifeng; Pawlik, Veronica; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanNano Letters (2022), 22 (9), 3591-3597CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of fcc.-Pd nanoplate templates, with 12 nm plates giving fcc.-Ru while 18-26 nm plates result in hcp.-Ru. Although Ru overlayers with a metastable fcc.- (high in bulk energy) or stable hcp.-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp.- (high in surface energy) and smooth fcc.-facets (low in surface energy), resp., on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The [email protected] outperform the [email protected] nanoplates toward ethylene glycol and glycerol oxidn. reactions.
- 20Janssen, A.; Nguyen, Q. N.; Lyu, Z.; Pawlik, V.; Wang, C.; Xia, Y. Phase-controlled deposition of Ru on Pd nanocrystal templates: effects of particle shape and size. J. Phys. Chem. C 2023, 127, 1280– 1291, DOI: 10.1021/acs.jpcc.2c08825Google ScholarThere is no corresponding record for this reference.
- 21Joo, S. H.; Park, J. Y.; Renzas, J. R.; Butcher, D. R.; Huang, W.; Somorjai, G. A. Size effect of ruthenium nanoparticles in catalytic carbon monoxide oxidation. Nano Lett. 2010, 10, 2709– 2713, DOI: 10.1021/nl101700jGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnvVejtr4%253D&md5=96783fc4b8f4474251d7540e668ea266Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide OxidationJoo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu; Somorjai, Gabor A.Nano Letters (2010), 10 (7), 2709-2713CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)CO oxidn. over Ru catalysts exhibits an unusual catalytic behavior. This work discusses particle size effect on CO oxidn. over Ru nano-particle (NP) catalysts. Uniform Ru NP with a tunable particle size of 2-6 nm were synthesized by a polyol redn. of ruthenium acetylacetonate precursor in the presence of a poly(vinylpyrrolidone) stabilizer. Catalyst activity measurement for CO oxidn. over 2-dimensional Ru NP arrays under oxidizing reaction conditions (40 Torr CO, 100 Torr O2) showed activity depended on Ru NP size. CO oxidn. activity increased with NP size; the 6 nm Ru NP catalyst exhibited 8-fold higher activity than 2 nm catalysts. Results provide the scientific basis for future design of Ru-based oxidn. catalysts.
- 22Li, W. Z.; Liu, J. X.; Gu, J.; Zhou, W.; Yao, S. Y.; Si, R.; Guo, Y.; Su, H. Y.; Yan, C. H.; Li, W. X. Chemical insights into the design and development of face-centered cubic ruthenium catalysts for Fischer–Tropsch synthesis. J. Am. Chem. Soc. 2017, 139, 2267– 2276, DOI: 10.1021/jacs.6b10375Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1KlsLw%253D&md5=1b859b177abeeedf8b343821b4d0d657Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch SynthesisLi, Wei-Zhen; Liu, Jin-Xun; Gu, Jun; Zhou, Wu; Yao, Si-Yu; Si, Rui; Guo, Yu; Su, Hai-Yan; Yan, Chun-Hua; Li, Wei-Xue; Zhang, Ya-Wen; Ma, DingJournal of the American Chemical Society (2017), 139 (6), 2267-2276CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Ruthenium is a promising low-temp. catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. The authors demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. D. functional theory calcns. show that upon CO dissocn. there are a no. of open facets with modest barrier available on the fcc. Ru but only a few step edges with a lower barrier on conventional hcp. Ru. Guided by theor. calcns., water-dispersible fcc. Ru catalysts contg. abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aq.-phase FTS, 37.8 molCO·molRu-1·h-1 at 433 K. The mass-specific activity of the fcc. Ru catalysts with an av. size of 6.8 nm is about three times larger than the previous best hcp. catalyst with a smaller size of 1.9 nm and a higher sp. surface area. The origin of the higher mass-specific activity of the fcc. Ru catalysts is identified exptl. from the 2 orders of magnitude higher d. of the active sites, despite its slightly higher apparent barrier. Exptl. results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.
- 23Li, L.; Liu, C.; Liu, S.; Wang, J.; Han, J.; Chan, T. S.; Li, Y.; Hu, Z.; Shao, Q.; Zhang, Q.; Huang, X. Phase engineering of a ruthenium nanostructure toward high-performance bifunctional hydrogen catalysis. ACS Nano 2022, 16, 14885– 14894, DOI: 10.1021/acsnano.2c05776Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xit1Wgs7jF&md5=636977cb45ebdeb375257e85adbb5ca8Phase Engineering of a Ruthenium Nanostructure toward High-Performance Bifunctional Hydrogen CatalysisLi, Leigang; Liu, Cheng; Liu, Shangheng; Wang, Juan; Han, Jiajia; Chan, Ting-Shan; Li, Youyong; Hu, Zhiwei; Shao, Qi; Zhang, Qiaobao; Huang, XiaoqingACS Nano (2022), 16 (9), 14885-14894CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The physicochem. properties and catalytic performance of transition metals are highly phase-dependent. Ru-based nanomaterials are superior catalysts toward hydrogen evolution reaction (HER) and hydrogen oxidn. reaction (HOR), but studies are mostly limited to conventional hexagonal-close-packed (hcp) Ru, mainly arising from the difficulty in synthesizing Ru with pure face-centered-cubic (fcc) phase. Herein, we report a crystal-phase-dependent catalytic study of MoOx-modified Ru (MoOx-Ru fcc and MoOx-Ru hcp) for bifunctional HER and HOR. MoOx-Ru fcc is proven to outperform MoOx-Ru hcp in catalyzing both HER and HOR with much higher catalytic activity and more durable stability. The modification effect of MoOx gives rise to optimal adsorption of H and OH esp. on fcc Ru, which thus has resulted in the superior catalytic performance. This work highlights the significance of phase engineering in constructing superior electrocatalysts and may stimulate more efforts on phase engineering of other metal-based materials for diversified applications.
- 24Kusada, K.; Kobayashi, H.; Yamamoto, T.; Matsumura, S.; Sumi, N.; Sato, K.; Nagaoka, K.; Kubota, Y.; Kitagawa, H. Discovery of face-centered-cubic ruthenium nanoparticles: facile size-controlled synthesis using the chemical reduction method. J. Am. Chem. Soc. 2013, 135, 5493– 5496, DOI: 10.1021/ja311261sGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXltlKmsr8%253D&md5=27d1e520b1c3b39da57fe6c0d65e0a48Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction MethodKusada, Kohei; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Matsumura, Syo; Sumi, Naoya; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kubota, Yoshiki; Kitagawa, HiroshiJournal of the American Chemical Society (2013), 135 (15), 5493-5496CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We report the first discovery of pure face-centered-cubic (fcc) Ru nanoparticles. Although the fcc structure does not exist in the bulk Ru phase diagram, fcc Ru was obtained at room temp. because of the nanosize effect. We succeeded in sep. synthesizing uniformly sized nanoparticles of both fcc and hcp Ru having diams. of 2-5.5 nm by simple chem. redn. methods with different metal precursors. The prepd. fcc and hcp nanoparticles were both supported on γ-Al2O3, and their catalytic activities in CO oxidn. were investigated and found to depend on their structure and size.
- 25Araki, N.; Kusada, K.; Yoshioka, S.; Sugiyama, T.; Ina, T.; Kitagawa, H. Observation of the formation processes of hexagonal close-packed and face-centered cubic Ru nanoparticles. Chem. Lett. 2019, 48, 1062– 1064, DOI: 10.1246/cl.190338Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1WqtrnF&md5=109dadd6a1c44f133fbdff09c87adca5Observation of the Formation Processes of Hexagonal Close-packed and Face-centered Cubic Ru NanoparticlesAraki, Naoki; Kusada, Kohei; Yoshioka, Satoru; Sugiyama, Takeharu; Ina, Toshiaki; Kitagawa, HiroshiChemistry Letters (2019), 48 (9), 1062-1064CODEN: CMLTAG; ISSN:0366-7022. (Chemical Society of Japan)Face-centered cubic (fcc) Ru nanoparticles (NPs) have been recently synthesized by reducing Ru(III) acetylacetonate, despite bulk Ru having a hcp. (hcp) structure. We obsd. the formation processes of fcc and hcp Ru NPs using X-ray diffraction and X-ray absorption fine structure. We concluded that the strong Ru-O bond between Ru and the acetylacetonate ligand leads to the formation of the fcc structure.
- 26Zhao, M.; Hood, Z. D.; Vara, M.; Gilroy, K. D.; Chi, M.; Xia, Y. Ruthenium nanoframes in the face-centered cubic phase: facile synthesis and their enhanced catalytic performance. ACS Nano 2019, 13, 7241– 7251, DOI: 10.1021/acsnano.9b02890Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVKqsrzI&md5=90c09098c30f29a99cd3c5dffbebb3ceRuthenium Nanoframes in the Face-Centered Cubic Phase: Facile Synthesis and Their Enhanced Catalytic PerformanceZhao, Ming; Hood, Zachary D.; Vara, Madeline; Gilroy, Kyle D.; Chi, Miaofang; Xia, YounanACS Nano (2019), 13 (6), 7241-7251CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Owing to their highly open structure and a large no. of low-coordination sites on the surface, noble-metal nanoframes are intriguing for catalytic applications. Here, we demonstrate the rational synthesis of Ru cuboctahedral nanoframes with enhanced catalytic performance toward hydrazine decompn. The synthesis starts from Pd nanocubes, which quickly undergo truncation at the corners as a consequence of oxidative etching caused by Br- ions. Afterward, the galvanic replacement reaction between Pd and Ru(III) ions dominates, leading to the selective deposition of Ru atoms on the corners and edges and thereby the fabrication of Pd@Ru core-frame cuboctahedra. Significantly, the deposited Ru atoms are crystd. in a face-centered cubic (fcc) phase instead of the hcp. (hcp) structure typical of bulk Ru. Upon the removal of Pd remaining in the core via chem. etching, we obtain Ru cuboctahedral nanoframes. By varying the amt. of the Ru(III) precursor, the ridge thickness of the nanoframes can be tuned from a few at. layers up to 10. Both the frame structure and fcc crystal phase of the Ru cuboctahedral nanoframes can be well preserved up to 300°C. When compared with hcp-Ru nanoparticles, the fcc-Ru nanoframes displayed substantial enhancement in terms of H2 selectivity toward hydrazine decompn. This work offers the opportunity to engineer both the morphol. and crystal phase of Ru nanocrystals for catalytic applications.
- 27Lin, J.-T.; Liu, Y.-H.; Tsao, C.-Y.; Wu, C.-Y.; Hsieh, C.-J.; Chen, M.-Z.; Chang, C.-W.; Hsiao, Y.-C.; Chen, H.-L.; Yang, T.-H. Toward a quantitative understanding of crystal-phase engineering of Ru nanocrystals. Chem. Mater. 2023, 35, 4276– 4285, DOI: 10.1021/acs.chemmater.3c00326Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtV2ksrbP&md5=1083f5b8422b7ca26665264f18235387Toward a Quantitative Understanding of Crystal-Phase Engineering of Ru NanocrystalsLin, Jui-Tai; Liu, Yi-Hong; Tsao, Chi-Yen; Wu, Cheng-Yu; Hsieh, Chia-Jui; Chen, Meng-Zhe; Chang, Chun-Wei; Hsiao, Yueh-Chun; Chen, Hsin-Lung; Yang, Tung-HanChemistry of Materials (2023), 35 (11), 4276-4285CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The crystal phase with a specific stacking sequence of atoms largely affects the catalytic performance of metal nanocrystals. Since the control of the phase at the same compn. is extremely difficult, the phase-dependent performance of metal nanocrystals is studied rarely. Here, we show the synthesis of Ru nanocrystals with different percentages of face-centered cubic (FCC) and hcp. (HCP) phases via kinetic control, further revealing a quant. correlation between the phase percentage of Ru nanocrystals and the initial redn. rate of Ru(III) precursors. Specifically, we manipulate the single parameter-initial redn. rate by controlling the Ru(III) injection rate into the dropwise synthesis at a fixed reaction temp. and correlate the kinetic data with the Ru phase percentage analyzed by at.-resoln. electron microscopy and synchrotron X-ray scattering. Based on the quant. anal., the ranges of initial redn. rates of Ru precursors can be detd. for synthesizing Ru nanocrystals with the percentages of unusual FCC phase from 9.0 to 55.1%. We demonstrate that a low initial redn. rate corresponds to the crystn. of the Ru HCP phase, while a high initial redn. rate favors the crystn. of the FCC lattice. Furthermore, we also systematically examine the catalytic performance of Ru nanocrystals with different phases.
- 28Ye, H.; Wang, Q.; Catalano, M.; Lu, N.; Vermeylen, J.; Kim, M. J.; Liu, Y.; Sun, Y.; Xia, X. Ru nanoframes with an fcc structure and enhanced catalytic properties. Nano Lett. 2016, 16, 2812– 2817, DOI: 10.1021/acs.nanolett.6b00607Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XksV2ksrs%253D&md5=d1ba68a214091adbb80e77ffab86e443Ru Nanoframes with an fcc Structure and Enhanced Catalytic PropertiesYe, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J.; Liu, Yuzi; Sun, Yugang; Xia, XiaohuNano Letters (2016), 16 (4), 2812-2817CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chem. etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chem. etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the redn. of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.
- 29Zhao, M.; Elnabawy, A. O.; Vara, M.; Xu, L.; Hood, Z. D.; Yang, X.; Gilroy, K. D.; Figueroa-Cosme, L.; Chi, M.; Mavrikakis, M.; Xia, Y. Facile synthesis of Ru-based octahedral nanocages with ultrathin walls in a face-centered cubic structure. Chem. Mater. 2017, 29, 9227– 9237, DOI: 10.1021/acs.chemmater.7b03092Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Gqsr7K&md5=230abaa6fd15610e5682cb3566709411Facile synthesis of Ru-based octahedral nanocages with ultrathin walls in face-centered cubic structureZhao, Ming; Elnabawy, Ahmed O.; Vara, Madeline; Xu, Lang; Hood, Zachary D.; Yang, Xuan; Gilroy, Kyle D.; Figueroa-Cosme, Legna; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanChemistry of Materials (2017), 29 (21), 9227-9237CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Noble-metal nanocages with ultrathin (less than 2 nm) walls and well-defined facets have received great interest owing to their remarkable utilization efficiency of atoms and facet-dependent catalytic activities toward various reactions. Here, we report the synthesis of Ru-based octahedral nanocages covered by {111} facets, together with ultrathin walls in a face-centered cubic (fcc) structure rather than the hcp. (hcp) of bulk Ru. The involvement of slow injection for the Ru(III) precursor, the introduction of KBr, and the use of elevated temp. were all instrumental to the formation of Pd@Ru core-shell octahedra with a conformal, uniform shell and a smooth surface. The {111} facets were well preserved during the selective removal of the Pd cores via wet etching, even when the Ru walls were only five at. layers in thickness. Through in situ XRD, we demonstrated that the fcc structure of the Ru nanocages was stable up to 300 °C. We also used first-principles, self-consistent d. functional theory calcns. to study the adsorption and dissocn. of N2 as a means to predict the catalytic performance toward ammonia synthesis. Our results suggested that the small proportions of Pd atoms left behind in the walls during etching could play a key role in stabilizing the adsorption of N2 as well as in reducing the activation energy barrier to N2 dissocn.
- 30Zhao, M.; Chen, Z.; Lyu, Z.; Hood, Z. D.; Xie, M.; Vara, M.; Chi, M.; Xia, Y. Ru octahedral nanocrystals with a face-centered cubic structure, {111} facets, thermal stability up to 400 °C, and enhanced catalytic activity. J. Am. Chem. Soc. 2019, 141, 7028– 7036, DOI: 10.1021/jacs.9b01640Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXntlejtLg%253D&md5=77fa31af38ac397f33c8c725290ef3edRu Octahedral Nanocrystals with a Face-Centered Cubic Structure, {111} Facets, Thermal Stability up to 400°C, and Enhanced Catalytic ActivityZhao, Ming; Chen, Zitao; Lyu, Zhiheng; Hood, Zachary D.; Xie, Minghao; Vara, Madeline; Chi, Miaofang; Xia, YounanJournal of the American Chemical Society (2019), 141 (17), 7028-7036CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Ruthenium nanocrystals with both a face-centered cubic (fcc) structure and well-controlled facets are attractive catalytic materials for various reactions. Here we report a simple method for the synthesis of Ru octahedral nanocrystals with an fcc structure and an edge length of 9 nm. The success of this synthesis relies on the use of 4.5 nm Rh cubes as seeds to facilitate the heterogeneous nucleation and overgrowth of Ru atoms. We choose Rh because it can resist oxidative etching under the harsh conditions for Ru overgrowth, it can be readily prepd. as nanocubes with edge lengths less than 5 nm, and its atoms have a size close to that of Ru atoms. During the seed-mediated growth, the at. packing of Ru overlayers follows an fcc lattice, in contrast to the conventional hcp. (hcp) lattice assocd. with bulk Ru. The final product takes an octahedral shape, with the surface enclosed by {111} facets. Our in situ measurements suggest that both the octahedral shape and the fcc crystal structure can be well preserved up to 400°C, which is more than 100°C higher than what was reported for Ru octahedral nanocages. When utilized as catalysts, the Ru octahedral nanocrystals exhibited 4.4-fold enhancement in terms of specific activity toward oxygen evolution relative to hcp-Ru nanoparticles. We also demonstrate that Ru{111} facets are more active than Ru{100} facets in catalyzing the oxygen evolution reaction. Altogether, this work offers an effective method for the synthesis of Ru nanocrystals with an fcc structure and well-defined {111} facets, as well as enhanced thermal stability and catalytic activity. We believe these nanocrystals will find use in various catalytic applications.
- 31Huo, D.; Cao, Z.; Li, J.; Xie, M.; Tao, J.; Xia, Y. Seed-mediated growth of Au nanospheres into hexagonal stars and the emergence of a hexagonal close-packed phase. Nano Lett. 2019, 19, 3115– 3121, DOI: 10.1021/acs.nanolett.9b00534Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtlKgu7s%253D&md5=b7376f3755b141cb1d65dc834b15fc58Seed-Mediated Growth of Au Nanospheres into Hexagonal Stars and the Emergence of a Hexagonal Close-Packed PhaseHuo, Da; Cao, Zhenming; Li, Jun; Xie, Minghao; Tao, Jing; Xia, YounanNano Letters (2019), 19 (5), 3115-3121CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Gold (Au) typically crystallizes in a cubic close-packed (ccp) structure to present a face-centered cubic (fcc) lattice or crystal phase. Herein, we demonstrate that Au nanoscale hexagonal stars featuring a hcp. (hcp) structure can be synthesized in an aq. system in the presence of fcc-Au nanospheres as the seeds. The success of this synthesis critically relies on the use of EDTA to complex with Au3+ ions (the precursor) and the introduction of 2-phospho-L-ascorbic acid trisodium salt (Asc-2P) as a novel reducing agent to maneuver the redn. kinetics. The use of Asc-2P favorably promotes the formation of hexagonal stars with uneven surfaces at the top and bottom faces, together with concave side faces around the edges. By varying the amt. of Asc-2P to fine-tune the redn. kinetics, we can adjust the concaveness of the side faces, with a faster redn. rate favoring greater concaveness and a red shift of the plasmon resonance peak to the near-IR. For the first time, our results suggest that the phosphate and hydroxyl groups can act synergistically in controlling the morphol. of Au nanocrystals. Most significantly, the newly deposited Au atoms can also crystallize in an hcp structure, leading to the observation of a phase transition from fcc to hcp along the growth direction. This new protocol based upon kinetic control can be potentially extended to other noble metals for the facile synthesis of nanocrystals featuring unprecedented structures or phases.
- 32Gloag, L.; Benedetti, T. M.; Cheong, S.; Marjo, C. E.; Gooding, J. J.; Tilley, R. D. Cubic-core hexagonal-branch mechanism to synthesize bimetallic branched and faceted Pd–Ru nanoparticles for oxygen evolution reaction electrocatalysis. J. Am. Chem. Soc. 2018, 140, 12760– 12764, DOI: 10.1021/jacs.8b09402Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVeisrfI&md5=75d644b447b050d3936cdc8b4225929bCubic-Core Hexagonal-Branch Mechanism To Synthesize Bimetallic Branched and Faceted Pd-Ru Nanoparticles for Oxygen Evolution Reaction ElectrocatalysisGloag, Lucy; Benedetti, Tania M.; Cheong, Soshan; Marjo, Christopher E.; Gooding, J. Justin; Tilley, Richard D.Journal of the American Chemical Society (2018), 140 (40), 12760-12764CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A major synthetic challenge is to make metal nanoparticles with nanosized branches and well-defined facets for high-performance catalysts. Here, we introduce a mechanism that uses the growth of hexagonal crystal structured branches off cubic crystal structured core nanoparticles. We control the growth to form Pd-core Ru-branch nanoparticles that have nanosized branches with low index Ru facets. We demonstrate that the branched and faceted structural features of the Pd-Ru nanoparticles retain high catalytic activity while also achieving high stability for the O evolution reaction.
- 33Yun, Q.; Ge, Y.; Huang, B.; Wa, Q.; Zhang, H. Ligand-assisted phase engineering of nanomaterials. Acc. Chem. Res. 2023, 56, 1780– 1790, DOI: 10.1021/acs.accounts.3c00121Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtFOrtLbF&md5=f4c2430b891fbcacd1fc0c03a2061edaLigand-Assisted Phase Engineering of NanomaterialsYun, Qinbai; Ge, Yiyao; Huang, Biao; Wa, Qingbo; Zhang, HuaAccounts of Chemical Research (2023), 56 (13), 1780-1790CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)The synthesis of monodisperse colloidal nanomaterials with well-defined structures is important for both fundamental research and practical application. To achieve it, wet-chem. methods with the usage of various ligands have been extensively explored to finely control the structure of nanomaterials. During the synthesis, ligands cap the surface and thus modulate the size, shape, and stability of nanomaterials in solvents. Besides these widely investigated roles of ligands, it has been recently discovered that ligands can affect the phase of nanomaterials, i.e., their at. arrangement, providing an effective strategy to realize the phase engineering of nanomaterials (PEN) by selecting appropriate ligands. Nanomaterials normally exist in the phases that are thermodynamically stable in their bulk states. Previous studies have shown that under high temp. or high pressure, nanomaterials can exist in unconventional phases which are unattainable in the bulks. Importantly, nanomaterials with unconventional phases exhibit unique properties and functions different from conventional-phase ones. Consequently, it is feasible to utilize the PEN to tune the physicochem. properties and application performance of nanomaterials. During wet-chem. synthesis, ligands binding to the surface of nanomaterials can modify their surface energy, which could significantly affect the Gibbs free energy of nanomaterials and thus det. the stability of different phases, making it possible to obtain nanomaterials with unconventional phases at mild reaction conditions. For instance, a series of Au nanomaterials with unconventional hexagonal phases have been prepd. with the assistance of oleylamine. Therefore, the rational design and selection of different ligands and deep understanding of their effect on the phase of nanomaterials would significantly accelerate the development of PEN and the discovery of novel functional nanomaterials for diverse applications. In this Account, we briefly summarize the recent progress in ligand-assisted PEN, elaborating the important roles of different ligands in the direct synthesis of nanomaterials with unconventional crystal phases and amorphous phase as well as the phase transformation of nanomaterials. We first introduce the background of this research topic, highlighting the concept of PEN and why ligands can modulate the phase of nanomaterials. Then we discuss the usage of four kinds of ligands, i.e., amines, fatty acids, sulfur-contg. ligands, and phosphorus-contg. ligands, in phase engineering of different nanomaterials, esp. metal, metal chalcogenide, and metal oxide nanomaterials. Finally, we provide our personal views of the challenges and future promising research directions in this exciting field.
- 34Nguyen, Q. N.; Chen, R.; Lyu, Z.; Xia, Y. Using reduction kinetics to control and predict the outcome of a colloidal synthesis of noble-metal nanocrystals. Inorg. Chem. 2021, 60, 4182– 4197, DOI: 10.1021/acs.inorgchem.0c03576Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisVWgsbo%253D&md5=af032e84596286f3c4e001f311fb6633Using reduction kinetics to control and predict outcome of colloidal synthesis of noble-metal nanocrystalsNguyen, Quynh N.; Chen, Ruhui; Lyu, Zhiheng; Xia, YounanInorganic Chemistry (2021), 60 (7), 4182-4197CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)Improving the performance of noble-metal nanocrystals in various applications critically depends on our ability to manipulate their synthesis in a rational, robust, and controllable fashion. Different from a conventional trial-and-error approach, the redn. kinetics of a colloidal synthesis has recently been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner. Here we present a brief viewpoint on the recent progress in leveraging redn. kinetics for controlling and predicting the outcome of a synthesis of noble-metal nanocrystals. With a focus on Pd nanocrystals, we first offer a discussion on the correlation between the initial redn. rate and the internal structure of the resultant seeds. The kinetic approaches for controlling both nucleation and growth in a one-pot setting are then introduced with an emphasis on manipulation of the redn. pathways taken by the precursor. We then illustrate how to extend the strategy into a bimetallic system for the prepn. of nanocrystals with different shapes and elemental distributions. Finally, the influence of speciation of the precursor on redn. kinetics is highlighted, followed by our perspectives on the challenges and future endeavors in achieving a controllable and predictable synthesis of noble-metal nanocrystals.
- 35Huang, X.; Li, S.; Huang, Y.; Wu, S.; Zhou, X.; Li, S.; Gan, C. L.; Boey, F.; Mirkin, C. A.; Zhang, H. Synthesis of hexagonal close-packed gold nanostructures. Nat. Commun. 2011, 2, 292, DOI: 10.1038/ncomms1291Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3MvntVKitg%253D%253D&md5=ea13bf98aea70fe14551044c2a82810bSynthesis of hexagonal close-packed gold nanostructuresHuang Xiao; Li Shaozhou; Huang Yizhong; Wu Shixin; Zhou Xiaozhu; Li Shuzhou; Gan Chee Lip; Boey Freddy; Mirkin Chad A; Zhang HuaNature communications (2011), 2 (), 292 ISSN:.Solid gold is usually most stable as a face-centred cubic (fcc) structure. To date, no one has synthesized a colloidal form of Au that is exclusively hexagonal close-packed (hcp) and stable under ambient conditions. Here we report the first in situ synthesis of dispersible hcp Au square sheets on graphene oxide sheets, which exhibit an edge length of 200-500 nm and a thickness of ~ 2.4 nm (~ 16 Au atomic layers). Interestingly, the Au square sheet transforms from hcp to a fcc structure on exposure to an electron beam during transmission electron microscopy analysis. In addition, as the square sheet grows thicker (from ~ 2.4 to 6 nm), fcc segments begin to appear. A detailed experimental analysis of these structures shows that for structures with ultrasmall dimensions (for example, <~ 6 nm thickness for the square sheets), the previously unobserved pure hcp structure becomes stable and isolable.
- 36Gao, Y.; Peng, X. Crystal structure control of CdSe nanocrystals in growth and nucleation: dominating effects of surface versus interior structure. J. Am. Chem. Soc. 2014, 136, 6724– 6732, DOI: 10.1021/ja5020025Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXlsl2rsL4%253D&md5=f84e66a009cffef23aff9efad06a4b99Crystal Structure Control of CdSe Nanocrystals in Growth and Nucleation: Dominating Effects of Surface versus Interior StructureGao, Yuan; Peng, XiaogangJournal of the American Chemical Society (2014), 136 (18), 6724-6732CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)For the most studied nanocrystal system in the literature, exptl. results in this paper revealed that formation of either Zn blende or wurtzite CdSe nanocrystals was dominated by the ligand-surface interaction, instead of the interior structure difference. This conclusion was considered to be reasonable, given the very small energy difference between wurtzite and Zn blende CdSe (only 1.4 meV per CdSe unit and ∼1000 times smaller than the energy of a single Cd-ligand bond). Cd carboxylate ligands as Cd fatty acid salts promoted formation of the Zn blende structure. Conversely, Cd phosphonate ligands with a long hydrocarbon chain favored the formation of the wurtzite structure. The effects of either Cd carboxylate or Cd phosphonate ligands play a detg. role during both nucleation and growth. Different from the authors' expectation, fatty amine is only a secondary factor for crystal structure detn. With an appropriate choice of capping ligands, it was possible to achieve precise control of the crystal structure of the CdSe nanocrystals in both nucleation and growth for either the Zn blende or wurtzite structure.
- 37Yao, Y.; He, D.; Lin, Y.; Feng, X.; Wang, X.; Yin, P.; Hong, X.; Zhou, G.; Wu, Y.; Li, Y. Modulating fcc and hcp ruthenium on the surface of palladium-copper alloy through tunable lattice mismatch. Angew. Chem., Int. Ed. 2016, 55, 5501– 5505, DOI: 10.1002/anie.201601016Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XkvVChsLg%253D&md5=09ddf4a02d945987bccb27c4f333210aModulating fcc and hcp Ruthenium on the Surface of Palladium-Copper Alloy through Tunable Lattice MismatchYao, Yancai; He, Dong Sheng; Lin, Yue; Feng, Xiaoqian; Wang, Xin; Yin, Peiqun; Hong, Xun; Zhou, Gang; Wu, Yuen; Li, YadongAngewandte Chemie, International Edition (2016), 55 (18), 5501-5505CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Herein, we report an epitaxial-growth-mediated method to grow fcc. Ru, which is thermodynamically unfavorable in the bulk form, on the surface of Pd-Cu alloy. Induced by the galvanic replacement between Ru and Pd-Cu alloy, a shape transformation from a Pd-Cu@Ru core-shell to a yolk-shell structure was obsd. during the epitaxial growth. The successful coating of the unconventional crystallog. structure is critically dependent on the moderate lattice mismatch between the fcc. Ru overlayer and PdCu3 alloy substrate. Further, both fcc. and hcp. Ru can be selectively grown through varying the lattice spacing of the Pd-Cu substrate. The presented findings provide a new synthetic pathway to control the crystallog. structure of metal nanomaterials.
- 38Gloag, L.; Benedetti, T. M.; Cheong, S.; Li, Y.; Chan, X.-H.; Lacroix, L.-M.; Chang, S. L. Y.; Arenal, R.; Florea, I.; Barron, H.; Barnard, A. S.; Henning, A. M.; Zhao, C.; Schuhmann, W.; Gooding, J. J.; Tilley, R. D. Three-dimensional branched and faceted gold-ruthenium nanoparticles: using nanostructure to improve stability in oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2018, 57, 10241– 10245, DOI: 10.1002/anie.201806300Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlWqtLrI&md5=1b3f33ff8ce574054cf34aa15fd1c46fThree-Dimensional Branched and Faceted Gold-Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution ElectrocatalysisGloag, Lucy; Benedetti, Tania M.; Cheong, Soshan; Li, Yibing; Chan, Xuan-Hao; Lacroix, Lise-Marie; Chang, Shery L. Y.; Arenal, Raul; Florea, Ileana; Barron, Hector; Barnard, Amanda S.; Henning, Anna M.; Zhao, Chuan; Schuhmann, Wolfgang; Gooding, J. Justin; Tilley, Richard D.Angewandte Chemie, International Edition (2018), 57 (32), 10241-10245CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the O evolution reaction. As improved stability of Ru catalysts was shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new soln. synthesis is presented in which hcp. structured Ru is grown on Au to form nanoparticles with 3-dimensional branches. Exposing low-index facets on these 3-dimensional branches creates stable reaction kinetics to achieve high activity and the highest stability obsd. for Ru nanoparticle O evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.
- 39Koenigsmann, C.; Semple, D. B.; Sutter, E.; Tobierre, S. E.; Wong, S. S. Ambient synthesis of high-quality ruthenium nanowires and the morphology-dependent electrocatalytic performance of platinum-decorated ruthenium nanowires and nanoparticles in the methanol oxidation reaction. ACS Appl. Mater. Interfaces 2013, 5, 5518– 5530, DOI: 10.1021/am4007462Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXptVeqtrc%253D&md5=2e54a3c1c282f97e46fdc240c054586aAmbient Synthesis of High-Quality Ruthenium Nanowires and the Morphology-Dependent Electrocatalytic Performance of Platinum-Decorated Ruthenium Nanowires and Nanoparticles in the Methanol Oxidation ReactionKoenigsmann, Christopher; Semple, Dara Bobb; Sutter, Eli; Tobierre, Sybil E.; Wong, Stanislaus S.ACS Applied Materials & Interfaces (2013), 5 (12), 5518-5530CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The synthesis is reported for first time of elemental ruthenium nanowires (Ru NWs), method for modifying their surfaces with platinum (Pt), and the morphol.-dependent methanol oxidn. reaction (MOR) performance of high-quality Pt-modified Ru NW electrocatalysts. The synthesis of the elemental Ru NWs was accomplished utilizing a template-based method under ambient conditions. As-prepd. Ru NWs are cryst. and elementally pure, maintain electrochem. properties analogous to elemental Ru, and can be generated with av. diams. ranging from 44-280 nm. The morphol.-dependent performance is examd. of the Ru NWs by comparison with com. Ru nanoparticle (NP)/carbon (C) systems after decorating the surfaces of these structures with Pt. It is demonstrated that the deposition of Pt onto the Ru NWs (Pt∼Ru NWs) results in a unique hierarchical structure, wherein the deposited Pt exists as discrete clusters on the surface. By contrast, it is found that the Pt-decorated com. Ru NP/C (Pt∼Ru NP/C) results in the formation of an alloy-type NP. The Pt∼Ru NPs (0.61 A/mg of Pt) possess nearly 2-fold higher Pt mass activity than analogous Pt∼Ru NW electrocatalysts (0.36 A/mg of Pt). On the basis of a long-term durability test, it is apparent that both catalysts undergo significant declines in performance, potentially resulting from aggregation and ripening in the case of Pt∼Ru NP/C and the effects of catalyst poisoning in the Pt∼Ru NWs. Both catalysts maintain comparable performance, despite a slightly enhanced performance in Pt∼Ru NP/C. In addn., the measured mass-normalized MOR activity of the Pt∼Ru NWs (0.36 A/mg of Pt) was significantly enhanced as compared with supported elemental Pt (Pt NP/C, 0.09 A/mg of Pt) and alloy-type PtRu (PtRu NP/C, 0.24 A/mg of Pt) NPs, both serving as com. stds.
- 40Yin, A. X.; Liu, W. C.; Ke, J.; Zhu, W.; Gu, J.; Zhang, Y. W.; Yan, C. H. Ru nanocrystals with shape-dependent surface-enhanced Raman spectra and catalytic properties: controlled synthesis and DFT calculations. J. Am. Chem. Soc. 2012, 134, 20479– 20489, DOI: 10.1021/ja3090934Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslCgsbzP&md5=14820d8b95f71d0765f699a6be7dca11Ru Nanocrystals with Shape-Dependent Surface-Enhanced Raman Spectra and Catalytic Properties: Controlled Synthesis and DFT CalculationsYin, An-Xiang; Liu, Wen-Chi; Ke, Jun; Zhu, Wei; Gu, Jun; Zhang, Ya-Wen; Yan, Chun-HuaJournal of the American Chemical Society (2012), 134 (50), 20479-20489CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Despite its multidisciplinary interests and technol. importance, the shape control of Ru nanocrystals still remains a great challenge. In this article, we demonstrated a facile hydrothermal approach toward the controlled synthesis of Ru nanocrystals with the assistance of first-principles calcns. For the first time, Ru triangular and irregular nanoplates as well as capped columns with tunable sizes were prepd. with high shape selectivity. In consistency with the exptl. observations and d. functional theory (DFT) calcns. confirmed that both the intrinsic characteristics of Ru crystals and the adsorption of certain reaction species were responsible for the shape control of Ru nanocrystals. Ultrathin Ru nanoplates exposed a large portion of (0001) facets due to the lower surface energy of Ru(0001). The selective adsorption of oxalate species on Ru(10-10) would retard the growth of the side planes of the Ru nanocrystals, while the gradual thermolysis of the oxalate species would eliminate their adsorption effects, leading to the shape evolution of Ru nanocrystals from prisms to capped columns. The surface-enhanced Raman spectra (SERS) signals of these Ru nanocrystals with 4-mercaptopyridine as mol. probes showed an enhancement sequence of capped columns > triangle nanoplates > nanospheres, probably due to the sharp corners and edges in the capped columns and nanoplates as well as the shrunk interparticle distance in their assemblies. CO-selective methanation tests on these Ru nanocrystals indicated that the nanoplates and nanospheres had comparable activities, but the former has much better CO selectivity than the latter.
- 41Watt, J.; Yu, C.; Chang, S. L. Y.; Cheong, S.; Tilley, R. D. Shape control from thermodynamic growth conditions: the case of hcp ruthenium hourglass nanocrystals. J. Am. Chem. Soc. 2013, 135, 606– 609, DOI: 10.1021/ja311366kGoogle Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvV2gsLjK&md5=e7b4a7878d6482542cb93d61c9481d53Shape Control from Thermodynamic Growth Conditions: The Case of hcp Ruthenium Hourglass NanocrystalsWatt, John; Yu, Chenlong; Chang, Shery L. Y.; Cheong, Soshan; Tilley, Richard D.Journal of the American Chemical Society (2013), 135 (2), 606-609CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Recent successes in forming different shaped fcc. (fcc) metal nanostructures has enabled a greater understanding of nanocrystal growth mechanisms. Here we extend this understanding to the synthesis of hexagonally close packed (hcp) metal nanostructures, to form uniquely faceted ruthenium nanocrystals with a well-defined hourglass shape. The hourglass nanocrystals are formed in a three-step thermodn. growth process with dodecylamine as the org. stabilizer. The hourglass nanocrystals are then shown to readily self-assemble to form a new type of nanocrystal superlattice.
- 42Rodrigues, T. S.; Zhao, M.; Yang, T.-H.; Gilroy, K. D.; da Silva, A. G. M.; Camargo, P. H. C.; Xia, Y. Synthesis of colloidal metal nanocrystals: a comprehensive review on the reductants. Chem.─Eur. J. 2018, 24, 16944– 16963, DOI: 10.1002/chem.201802194Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFyjs7jJ&md5=0442b9624f8162ae7d3c27c1d3a789ebSynthesis of Colloidal Metal Nanocrystals: A Comprehensive Review on the ReductantsRodrigues, Thenner S.; Zhao, Ming; Yang, Tung-Han; Gilroy, Kyle D.; da Silva, Anderson G. M.; Camargo, Pedro H. C.; Xia, YounanChemistry - A European Journal (2018), 24 (64), 16944-16963CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)There is a growing interest in controlling the synthesis of colloidal metal nanocrystals and thus tailoring their properties toward various applications. In this context, choosing an appropriate combination of reagents (e.g., salt precursor, reductant, capping agent, and stabilizer) plays a pivotal role in enabling the synthesis of metal nanocrystals with diversified sizes, shapes, and structures. Here we present a comprehensive review that highlights one of the key reagents for the synthesis of metal nanocrystals via chem. redn.: the reductants. We start with a brief introduction to the compds. commonly employed as reductants in the colloidal synthesis of metal nanocrystals by showing their oxidn. half-reactions and the corresponding oxidn. potentials. Then we offer specific examples pertaining to the controlled synthesis of metal nanocrystals, followed by some fundamental aspects covering the general mechanisms of metal ion redn. based on the Marcus Theory. Afterwards, we present a case-by-case discussion on a wide variety of reductants, including their major properties, redn. mechanisms, and addnl. effects on the final products. We illustrate these aspects by selecting key examples from the literature and paying close attention to the underlying mechanism in each case. At the end, we conclude by summarizing the highlights of the review and providing some perspectives on future directions.
- 43Holder, C. F.; Schaak, R. E. Tutorial on Powder X-ray Diffraction for Characterizing Nanoscale Materials. ACS Nano 2019, 13, 7359– 7365, DOI: 10.1021/acsnano.9b05157Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtl2iu7%252FN&md5=1cc19bb0dce3776f4aefcb3eee6a308bTutorial on Powder X-ray Diffraction for Characterizing Nanoscale MaterialsHolder, Cameron F.; Schaak, Raymond E.ACS Nano (2019), 13 (7), 7359-7365CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)A review. The authors provide the broad nanoscience and nanotechnol. communities with a brief tutorial on some of the key aspects of powder XRD data that are often encountered when analyzing samples of nanoscale materials, with an emphasis on inorg. nanoparticles of various sizes, shapes, and dimensionalities.
- 44Nguyen, Q. N.; Wang, C.; Shang, Y.; Janssen, A.; Xia, Y. Colloidal synthesis of metal nanocrystals: from asymmetrical growth to symmetry breaking. Chem. Rev. 2023, 123, 3693– 3760, DOI: 10.1021/acs.chemrev.2c00468Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFGnsb%252FJ&md5=75b8e44b38e7c05d440d24c394e2107bColloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry BreakingNguyen, Quynh N.; Wang, Chenxiao; Shang, Yuxin; Janssen, Annemieke; Xia, YounanChemical Reviews (Washington, DC, United States) (2023), 123 (7), 3693-3760CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Nanocrystals offer a unique platform for tailoring the physicochem. properties of solid materials to enhance their performances in various applications. While most work on controlling their shapes revolves around sym. growth, the introduction of asym. growth and thus symmetry breaking has also emerged as a powerful route to enrich metal nanocrystals with new shapes and complex morphologies, as well as unprecedented properties and functionalities. The success of this route critically relies on our ability to lift the confinement on symmetry by the underlying unit cell of the crystal structure and/or the initial seed in a systematic manner. This Review aims to provide an account of recent progress in understanding and controlling asym. growth and symmetry breaking in a colloidal synthesis of noble-metal nanocrystals. With a touch on both the nucleation and growth steps, we discuss a no. of methods capable of generating seeds with diverse symmetry while achieving asym. growth for mono-, bi-, and multimetallic systems. We then showcase a variety of symmetry-broken nanocrystals that have been reported, together with insights into their growth mechanisms. We also highlight their properties and applications and conclude with perspectives on future directions in developing this class of nanomaterials. It is hoped that the concepts and existing challenges outlined in this Review will drive further research in understanding and controlling the symmetry breaking process.
- 45Yin, X.; Shi, M.; Wu, J.; Pan, Y.-T.; Gray, D. L.; Bertke, J. A.; Yang, H. Quantitative analysis of different formation modes of platinum nanocrystals controlled by ligand chemistry. Nano Lett. 2017, 17, 6146– 6150, DOI: 10.1021/acs.nanolett.7b02751Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsVelurjO&md5=7d20979f2314047ba452555bbcae5cf5Quantitative Analysis of Different Formation Modes of Platinum Nanocrystals Controlled by Ligand ChemistryYin, Xi; Shi, Miao; Wu, Jianbo; Pan, Yung-Tin; Gray, Danielle L.; Bertke, Jeffery A.; Yang, HongNano Letters (2017), 17 (10), 6146-6150CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The authors report that spontaneous ligand replacement and anion exchange control the form of coordinated Pt-ligand intermediates in the system of platinum acetylacetonate [Pt(acac)2], primary aliph. amine, and carboxylic acid ligands. The formed intermediates govern the formation mode of Pt nanocrystals, leading to either a pseudo two-step or a one-step mechanism by switching on or off an autocatalytic surface growth. This finding shows the importance of metal-ligand complexation at the prenucleation stage and represents a crit. step forward for the designed synthesis of nanocrystal-based materials.
- 46Yang, T.-H.; Zhou, S.; Gilroy, K. D.; Figueroa-Cosme, L.; Lee, Y.-H.; Wu, J.-M.; Xia, Y. Autocatalytic surface reduction and its role in controlling seed-mediated growth of colloidal metal nanocrystals. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 13619– 13624, DOI: 10.1073/pnas.1713907114Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFGns7%252FF&md5=df6ee52ebf5fabf54a61e82bf5d64389Autocatalytic surface reduction and its role in controlling seed-mediated growth of colloidal metal nanocrystalsYang, Tung-Han; Zhou, Shan; Gilroy, Kyle D.; Figueroa-Cosme, Legna; Lee, Yi-Hsien; Wu, Jenn-Ming; Xia, YounanProceedings of the National Academy of Sciences of the United States of America (2017), 114 (52), 13619-13624CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)The growth of colloidal metal nanocrystals typically involves an autocatalytic process, where the salt precursor is adsorbed on a growing nanocrystal surface, followed by chem. redn. to atoms for their incorporation into the nanocrystal. Despite its universal role in colloidal nanocrystal synthesis, it is still poorly understood and controlled in terms of kinetics. Using well-defined nanocrystals as seeds (including those with different types of facets, sizes, internal twin structure) this work quant. analyzed the kinetics of autocatalytic surface redn. to control the evolution of nanocrystals as predictable shapes. Kinetic measurements demonstrated the activation energy barrier to autocatalytic surface redn. highly depended on type of facet and presence of twin boundary, corresponding to distinctive growth patterns and products. The autocatalytic process effectively eliminates homogeneous nucleation and activates and sustains octahedral nanocrystal growth. This work was a major step toward quant. understanding and controlling the autocatalytic process involved in colloidal metal nanocrystal synthesis.
- 47Yang, T.-H.; Peng, H.-C.; Zhou, S.; Lee, C.-T.; Bao, S.; Lee, Y.-H.; Wu, J.-M.; Xia, Y. Toward a quantitative understanding of the reduction pathways of a salt precursor in the synthesis of metal nanocrystals. Nano Lett. 2017, 17, 334– 340, DOI: 10.1021/acs.nanolett.6b04151Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitVKqtbnK&md5=eabdbd8fcf7f308996d8e3fb3dd42439Toward a Quantitative Understanding of the Reduction Pathways of a Salt Precursor in the Synthesis of Metal NanocrystalsYang, Tung-Han; Peng, Hsin-Chieh; Zhou, Shan; Lee, Chi-Ta; Bao, Shixiong; Lee, Yi-Hsien; Wu, Jenn-Ming; Xia, YounanNano Letters (2017), 17 (1), 334-340CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Despite the pivotal role played by the redn. of a salt precursor in the synthesis of metal nanocrystals, it is still unclear how the precursor is reduced. The precursor can be reduced to an atom in the soln. phase, followed by its deposition onto the surface of a growing nanocrystal. Alternatively, the precursor can adsorb onto the surface of a growing nanocrystal, followed by redn. through an autocatalytic process. With Pd as an example, here we demonstrate that the pathway has a correlation with the redn. kinetics involved. Quant. analyses of the redn. kinetics of PdCl42- and PdBr42- by ascorbic acid at room temp. in the absence and presence of Pd nanocubes, resp., suggest that PdCl42- was reduced in the soln. phase while PdBr42- was reduced on the surface of a growing nanocrystal. These results demonstrate that the redn. pathway of PdBr42- by ascorbic acid could be switched from surface to soln. by raising the reaction temp.
- 48Xia, X.; Xie, S.; Liu, M.; Peng, H. C.; Lu, N.; Wang, J.; Kim, M. J.; Xia, Y. On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals. Proc. Natl. Acad. Sci. U.S.A 2013, 110, 6669– 6673, DOI: 10.1073/pnas.1222109110Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXot1Ghs74%253D&md5=68e4936799994c2dbcdbfd8f0ce541d9On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystalsXia, Xiaohu; Xie, Shuifen; Liu, Maochang; Peng, Hsin-Chieh; Lu, Ning; Wang, Jinguo; Kim, Moon J.; Xia, YounanProceedings of the National Academy of Sciences of the United States of America (2013), 110 (17), 6669-6673, S6669/1-S6669/6CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Controlling the shape or morphol. of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addn. of at. species. In this case, manipulating the rates at which the at. species are added onto different crystallog. planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphol. taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. The authors demonstrate that the growth pathway of a seed is indeed detd. by the ratio between the rates for atom deposition and surface diffusion. Surface diffusion needs to be taken into account when controlling the shape or morphol. of metal nanocrystals.
- 49Janssen, A.; Pawlik, V.; von Rueden, A. D.; Xu, L.; Wang, C.; Mavrikakis, M.; Xia, Y. Facile synthesis of palladium-based nanocrystals with different crystal phases and a comparison of their catalytic properties. Adv. Mater. 2021, 33, 2103801 DOI: 10.1002/adma.202103801Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXit1WjsL7J&md5=f78c38c9e04d1c1259f2624a9a78fb45Facile synthesis of palladium-based nanocrystals with different crystal phases and comparison of their catalytic propertiesJanssen, Annemieke; Pawlik, Veronica; von Rueden, Alexander D.; Xu, Lang; Wang, Chenxiao; Mavrikakis, Manos; Xia, YounanAdvanced Materials (Weinheim, Germany) (2021), 33 (49), 2103801CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A relatively unexplored aspect of noble-metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, a method is reported for the facile synthesis of Ru@Pd core-shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell takes either an hcp or face-centered cubic (fcc) phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking the hcp phase whereas the thicker ones revert to fcc. The injection rate provides an exptl. knob for controlling the phase, with one-shot and drop-wise injection of the Pd precursor corresponding to fcc-Pd and hcp-Pd shells, resp. When these nanocrystals are tested as catalysts toward formic acid oxidn., the Ru@Pdhcp nanocrystals outperform Ru@Pdfcc in terms of both specific activity and peak potential. D. functional theory calcns. are also performed to elucidate the origin of this performance enhancement.
- 50Zhang, H.; Li, W.; Jin, M.; Zeng, J.; Yu, T.; Yang, D.; Xia, Y. Controlling the morphology of rhodium nanocrystals by manipulating the growth kinetics with a syringe pump. Nano Lett. 2011, 11, 898– 903, DOI: 10.1021/nl104347jGoogle Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmsFak&md5=8fae00ef1c1bbe3de1a06bdd90784536Controlling the Morphology of Rhodium Nanocrystals by Manipulating the Growth Kinetics with a Syringe PumpZhang, Hui; Li, Weiyang; Jin, Mingshang; Zeng, Jie; Yu, Taekyung; Yang, Deren; Xia, YounanNano Letters (2011), 11 (2), 898-903CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Noble-metal nanocrystals with well-defined and controllable morphologies are of great importance to applications in catalysis, plasmonics, and surface-enhanced spectroscopy. Many synthetic approaches have been demonstrated for controlling the growth habit and thus morphol. of metal nanocrystals, but most of them are based on a thermodn. approach, including the use of a capping agent. While thermodn. control has shown its power in generating nanocrystals with a myriad of different morphologies, it is ultimately limited by the obligation to minimize the surface energy of a system. As a result, it is impractical to use thermodn. control to generate nanocrystals having high-energy facets and/or a neg. curvature. Using rhodium as an example, here we demonstrate a general method based on kinetic control with a syringe pump that can be potentially extended to other noble metals and even other solid materials. For the first time, we were able to produce concave nanocubes with a large fraction of {110} facets and octapods with a cubic symmetry in high yields by simply controlling the injection rate at which the precursor was added into the reaction soln. The concave nanocubes with {110} facets and a unique cavity structure on the surface are important for a variety of applications.
- 51Zhao, M.; Chen, Z.; Shi, Y.; Hood, Z. D.; Lyu, Z.; Xie, M.; Chi, M.; Xia, Y. Kinetically controlled synthesis of rhodium nanocrystals with different shapes and a comparison study of their thermal and catalytic Properties. J. Am. Chem. Soc. 2021, 143, 6293– 6302, DOI: 10.1021/jacs.1c02734Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXos1Shurg%253D&md5=827bee34159d246fdd39d05625e1388eKinetically Controlled Synthesis of Rhodium Nanocrystals with Different Shapes and a Comparison Study of Their Thermal and Catalytic PropertiesZhao, Ming; Chen, Zitao; Shi, Yifeng; Hood, Zachary D.; Lyu, Zhiheng; Xie, Minghao; Chi, Miaofang; Xia, YounanJournal of the American Chemical Society (2021), 143 (16), 6293-6302CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The authors report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable redn. kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temp. to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500°, resp. When tested as catalysts for hydrazine decompn., the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H2 selectivity relative to the cubic counterpart. As for EtOH oxidn., the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.
- 52Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. The surface energy of metals. Surf. Sci. 1998, 411, 186– 202, DOI: 10.1016/S0039-6028(98)00363-XGoogle Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXlvFGnurk%253D&md5=84f3dd83df818f90bfe80a23b3c7b778The surface energy of metalsVitos, L.; Ruban, A. V.; Skriver, H. L.; Kollar, J.Surface Science (1998), 411 (1/2), 186-202CODEN: SUSCAS; ISSN:0039-6028. (Elsevier Science B.V.)The authors used d. functional theory to establish a database of surface energies for low index surfaces of 60 metals in the periodic table. The data may be used as a consistent starting point for models of surface science phenomena. The accuracy of the database is established in a comparison with other d. functional theory results and the calcd. surface energy anisotropies are applied in a detn. of the equil. shape of nano-crystals of Fe, Cu, Mo, Ta, Pt and Pb.
- 53Wang, Y.; Peng, H.-C.; Liu, J.; Huang, C. Z.; Xia, Y. Use of reduction rate as a quantitative knob for controlling the twin structure and shape of palladium nanocrystals. Nano Lett. 2015, 15, 1445– 1450, DOI: 10.1021/acs.nanolett.5b00158Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsF2ns7g%253D&md5=0d6c8af7184c76046474f291c01615a9Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium NanocrystalsWang, Yi; Peng, Hsin-Chieh; Liu, Jingyue; Huang, Cheng Zhi; Xia, YounanNano Letters (2015), 15 (2), 1445-1450CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Kinetic control is a powerful means for maneuvering the twin structure and shape of metal nanocrystals and thus optimizing their performance in a variety of applications. However, there is only a vague understanding of the explicit roles played by reaction kinetics due to the lack of quant. information about the kinetic parameters. With Pd as an example, here we demonstrate that kinetic parameters, including rate const. and activation energy, can be derived from spectroscopic measurements and then used to calc. the initial redn. rate and further have this parameter quant. correlated with the twin structure of a seed and nanocrystal. On a quant. basis, we were able to det. the ranges of initial redn. rates required for the formation of nanocrystals with a specific twin structure, including single-crystal, multiply twinned, and stacking fault-lined. This work represents a major step forward toward the deterministic syntheses of colloidal noble-metal nanocrystals with specific twin structures and shapes.
- 54Plyuto, Y. V.; Babich, I. V.; Sharanda, L. F.; Marco De Wit, A.; Mol, J. C. Thermolysis of Ru(acac)3 supported on silica and alumina. Thermochim. Acta 1999, 335, 87– 89, DOI: 10.1016/S0040-6031(99)00148-3Google ScholarThere is no corresponding record for this reference.
- 55Morozova, N. B.; Gelfond, N. V.; Semyannikov, P. P.; Trubin, S. V.; Igumenov, I. K.; Gutakovskii, A. K.; Latyshev, A. V. Preparation of thin films of platinum group metals by pulsed MOCVD. II. Deposition of Ru layers. J. Struct. Chem. 2012, 53, 725– 733, DOI: 10.1134/S0022476612040154Google ScholarThere is no corresponding record for this reference.
- 56Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Ahmari, S. A.; Alkayali, W. Z. Kinetic analysis of thermal decomposition of unirradiated and γ-irradiated tris(acetylacetonato)-ruthenium(III) [Ru(acac)3]. Prog. React. Kinet. Mech. 2007, 32, 1– 27, DOI: 10.3184/146867807X217337Google ScholarThere is no corresponding record for this reference.
- 57Kucharyson, J. F.; Gaudet, J. R.; Wyvratt, B. M.; Thompson, L. T. Characterization of structural and electronic transitions during reduction and oxidation of Ru(acac)3 flow battery electrolytes by using X-ray absorption spectroscopy. ChemElectroChem. 2016, 3, 1875– 1883, DOI: 10.1002/celc.201600360Google ScholarThere is no corresponding record for this reference.
- 58Vydrov, O. A.; Scuseria, G. E.; Perdew, J. P. Tests of functionals for systems with fractional electron number. J. Chem. Phys. 2007, 126, 154109 DOI: 10.1063/1.2723119Google Scholar58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXkvF2rsbw%253D&md5=5ecdccfa19dff53b01250b7599776e54Tests of functionals for systems with fractional electron numberVydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.Journal of Chemical Physics (2007), 126 (15), 154109/1-154109/9CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)In the exact theory, the ground state energy of an open system varies linearly when the electron no. is changed between two adjacent integers. This linear dependence is not reproduced by common approx. d. functionals. Deviation from linearity in this dependence has been suggested as a basis for the concept of many-electron self-interaction error (SIE). In this paper, we quantify many-electron SIE of a no. of approxns. by performing calcns. on fractionally charged atoms. We demonstrate the direct relevance of these studies to such problems of common approx. functionals as instabilities of anions, spurious fractional charges on dissocd. atoms, and poor description of charge transfer. Semilocal approxns. have the largest many-electron SIE, which is only slightly reduced in typical global hybrids. In these approxns. the energy vs. fractional electron no. curves upward, while in Hartree-Fock theory the energy curves downward. Perdew-Zunger self-interaction correction [Phys. Rev. B 23, 5048 (1981)] significantly reduces the many-electron SIE of semilocal functionals but impairs their accuracy for equil. properties. In contrast, a long-range cor. hybrid functional can be nearly many-electron SIE-free in many cases (for reasons we discuss) and at the same time performs remarkably well for many mol. properties.
- 59Raebiger, H.; Lany, S.; Zunger, A. Charge self-regulation upon changing the oxidation state of transition metals in insulators. Nature 2008, 453, 763– 766, DOI: 10.1038/nature07009Google Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXmvVGmsb8%253D&md5=d77ea901d289492ef9c8a231f062a493Charge self-regulation upon changing the oxidation state of transition metals in insulatorsRaebiger, Hannes; Lany, Stephan; Zunger, AlexNature (London, United Kingdom) (2008), 453 (7196), 763-766CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Transition-metal atoms embedded in an ionic or semiconducting crystal can exist in various oxidn. states that have distinct signatures in X-ray photoemission spectroscopy and ionic radii' which vary with the oxidn. state of the atom. We explain this peculiar tendency of transition-metal atoms to maintain a const. local charge under external perturbations in terms of an inherent, homeostasis-like neg. feedback. We show that signatures of oxidn. states and multivalence-such as X-ray photoemission core-level shifts, ionic radii and variations in local magnetization-that have often been interpreted as literal charge transfer are instead a consequence of the neg.-feedback charge regulation.
- 60Stampfl, C.; Scheffler, M. Theoretical study of O adlayers on Ru(0001). Phys. Rev. B 1996, 54, 2868– 2872, DOI: 10.1103/PhysRevB.54.2868Google ScholarThere is no corresponding record for this reference.
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- 1Cao, S.; Tao, F. F.; Tang, Y.; Li, Y.; Yu, J. Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts. Chem. Soc. Rev. 2016, 45, 4747– 4765, DOI: 10.1039/C6CS00094K1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XpsVGgu74%253D&md5=939a2cea2e3eb6acdd78183850bc1c3dSize- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalystsCao, Shaowen; Tao, Franklin; Tang, Yu; Li, Yuting; Yu, JiaguoChemical Society Reviews (2016), 45 (17), 4747-4765CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)Heterogeneous catalysis is one of the most important chem. processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liq. interfaces with a purpose of establishing correlations of size- and shape-dependent chem. and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a mol. level.
- 2Shi, Y.; Lyu, Z.; Zhao, M.; Chen, R.; Nguyen, Q. N.; Xia, Y. Noble-metal nanocrystals with controlled shapes for catalytic and electrocatalytic applications. Chem. Rev. 2021, 121, 649– 735, DOI: 10.1021/acs.chemrev.0c004542https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtlOgt7rE&md5=230eadee842f06379f791dafc4335e1cNoble-Metal Nanocrystals with Controlled Shapes for Catalytic and Electrocatalytic ApplicationsShi, Yifeng; Lyu, Zhiheng; Zhao, Ming; Chen, Ruhui; Nguyen, Quynh N.; Xia, YounanChemical Reviews (Washington, DC, United States) (2021), 121 (2), 649-735CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. The successful synthesis of noble-metal nanocrystals with controlled shapes offers many opportunities to not only maneuver their physicochem. properties but also optimize their figures of merit in a wide variety of applications. In particular, heterogeneous catalysis and surface science have benefited enormously from the availability of this new class of nanomaterials as the at. structure presented on the surface of a nanocrystal is ultimately detd. by its geometric shape. The immediate advantages may include significant enhancement in catalytic activity and/or selectivity and substantial redn. in materials cost while providing a well-defined model system for mechanistic study. With a focus on the monometallic system, this article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addn. to their remarkable performance in a large no. of catalytic and electrocatalytic reactions. We hope that this article offers the impetus and roadmap for the development of next-generation catalysts vital to a broad range of industrial applications.
- 3Xie, C.; Niu, Z.; Kim, D.; Li, M.; Yang, P. Surface and interface control in nanoparticle catalysis. Chem. Rev. 2020, 120, 1184– 1249, DOI: 10.1021/acs.chemrev.9b002203https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvV2hs7%252FM&md5=4a9631d9bd20ee9ab785f91b721f62baSurface and Interface Control in Nanoparticle CatalysisXie, Chenlu; Niu, Zhiqiang; Kim, Dohyung; Li, Mufan; Yang, PeidongChemical Reviews (Washington, DC, United States) (2020), 120 (2), 1184-1249CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. The surface and interfaces of heterogeneous catalysts are essential to their performance as they are often considered to be active sites for catalytic reactions. With the development of nanoscience, the ability to tune surface and interface of nanostructures has provided a versatile tool for the development and optimization of a heterogeneous catalyst. In this Review, we present the surface and interface control of nanoparticle catalysts in the context of oxygen redn. reaction (ORR), electrochem. CO2 redn. reaction (CO2 RR), and tandem catalysis in three sections. In the first section, we start with the activity of ORR on the nanoscale surface and then focus on the approaches to optimize the performance of Pt-based catalyst including using alloying, core-shell structure, and high surface area open structures. In the section of CO2 RR, where the surface compn. of the catalysts plays a dominant role, we cover its reaction fundamentals and the performance of different nanosized metal catalysts. For tandem catalysis, where adjacent catalytic interfaces in a single nanostructure catalyze sequential reactions, we describe its concept and principle, catalyst synthesis methodol., and application in different reactions.
- 4Li, J.; Sun, S. Intermetallic nanoparticles: synthetic control and their enhanced electrocatalysis. Acc. Chem. Res. 2019, 52, 2015– 2025, DOI: 10.1021/acs.accounts.9b001724https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1Kis7zK&md5=132569abe7c3cc95c0ac8e279812c575Intermetallic Nanoparticles: Synthetic Control and Their Enhanced ElectrocatalysisLi, Junrui; Sun, ShouhengAccounts of Chemical Research (2019), 52 (7), 2015-2025CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Intermetallic nanoparticles (NPs) described in this Account are a class of metallic alloy NPs within which metal atoms are bonded via strong d-orbital interaction and ordered anisotropically in a specific crystallog. direction. Compared to the common metallic alloy NPs with solid soln. structure, intermetallic NPs are generally more stable against chem. oxidn. and etching. The strict stoichiometry requirement, well-defined atom binding environment and layered at. arrangement also make intermetallic NPs an ideal model for understanding their phys. and catalytic properties. This account summarizes the synthetic principles and strategies developed to obtain monodisperse intermetallic NPs, esp. tetragonal L10-NPs. The thermodn. and kinetics involved in the conversion between disordered and ordered structures are briefly discussed. The synthetic methods are grouped into two slightly different categories: soln.-phase synthesis followed by solid state annealing and direct soln.-phase synthesis. In the former method, high-surface-area supports are often needed to disperse NPs and to prevent them from aggregation, while in the latter method such supports are not required since the structure conversion temp. is lowered to a level that the conversion can proceed in the soln. reaction condition. In any of these two synthetic approaches, various factors influencing intermetallic structure formation should be carefully controlled to ensure more complete structural transition within NPs. Using representative synthetic examples, we highlight the strategies explored to facilitate the formation of intermetallic structure, including the introduction of vacancies/defects within NP structures and the control of atom addn. rate/seed-mediated diffusion to lower the energy barrier. These strategies illustrate how the concept of thermodn. and kinetics can be used to design the synthesis of intermetallic NPs. Addnl., to correlate NP structure and catalysis, we introduce briefly the d-band theory to explain how the electronic, strain and ensemble effects can be used to tune NP catalysis. We focus specifically on Pt-, Pd-, and Au-based L10-NPs and demonstrate how these L10-NPs could be prepd. to show much enhanced catalysis for electrochem. reactions, including oxygen redn. reaction (ORR), hydrogen evolution reaction (HER), formic acid oxidn. reaction (FAOR), and thermo-oxidn. reaction of CO. Due to the enhanced metal atom stability in the "sandwich"-type structure, the roles of the first-row transition metal atoms in catalysis are better understood to achieve catalysis optimization. This concept can be extended to other alloy NPs, demonstrating great potentials in using intermetallic structures to control NP redn. and oxidn. catalysis for important chem. and energy applications.
- 5Chen, Y.; Lai, Z.; Zhang, X.; Fan, Z.; He, Q.; Tan, C.; Zhang, H. Phase engineering of nanomaterials. Nat. Rev. Chem. 2020, 4, 243– 256, DOI: 10.1038/s41570-020-0173-45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmtFynsb0%253D&md5=45377e0eb0774ed5c9ef5bd96be8c551Phase engineering of nanomaterialsChen, Ye; Lai, Zhuangchai; Zhang, Xiao; Fan, Zhanxi; He, Qiyuan; Tan, Chaoliang; Zhang, HuaNature Reviews Chemistry (2020), 4 (5), 243-256CODEN: NRCAF7; ISSN:2397-3358. (Nature Research)A review. Abstr.: Phase has emerged as an important structural parameter - in addn. to compn., morphol., architecture, facet, size and dimensionality - that dets. the properties and functionalities of nanomaterials. In particular, unconventional phases in nanomaterials that are unattainable in the bulk state can potentially endow nanomaterials with intriguing properties and innovative applications. Great progress has been made in the phase engineering of nanomaterials (PEN), including synthesis of nanomaterials with unconventional phases and phase transformation of nanomaterials. This Review provides an overview on the recent progress in PEN. We discuss various strategies used to synthesize nanomaterials with unconventional phases and induce phase transformation of nanomaterials, by taking noble metals and layered transition metal dichalcogenides as typical examples. Moreover, we also highlight recent advances in the prepn. of amorphous nanomaterials, amorphous-cryst. and crystal phase-based hetero-nanostructures. We also provide personal perspectives on challenges and opportunities in this emerging field, including exploration of phase-dependent properties and applications, rational design of phase-based heterostructures and extension of the concept of phase engineering to a wider range of materials.
- 6Yao, Q.; Yu, Z.; Li, L.; Huang, X. Strain and surface engineering of multicomponent metallic nanomaterials with unconventional phases. Chem. Rev. 2023, 123, 9676– 9717, DOI: 10.1021/acs.chemrev.3c002526https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsVamsLzE&md5=2187e8afcdadc710f98f5602609bf442Strain and Surface Engineering of Multicomponent Metallic Nanomaterials with Unconventional PhasesYao, Qing; Yu, Zhiyong; Li, Leigang; Huang, XiaoqingChemical Reviews (Washington, DC, United States) (2023), 123 (15), 9676-9717CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Multicomponent metallic nanomaterials with unconventional phases show great prospects in electrochem. energy storage and conversion, owing to unique crystal structures and abundant structural effects. In this review, we emphasize the progress in the strain and surface engineering of these novel nanomaterials. We start with a brief introduction of the structural configurations of these materials, based on the interaction types between the components. Next, the fundamentals of strain, strain effect in relevant metallic nanomaterials with unconventional phases, and their formation mechanisms are discussed. Then the progress in surface engineering of these multicomponent metallic nanomaterials is demonstrated from the aspects of morphol. control, crystallinity control, surface modification, and surface reconstruction. Moreover, the applications of the strain- and surface-engineered unconventional nanomaterials mainly in electrocatalysis are also introduced, where in addtion to the catalytic performance, the structure-performance correlations are highlighted. Finally, the challenges and opportunities in this promising field are prospected.
- 7Zhao, M.; Xia, Y. Crystal-phase and surface-structure engineering of ruthenium nanocrystals. Nat. Rev. Mater. 2020, 5, 440– 459, DOI: 10.1038/s41578-020-0183-37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlslGgsLk%253D&md5=7ffb8f8b136f97ed3f2325cfb3606d89Crystal-phase and surface-structure engineering of ruthenium nanocrystalsZhao, Ming; Xia, YounanNature Reviews Materials (2020), 5 (6), 440-459CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Metal nanocrystals with controlled shapes or surface structures have received increasing attention, owing to their desirable properties for applications ranging from catalysis to photonics, energy and biomedicine. Most studies, however, have been limited to nanocrystals with the same crystal phase as the bulk material. Engineering the phase of metal nanocrystals while simultaneously attaining shape-controlled synthesis has recently emerged as a new frontier of research. Here, we use Ru as an example to evaluate recent progress in the synthesis of metal nanocrystals featuring different crystal phases and well-controlled shapes. We first discuss synthetic strategies for controlling the crystal phase and shape of Ru nanocrystals, with a focus on new mechanistic insights. We then highlight the major factors that affect the packing of Ru atoms and, thus, the crystal phase, followed by an examn. of the thermal stability of Ru nanocrystals in terms of both crystal phase and shape. Next, we showcase the successful implementation of these Ru nanocrystals in various catalytic applications. Finally, we end with a discussion of the challenges and opportunities in the field, including leveraging the lessons learned from Ru to engineer the crystal phase and surface structure of other metals.
- 8Janssen, A.; Nguyen, Q. N.; Xia, Y. Colloidal metal nanocrystals with metastable crystal structures. Angew. Chem., Int. Ed. 2021, 60, 12192– 12203, DOI: 10.1002/anie.2020170768https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXjtVSru7w%253D&md5=575c630a9097508370f7c6e8d6a81f18Colloidal Metal Nanocrystals with Metastable Crystal StructuresJanssen, Annemieke; Nguyen, Quynh N.; Xia, YounanAngewandte Chemie, International Edition (2021), 60 (22), 12192-12203CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. In addn. to the conventional knobs such as compn., size, shape, and defect structure, the crystal structure (or phase) of metal nanocrystals offers a new avenue for engineering their properties. Various strategies have recently been developed for the fabrication of colloidal metal nanocrystals in metastable phases different from their bulk counterparts. With a focus on noble metals, we begin with a brief introduction to their at. packing, followed by a discussion about five major synthetic approaches to their colloidal nanocrystals in unconventional phases. We then highlight the success of synthesis in terms of mechanistic insights and exptl. controls, as well as the enhanced catalytic properties. We end this Minireview with perspectives on the remaining issues and future opportunities.
- 9Fan, Z.; Zhang, H. Template synthesis of noble metal nanocrystals with unusual crystal structures and their catalytic applications. Acc. Chem. Res. 2016, 49, 2841– 2850, DOI: 10.1021/acs.accounts.6b005279https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitVajtrbK&md5=1f5d1620bb7d019ad0d3a18d503220beTemplate Synthesis of Noble Metal Nanocrystals with Unusual Crystal Structures and Their Catalytic ApplicationsFan, Zhanxi; Zhang, HuaAccounts of Chemical Research (2016), 49 (12), 2841-2850CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. The authors review the recent research progress on the crystal structure control of noble metal nanocrystals with a template synthetic approach and their crystal structure-dependent catalytic properties. The authors describe the template synthetic methods, such as epitaxial growth and galvanic replacement reaction methods, in which a presynthesized noble metal nanocrystal with either new or common crystal structure is used as the template to direct the growth of unusual crystal structures of other noble metals. The template synthetic strategy described here provides an efficient, simple and straightforward way to synthesize unusual crystal structures of noble metal nanocrystals, which might not be easily synthesized by commonly used chem. synthesis. To be specific, by using the epitaxial growth method, a series of noble metal nanocrystals with unusual crystal structures has been obtained, such as hcp. Ag, 4H Ag, Pd, Pt, Ir, Rh, Os, and Ru, and face-centered cubic Ru nanostructures. Meanwhile, the galvanic replacement reaction method offers an efficient way to synthesize noble metal alloy nanocrystals with unusual crystal structures, such as 4H PdAg, PtAg, and PtPdAg nanostructures. The stability of noble metal nanocrystals with unusual crystal structures is discussed. The authors demonstrate the catalytic applications of the resultant noble metal nanocrystals with unusual crystal structures toward different chem. reactions like hydrogen evolution reaction, hydrogen oxidn. reaction and org. reactions. The relationship between crystal structures of noble metal nanocrystals and their catalytic performances is discussed.
- 10Fan, Z.; Chen, Y.; Zhu, Y.; Wang, J.; Li, B.; Zong, Y.; Han, Y.; Zhang, H. Epitaxial growth of unusual 4H hexagonal Ir, Rh, Os, Ru, and Cu nanostructures on 4H Au nanoribbons. Chem. Sci. 2017, 8, 795– 799, DOI: 10.1039/C6SC02953AThere is no corresponding record for this reference.
- 11Ge, Y.; Huang, Z.; Ling, C.; Chen, B.; Liu, G.; Zhou, M.; Liu, J.; Zhang, X.; Cheng, H.; Liu, G. Phase-selective epitaxial growth of heterophase nanostructures on unconventional 2H-Pd nanoparticles. J. Am. Chem. Soc. 2020, 142, 18971– 18980, DOI: 10.1021/jacs.0c0946111https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitV2qtrrO&md5=330aa30ecd6c39378a71aa1b3efaec7aPhase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd NanoparticlesGe, Yiyao; Huang, Zhiqi; Ling, Chongyi; Chen, Bo; Liu, Guigao; Zhou, Ming; Liu, Jiawei; Zhang, Xiao; Cheng, Hongfei; Liu, Guanghua; Du, Yonghua; Sun, Cheng-Jun; Tan, Chaoliang; Huang, Jingtao; Yin, Pengfei; Fan, Zhanxi; Chen, Ye; Yang, Nailiang; Zhang, HuaJournal of the American Chemical Society (2020), 142 (44), 18971-18980CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the prepn. of Pd nanoparticles with an unconventional hcp. (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepd. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochem. carbon dioxide redn. reaction (CO2RR) for prodn. of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (vs. the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochem. cells.
- 12Zhou, X.; Ma, Y.; Ge, Y.; Zhu, S.; Cui, Y.; Chen, B.; Liao, L.; Yun, Q.; He, Z.; Long, H. Preparation of Au@Pd core-shell nanorods with fcc-2H-fcc heterophase for highly efficient electrocatalytic alcohol oxidation. J. Am. Chem. Soc. 2022, 144, 547– 555, DOI: 10.1021/jacs.1c1131312https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXislyht7%252FO&md5=86a946cf219a55e6aeac513a2366aaa8Preparation of Au@Pd Core-Shell Nanorods with fcc-2H-fcc. Heterophase for Highly Efficient Electrocatalytic Alcohol OxidationZhou, Xichen; Ma, Yangbo; Ge, Yiyao; Zhu, Shangqian; Cui, Yu; Chen, Bo; Liao, Lingwen; Yun, Qinbai; He, Zhen; Long, Huiwu; Li, Lujiang; Huang, Biao; Luo, Qinxin; Zhai, Li; Wang, Xixi; Bai, Licheng; Wang, Gang; Guan, Zhiqiang; Chen, Ye; Lee, Chun-Sing; Wang, Jinlan; Ling, Chongyi; Shao, Minhua; Fan, Zhanxi; Zhang, HuaJournal of the American Chemical Society (2022), 144 (1), 547-555CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and studying the structure-dependent catalytic performance. Here, a wet-chem. synthesis method was used to prep. Au@Pd core-shell nanorods with a unique fcc.-2H-fcc. heterophase (fcc.: fcc.; 2H: hcp. with a stacking sequence of AB). The obtained fcc.-2H-fcc. heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic EtOH oxidn. performance with a mass activity ≤6.82 A mgPd-1, which is 2.44, 6.96, and 6.43 times those of 2H-Pd nanoparticles, fcc.-Pd nanoparticles, and com. Pd/C, resp. The operando IR reflection absorption spectroscopy reveals a C2 pathway with fast reaction kinetics for the EtOH oxidn. on the prepd. heterophase Au@Pd nanorods. The authors' exptl. results together with d. functional theory calcns. indicate that the enhanced performance of heterophase Au@Pd nanorods can be attributed to the unconventional 2H phase, the 2H/fcc. phase boundary, and the lattice expansion of the Pd shell. Also, the heterophase Au@Pd nanorods can also serve as an efficient catalyst for the electrochem. oxidn. of MeOH, ethylene glycol, and glycerol. The authors' work in the area of phase engineering of nanomaterials (PENs) opens the way for developing high-performance electrocatalysts toward future practical applications.
- 13Tan, X.; Geng, S.; Ji, Y.; Shao, Q.; Zhu, T.; Wang, P.; Li, Y.; Huang, X. Closest packing polymorphism interfaced metastable transition metal for efficient hydrogen evolution. Adv. Mater. 2020, 32, 2002857 DOI: 10.1002/adma.20200285713https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhslWqur7J&md5=6a07d2671678fddbe2b58c40626c6f36Closest Packing Polymorphism Interfaced Metastable Transition Metal for Efficient Hydrogen EvolutionTan, Xinyue; Geng, Shize; Ji, Yujin; Shao, Qi; Zhu, Ting; Wang, Pengtang; Li, Youyong; Huang, XiaoqingAdvanced Materials (Weinheim, Germany) (2020), 32 (40), 2002857CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Metastable materials are promising because of their catalytic properties, high-energy structure, and unique electronic environment. However, the unstable nature inherited from the metastability hinders further performance improvement and practical applications of these materials. Herein, this limitation is successfully addressed by constructing an in situ polymorphism interface (inf) between the metastable hexagonal-close-packed (hcp) phase and its stable counterpart (face-centered cubic, fcc) in cobalt-nickel (CoNi) alloy. Calcns. reveal that the interfacial synergism derived from the hcp and fcc phases lowers the formation energy and enhances stability. Consequently, the optimized CoNi-inf exhibits an exceptionally low potential of 72 mV at 10 mA cm-2 and a Tafel slope of 57 mV dec-1 for the hydrogen evolution reaction (HER) in 1.0 M KOH. Furthermore, it is superior to most state-of-the-art non-noble-metal-based HER catalysts. No noticeable activity decay or structural changes are obsd. even over 14 h of catalysis. The computational simulation further rationalizes that the interface of CoNi-inf with a suitable d-band center provides uniform sites for hydrogen adsorption, leading to a distinguished HER catalytic activity. This work, therefore, presents a new route for designing metastable catalysts for potential energy conversion.
- 14Xia, Y.; Gilroy, K. D.; Peng, H. C.; Xia, X. Seed-mediated growth of colloidal metal nanocrystals. Angew. Chem., Int. Ed. 2017, 56, 60– 95, DOI: 10.1002/anie.20160473114https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitV2mtLzO&md5=3a4a218eb28c15ac3691bb5822262b16Seed-Mediated Growth of Colloidal Metal NanocrystalsXia, Younan; Gilroy, Kyle D.; Peng, Hsin-Chieh; Xia, XiaohuAngewandte Chemie, International Edition (2017), 56 (1), 60-95CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Seed-mediated growth is a powerful and versatile approach for the synthesis of colloidal metal nanocrystals. The vast allure of this approach mainly stems from the staggering degree of control one can achieve over the size, shape, compn., and structure of nanocrystals. These parameters not only control the properties of nanocrystals but also det. their relevance to, and performance in, various applications. The ingenuity and artistry inherent to seed-mediated growth offer extensive promise, enhancing a no. of existing applications and opening the door to new developments. This Review demonstrates how the diversity of metal nanocrystals can be expanded with endless opportunities by using seeds with well-defined and controllable internal structures in conjunction with a proper combination of capping agent and redn. kinetics. New capabilities and future directions are also highlighted.
- 15Gilroy, K. D.; Yang, X.; Xie, S.; Zhao, M.; Qin, D.; Xia, Y. Shape-controlled synthesis of colloidal metal nanocrystals by replicating the surface atomic structure on the seed. Adv. Mater. 2018, 30, 1706312 DOI: 10.1002/adma.201706312There is no corresponding record for this reference.
- 16Zhao, M.; Xu, L.; Vara, M.; Elnabawy, A. O.; Gilroy, K. D.; Hood, Z. D.; Zhou, S.; Figueroa-Cosme, L.; Chi, M.; Mavrikakis, M.; Xia, Y. Synthesis of Ru icosahedral nanocages with a face-centered-cubic structure and evaluation of their catalytic properties. ACS Catal. 2018, 8, 6948– 6960, DOI: 10.1021/acscatal.8b0091016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVagsrnP&md5=bdf4a3093dc2e2feedf622514e501ff2Synthesis of Ru Icosahedral Nanocages with a Face-Centered-Cubic Structure and Evaluation of Their Catalytic PropertiesZhao, Ming; Xu, Lang; Vara, Madeline; Elnabawy, Ahmed O.; Gilroy, Kyle D.; Hood, Zachary D.; Zhou, Shan; Figueroa-Cosme, Legna; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanACS Catalysis (2018), 8 (8), 6948-6960CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Owing to the presence of {111} facets, twin boundaries, and strain fields on the surface, noble-metal nanocrystals with an icosahedral shape have been reported with stellar performance toward an array of catalytic reactions. Here, we report the successful synthesis of Ru icosahedral nanocages with a face-centered cubic (fcc) structure by conformally coating Pd icosahedral seeds with ultrathin Ru shells, followed by selective removal of the Pd cores via chem. etching. We discovered that the presence of bromide ions was crit. to the layer-by-layer deposition of Ru atoms. According to in situ XRD, the fcc structure in the Ru nanocages could be retained up to 300 °C before it was transformed into the conventional hcp. (hcp) structure. Addnl., the icosahedral shape of the Ru nanocages could be largely preserved up to 300 °C. The Ru icosahedral nanocages with twin boundaries on the surface exhibited greatly enhanced activities toward both the redn. of 4-nitrophenol and decompn. of hydrazine than their cubic and octahedral counterparts. When benchmarked against the parental Pd@Ru core-shell nanocrystals, all the Ru nanocages displayed superior catalytic activities. First-principles d. functional theory calcns. also suggest that the fcc-Ru icosahedral nanocages contg. residual Pd atoms are more promising than the conventional hcp-Ru solid nanoparticles in catalyzing nitrogen redn. for ammonia synthesis. With the subsurface impurities of Pd, the twin boundary regions of the icosahedral nanocages are able to stabilize the N2 dissocn. transition state, reducing the overall reaction barrier and promoting the competition with the N2 desorption process.
- 17Zhao, M.; Figueroa-Cosme, L.; Elnabawy, A. O.; Vara, M.; Yang, X.; Roling, L. T.; Chi, M.; Mavrikakis, M.; Xia, Y. Synthesis and characterization of Ru cubic nanocages with a face-centered cubic structure by templating with Pd nanocubes. Nano Lett. 2016, 16, 5310– 5317, DOI: 10.1021/acs.nanolett.6b0279517https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1Ggtr3E&md5=d343198af41c4dde7d954e17ab8601c3Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd NanocubesZhao, Ming; Figueroa-Cosme, Legna; Elnabawy, Ahmed O.; Vara, Madeline; Yang, Xuan; Roling, Luke T.; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanNano Letters (2016), 16 (8), 5310-5317CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Ru cubic nanocages with ultrathin walls, in which the atoms are crystd. in fcc. rather than hcp. structure, have been prepd. The key to the success of this synthesis was to ensure layer-by-layer deposition of Ru atoms on the surface of Pd cubic seeds by controlling the reaction temp. and the injection rate of a Ru(III) precursor. By selectively etching away the Pd from the Pd@Ru core-shell nanocubes, the authors obtained Ru nanocages with an av. wall thickness of 1.1 nm or about six at. layers. The Ru nanocages adopted an fcc. crystal structure rather than the hcp. structure obsd. in bulk Ru. The synthesis was applied to Pd cubic seeds with different edge lengths in the range of 6-18 nm, with smaller seeds being more favorable for the formation of Ru shells with a flat, smooth surface due to shorter distance for the surface diffusion of the Ru adatoms. Self-consistent d. functional theory calcns. indicated that these unique fcc.-structured Ru nanocages might possess promising catalytic properties for ammonia synthesis compared to hcp. Ru(0001), on the basis of strengthened binding of at. N and substantially reduced activation energies for N2 dissocn., which is the rate-detg. step for ammonia synthesis on hcp. Ru catalysts.
- 18Gu, J.; Guo, Y.; Jiang, Y.-Y.; Zhu, W.; Xu, Y.-S.; Zhao, Z.-Q.; Liu, J.-X.; Li, W.-X.; Jin, C.-H.; Yan, C.-H.; Zhang, Y. W. Robust phase control through hetero-seeded epitaxial growth for face-centered cubic Pt@Ru nanotetrahedrons with superior hydrogen electro-oxidation activity. J. Phys. Chem. C 2015, 119, 17697– 17706, DOI: 10.1021/acs.jpcc.5b0458718https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1Sgs7bE&md5=43459bdacdb1a28d51f3b245262737cfRobust Phase Control through Hetero-Seeded Epitaxial Growth for Face-Centered Cubic Pt@Ru Nanotetrahedrons with Superior Hydrogen Electro-Oxidation ActivityGu, Jun; Guo, Yu; Jiang, Ying-Ying; Zhu, Wei; Xu, Yan-Shuang; Zhao, Ze-Qiong; Liu, Jin-Xun; Li, Wei-Xue; Jin, Chuan-Hong; Yan, Chun-Hua; Zhang, Ya-WenJournal of Physical Chemistry C (2015), 119 (31), 17697-17706CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Controllable synthesis of metallic nanocrystals (NCs) with tunable phase, uniform shape, and size is of multidisciplinary interests but has still remained challenging. Herein, a robust phase control strategy is developed, in which seeds with a given phase are added to guide the epitaxial growth of the target metal to inherit the seeds' phase. Through this strategy, M@Ru (M = Pt, Pd) NCs in the fcc. phase, a metastable phase for Ru under ambient conditions, were synthesized with the hydrothermal method. The Pt@Ru NCs showed not only the pure fcc. phase but also high morphol. selectivity to tetrahedrons surrounded by {111} facets. As revealed by d. function theory (DFT) calcns., the preferentially epitaxial growth of Ru atom layers on the nonclosest-packed facets of hetero fcc. metal seeds gave fcc. Ru shells. Also, the fcc. Pt@Ru tetrahedrons/C showed electrocatalytic activity enhancement with more than an order of magnitude toward H oxidn. reaction (HOR) in acidic electrolyte compared with hydrothermally synthesized Ru/C. Electrochem. measurement combined with DFT calcns. revealed that the optimum HOR activity should be achieved on well-crystd. fcc. Ru catalysts exposing max. {111} facets.
- 19Janssen, A.; Lyu, Z.; Figueras-Valls, M.; Chao, H.-Y.; Shi, Y.; Pawlik, V.; Chi, M.; Mavrikakis, M.; Xia, Y. Phase-controlled synthesis of Ru nanocrystals via template-directed growth: surface energy versus bulk energy. Nano Lett. 2022, 22, 3591– 3597, DOI: 10.1021/acs.nanolett.1c0500919https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhtVaqurbF&md5=4fd2b4cffaf9664ac87b8f3467ac15d1Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk EnergyJanssen, Annemieke; Lyu, Zhiheng; Figueras-Valls, Marc; Chao, Hsin-Yun; Shi, Yifeng; Pawlik, Veronica; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanNano Letters (2022), 22 (9), 3591-3597CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of fcc.-Pd nanoplate templates, with 12 nm plates giving fcc.-Ru while 18-26 nm plates result in hcp.-Ru. Although Ru overlayers with a metastable fcc.- (high in bulk energy) or stable hcp.-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp.- (high in surface energy) and smooth fcc.-facets (low in surface energy), resp., on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The [email protected] outperform the [email protected] nanoplates toward ethylene glycol and glycerol oxidn. reactions.
- 20Janssen, A.; Nguyen, Q. N.; Lyu, Z.; Pawlik, V.; Wang, C.; Xia, Y. Phase-controlled deposition of Ru on Pd nanocrystal templates: effects of particle shape and size. J. Phys. Chem. C 2023, 127, 1280– 1291, DOI: 10.1021/acs.jpcc.2c08825There is no corresponding record for this reference.
- 21Joo, S. H.; Park, J. Y.; Renzas, J. R.; Butcher, D. R.; Huang, W.; Somorjai, G. A. Size effect of ruthenium nanoparticles in catalytic carbon monoxide oxidation. Nano Lett. 2010, 10, 2709– 2713, DOI: 10.1021/nl101700j21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnvVejtr4%253D&md5=96783fc4b8f4474251d7540e668ea266Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide OxidationJoo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu; Somorjai, Gabor A.Nano Letters (2010), 10 (7), 2709-2713CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)CO oxidn. over Ru catalysts exhibits an unusual catalytic behavior. This work discusses particle size effect on CO oxidn. over Ru nano-particle (NP) catalysts. Uniform Ru NP with a tunable particle size of 2-6 nm were synthesized by a polyol redn. of ruthenium acetylacetonate precursor in the presence of a poly(vinylpyrrolidone) stabilizer. Catalyst activity measurement for CO oxidn. over 2-dimensional Ru NP arrays under oxidizing reaction conditions (40 Torr CO, 100 Torr O2) showed activity depended on Ru NP size. CO oxidn. activity increased with NP size; the 6 nm Ru NP catalyst exhibited 8-fold higher activity than 2 nm catalysts. Results provide the scientific basis for future design of Ru-based oxidn. catalysts.
- 22Li, W. Z.; Liu, J. X.; Gu, J.; Zhou, W.; Yao, S. Y.; Si, R.; Guo, Y.; Su, H. Y.; Yan, C. H.; Li, W. X. Chemical insights into the design and development of face-centered cubic ruthenium catalysts for Fischer–Tropsch synthesis. J. Am. Chem. Soc. 2017, 139, 2267– 2276, DOI: 10.1021/jacs.6b1037522https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1KlsLw%253D&md5=1b859b177abeeedf8b343821b4d0d657Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch SynthesisLi, Wei-Zhen; Liu, Jin-Xun; Gu, Jun; Zhou, Wu; Yao, Si-Yu; Si, Rui; Guo, Yu; Su, Hai-Yan; Yan, Chun-Hua; Li, Wei-Xue; Zhang, Ya-Wen; Ma, DingJournal of the American Chemical Society (2017), 139 (6), 2267-2276CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Ruthenium is a promising low-temp. catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. The authors demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. D. functional theory calcns. show that upon CO dissocn. there are a no. of open facets with modest barrier available on the fcc. Ru but only a few step edges with a lower barrier on conventional hcp. Ru. Guided by theor. calcns., water-dispersible fcc. Ru catalysts contg. abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aq.-phase FTS, 37.8 molCO·molRu-1·h-1 at 433 K. The mass-specific activity of the fcc. Ru catalysts with an av. size of 6.8 nm is about three times larger than the previous best hcp. catalyst with a smaller size of 1.9 nm and a higher sp. surface area. The origin of the higher mass-specific activity of the fcc. Ru catalysts is identified exptl. from the 2 orders of magnitude higher d. of the active sites, despite its slightly higher apparent barrier. Exptl. results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.
- 23Li, L.; Liu, C.; Liu, S.; Wang, J.; Han, J.; Chan, T. S.; Li, Y.; Hu, Z.; Shao, Q.; Zhang, Q.; Huang, X. Phase engineering of a ruthenium nanostructure toward high-performance bifunctional hydrogen catalysis. ACS Nano 2022, 16, 14885– 14894, DOI: 10.1021/acsnano.2c0577623https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xit1Wgs7jF&md5=636977cb45ebdeb375257e85adbb5ca8Phase Engineering of a Ruthenium Nanostructure toward High-Performance Bifunctional Hydrogen CatalysisLi, Leigang; Liu, Cheng; Liu, Shangheng; Wang, Juan; Han, Jiajia; Chan, Ting-Shan; Li, Youyong; Hu, Zhiwei; Shao, Qi; Zhang, Qiaobao; Huang, XiaoqingACS Nano (2022), 16 (9), 14885-14894CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The physicochem. properties and catalytic performance of transition metals are highly phase-dependent. Ru-based nanomaterials are superior catalysts toward hydrogen evolution reaction (HER) and hydrogen oxidn. reaction (HOR), but studies are mostly limited to conventional hexagonal-close-packed (hcp) Ru, mainly arising from the difficulty in synthesizing Ru with pure face-centered-cubic (fcc) phase. Herein, we report a crystal-phase-dependent catalytic study of MoOx-modified Ru (MoOx-Ru fcc and MoOx-Ru hcp) for bifunctional HER and HOR. MoOx-Ru fcc is proven to outperform MoOx-Ru hcp in catalyzing both HER and HOR with much higher catalytic activity and more durable stability. The modification effect of MoOx gives rise to optimal adsorption of H and OH esp. on fcc Ru, which thus has resulted in the superior catalytic performance. This work highlights the significance of phase engineering in constructing superior electrocatalysts and may stimulate more efforts on phase engineering of other metal-based materials for diversified applications.
- 24Kusada, K.; Kobayashi, H.; Yamamoto, T.; Matsumura, S.; Sumi, N.; Sato, K.; Nagaoka, K.; Kubota, Y.; Kitagawa, H. Discovery of face-centered-cubic ruthenium nanoparticles: facile size-controlled synthesis using the chemical reduction method. J. Am. Chem. Soc. 2013, 135, 5493– 5496, DOI: 10.1021/ja311261s24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXltlKmsr8%253D&md5=27d1e520b1c3b39da57fe6c0d65e0a48Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction MethodKusada, Kohei; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Matsumura, Syo; Sumi, Naoya; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kubota, Yoshiki; Kitagawa, HiroshiJournal of the American Chemical Society (2013), 135 (15), 5493-5496CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We report the first discovery of pure face-centered-cubic (fcc) Ru nanoparticles. Although the fcc structure does not exist in the bulk Ru phase diagram, fcc Ru was obtained at room temp. because of the nanosize effect. We succeeded in sep. synthesizing uniformly sized nanoparticles of both fcc and hcp Ru having diams. of 2-5.5 nm by simple chem. redn. methods with different metal precursors. The prepd. fcc and hcp nanoparticles were both supported on γ-Al2O3, and their catalytic activities in CO oxidn. were investigated and found to depend on their structure and size.
- 25Araki, N.; Kusada, K.; Yoshioka, S.; Sugiyama, T.; Ina, T.; Kitagawa, H. Observation of the formation processes of hexagonal close-packed and face-centered cubic Ru nanoparticles. Chem. Lett. 2019, 48, 1062– 1064, DOI: 10.1246/cl.19033825https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1WqtrnF&md5=109dadd6a1c44f133fbdff09c87adca5Observation of the Formation Processes of Hexagonal Close-packed and Face-centered Cubic Ru NanoparticlesAraki, Naoki; Kusada, Kohei; Yoshioka, Satoru; Sugiyama, Takeharu; Ina, Toshiaki; Kitagawa, HiroshiChemistry Letters (2019), 48 (9), 1062-1064CODEN: CMLTAG; ISSN:0366-7022. (Chemical Society of Japan)Face-centered cubic (fcc) Ru nanoparticles (NPs) have been recently synthesized by reducing Ru(III) acetylacetonate, despite bulk Ru having a hcp. (hcp) structure. We obsd. the formation processes of fcc and hcp Ru NPs using X-ray diffraction and X-ray absorption fine structure. We concluded that the strong Ru-O bond between Ru and the acetylacetonate ligand leads to the formation of the fcc structure.
- 26Zhao, M.; Hood, Z. D.; Vara, M.; Gilroy, K. D.; Chi, M.; Xia, Y. Ruthenium nanoframes in the face-centered cubic phase: facile synthesis and their enhanced catalytic performance. ACS Nano 2019, 13, 7241– 7251, DOI: 10.1021/acsnano.9b0289026https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVKqsrzI&md5=90c09098c30f29a99cd3c5dffbebb3ceRuthenium Nanoframes in the Face-Centered Cubic Phase: Facile Synthesis and Their Enhanced Catalytic PerformanceZhao, Ming; Hood, Zachary D.; Vara, Madeline; Gilroy, Kyle D.; Chi, Miaofang; Xia, YounanACS Nano (2019), 13 (6), 7241-7251CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Owing to their highly open structure and a large no. of low-coordination sites on the surface, noble-metal nanoframes are intriguing for catalytic applications. Here, we demonstrate the rational synthesis of Ru cuboctahedral nanoframes with enhanced catalytic performance toward hydrazine decompn. The synthesis starts from Pd nanocubes, which quickly undergo truncation at the corners as a consequence of oxidative etching caused by Br- ions. Afterward, the galvanic replacement reaction between Pd and Ru(III) ions dominates, leading to the selective deposition of Ru atoms on the corners and edges and thereby the fabrication of Pd@Ru core-frame cuboctahedra. Significantly, the deposited Ru atoms are crystd. in a face-centered cubic (fcc) phase instead of the hcp. (hcp) structure typical of bulk Ru. Upon the removal of Pd remaining in the core via chem. etching, we obtain Ru cuboctahedral nanoframes. By varying the amt. of the Ru(III) precursor, the ridge thickness of the nanoframes can be tuned from a few at. layers up to 10. Both the frame structure and fcc crystal phase of the Ru cuboctahedral nanoframes can be well preserved up to 300°C. When compared with hcp-Ru nanoparticles, the fcc-Ru nanoframes displayed substantial enhancement in terms of H2 selectivity toward hydrazine decompn. This work offers the opportunity to engineer both the morphol. and crystal phase of Ru nanocrystals for catalytic applications.
- 27Lin, J.-T.; Liu, Y.-H.; Tsao, C.-Y.; Wu, C.-Y.; Hsieh, C.-J.; Chen, M.-Z.; Chang, C.-W.; Hsiao, Y.-C.; Chen, H.-L.; Yang, T.-H. Toward a quantitative understanding of crystal-phase engineering of Ru nanocrystals. Chem. Mater. 2023, 35, 4276– 4285, DOI: 10.1021/acs.chemmater.3c0032627https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtV2ksrbP&md5=1083f5b8422b7ca26665264f18235387Toward a Quantitative Understanding of Crystal-Phase Engineering of Ru NanocrystalsLin, Jui-Tai; Liu, Yi-Hong; Tsao, Chi-Yen; Wu, Cheng-Yu; Hsieh, Chia-Jui; Chen, Meng-Zhe; Chang, Chun-Wei; Hsiao, Yueh-Chun; Chen, Hsin-Lung; Yang, Tung-HanChemistry of Materials (2023), 35 (11), 4276-4285CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The crystal phase with a specific stacking sequence of atoms largely affects the catalytic performance of metal nanocrystals. Since the control of the phase at the same compn. is extremely difficult, the phase-dependent performance of metal nanocrystals is studied rarely. Here, we show the synthesis of Ru nanocrystals with different percentages of face-centered cubic (FCC) and hcp. (HCP) phases via kinetic control, further revealing a quant. correlation between the phase percentage of Ru nanocrystals and the initial redn. rate of Ru(III) precursors. Specifically, we manipulate the single parameter-initial redn. rate by controlling the Ru(III) injection rate into the dropwise synthesis at a fixed reaction temp. and correlate the kinetic data with the Ru phase percentage analyzed by at.-resoln. electron microscopy and synchrotron X-ray scattering. Based on the quant. anal., the ranges of initial redn. rates of Ru precursors can be detd. for synthesizing Ru nanocrystals with the percentages of unusual FCC phase from 9.0 to 55.1%. We demonstrate that a low initial redn. rate corresponds to the crystn. of the Ru HCP phase, while a high initial redn. rate favors the crystn. of the FCC lattice. Furthermore, we also systematically examine the catalytic performance of Ru nanocrystals with different phases.
- 28Ye, H.; Wang, Q.; Catalano, M.; Lu, N.; Vermeylen, J.; Kim, M. J.; Liu, Y.; Sun, Y.; Xia, X. Ru nanoframes with an fcc structure and enhanced catalytic properties. Nano Lett. 2016, 16, 2812– 2817, DOI: 10.1021/acs.nanolett.6b0060728https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XksV2ksrs%253D&md5=d1ba68a214091adbb80e77ffab86e443Ru Nanoframes with an fcc Structure and Enhanced Catalytic PropertiesYe, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J.; Liu, Yuzi; Sun, Yugang; Xia, XiaohuNano Letters (2016), 16 (4), 2812-2817CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chem. etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chem. etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the redn. of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.
- 29Zhao, M.; Elnabawy, A. O.; Vara, M.; Xu, L.; Hood, Z. D.; Yang, X.; Gilroy, K. D.; Figueroa-Cosme, L.; Chi, M.; Mavrikakis, M.; Xia, Y. Facile synthesis of Ru-based octahedral nanocages with ultrathin walls in a face-centered cubic structure. Chem. Mater. 2017, 29, 9227– 9237, DOI: 10.1021/acs.chemmater.7b0309229https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Gqsr7K&md5=230abaa6fd15610e5682cb3566709411Facile synthesis of Ru-based octahedral nanocages with ultrathin walls in face-centered cubic structureZhao, Ming; Elnabawy, Ahmed O.; Vara, Madeline; Xu, Lang; Hood, Zachary D.; Yang, Xuan; Gilroy, Kyle D.; Figueroa-Cosme, Legna; Chi, Miaofang; Mavrikakis, Manos; Xia, YounanChemistry of Materials (2017), 29 (21), 9227-9237CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Noble-metal nanocages with ultrathin (less than 2 nm) walls and well-defined facets have received great interest owing to their remarkable utilization efficiency of atoms and facet-dependent catalytic activities toward various reactions. Here, we report the synthesis of Ru-based octahedral nanocages covered by {111} facets, together with ultrathin walls in a face-centered cubic (fcc) structure rather than the hcp. (hcp) of bulk Ru. The involvement of slow injection for the Ru(III) precursor, the introduction of KBr, and the use of elevated temp. were all instrumental to the formation of Pd@Ru core-shell octahedra with a conformal, uniform shell and a smooth surface. The {111} facets were well preserved during the selective removal of the Pd cores via wet etching, even when the Ru walls were only five at. layers in thickness. Through in situ XRD, we demonstrated that the fcc structure of the Ru nanocages was stable up to 300 °C. We also used first-principles, self-consistent d. functional theory calcns. to study the adsorption and dissocn. of N2 as a means to predict the catalytic performance toward ammonia synthesis. Our results suggested that the small proportions of Pd atoms left behind in the walls during etching could play a key role in stabilizing the adsorption of N2 as well as in reducing the activation energy barrier to N2 dissocn.
- 30Zhao, M.; Chen, Z.; Lyu, Z.; Hood, Z. D.; Xie, M.; Vara, M.; Chi, M.; Xia, Y. Ru octahedral nanocrystals with a face-centered cubic structure, {111} facets, thermal stability up to 400 °C, and enhanced catalytic activity. J. Am. Chem. Soc. 2019, 141, 7028– 7036, DOI: 10.1021/jacs.9b0164030https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXntlejtLg%253D&md5=77fa31af38ac397f33c8c725290ef3edRu Octahedral Nanocrystals with a Face-Centered Cubic Structure, {111} Facets, Thermal Stability up to 400°C, and Enhanced Catalytic ActivityZhao, Ming; Chen, Zitao; Lyu, Zhiheng; Hood, Zachary D.; Xie, Minghao; Vara, Madeline; Chi, Miaofang; Xia, YounanJournal of the American Chemical Society (2019), 141 (17), 7028-7036CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Ruthenium nanocrystals with both a face-centered cubic (fcc) structure and well-controlled facets are attractive catalytic materials for various reactions. Here we report a simple method for the synthesis of Ru octahedral nanocrystals with an fcc structure and an edge length of 9 nm. The success of this synthesis relies on the use of 4.5 nm Rh cubes as seeds to facilitate the heterogeneous nucleation and overgrowth of Ru atoms. We choose Rh because it can resist oxidative etching under the harsh conditions for Ru overgrowth, it can be readily prepd. as nanocubes with edge lengths less than 5 nm, and its atoms have a size close to that of Ru atoms. During the seed-mediated growth, the at. packing of Ru overlayers follows an fcc lattice, in contrast to the conventional hcp. (hcp) lattice assocd. with bulk Ru. The final product takes an octahedral shape, with the surface enclosed by {111} facets. Our in situ measurements suggest that both the octahedral shape and the fcc crystal structure can be well preserved up to 400°C, which is more than 100°C higher than what was reported for Ru octahedral nanocages. When utilized as catalysts, the Ru octahedral nanocrystals exhibited 4.4-fold enhancement in terms of specific activity toward oxygen evolution relative to hcp-Ru nanoparticles. We also demonstrate that Ru{111} facets are more active than Ru{100} facets in catalyzing the oxygen evolution reaction. Altogether, this work offers an effective method for the synthesis of Ru nanocrystals with an fcc structure and well-defined {111} facets, as well as enhanced thermal stability and catalytic activity. We believe these nanocrystals will find use in various catalytic applications.
- 31Huo, D.; Cao, Z.; Li, J.; Xie, M.; Tao, J.; Xia, Y. Seed-mediated growth of Au nanospheres into hexagonal stars and the emergence of a hexagonal close-packed phase. Nano Lett. 2019, 19, 3115– 3121, DOI: 10.1021/acs.nanolett.9b0053431https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtlKgu7s%253D&md5=b7376f3755b141cb1d65dc834b15fc58Seed-Mediated Growth of Au Nanospheres into Hexagonal Stars and the Emergence of a Hexagonal Close-Packed PhaseHuo, Da; Cao, Zhenming; Li, Jun; Xie, Minghao; Tao, Jing; Xia, YounanNano Letters (2019), 19 (5), 3115-3121CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Gold (Au) typically crystallizes in a cubic close-packed (ccp) structure to present a face-centered cubic (fcc) lattice or crystal phase. Herein, we demonstrate that Au nanoscale hexagonal stars featuring a hcp. (hcp) structure can be synthesized in an aq. system in the presence of fcc-Au nanospheres as the seeds. The success of this synthesis critically relies on the use of EDTA to complex with Au3+ ions (the precursor) and the introduction of 2-phospho-L-ascorbic acid trisodium salt (Asc-2P) as a novel reducing agent to maneuver the redn. kinetics. The use of Asc-2P favorably promotes the formation of hexagonal stars with uneven surfaces at the top and bottom faces, together with concave side faces around the edges. By varying the amt. of Asc-2P to fine-tune the redn. kinetics, we can adjust the concaveness of the side faces, with a faster redn. rate favoring greater concaveness and a red shift of the plasmon resonance peak to the near-IR. For the first time, our results suggest that the phosphate and hydroxyl groups can act synergistically in controlling the morphol. of Au nanocrystals. Most significantly, the newly deposited Au atoms can also crystallize in an hcp structure, leading to the observation of a phase transition from fcc to hcp along the growth direction. This new protocol based upon kinetic control can be potentially extended to other noble metals for the facile synthesis of nanocrystals featuring unprecedented structures or phases.
- 32Gloag, L.; Benedetti, T. M.; Cheong, S.; Marjo, C. E.; Gooding, J. J.; Tilley, R. D. Cubic-core hexagonal-branch mechanism to synthesize bimetallic branched and faceted Pd–Ru nanoparticles for oxygen evolution reaction electrocatalysis. J. Am. Chem. Soc. 2018, 140, 12760– 12764, DOI: 10.1021/jacs.8b0940232https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVeisrfI&md5=75d644b447b050d3936cdc8b4225929bCubic-Core Hexagonal-Branch Mechanism To Synthesize Bimetallic Branched and Faceted Pd-Ru Nanoparticles for Oxygen Evolution Reaction ElectrocatalysisGloag, Lucy; Benedetti, Tania M.; Cheong, Soshan; Marjo, Christopher E.; Gooding, J. Justin; Tilley, Richard D.Journal of the American Chemical Society (2018), 140 (40), 12760-12764CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A major synthetic challenge is to make metal nanoparticles with nanosized branches and well-defined facets for high-performance catalysts. Here, we introduce a mechanism that uses the growth of hexagonal crystal structured branches off cubic crystal structured core nanoparticles. We control the growth to form Pd-core Ru-branch nanoparticles that have nanosized branches with low index Ru facets. We demonstrate that the branched and faceted structural features of the Pd-Ru nanoparticles retain high catalytic activity while also achieving high stability for the O evolution reaction.
- 33Yun, Q.; Ge, Y.; Huang, B.; Wa, Q.; Zhang, H. Ligand-assisted phase engineering of nanomaterials. Acc. Chem. Res. 2023, 56, 1780– 1790, DOI: 10.1021/acs.accounts.3c0012133https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtFOrtLbF&md5=f4c2430b891fbcacd1fc0c03a2061edaLigand-Assisted Phase Engineering of NanomaterialsYun, Qinbai; Ge, Yiyao; Huang, Biao; Wa, Qingbo; Zhang, HuaAccounts of Chemical Research (2023), 56 (13), 1780-1790CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)The synthesis of monodisperse colloidal nanomaterials with well-defined structures is important for both fundamental research and practical application. To achieve it, wet-chem. methods with the usage of various ligands have been extensively explored to finely control the structure of nanomaterials. During the synthesis, ligands cap the surface and thus modulate the size, shape, and stability of nanomaterials in solvents. Besides these widely investigated roles of ligands, it has been recently discovered that ligands can affect the phase of nanomaterials, i.e., their at. arrangement, providing an effective strategy to realize the phase engineering of nanomaterials (PEN) by selecting appropriate ligands. Nanomaterials normally exist in the phases that are thermodynamically stable in their bulk states. Previous studies have shown that under high temp. or high pressure, nanomaterials can exist in unconventional phases which are unattainable in the bulks. Importantly, nanomaterials with unconventional phases exhibit unique properties and functions different from conventional-phase ones. Consequently, it is feasible to utilize the PEN to tune the physicochem. properties and application performance of nanomaterials. During wet-chem. synthesis, ligands binding to the surface of nanomaterials can modify their surface energy, which could significantly affect the Gibbs free energy of nanomaterials and thus det. the stability of different phases, making it possible to obtain nanomaterials with unconventional phases at mild reaction conditions. For instance, a series of Au nanomaterials with unconventional hexagonal phases have been prepd. with the assistance of oleylamine. Therefore, the rational design and selection of different ligands and deep understanding of their effect on the phase of nanomaterials would significantly accelerate the development of PEN and the discovery of novel functional nanomaterials for diverse applications. In this Account, we briefly summarize the recent progress in ligand-assisted PEN, elaborating the important roles of different ligands in the direct synthesis of nanomaterials with unconventional crystal phases and amorphous phase as well as the phase transformation of nanomaterials. We first introduce the background of this research topic, highlighting the concept of PEN and why ligands can modulate the phase of nanomaterials. Then we discuss the usage of four kinds of ligands, i.e., amines, fatty acids, sulfur-contg. ligands, and phosphorus-contg. ligands, in phase engineering of different nanomaterials, esp. metal, metal chalcogenide, and metal oxide nanomaterials. Finally, we provide our personal views of the challenges and future promising research directions in this exciting field.
- 34Nguyen, Q. N.; Chen, R.; Lyu, Z.; Xia, Y. Using reduction kinetics to control and predict the outcome of a colloidal synthesis of noble-metal nanocrystals. Inorg. Chem. 2021, 60, 4182– 4197, DOI: 10.1021/acs.inorgchem.0c0357634https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisVWgsbo%253D&md5=af032e84596286f3c4e001f311fb6633Using reduction kinetics to control and predict outcome of colloidal synthesis of noble-metal nanocrystalsNguyen, Quynh N.; Chen, Ruhui; Lyu, Zhiheng; Xia, YounanInorganic Chemistry (2021), 60 (7), 4182-4197CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)Improving the performance of noble-metal nanocrystals in various applications critically depends on our ability to manipulate their synthesis in a rational, robust, and controllable fashion. Different from a conventional trial-and-error approach, the redn. kinetics of a colloidal synthesis has recently been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner. Here we present a brief viewpoint on the recent progress in leveraging redn. kinetics for controlling and predicting the outcome of a synthesis of noble-metal nanocrystals. With a focus on Pd nanocrystals, we first offer a discussion on the correlation between the initial redn. rate and the internal structure of the resultant seeds. The kinetic approaches for controlling both nucleation and growth in a one-pot setting are then introduced with an emphasis on manipulation of the redn. pathways taken by the precursor. We then illustrate how to extend the strategy into a bimetallic system for the prepn. of nanocrystals with different shapes and elemental distributions. Finally, the influence of speciation of the precursor on redn. kinetics is highlighted, followed by our perspectives on the challenges and future endeavors in achieving a controllable and predictable synthesis of noble-metal nanocrystals.
- 35Huang, X.; Li, S.; Huang, Y.; Wu, S.; Zhou, X.; Li, S.; Gan, C. L.; Boey, F.; Mirkin, C. A.; Zhang, H. Synthesis of hexagonal close-packed gold nanostructures. Nat. Commun. 2011, 2, 292, DOI: 10.1038/ncomms129135https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3MvntVKitg%253D%253D&md5=ea13bf98aea70fe14551044c2a82810bSynthesis of hexagonal close-packed gold nanostructuresHuang Xiao; Li Shaozhou; Huang Yizhong; Wu Shixin; Zhou Xiaozhu; Li Shuzhou; Gan Chee Lip; Boey Freddy; Mirkin Chad A; Zhang HuaNature communications (2011), 2 (), 292 ISSN:.Solid gold is usually most stable as a face-centred cubic (fcc) structure. To date, no one has synthesized a colloidal form of Au that is exclusively hexagonal close-packed (hcp) and stable under ambient conditions. Here we report the first in situ synthesis of dispersible hcp Au square sheets on graphene oxide sheets, which exhibit an edge length of 200-500 nm and a thickness of ~ 2.4 nm (~ 16 Au atomic layers). Interestingly, the Au square sheet transforms from hcp to a fcc structure on exposure to an electron beam during transmission electron microscopy analysis. In addition, as the square sheet grows thicker (from ~ 2.4 to 6 nm), fcc segments begin to appear. A detailed experimental analysis of these structures shows that for structures with ultrasmall dimensions (for example, <~ 6 nm thickness for the square sheets), the previously unobserved pure hcp structure becomes stable and isolable.
- 36Gao, Y.; Peng, X. Crystal structure control of CdSe nanocrystals in growth and nucleation: dominating effects of surface versus interior structure. J. Am. Chem. Soc. 2014, 136, 6724– 6732, DOI: 10.1021/ja502002536https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXlsl2rsL4%253D&md5=f84e66a009cffef23aff9efad06a4b99Crystal Structure Control of CdSe Nanocrystals in Growth and Nucleation: Dominating Effects of Surface versus Interior StructureGao, Yuan; Peng, XiaogangJournal of the American Chemical Society (2014), 136 (18), 6724-6732CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)For the most studied nanocrystal system in the literature, exptl. results in this paper revealed that formation of either Zn blende or wurtzite CdSe nanocrystals was dominated by the ligand-surface interaction, instead of the interior structure difference. This conclusion was considered to be reasonable, given the very small energy difference between wurtzite and Zn blende CdSe (only 1.4 meV per CdSe unit and ∼1000 times smaller than the energy of a single Cd-ligand bond). Cd carboxylate ligands as Cd fatty acid salts promoted formation of the Zn blende structure. Conversely, Cd phosphonate ligands with a long hydrocarbon chain favored the formation of the wurtzite structure. The effects of either Cd carboxylate or Cd phosphonate ligands play a detg. role during both nucleation and growth. Different from the authors' expectation, fatty amine is only a secondary factor for crystal structure detn. With an appropriate choice of capping ligands, it was possible to achieve precise control of the crystal structure of the CdSe nanocrystals in both nucleation and growth for either the Zn blende or wurtzite structure.
- 37Yao, Y.; He, D.; Lin, Y.; Feng, X.; Wang, X.; Yin, P.; Hong, X.; Zhou, G.; Wu, Y.; Li, Y. Modulating fcc and hcp ruthenium on the surface of palladium-copper alloy through tunable lattice mismatch. Angew. Chem., Int. Ed. 2016, 55, 5501– 5505, DOI: 10.1002/anie.20160101637https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XkvVChsLg%253D&md5=09ddf4a02d945987bccb27c4f333210aModulating fcc and hcp Ruthenium on the Surface of Palladium-Copper Alloy through Tunable Lattice MismatchYao, Yancai; He, Dong Sheng; Lin, Yue; Feng, Xiaoqian; Wang, Xin; Yin, Peiqun; Hong, Xun; Zhou, Gang; Wu, Yuen; Li, YadongAngewandte Chemie, International Edition (2016), 55 (18), 5501-5505CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Herein, we report an epitaxial-growth-mediated method to grow fcc. Ru, which is thermodynamically unfavorable in the bulk form, on the surface of Pd-Cu alloy. Induced by the galvanic replacement between Ru and Pd-Cu alloy, a shape transformation from a Pd-Cu@Ru core-shell to a yolk-shell structure was obsd. during the epitaxial growth. The successful coating of the unconventional crystallog. structure is critically dependent on the moderate lattice mismatch between the fcc. Ru overlayer and PdCu3 alloy substrate. Further, both fcc. and hcp. Ru can be selectively grown through varying the lattice spacing of the Pd-Cu substrate. The presented findings provide a new synthetic pathway to control the crystallog. structure of metal nanomaterials.
- 38Gloag, L.; Benedetti, T. M.; Cheong, S.; Li, Y.; Chan, X.-H.; Lacroix, L.-M.; Chang, S. L. Y.; Arenal, R.; Florea, I.; Barron, H.; Barnard, A. S.; Henning, A. M.; Zhao, C.; Schuhmann, W.; Gooding, J. J.; Tilley, R. D. Three-dimensional branched and faceted gold-ruthenium nanoparticles: using nanostructure to improve stability in oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2018, 57, 10241– 10245, DOI: 10.1002/anie.20180630038https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlWqtLrI&md5=1b3f33ff8ce574054cf34aa15fd1c46fThree-Dimensional Branched and Faceted Gold-Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution ElectrocatalysisGloag, Lucy; Benedetti, Tania M.; Cheong, Soshan; Li, Yibing; Chan, Xuan-Hao; Lacroix, Lise-Marie; Chang, Shery L. Y.; Arenal, Raul; Florea, Ileana; Barron, Hector; Barnard, Amanda S.; Henning, Anna M.; Zhao, Chuan; Schuhmann, Wolfgang; Gooding, J. Justin; Tilley, Richard D.Angewandte Chemie, International Edition (2018), 57 (32), 10241-10245CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the O evolution reaction. As improved stability of Ru catalysts was shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new soln. synthesis is presented in which hcp. structured Ru is grown on Au to form nanoparticles with 3-dimensional branches. Exposing low-index facets on these 3-dimensional branches creates stable reaction kinetics to achieve high activity and the highest stability obsd. for Ru nanoparticle O evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.
- 39Koenigsmann, C.; Semple, D. B.; Sutter, E.; Tobierre, S. E.; Wong, S. S. Ambient synthesis of high-quality ruthenium nanowires and the morphology-dependent electrocatalytic performance of platinum-decorated ruthenium nanowires and nanoparticles in the methanol oxidation reaction. ACS Appl. Mater. Interfaces 2013, 5, 5518– 5530, DOI: 10.1021/am400746239https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXptVeqtrc%253D&md5=2e54a3c1c282f97e46fdc240c054586aAmbient Synthesis of High-Quality Ruthenium Nanowires and the Morphology-Dependent Electrocatalytic Performance of Platinum-Decorated Ruthenium Nanowires and Nanoparticles in the Methanol Oxidation ReactionKoenigsmann, Christopher; Semple, Dara Bobb; Sutter, Eli; Tobierre, Sybil E.; Wong, Stanislaus S.ACS Applied Materials & Interfaces (2013), 5 (12), 5518-5530CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The synthesis is reported for first time of elemental ruthenium nanowires (Ru NWs), method for modifying their surfaces with platinum (Pt), and the morphol.-dependent methanol oxidn. reaction (MOR) performance of high-quality Pt-modified Ru NW electrocatalysts. The synthesis of the elemental Ru NWs was accomplished utilizing a template-based method under ambient conditions. As-prepd. Ru NWs are cryst. and elementally pure, maintain electrochem. properties analogous to elemental Ru, and can be generated with av. diams. ranging from 44-280 nm. The morphol.-dependent performance is examd. of the Ru NWs by comparison with com. Ru nanoparticle (NP)/carbon (C) systems after decorating the surfaces of these structures with Pt. It is demonstrated that the deposition of Pt onto the Ru NWs (Pt∼Ru NWs) results in a unique hierarchical structure, wherein the deposited Pt exists as discrete clusters on the surface. By contrast, it is found that the Pt-decorated com. Ru NP/C (Pt∼Ru NP/C) results in the formation of an alloy-type NP. The Pt∼Ru NPs (0.61 A/mg of Pt) possess nearly 2-fold higher Pt mass activity than analogous Pt∼Ru NW electrocatalysts (0.36 A/mg of Pt). On the basis of a long-term durability test, it is apparent that both catalysts undergo significant declines in performance, potentially resulting from aggregation and ripening in the case of Pt∼Ru NP/C and the effects of catalyst poisoning in the Pt∼Ru NWs. Both catalysts maintain comparable performance, despite a slightly enhanced performance in Pt∼Ru NP/C. In addn., the measured mass-normalized MOR activity of the Pt∼Ru NWs (0.36 A/mg of Pt) was significantly enhanced as compared with supported elemental Pt (Pt NP/C, 0.09 A/mg of Pt) and alloy-type PtRu (PtRu NP/C, 0.24 A/mg of Pt) NPs, both serving as com. stds.
- 40Yin, A. X.; Liu, W. C.; Ke, J.; Zhu, W.; Gu, J.; Zhang, Y. W.; Yan, C. H. Ru nanocrystals with shape-dependent surface-enhanced Raman spectra and catalytic properties: controlled synthesis and DFT calculations. J. Am. Chem. Soc. 2012, 134, 20479– 20489, DOI: 10.1021/ja309093440https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslCgsbzP&md5=14820d8b95f71d0765f699a6be7dca11Ru Nanocrystals with Shape-Dependent Surface-Enhanced Raman Spectra and Catalytic Properties: Controlled Synthesis and DFT CalculationsYin, An-Xiang; Liu, Wen-Chi; Ke, Jun; Zhu, Wei; Gu, Jun; Zhang, Ya-Wen; Yan, Chun-HuaJournal of the American Chemical Society (2012), 134 (50), 20479-20489CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Despite its multidisciplinary interests and technol. importance, the shape control of Ru nanocrystals still remains a great challenge. In this article, we demonstrated a facile hydrothermal approach toward the controlled synthesis of Ru nanocrystals with the assistance of first-principles calcns. For the first time, Ru triangular and irregular nanoplates as well as capped columns with tunable sizes were prepd. with high shape selectivity. In consistency with the exptl. observations and d. functional theory (DFT) calcns. confirmed that both the intrinsic characteristics of Ru crystals and the adsorption of certain reaction species were responsible for the shape control of Ru nanocrystals. Ultrathin Ru nanoplates exposed a large portion of (0001) facets due to the lower surface energy of Ru(0001). The selective adsorption of oxalate species on Ru(10-10) would retard the growth of the side planes of the Ru nanocrystals, while the gradual thermolysis of the oxalate species would eliminate their adsorption effects, leading to the shape evolution of Ru nanocrystals from prisms to capped columns. The surface-enhanced Raman spectra (SERS) signals of these Ru nanocrystals with 4-mercaptopyridine as mol. probes showed an enhancement sequence of capped columns > triangle nanoplates > nanospheres, probably due to the sharp corners and edges in the capped columns and nanoplates as well as the shrunk interparticle distance in their assemblies. CO-selective methanation tests on these Ru nanocrystals indicated that the nanoplates and nanospheres had comparable activities, but the former has much better CO selectivity than the latter.
- 41Watt, J.; Yu, C.; Chang, S. L. Y.; Cheong, S.; Tilley, R. D. Shape control from thermodynamic growth conditions: the case of hcp ruthenium hourglass nanocrystals. J. Am. Chem. Soc. 2013, 135, 606– 609, DOI: 10.1021/ja311366k41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvV2gsLjK&md5=e7b4a7878d6482542cb93d61c9481d53Shape Control from Thermodynamic Growth Conditions: The Case of hcp Ruthenium Hourglass NanocrystalsWatt, John; Yu, Chenlong; Chang, Shery L. Y.; Cheong, Soshan; Tilley, Richard D.Journal of the American Chemical Society (2013), 135 (2), 606-609CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Recent successes in forming different shaped fcc. (fcc) metal nanostructures has enabled a greater understanding of nanocrystal growth mechanisms. Here we extend this understanding to the synthesis of hexagonally close packed (hcp) metal nanostructures, to form uniquely faceted ruthenium nanocrystals with a well-defined hourglass shape. The hourglass nanocrystals are formed in a three-step thermodn. growth process with dodecylamine as the org. stabilizer. The hourglass nanocrystals are then shown to readily self-assemble to form a new type of nanocrystal superlattice.
- 42Rodrigues, T. S.; Zhao, M.; Yang, T.-H.; Gilroy, K. D.; da Silva, A. G. M.; Camargo, P. H. C.; Xia, Y. Synthesis of colloidal metal nanocrystals: a comprehensive review on the reductants. Chem.─Eur. J. 2018, 24, 16944– 16963, DOI: 10.1002/chem.20180219442https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFyjs7jJ&md5=0442b9624f8162ae7d3c27c1d3a789ebSynthesis of Colloidal Metal Nanocrystals: A Comprehensive Review on the ReductantsRodrigues, Thenner S.; Zhao, Ming; Yang, Tung-Han; Gilroy, Kyle D.; da Silva, Anderson G. M.; Camargo, Pedro H. C.; Xia, YounanChemistry - A European Journal (2018), 24 (64), 16944-16963CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)There is a growing interest in controlling the synthesis of colloidal metal nanocrystals and thus tailoring their properties toward various applications. In this context, choosing an appropriate combination of reagents (e.g., salt precursor, reductant, capping agent, and stabilizer) plays a pivotal role in enabling the synthesis of metal nanocrystals with diversified sizes, shapes, and structures. Here we present a comprehensive review that highlights one of the key reagents for the synthesis of metal nanocrystals via chem. redn.: the reductants. We start with a brief introduction to the compds. commonly employed as reductants in the colloidal synthesis of metal nanocrystals by showing their oxidn. half-reactions and the corresponding oxidn. potentials. Then we offer specific examples pertaining to the controlled synthesis of metal nanocrystals, followed by some fundamental aspects covering the general mechanisms of metal ion redn. based on the Marcus Theory. Afterwards, we present a case-by-case discussion on a wide variety of reductants, including their major properties, redn. mechanisms, and addnl. effects on the final products. We illustrate these aspects by selecting key examples from the literature and paying close attention to the underlying mechanism in each case. At the end, we conclude by summarizing the highlights of the review and providing some perspectives on future directions.
- 43Holder, C. F.; Schaak, R. E. Tutorial on Powder X-ray Diffraction for Characterizing Nanoscale Materials. ACS Nano 2019, 13, 7359– 7365, DOI: 10.1021/acsnano.9b0515743https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtl2iu7%252FN&md5=1cc19bb0dce3776f4aefcb3eee6a308bTutorial on Powder X-ray Diffraction for Characterizing Nanoscale MaterialsHolder, Cameron F.; Schaak, Raymond E.ACS Nano (2019), 13 (7), 7359-7365CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)A review. The authors provide the broad nanoscience and nanotechnol. communities with a brief tutorial on some of the key aspects of powder XRD data that are often encountered when analyzing samples of nanoscale materials, with an emphasis on inorg. nanoparticles of various sizes, shapes, and dimensionalities.
- 44Nguyen, Q. N.; Wang, C.; Shang, Y.; Janssen, A.; Xia, Y. Colloidal synthesis of metal nanocrystals: from asymmetrical growth to symmetry breaking. Chem. Rev. 2023, 123, 3693– 3760, DOI: 10.1021/acs.chemrev.2c0046844https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFGnsb%252FJ&md5=75b8e44b38e7c05d440d24c394e2107bColloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry BreakingNguyen, Quynh N.; Wang, Chenxiao; Shang, Yuxin; Janssen, Annemieke; Xia, YounanChemical Reviews (Washington, DC, United States) (2023), 123 (7), 3693-3760CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Nanocrystals offer a unique platform for tailoring the physicochem. properties of solid materials to enhance their performances in various applications. While most work on controlling their shapes revolves around sym. growth, the introduction of asym. growth and thus symmetry breaking has also emerged as a powerful route to enrich metal nanocrystals with new shapes and complex morphologies, as well as unprecedented properties and functionalities. The success of this route critically relies on our ability to lift the confinement on symmetry by the underlying unit cell of the crystal structure and/or the initial seed in a systematic manner. This Review aims to provide an account of recent progress in understanding and controlling asym. growth and symmetry breaking in a colloidal synthesis of noble-metal nanocrystals. With a touch on both the nucleation and growth steps, we discuss a no. of methods capable of generating seeds with diverse symmetry while achieving asym. growth for mono-, bi-, and multimetallic systems. We then showcase a variety of symmetry-broken nanocrystals that have been reported, together with insights into their growth mechanisms. We also highlight their properties and applications and conclude with perspectives on future directions in developing this class of nanomaterials. It is hoped that the concepts and existing challenges outlined in this Review will drive further research in understanding and controlling the symmetry breaking process.
- 45Yin, X.; Shi, M.; Wu, J.; Pan, Y.-T.; Gray, D. L.; Bertke, J. A.; Yang, H. Quantitative analysis of different formation modes of platinum nanocrystals controlled by ligand chemistry. Nano Lett. 2017, 17, 6146– 6150, DOI: 10.1021/acs.nanolett.7b0275145https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsVelurjO&md5=7d20979f2314047ba452555bbcae5cf5Quantitative Analysis of Different Formation Modes of Platinum Nanocrystals Controlled by Ligand ChemistryYin, Xi; Shi, Miao; Wu, Jianbo; Pan, Yung-Tin; Gray, Danielle L.; Bertke, Jeffery A.; Yang, HongNano Letters (2017), 17 (10), 6146-6150CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The authors report that spontaneous ligand replacement and anion exchange control the form of coordinated Pt-ligand intermediates in the system of platinum acetylacetonate [Pt(acac)2], primary aliph. amine, and carboxylic acid ligands. The formed intermediates govern the formation mode of Pt nanocrystals, leading to either a pseudo two-step or a one-step mechanism by switching on or off an autocatalytic surface growth. This finding shows the importance of metal-ligand complexation at the prenucleation stage and represents a crit. step forward for the designed synthesis of nanocrystal-based materials.
- 46Yang, T.-H.; Zhou, S.; Gilroy, K. D.; Figueroa-Cosme, L.; Lee, Y.-H.; Wu, J.-M.; Xia, Y. Autocatalytic surface reduction and its role in controlling seed-mediated growth of colloidal metal nanocrystals. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 13619– 13624, DOI: 10.1073/pnas.171390711446https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFGns7%252FF&md5=df6ee52ebf5fabf54a61e82bf5d64389Autocatalytic surface reduction and its role in controlling seed-mediated growth of colloidal metal nanocrystalsYang, Tung-Han; Zhou, Shan; Gilroy, Kyle D.; Figueroa-Cosme, Legna; Lee, Yi-Hsien; Wu, Jenn-Ming; Xia, YounanProceedings of the National Academy of Sciences of the United States of America (2017), 114 (52), 13619-13624CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)The growth of colloidal metal nanocrystals typically involves an autocatalytic process, where the salt precursor is adsorbed on a growing nanocrystal surface, followed by chem. redn. to atoms for their incorporation into the nanocrystal. Despite its universal role in colloidal nanocrystal synthesis, it is still poorly understood and controlled in terms of kinetics. Using well-defined nanocrystals as seeds (including those with different types of facets, sizes, internal twin structure) this work quant. analyzed the kinetics of autocatalytic surface redn. to control the evolution of nanocrystals as predictable shapes. Kinetic measurements demonstrated the activation energy barrier to autocatalytic surface redn. highly depended on type of facet and presence of twin boundary, corresponding to distinctive growth patterns and products. The autocatalytic process effectively eliminates homogeneous nucleation and activates and sustains octahedral nanocrystal growth. This work was a major step toward quant. understanding and controlling the autocatalytic process involved in colloidal metal nanocrystal synthesis.
- 47Yang, T.-H.; Peng, H.-C.; Zhou, S.; Lee, C.-T.; Bao, S.; Lee, Y.-H.; Wu, J.-M.; Xia, Y. Toward a quantitative understanding of the reduction pathways of a salt precursor in the synthesis of metal nanocrystals. Nano Lett. 2017, 17, 334– 340, DOI: 10.1021/acs.nanolett.6b0415147https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitVKqtbnK&md5=eabdbd8fcf7f308996d8e3fb3dd42439Toward a Quantitative Understanding of the Reduction Pathways of a Salt Precursor in the Synthesis of Metal NanocrystalsYang, Tung-Han; Peng, Hsin-Chieh; Zhou, Shan; Lee, Chi-Ta; Bao, Shixiong; Lee, Yi-Hsien; Wu, Jenn-Ming; Xia, YounanNano Letters (2017), 17 (1), 334-340CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Despite the pivotal role played by the redn. of a salt precursor in the synthesis of metal nanocrystals, it is still unclear how the precursor is reduced. The precursor can be reduced to an atom in the soln. phase, followed by its deposition onto the surface of a growing nanocrystal. Alternatively, the precursor can adsorb onto the surface of a growing nanocrystal, followed by redn. through an autocatalytic process. With Pd as an example, here we demonstrate that the pathway has a correlation with the redn. kinetics involved. Quant. analyses of the redn. kinetics of PdCl42- and PdBr42- by ascorbic acid at room temp. in the absence and presence of Pd nanocubes, resp., suggest that PdCl42- was reduced in the soln. phase while PdBr42- was reduced on the surface of a growing nanocrystal. These results demonstrate that the redn. pathway of PdBr42- by ascorbic acid could be switched from surface to soln. by raising the reaction temp.
- 48Xia, X.; Xie, S.; Liu, M.; Peng, H. C.; Lu, N.; Wang, J.; Kim, M. J.; Xia, Y. On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals. Proc. Natl. Acad. Sci. U.S.A 2013, 110, 6669– 6673, DOI: 10.1073/pnas.122210911048https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXot1Ghs74%253D&md5=68e4936799994c2dbcdbfd8f0ce541d9On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystalsXia, Xiaohu; Xie, Shuifen; Liu, Maochang; Peng, Hsin-Chieh; Lu, Ning; Wang, Jinguo; Kim, Moon J.; Xia, YounanProceedings of the National Academy of Sciences of the United States of America (2013), 110 (17), 6669-6673, S6669/1-S6669/6CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Controlling the shape or morphol. of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addn. of at. species. In this case, manipulating the rates at which the at. species are added onto different crystallog. planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphol. taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. The authors demonstrate that the growth pathway of a seed is indeed detd. by the ratio between the rates for atom deposition and surface diffusion. Surface diffusion needs to be taken into account when controlling the shape or morphol. of metal nanocrystals.
- 49Janssen, A.; Pawlik, V.; von Rueden, A. D.; Xu, L.; Wang, C.; Mavrikakis, M.; Xia, Y. Facile synthesis of palladium-based nanocrystals with different crystal phases and a comparison of their catalytic properties. Adv. Mater. 2021, 33, 2103801 DOI: 10.1002/adma.20210380149https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXit1WjsL7J&md5=f78c38c9e04d1c1259f2624a9a78fb45Facile synthesis of palladium-based nanocrystals with different crystal phases and comparison of their catalytic propertiesJanssen, Annemieke; Pawlik, Veronica; von Rueden, Alexander D.; Xu, Lang; Wang, Chenxiao; Mavrikakis, Manos; Xia, YounanAdvanced Materials (Weinheim, Germany) (2021), 33 (49), 2103801CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A relatively unexplored aspect of noble-metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, a method is reported for the facile synthesis of Ru@Pd core-shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell takes either an hcp or face-centered cubic (fcc) phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking the hcp phase whereas the thicker ones revert to fcc. The injection rate provides an exptl. knob for controlling the phase, with one-shot and drop-wise injection of the Pd precursor corresponding to fcc-Pd and hcp-Pd shells, resp. When these nanocrystals are tested as catalysts toward formic acid oxidn., the Ru@Pdhcp nanocrystals outperform Ru@Pdfcc in terms of both specific activity and peak potential. D. functional theory calcns. are also performed to elucidate the origin of this performance enhancement.
- 50Zhang, H.; Li, W.; Jin, M.; Zeng, J.; Yu, T.; Yang, D.; Xia, Y. Controlling the morphology of rhodium nanocrystals by manipulating the growth kinetics with a syringe pump. Nano Lett. 2011, 11, 898– 903, DOI: 10.1021/nl104347j50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmsFak&md5=8fae00ef1c1bbe3de1a06bdd90784536Controlling the Morphology of Rhodium Nanocrystals by Manipulating the Growth Kinetics with a Syringe PumpZhang, Hui; Li, Weiyang; Jin, Mingshang; Zeng, Jie; Yu, Taekyung; Yang, Deren; Xia, YounanNano Letters (2011), 11 (2), 898-903CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Noble-metal nanocrystals with well-defined and controllable morphologies are of great importance to applications in catalysis, plasmonics, and surface-enhanced spectroscopy. Many synthetic approaches have been demonstrated for controlling the growth habit and thus morphol. of metal nanocrystals, but most of them are based on a thermodn. approach, including the use of a capping agent. While thermodn. control has shown its power in generating nanocrystals with a myriad of different morphologies, it is ultimately limited by the obligation to minimize the surface energy of a system. As a result, it is impractical to use thermodn. control to generate nanocrystals having high-energy facets and/or a neg. curvature. Using rhodium as an example, here we demonstrate a general method based on kinetic control with a syringe pump that can be potentially extended to other noble metals and even other solid materials. For the first time, we were able to produce concave nanocubes with a large fraction of {110} facets and octapods with a cubic symmetry in high yields by simply controlling the injection rate at which the precursor was added into the reaction soln. The concave nanocubes with {110} facets and a unique cavity structure on the surface are important for a variety of applications.
- 51Zhao, M.; Chen, Z.; Shi, Y.; Hood, Z. D.; Lyu, Z.; Xie, M.; Chi, M.; Xia, Y. Kinetically controlled synthesis of rhodium nanocrystals with different shapes and a comparison study of their thermal and catalytic Properties. J. Am. Chem. Soc. 2021, 143, 6293– 6302, DOI: 10.1021/jacs.1c0273451https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXos1Shurg%253D&md5=827bee34159d246fdd39d05625e1388eKinetically Controlled Synthesis of Rhodium Nanocrystals with Different Shapes and a Comparison Study of Their Thermal and Catalytic PropertiesZhao, Ming; Chen, Zitao; Shi, Yifeng; Hood, Zachary D.; Lyu, Zhiheng; Xie, Minghao; Chi, Miaofang; Xia, YounanJournal of the American Chemical Society (2021), 143 (16), 6293-6302CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The authors report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable redn. kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temp. to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500°, resp. When tested as catalysts for hydrazine decompn., the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H2 selectivity relative to the cubic counterpart. As for EtOH oxidn., the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.
- 52Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. The surface energy of metals. Surf. Sci. 1998, 411, 186– 202, DOI: 10.1016/S0039-6028(98)00363-X52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXlvFGnurk%253D&md5=84f3dd83df818f90bfe80a23b3c7b778The surface energy of metalsVitos, L.; Ruban, A. V.; Skriver, H. L.; Kollar, J.Surface Science (1998), 411 (1/2), 186-202CODEN: SUSCAS; ISSN:0039-6028. (Elsevier Science B.V.)The authors used d. functional theory to establish a database of surface energies for low index surfaces of 60 metals in the periodic table. The data may be used as a consistent starting point for models of surface science phenomena. The accuracy of the database is established in a comparison with other d. functional theory results and the calcd. surface energy anisotropies are applied in a detn. of the equil. shape of nano-crystals of Fe, Cu, Mo, Ta, Pt and Pb.
- 53Wang, Y.; Peng, H.-C.; Liu, J.; Huang, C. Z.; Xia, Y. Use of reduction rate as a quantitative knob for controlling the twin structure and shape of palladium nanocrystals. Nano Lett. 2015, 15, 1445– 1450, DOI: 10.1021/acs.nanolett.5b0015853https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsF2ns7g%253D&md5=0d6c8af7184c76046474f291c01615a9Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium NanocrystalsWang, Yi; Peng, Hsin-Chieh; Liu, Jingyue; Huang, Cheng Zhi; Xia, YounanNano Letters (2015), 15 (2), 1445-1450CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Kinetic control is a powerful means for maneuvering the twin structure and shape of metal nanocrystals and thus optimizing their performance in a variety of applications. However, there is only a vague understanding of the explicit roles played by reaction kinetics due to the lack of quant. information about the kinetic parameters. With Pd as an example, here we demonstrate that kinetic parameters, including rate const. and activation energy, can be derived from spectroscopic measurements and then used to calc. the initial redn. rate and further have this parameter quant. correlated with the twin structure of a seed and nanocrystal. On a quant. basis, we were able to det. the ranges of initial redn. rates required for the formation of nanocrystals with a specific twin structure, including single-crystal, multiply twinned, and stacking fault-lined. This work represents a major step forward toward the deterministic syntheses of colloidal noble-metal nanocrystals with specific twin structures and shapes.
- 54Plyuto, Y. V.; Babich, I. V.; Sharanda, L. F.; Marco De Wit, A.; Mol, J. C. Thermolysis of Ru(acac)3 supported on silica and alumina. Thermochim. Acta 1999, 335, 87– 89, DOI: 10.1016/S0040-6031(99)00148-3There is no corresponding record for this reference.
- 55Morozova, N. B.; Gelfond, N. V.; Semyannikov, P. P.; Trubin, S. V.; Igumenov, I. K.; Gutakovskii, A. K.; Latyshev, A. V. Preparation of thin films of platinum group metals by pulsed MOCVD. II. Deposition of Ru layers. J. Struct. Chem. 2012, 53, 725– 733, DOI: 10.1134/S0022476612040154There is no corresponding record for this reference.
- 56Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Ahmari, S. A.; Alkayali, W. Z. Kinetic analysis of thermal decomposition of unirradiated and γ-irradiated tris(acetylacetonato)-ruthenium(III) [Ru(acac)3]. Prog. React. Kinet. Mech. 2007, 32, 1– 27, DOI: 10.3184/146867807X217337There is no corresponding record for this reference.
- 57Kucharyson, J. F.; Gaudet, J. R.; Wyvratt, B. M.; Thompson, L. T. Characterization of structural and electronic transitions during reduction and oxidation of Ru(acac)3 flow battery electrolytes by using X-ray absorption spectroscopy. ChemElectroChem. 2016, 3, 1875– 1883, DOI: 10.1002/celc.201600360There is no corresponding record for this reference.
- 58Vydrov, O. A.; Scuseria, G. E.; Perdew, J. P. Tests of functionals for systems with fractional electron number. J. Chem. Phys. 2007, 126, 154109 DOI: 10.1063/1.272311958https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXkvF2rsbw%253D&md5=5ecdccfa19dff53b01250b7599776e54Tests of functionals for systems with fractional electron numberVydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.Journal of Chemical Physics (2007), 126 (15), 154109/1-154109/9CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)In the exact theory, the ground state energy of an open system varies linearly when the electron no. is changed between two adjacent integers. This linear dependence is not reproduced by common approx. d. functionals. Deviation from linearity in this dependence has been suggested as a basis for the concept of many-electron self-interaction error (SIE). In this paper, we quantify many-electron SIE of a no. of approxns. by performing calcns. on fractionally charged atoms. We demonstrate the direct relevance of these studies to such problems of common approx. functionals as instabilities of anions, spurious fractional charges on dissocd. atoms, and poor description of charge transfer. Semilocal approxns. have the largest many-electron SIE, which is only slightly reduced in typical global hybrids. In these approxns. the energy vs. fractional electron no. curves upward, while in Hartree-Fock theory the energy curves downward. Perdew-Zunger self-interaction correction [Phys. Rev. B 23, 5048 (1981)] significantly reduces the many-electron SIE of semilocal functionals but impairs their accuracy for equil. properties. In contrast, a long-range cor. hybrid functional can be nearly many-electron SIE-free in many cases (for reasons we discuss) and at the same time performs remarkably well for many mol. properties.
- 59Raebiger, H.; Lany, S.; Zunger, A. Charge self-regulation upon changing the oxidation state of transition metals in insulators. Nature 2008, 453, 763– 766, DOI: 10.1038/nature0700959https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXmvVGmsb8%253D&md5=d77ea901d289492ef9c8a231f062a493Charge self-regulation upon changing the oxidation state of transition metals in insulatorsRaebiger, Hannes; Lany, Stephan; Zunger, AlexNature (London, United Kingdom) (2008), 453 (7196), 763-766CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Transition-metal atoms embedded in an ionic or semiconducting crystal can exist in various oxidn. states that have distinct signatures in X-ray photoemission spectroscopy and ionic radii' which vary with the oxidn. state of the atom. We explain this peculiar tendency of transition-metal atoms to maintain a const. local charge under external perturbations in terms of an inherent, homeostasis-like neg. feedback. We show that signatures of oxidn. states and multivalence-such as X-ray photoemission core-level shifts, ionic radii and variations in local magnetization-that have often been interpreted as literal charge transfer are instead a consequence of the neg.-feedback charge regulation.
- 60Stampfl, C.; Scheffler, M. Theoretical study of O adlayers on Ru(0001). Phys. Rev. B 1996, 54, 2868– 2872, DOI: 10.1103/PhysRevB.54.2868There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.4c01725.
Descriptions of synthetic protocols, computational details, additional TEM and HRTEM images, and XRD patterns of the initial Ru seeds and samples prepared under different conditions, as well as results from additional computational analyses (PDF)
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