ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Chem. Mater. 2018, 30, 8, 2641-2650
RETURN TO ISSUEPREVArticleNEXT

Factors Governing MgO(111) Faceting in the Thermal Decomposition of Oxide Precursors

  • Mariano D. Susman
    Mariano D. Susman
    Department of Chemical and Biomolecular Engineering, University of Houston, 4726 Calhoun Road, Houston, Texas 77204, United States
    More by Mariano D. Susman
  • , 
  • Hien N. Pham
    Hien N. Pham
    Department of Chemical and Biological Engineering and Center for Microengineered Materials, University of New Mexico, Albuquerque, New Mexico 87131-0001, United States
    More by Hien N. Pham
  • , 
  • Abhaya K. Datye
    Abhaya K. Datye
    Department of Chemical and Biological Engineering and Center for Microengineered Materials, University of New Mexico, Albuquerque, New Mexico 87131-0001, United States
    More by Abhaya K. Datye
  • , 
  • Sivadinarayana Chinta
    Sivadinarayana Chinta
    SABIC Technology Center, 1600 Industrial Blvd., Sugar Land, Houston, Texas 77478, United States
    More by Sivadinarayana Chinta
  • , and 
  • Jeffrey D. Rimer*
    Jeffrey D. Rimer
    Department of Chemical and Biomolecular Engineering, University of Houston, 4726 Calhoun Road, Houston, Texas 77204, United States
    *E-mail: [email protected] (J.D.R.).
    More by Jeffrey D. Rimer
    Orcidhttp://orcid.org/0000-0002-2296-3428
Cite this: Chem. Mater. 2018, 30, 8, 2641–2650
Publication Date (Web):February 9, 2018
https://doi.org/10.1021/acs.chemmater.7b05302
Copyright © 2018 American Chemical Society
Request reuse permissions

    Article Views

    1653

    Altmetric

    -

    Citations

    31
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (6 MB)
    Get e-Alerts
    Supporting Info (1)»
    SUBJECTS:

    Abstract

    Abstract Image

    The preparation of metal oxide particles, such as MgO, NiO, and ZnO, exposing polar facets via the decomposition of suitable precursors in air, molten salts, ionic liquids, or other media has been reported; however, the main driving force(s) and factors that determine their morphology have largely remained elusive. For instance, the adsorption of ions within a molten medium on a growing oxide surface has been proposed to stabilize MgO{111} facets by the so-called molten salt route (MSR). In this article, we examine the thermal decomposition of MgO precursors to assess the influence of precursor decomposition pathways, including the physical state of the reaction intermediates and the possibility of dissolution–recrystallization processes in the formation of octahedral MgO particles. We found that solid-to-solid conversions and recrystallizations in molten nitrates or chlorides are usually incapable of producing well-defined MgO{111} facets, indicating that ion adsorption on MgO may not be the main morphological driving force. Here, we show for Mg(NO3)2·6H2O, the most suited MgO(111) precursor, that its decomposition trajectory is crucial in determining the exposure of {111} facets. The decomposition trajectory may be regulated by using controlled heating profiles, regulated atmospheres, or by incorporating particular salts in the reaction mixture. Our findings indicate that, for neat Mg(NO3)2·6H2O decomposition in air, MgO{111} facets are promoted via magnesium nitrate intermediates in the molten state and in the presence of residual water. These conditions can be achieved by heating the hexahydrate precursor at high rates. On the contrary, decomposition of anhydrous Mg(NO3)2 results in ill-defined MgO morphologies. In a molten NaNO3:KNO3 medium, the formation of liquid eutectic mixtures facilitate H2O retention and ionic mobility, from which well-defined octahedral MgO crystals form, thereby emphasizing the crucial role of water in Mg(II)-nitrate systems. In a NaCl:KCl ionic medium, precursor decomposition occurs via a K3NaMgCl6 intermediate, which melts before converting to the oxide. MgO(111) forms under local melting of the intermediate (before NaCl:KCl melts) and when the H2O content is negligible. In summary, the formation of polar MgO(111) particles is facilitated in molten salt media when MgO is generated via a liquid-to-solid reaction (with intermediates in the molten state). The presence of residual water and ions impact MgO(111) crystallization in ways that still remain elusive, but are not necessarily governed by adsorption–stabilization processes.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b05302.

    • PXRD patterns of precursors decomposed at different conditions, SEM images of MgO produced by decomposition and recrystallization in NaNO3:KNO3 (3:2) and in NaCl:KCl (1:1) up to 550 °C, TGA/DTA-DSC curves reported in literature for the tested precursors, description of the temperature ramps used for stepwise treatments, physical state(s) of the systems, and a scheme describing the impact of molten nitrates on MgO morphology (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 31 publications.

    1. Raiven I. Balderas, Cristian V. Ciobanu, Ryan M. Richards. (111) Faceted Metal Oxides: A Review of Synthetic Methods. Crystal Growth & Design 2022, 22 (10) , 6296-6322. https://doi.org/10.1021/acs.cgd.2c00409
    2. Daniel Thomele, Stefan O. Baumann, Johannes Schneider, Andreas K. Sternig, Sarah Shulda, Ryan M. Richards, Thomas Schwab, Gregor A. Zickler, Gilles R. Bourret, Oliver Diwald. Cubes to Cubes: Organization of MgO Particles into One-Dimensional and Two-Dimensional Nanostructures. Crystal Growth & Design 2021, 21 (8) , 4674-4682. https://doi.org/10.1021/acs.cgd.1c00535
    3. Mariano D. Susman, Sivadinarayana Chinta, Jeffrey D. Rimer. High-Index (Ni,Mg)O Crystallization during Molten Salt Synthesis. Chemistry of Materials 2021, 33 (9) , 3155-3163. https://doi.org/10.1021/acs.chemmater.0c04837
    4. Santosh K. Gupta, Yuanbing Mao. Recent Developments on Molten Salt Synthesis of Inorganic Nanomaterials: A Review. The Journal of Physical Chemistry C 2021, 125 (12) , 6508-6533. https://doi.org/10.1021/acs.jpcc.0c10981
    5. Tsutomu Shinagawa, Masaya Chigane, Masanobu Izaki. Electrochemical Growth of Mg(OH)x Layered Films Stacked Parallel to the Substrates and Their Thermal Conversion to (111)-Oriented Nanoporous MgO Films. ACS Omega 2021, 6 (3) , 2312-2317. https://doi.org/10.1021/acsomega.0c05619
    6. Yuan Zhong, Junsheng Yuan, Min Wang, Jinli Li. Phase Diagrams of Binary Systems Mg(NO3)2-KNO3, Mg(NO3)2-LiNO3 and ternary system Mg(NO3)2-LiNO3-NaNO3. Journal of Chemical & Engineering Data 2020, 65 (7) , 3420-3427. https://doi.org/10.1021/acs.jced.9b01091
    7. Trang Q. Tran, Weiqing Zheng, George Tsilomelekis. Molten Salt Hydrates in the Synthesis of TiO2 Flakes. ACS Omega 2019, 4 (25) , 21302-21310. https://doi.org/10.1021/acsomega.9b02850
    8. Xiyang Wang, Keke Huang, Long Yuan, Shuang Li, Wei Ma, Zhongyuan Liu, Shouhua Feng. Molten Salt Flux Synthesis, Crystal Facet Design, Characterization, Electronic Structure, and Catalytic Properties of Perovskite Cobaltite. ACS Applied Materials & Interfaces 2018, 10 (33) , 28219-28231. https://doi.org/10.1021/acsami.8b08621
    9. Hawzhin Amanollahi, Gholamreza Moussavi, Somayeh Ostovar, Stefanos Giannakis. From waste to wealth: Using MgO nanoparticles to transform ammonium into a valuable resource. Journal of Water Process Engineering 2023, 56 , 104331. https://doi.org/10.1016/j.jwpe.2023.104331
    10. Ding Zhao, Baozhong Ma, Chengyan Wang, Yongqiang Chen. The regeneration of HNO3 and MgO via multistep pyrolysis of Mg(NO3)2⋅6H2O and thermodynamic analysis of critical intermediate product. Journal of Thermal Analysis and Calorimetry 2023, 148 (17) , 9047-9061. https://doi.org/10.1007/s10973-023-12284-0
    11. Qi Shen, Hao Yan, Xunchun Yuan, Ruiying Li, Dekang Kong, Wenxiang Zhang, Hanyang Zhang, Yibin Liu, Xiaobo Chen, Xiang Feng, Xin Zhou, Chaohe Yang. Tailoring morphology of MgO catalyst for the enhanced coupling reaction of CO2 and glycerol to glycerol carbonate. Fuel 2023, 335 , 126972. https://doi.org/10.1016/j.fuel.2022.126972
    12. Tsutomu Shinagawa, Masanobu Izaki. Template-free formation of oriented oxide nanowalls via topotactic-like pseudomorphic transformation: [110]-MgO(111) nanowall arrays. Materials Advances 2022, 3 (19) , 7257-7264. https://doi.org/10.1039/D2MA00493C
    13. Stephen J. Cox. A theory for the stabilization of polar crystal surfaces by a liquid environment. The Journal of Chemical Physics 2022, 157 (9) https://doi.org/10.1063/5.0097531
    14. Meng-hui Zhang, Liang Zhao, Han-lu Xu, Wen-chang Wu, Hui Dong. Study on the thermal decomposition mechanism of Mg(NO 3 ) 2 ·6H 2 O from the perspective of resource utilization of magnesium slag. Environmental Technology 2022, , 1-28. https://doi.org/10.1080/09593330.2022.2121182
    15. David Portehault, Isabel Gómez-Recio, Marzena A. Baron, Valentina Musumeci, Cyril Aymonier, Virgile Rouchon, Yann Le Godec. Geoinspired syntheses of materials and nanomaterials. Chemical Society Reviews 2022, 51 (11) , 4828-4866. https://doi.org/10.1039/D0CS01283A
    16. Shengdi Zhang, Xiang Li, Yanxia Sun, Jinbo Zeng, Shenglong Zhu, Wenqi Song, Yuan Zhou, Xiufeng Ren, Chunxi Hai, Yue Shen. Low-cost magnesium-based eutectic salt hydrate phase change material with enhanced thermal performance for energy storage. Solar Energy Materials and Solar Cells 2022, 238 , 111620. https://doi.org/10.1016/j.solmat.2022.111620
    17. Ding Zhao, Baozhong Ma, Chengyan Wang, Yuqing Zhang, Shuyang Shi, Yongqiang Chen. Investigation of the thermal behavior of Mg(NO3)2·6H2O and its application for the regeneration of HNO3 and MgO. Chemical Engineering Journal 2022, 433 , 133804. https://doi.org/10.1016/j.cej.2021.133804
    18. Raffaele Cheula, Mariano D. Susman, David H. West, Sivadinarayana Chinta, Jeffrey D. Rimer, Matteo Maestri. Local Ordering of Molten Salts at NiO Crystal Interfaces Promotes High‐Index Faceting. Angewandte Chemie 2021, 133 (48) , 25595-25600. https://doi.org/10.1002/ange.202105018
    19. Raffaele Cheula, Mariano D. Susman, David H. West, Sivadinarayana Chinta, Jeffrey D. Rimer, Matteo Maestri. Local Ordering of Molten Salts at NiO Crystal Interfaces Promotes High‐Index Faceting. Angewandte Chemie International Edition 2021, 60 (48) , 25391-25396. https://doi.org/10.1002/anie.202105018
    20. Alexander H. Bork, Margarita Rekhtina, Elena Willinger, Pedro Castro-Fernández, Jakub Drnec, Paula M. Abdala, Christoph R. Müller. Peering into buried interfaces with X-rays and electrons to unveil MgCO 3 formation during CO 2 capture in molten salt-promoted MgO. Proceedings of the National Academy of Sciences 2021, 118 (26) https://doi.org/10.1073/pnas.2103971118
    21. Pengxin Liu, Paula Macarena Abdala, Guillaume Goubert, Marc‐Georg Willinger, Christophe Copéret. Ultrathin Single Crystalline MgO(111) Nanosheets**. Angewandte Chemie 2021, 133 (6) , 3291-3297. https://doi.org/10.1002/ange.202013196
    22. Pengxin Liu, Paula Macarena Abdala, Guillaume Goubert, Marc‐Georg Willinger, Christophe Copéret. Ultrathin Single Crystalline MgO(111) Nanosheets**. Angewandte Chemie International Edition 2021, 60 (6) , 3254-3260. https://doi.org/10.1002/anie.202013196
    23. Xiaohui Zhao, Mariano D. Susman, Jeffrey D. Rimer, Praveen Bollini. Tuning selectivity in nickel oxide-catalyzed oxidative dehydrogenation of ethane through control over non-stoichiometric oxygen density. Catalysis Science & Technology 2021, 11 (2) , 531-541. https://doi.org/10.1039/D0CY01732A
    24. Mariano D. Susman, Hien N. Pham, Xiaohui Zhao, David H. West, Sivadinarayana Chinta, Praveen Bollini, Abhaya K. Datye, Jeffrey D. Rimer. Synthesis of NiO Crystals Exposing Stable High‐Index Facets. Angewandte Chemie 2020, 132 (35) , 15231-15235. https://doi.org/10.1002/ange.202003390
    25. Mariano D. Susman, Hien N. Pham, Xiaohui Zhao, David H. West, Sivadinarayana Chinta, Praveen Bollini, Abhaya K. Datye, Jeffrey D. Rimer. Synthesis of NiO Crystals Exposing Stable High‐Index Facets. Angewandte Chemie International Edition 2020, 59 (35) , 15119-15123. https://doi.org/10.1002/anie.202003390
    26. Margarita Rekhtina, Alessandro Dal Pozzo, Dragos Stoian, Andac Armutlulu, Felix Donat, Maria V. Blanco, Zhu-Jun Wang, Marc-Georg Willinger, Alexey Fedorov, Paula M. Abdala, Christoph R. Müller. Effect of molten sodium nitrate on the decomposition pathways of hydrated magnesium hydroxycarbonate to magnesium oxide probed by in situ total scattering. Nanoscale 2020, 12 (31) , 16462-16473. https://doi.org/10.1039/D0NR01760D
    27. Changming Fang, Zhongyun Fan. Atomic ordering at the interfaces between liquid Al and solid MgO: An Ab Initio molecular dynamics study. Philosophical Magazine Letters 2020, 100 (5) , 235-244. https://doi.org/10.1080/09500839.2020.1750722
    28. Xirui Yan, Zixin Tian, Wencai Peng, Jianshu Zhang, Yanbin Tong, Jun Li, Dekui Sun, Hui Ge, Jinli Zhang. Synthesis of nano-octahedral MgO via a solvothermal-solid-decomposition method for the removal of methyl orange from aqueous solutions. RSC Advances 2020, 10 (18) , 10681-10688. https://doi.org/10.1039/C9RA10296E
    29. M. A. A. Aziz, A. A. Jalil, S. Wongsakulphasatch, Dai-Viet N. Vo. Understanding the role of surface basic sites of catalysts in CO 2 activation in dry reforming of methane: a short review. Catalysis Science & Technology 2020, 10 (1) , 35-45. https://doi.org/10.1039/C9CY01519A
    30. Gilles R. Bourret, Oliver Diwald. Thin water films covering oxide nanomaterials: Stability issues and influences on materials processing. Journal of Materials Research 2019, 34 (3) , 428-441. https://doi.org/10.1557/jmr.2018.429
    31. Jeffrey D. Rimer, Aseem Chawla, Thuy T. Le. Crystal Engineering for Catalysis. Annual Review of Chemical and Biomolecular Engineering 2018, 9 (1) , 283-309. https://doi.org/10.1146/annurev-chembioeng-060817-083953
    Download PDF

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect