ACS Publications. Most Trusted. Most Cited. Most Read
Conflicting Roles of Coordination Number on Catalytic Performance of Single-Atom Pt Catalysts
My Activity
    Research Article

    Conflicting Roles of Coordination Number on Catalytic Performance of Single-Atom Pt Catalysts
    Click to copy article linkArticle link copied!

    • Dahong Huang
      Dahong Huang
      School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, Guangdong 523808, P.R. China
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      More by Dahong Huang
    • Ning He
      Ning He
      School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P.R. China
      More by Ning He
    • Qianhong Zhu
      Qianhong Zhu
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      More by Qianhong Zhu
    • Chiheng Chu
      Chiheng Chu
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      More by Chiheng Chu
    • Seunghyun Weon
      Seunghyun Weon
      School of Health and Environmental Science, Korea University, Seoul 02841, Korea
    • Kali Rigby
      Kali Rigby
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      More by Kali Rigby
    • Xuechen Zhou
      Xuechen Zhou
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      More by Xuechen Zhou
    • Lei Xu
      Lei Xu
      School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, Guangdong 523808, P.R. China
      More by Lei Xu
    • Junfeng Niu*
      Junfeng Niu
      School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, Guangdong 523808, P.R. China
      *Email: [email protected]. Tel/Fax: +86-769-22863180.
      More by Junfeng Niu
    • Eli Stavitski
      Eli Stavitski
      National Synchrotron Light Source- II, Brookhaven National Laboratory, Upton, New York 11973, United States
    • Jae-Hong Kim*
      Jae-Hong Kim
      Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States
      *Email: [email protected]. Tel.: +1-203-432-4386. Fax: +1-203-432-4387.
      More by Jae-Hong Kim
    Other Access OptionsSupporting Information (1)

    ACS Catalysis

    Cite this: ACS Catal. 2021, 11, 9, 5586–5592
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.1c00627
    Published April 22, 2021
    Copyright © 2021 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Tailoring the coordination number (CN) of metal atoms has been increasingly recognized as one of the strategies to enhance the catalytic performance of single-atom catalysts (SACs). We here present the single-atom Pt loaded onto a semiconductor SiC substrate (Pt1/SiC) with a high loading of up to 9.6 wt % and a precise control of its CN from 3 to 5. The CN tuning was enabled by binding organic linkers on the substrate surface and retaining the metal-linker bonds after photoreduction and mild thermal treatment from 80 to 160 °C. At a higher temperature, Pt became coordinated with additional oxygen atoms from the surface Si–OH groups and organic linkers. This resulted in the increase of the CN from 3 for Pt1 treated at 80 °C to 5 at 160 °C. The Pt1/SiCs with varying CNs effectively broke C–Br bonds in the model brominated compounds through both thermocatalysis using H2 and photocatalysis using H+ as the source for strongly reducing atomic hydrogen (Hatom). The thermocatalytic debromination kinetics increased with the decreasing CN. However, photocatalytic debromination kinetics were independent of the CN, contradictory to the prevalent understanding in literature. We attribute the differential CN effects on these two catalytic schemes to the differences in the pathways for the formation of Hatom as well as the rate-limiting step of the overall reaction pathways. Our study presents a unique and important example as to how the performance of SACs and the role of CN can significantly vary depending on the catalytic schemes.

    Copyright © 2021 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.1c00627.

    • Calculations of the density of Pt atoms, materials, details of the catalyst preparation, assessments of photocatalytic and thermocatalytic performances, DFT computational details; supplementary characterizations with XPS, AC-HAADF-STEM, X-ray powder diffraction, high-resolution transmission electron microscopy, XAFS; photocatalytic and thermocatalytic kinetics, recycling experiments, carbon and bromine mass balances, HPLC spectrums, energy profiles for hydrodebromination, Arrhenius plot for the calculation of apparent activation energy, optimized structures involved in two catalyses (PDF)

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 28 publications.

    1. Honghui Gong, Longxing Wei, Qi Li, Juan Zhang, Fei Wang, Jing Ren, Xian-Lei Shi. Electron-Rich Ru Supported on N-Doped Coffee Biochar for Selective Reductive Amination of Furfural to Furfurylamine. Langmuir 2024, 40 (17) , 8950-8960. https://doi.org/10.1021/acs.langmuir.4c00112
    2. Wei Ran, Huachao Zhao, Xiaoling Zhang, Shiwei Li, Jie-Fang Sun, Jingfu Liu, Rui Liu, Guibin Jiang. Critical Review of Pd-Catalyzed Reduction Process for Treatment of Waterborne Pollutants. Environmental Science & Technology 2024, 58 (7) , 3079-3097. https://doi.org/10.1021/acs.est.3c09198
    3. Bingxin Dou, Guanlong Wang, Xiaoli Dong, Xiufang Zhang. Improved H2O2 Electrosynthesis on S-doped Co–N–C through Cooperation of Co–S and Thiophene S. ACS Applied Materials & Interfaces 2024, 16 (6) , 7374-7383. https://doi.org/10.1021/acsami.3c18879
    4. Jinwook Lee, Jooyoun Kim. Cooperative Design of the Ag3PO4/NH2-MIL-88B (Fe/Co) Heterojunction Integrated with Conductive Polypyrrole for Advanced Photocatalytic Water Purification. ACS Omega 2024, 9 (5) , 5942-5953. https://doi.org/10.1021/acsomega.3c09625
    5. Liangzhong Li, Chenyu Yang, Yile Yan, Xian Xiao, Yang Yu, Chang Liu, Ruixue Ma, Lun Lu, Xiaoyun Fan, Da Chen, Yabing Meng, Long Yan, Yunjiang Yu. Engineering Hexacoordination-Structured Co Single-Atom Sites (Co–N4+2) to Boost Peroxydisulfate Activation in Advanced Oxidation Processes. ACS ES&T Engineering 2023, 3 (11) , 1908-1917. https://doi.org/10.1021/acsestengg.3c00262
    6. Kali Rigby, Dahong Huang, Denis Leshchev, Hyun Jeong Lim, Hyeyeon Choi, Aidan Francis Meese, Seunghyun Weon, Eli Stavitski, Jae-Hong Kim. Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions. Environmental Science & Technology 2023, 57 (36) , 13681-13690. https://doi.org/10.1021/acs.est.3c03346
    7. Jing Wang, Yongbing Xie, Guangfei Yu, Lichang Yin, Jiadong Xiao, Yuxian Wang, Weiguang Lv, Zhi Sun, Jae-Hong Kim, Hongbin Cao. Manipulating Selectivity of Hydroxyl Radical Generation by Single-Atom Catalysts in Catalytic Ozonation: Surface or Solution. Environmental Science & Technology 2022, 56 (24) , 17753-17762. https://doi.org/10.1021/acs.est.2c06836
    8. Xuanhao Wu, Jae-Hong Kim. Outlook on Single Atom Catalysts for Persulfate-Based Advanced Oxidation. ACS ES&T Engineering 2022, 2 (10) , 1776-1796. https://doi.org/10.1021/acsestengg.2c00187
    9. Baljeet Singh, Manoj B. Gawande, Arun D. Kute, Rajender S. Varma, Paolo Fornasiero, Peter McNeice, Rajenahally V. Jagadeesh, Matthias Beller, Radek Zbořil. Single-Atom (Iron-Based) Catalysts: Synthesis and Applications. Chemical Reviews 2021, 121 (21) , 13620-13697. https://doi.org/10.1021/acs.chemrev.1c00158
    10. Dahong Huang, David J. Kim, Kali Rigby, Xuechen Zhou, Xuanhao Wu, Aidan Meese, Junfeng Niu, Eli Stavitski, Jae-Hong Kim. Elucidating the Role of Single-Atom Pd for Electrocatalytic Hydrodechlorination. Environmental Science & Technology 2021, 55 (19) , 13306-13316. https://doi.org/10.1021/acs.est.1c04294
    11. Hanyu Hu, Yanyan Zhao, Yue Zhang, Jiangbo Xi, Jian Xiao, Sufeng Cao. Performance Regulation of Single-Atom Catalyst by Modulating the Microenvironment of Metal Sites. Topics in Current Chemistry 2023, 381 (5) https://doi.org/10.1007/s41061-023-00434-9
    12. Zhongsen Wang, Ming Cheng, Yi Liu, Zewei Wu, Huayu Gu, Yi Huang, Lizhi Zhang, Xiao Liu. Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis. Angewandte Chemie 2023, 135 (22) https://doi.org/10.1002/ange.202301483
    13. Zhongsen Wang, Ming Cheng, Yi Liu, Zewei Wu, Huayu Gu, Yi Huang, Lizhi Zhang, Xiao Liu. Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis. Angewandte Chemie International Edition 2023, 62 (22) https://doi.org/10.1002/anie.202301483
    14. Dan Sun, Yajie Chen, Xinyan Yu, Yuejia Yin, Guohui Tian. Engineering high-coordinated cerium single-atom sites on carbon nitride nanosheets for efficient photocatalytic amine oxidation and water splitting into hydrogen. Chemical Engineering Journal 2023, 462 , 142084. https://doi.org/10.1016/j.cej.2023.142084
    15. Haiyan An, Liangliang Liu, Nan Song, Hongmei Zhu, Yu Tang. Rational design and synthesis of cerium dioxide-based nanocomposites. Nano Research 2023, 16 (3) , 3622-3640. https://doi.org/10.1007/s12274-022-4941-y
    16. Joshua Meléndez-Rivera, Juan A. Santana. Density Functional Calculations of the Sequential Adsorption of Hydrogen on Single Atom and Small Clusters of Pd and Pt Supported on Au(111). Electrocatalysis 2023, 14 (2) , 325-331. https://doi.org/10.1007/s12678-022-00802-x
    17. Shang Li, Yuxing Xu, Hengwei Wang, Botao Teng, Qin Liu, Qiuhua Li, Lulu Xu, Xinyu Liu, Junling Lu. Tuning the CO 2 Hydrogenation Selectivity of Rhodium Single‐Atom Catalysts on Zirconium Dioxide with Alkali Ions. Angewandte Chemie 2023, 135 (8) https://doi.org/10.1002/ange.202218167
    18. Shang Li, Yuxing Xu, Hengwei Wang, Botao Teng, Qin Liu, Qiuhua Li, Lulu Xu, Xinyu Liu, Junling Lu. Tuning the CO 2 Hydrogenation Selectivity of Rhodium Single‐Atom Catalysts on Zirconium Dioxide with Alkali Ions. Angewandte Chemie International Edition 2023, 62 (8) https://doi.org/10.1002/anie.202218167
    19. Xueshan Hu, Daxian Zuo, Shaoru Cheng, Sihui Chen, Yang Liu, Wenzhong Bao, Sili Deng, Stephen J. Harris, Jiayu Wan. Ultrafast materials synthesis and manufacturing techniques for emerging energy and environmental applications. Chemical Society Reviews 2023, 52 (3) , 1103-1128. https://doi.org/10.1039/D2CS00322H
    20. Chong Wang, Chen Guo. Nitrogen atom coordination tuned transition metal catalysts for NO oxidation and reduction. Chemosphere 2022, 309 , 136735. https://doi.org/10.1016/j.chemosphere.2022.136735
    21. Wei Tan, Shaohua Xie, Duy Le, Weijian Diao, Meiyu Wang, Ke-Bin Low, Dave Austin, Sampyo Hong, Fei Gao, Lin Dong, Lu Ma, Steven N. Ehrlich, Talat S. Rahman, Fudong Liu. Fine-tuned local coordination environment of Pt single atoms on ceria controls catalytic reactivity. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-34797-2
    22. Bin Han, Yu Luo, Yuanfang Lin, Bo Weng, Dehua Xia, Yang Zhou, Chaoting Guan, Zhen Wang, Xipeng Wei, Jin Jiang. Microenvironment engineering of single-atom catalysts for persulfate-based advanced oxidation processes. Chemical Engineering Journal 2022, 447 , 137551. https://doi.org/10.1016/j.cej.2022.137551
    23. Weiqiong Zheng, Ran Zhu, Huijuan Wu, Tian Ma, Hongju Zhou, Mi Zhou, Chao He, Xikui Liu, Shuang Li, Chong Cheng. Tailoring Bond Microenvironments and Reaction Pathways of Single‐Atom Catalysts for Efficient Water Electrolysis. Angewandte Chemie 2022, 134 (41) https://doi.org/10.1002/ange.202208667
    24. Weiqiong Zheng, Ran Zhu, Huijuan Wu, Tian Ma, Hongju Zhou, Mi Zhou, Chao He, Xikui Liu, Shuang Li, Chong Cheng. Tailoring Bond Microenvironments and Reaction Pathways of Single‐Atom Catalysts for Efficient Water Electrolysis. Angewandte Chemie International Edition 2022, 61 (41) https://doi.org/10.1002/anie.202208667
    25. Wenjing Xu, Hao Tang, Hongfei Gu, Hongyan Xi, Pengfei Wu, Benliang Liang, Qingqing Liu, Wenxing Chen. Research progress of asymmetrically coordinated single-atom catalysts for electrocatalytic reactions. Journal of Materials Chemistry A 2022, 10 (28) , 14732-14746. https://doi.org/10.1039/D2TA03034A
    26. Shangchun Lv, Mengxi Pei, Yuxiang Liu, Zhichun Si, Xiaodong Wu, Rui Ran, Duan Weng, Feiyu Kang. An isolation strategy to anchor atomic Ni or Co cocatalysts on TiO2(A) for photocatalytic hydrogen production. Nano Research 2022, 15 (7) , 5848-5856. https://doi.org/10.1007/s12274-022-4217-6
    27. Zhun Zhang, Hengyu Li, Danfeng Wu, Lina Zhang, Jiwei Li, Junli Xu, Sen Lin, Abhaya K. Datye, Haifeng Xiong. Coordination structure at work: Atomically dispersed heterogeneous catalysts. Coordination Chemistry Reviews 2022, 460 , 214469. https://doi.org/10.1016/j.ccr.2022.214469
    28. Baisong Chang, Liqin Zhang, Shaolong Wu, Ziyan Sun, Zhen Cheng. Engineering single-atom catalysts toward biomedical applications. Chemical Society Reviews 2022, 51 (9) , 3688-3734. https://doi.org/10.1039/D1CS00421B

    ACS Catalysis

    Cite this: ACS Catal. 2021, 11, 9, 5586–5592
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.1c00627
    Published April 22, 2021
    Copyright © 2021 American Chemical Society

    Article Views

    4599

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.