ACS Publications. Most Trusted. Most Cited. Most Read
Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Catal. 2020, 10, 17, 10051-10059
    Research Article

    Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (2)

    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 17, 10051–10059
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.0c02300
    Published August 6, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VOx) species immobilized over Zr-NU-1000 and Hf-MOF-808 (which have nodes containing six Zr(IV) or Hf(IV) ions, respectively) were recently characterized experimentally (Otake et al. J. Am. Chem. Soc.2018,140, 8652) and were reported to be active for the selective oxidation of benzyl alcohol to benzaldehyde. Here, we report a detailed computational investigation of these VOx-incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VOx attachment, various structures are explored, and their relative stabilities and computed IR spectral features are reported. Mechanisms for the selective oxidation reaction are investigated. The analysis of electron flow in the turnover-limiting C–H activation step shows that the hydrogen-atom abstraction process involves a concerted proton-coupled electron-transfer mechanism. The results of this study suggest that in addition to the identity of the metal in the node, the MOF node architecture plays a crucial role in driving the catalytic activities of V-MOFs.

    Copyright © 2020 American Chemical Society

    Subjects

    what are subjects

    Keywords

    what are keywords

    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.0c02300.

    • Computational details, various VOx conformers, corresponding IR data, and IBO transformations (PDF)

    • Cartesian coordinates of the optimized structure (XYZ)

    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

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 21 publications.

    1. Thang D. Pham, Debabrata Sengupta, Omar K. Farha, Randall Q. Snurr. Investigation of Anionic Metal–Organic Frameworks with Extra-Framework Cations for Room Temperature Hydrogen Storage. Chemistry of Materials 2024, 36 (8) , 3794-3802. https://doi.org/10.1021/acs.chemmater.4c00126
    2. Michael A. Denchy, Linjie Wang, Benjamin R. Bilik, Lucas Hansen, Sandra Albornoz, Francisco Lizano, Nicolas Blando, Zachary Hicks, Gerd Gantefoer, Kit H. Bowen. Ultrasmall Cluster Model for Investigating Single Atom Catalysis: Dehydrogenation of 1-Propanamine by Size-Selected Pt1Zr2O7 Clusters Supported on HOPG. The Journal of Physical Chemistry A 2022, 126 (42) , 7578-7590. https://doi.org/10.1021/acs.jpca.2c03149
    3. Yifang Zhao, Lian Wu, Kun Wu, Rong-Jia Wei, Heng Zeng, Hao Pang, Weigang Lu, Dan Li. Host-guest interactions in the confined spaces of metal–organic frameworks: Design principles, characterizations, and applications. Coordination Chemistry Reviews 2025, 524 , 216302. https://doi.org/10.1016/j.ccr.2024.216302
    4. Duygu Hacıefendioğlu, Ali Tuncel. Switching of selectivity from benzaldehyde to benzoic acid using MIL-100(V) as a heterogeneous catalyst in aerobic oxidation of benzyl alcohol. Catalysis Science & Technology 2024, 14 (22) , 6524-6536. https://doi.org/10.1039/D4CY00832D
    5. I. Bosque, J. C. Gonzalez‐Gomez. Ligand‐Promoted Catalyzed Reactions. 2024, 507-540. https://doi.org/10.1002/9781119716846.ch12
    6. Hai-Yu Li, Xiang-Jing Kong, Song-De Han, Jiandong Pang, Tao He, Guo-Ming Wang, Xian-He Bu. Metalation of metal–organic frameworks: fundamentals and applications. Chemical Society Reviews 2024, 53 (11) , 5626-5676. https://doi.org/10.1039/D3CS00873H
    7. Minghui Lv, Cheng‐Xing Cui, Niu Huang, Mingzhu Wu, Qiao Wang, Tao Gao, Yong Zheng, Hui Li, Wei Liu, Yingping Huang, Tianyi Ma, Liqun Ye. Precisely Engineering Asymmetric Atomic CoN 4 by Electron Donating and Extracting for Oxygen Reduction Reaction. Angewandte Chemie 2024, 136 (21) https://doi.org/10.1002/ange.202315802
    8. Minghui Lv, Cheng‐Xing Cui, Niu Huang, Mingzhu Wu, Qiao Wang, Tao Gao, Yong Zheng, Hui Li, Wei Liu, Yingping Huang, Tianyi Ma, Liqun Ye. Precisely Engineering Asymmetric Atomic CoN 4 by Electron Donating and Extracting for Oxygen Reduction Reaction. Angewandte Chemie International Edition 2024, 63 (21) https://doi.org/10.1002/anie.202315802
    9. Yuyao Qin, Liwen Li, Huixian Liu, Jinyu Han, Hua Wang, Xinli Zhu, Qingfeng Ge. Anionic oxyl radical formed on CrVI-oxo anchored on the defect site of the UiO-66 node facilitates methane to methanol conversion. The Journal of Chemical Physics 2024, 160 (13) https://doi.org/10.1063/5.0201753
    10. Mukunda Mandal, Joshua A. Buss, Si-Jie Chen, Christopher J. Cramer, Shannon S. Stahl. Mechanistic insights into radical formation and functionalization in copper/ N -fluorobenzenesulfonimide radical-relay reactions. Chemical Science 2024, 15 (4) , 1364-1373. https://doi.org/10.1039/D3SC03597B
    11. Duygu Hacıefendioğlu, Ali Tuncel. Switching of Selectivity from Benzaldehyde to Benzoic Acid Using Mil-100(V) as a Heterogeneous Catalyst in Aerobic Oxidation of Benzyl Alcohol. 2024https://doi.org/10.2139/ssrn.4856607
    12. Minghao Liu, Shuai Yang, Xiubei Yang, Cheng-Xing Cui, Guojuan Liu, Xuewen Li, Jun He, George Zheng Chen, Qing Xu, Gaofeng Zeng. Post-synthetic modification of covalent organic frameworks for CO2 electroreduction. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-39544-9
    13. Yanan Wang, Shuyi Cao, Jiangyuan Zhao, Xiongfu Zhang, Xiaohang Du, Jingde Li, Feichao Wu. Conductive vanadium-based metal-organic framework nanosheets membranes as polysulfide inhibitors for lithium-sulfur batteries. Journal of Alloys and Compounds 2023, 960 , 170922. https://doi.org/10.1016/j.jallcom.2023.170922
    14. Samik Gupta. Recent reports on vanadium based coordination polymers and MOFs. Reviews in Inorganic Chemistry 2023, 43 (3) , 465-493. https://doi.org/10.1515/revic-2022-0021
    15. Indrani Choudhuri, Jingyun Ye, Donald G. Truhlar. Computational quantum chemistry of metal–organic frameworks. Chemical Physics Reviews 2023, 4 (3) https://doi.org/10.1063/5.0153656
    16. Ting Zhou, Jianneng Liang, Shenghua Ye, Qianling Zhang, Jianhong Liu. Fundamental, application and opportunities of single atom catalysts for Li-S batteries. Energy Storage Materials 2023, 55 , 322-355. https://doi.org/10.1016/j.ensm.2022.12.002
    17. Yang Zhang, Guowu Zhan, Yibo Song, Yiping Liu, Jiale Huang, Shu-Feng Zhou, Kok Bing Tan, Qingbiao Li. Utilization of waste vanadium-bearing resources in the preparation of rare-earth vanadate catalysts for semi-hydrogenation of α,β-unsaturated aldehydes. Frontiers of Chemical Science and Engineering 2022, 16 (12) , 1793-1806. https://doi.org/10.1007/s11705-022-2191-x
    18. Jian Liu, Ying Yang, Timothy A. Goetjen, Joseph T. Hupp. Carbon-efficient conversion of natural gas and natural-gas condensates to chemical products and intermediate feedstocks via catalytic metal–organic framework (MOF) chemistry. Energy & Environmental Science 2022, 15 (7) , 2819-2842. https://doi.org/10.1039/D2EE01010K
    19. Ken-ichi OTAKE. Direct Observation of Structural Changes of Active Catalytic Sites on Porous Coordination Polymer. Nihon Kessho Gakkaishi 2022, 64 (2) , 107-108. https://doi.org/10.5940/jcrsj.64.107
    20. Khaled M. Elsabawy, Ahmed M. Fallatah, Zeid O. Owidah. Synthesis of newly crystalline-porous- Pd(II)- (E,E)-2, 4-hexadienoic acid complex-leads to 3D-MOFs for hydrogen storage. Journal of Molecular Structure 2022, 1250 , 131723. https://doi.org/10.1016/j.molstruc.2021.131723
    21. Yifan Shao, Wan Nie, Chengyu Yao, Lina Ye, Haizhu Yu. DFT insights into the Ni-catalyzed regioselective hydrocarboxylation of unsaturated alkenes with CO 2. Dalton Transactions 2021, 50 (42) , 15084-15093. https://doi.org/10.1039/D1DT02486H
    22. Wenlong Xiang, Yueping Zhang, Yifei Chen, Chang-jun Liu, Xin Tu. Synthesis, characterization and application of defective metal–organic frameworks: current status and perspectives. Journal of Materials Chemistry A 2020, 8 (41) , 21526-21546. https://doi.org/10.1039/D0TA08009H
    Download PDF
    Go to ACS Catalysis
    Get e-Alerts
    Get e-Alerts

    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 17, 10051–10059
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.0c02300
    Published August 6, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

    Article Views

    3606

    Altmetric

    -

    Citations

    21
    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.