ACS Publications. Most Trusted. Most Cited. Most Read
Fundamental Insights into the Reactivity and Utilization of Open Metal Sites in Cu(I)-MFU-4l

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Organometallics 2019, 38, 18, 3453-3459
    Article

    Fundamental Insights into the Reactivity and Utilization of Open Metal Sites in Cu(I)-MFU-4l
    Click to copy article linkArticle link copied!

    • Lin Li
      Lin Li
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      More by Lin Li
    • Yahui Yang
      Yahui Yang
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      More by Yahui Yang
    • Mona H. Mohamed
      Mona H. Mohamed
      Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      Chemistry Department, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, Egypt
      More by Mona H. Mohamed
    • Sen Zhang
      Sen Zhang
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      More by Sen Zhang
    • Götz Veser
      Götz Veser
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      More by Götz Veser
    • Nathaniel L. Rosi
      Nathaniel L. Rosi
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      More by Nathaniel L. Rosi
      Orcidhttp://orcid.org/0000-0001-8025-8906
    • J. Karl Johnson*
      J. Karl Johnson
      Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
      *E-mail for J.K.J.: [email protected]
      More by J. Karl Johnson
      Orcidhttp://orcid.org/0000-0002-3608-8003
    Other Access OptionsSupporting Information (2)

    Organometallics

    Cite this: Organometallics 2019, 38, 18, 3453–3459
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.9b00351
    Published August 21, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Metal–organic frameworks (MOFs) having open metal sites have the potential to approach the activity of homogeneous organometallic complexes, thus combining the advantages of homogeneous and heterogeneous catalysis. We present a fundamental study of the effectiveness of incorporating open metal sites into MOFs. We have modeled the binding of a series of adsorbates in a Cu(I)-substituted MOF, Cu(I)-MFU-4l, using density functional theory and compared the activity of the Cu(I) sites in Cu(I)-MFU-4l with that of two different Cu(I) scorpionate complexes. The computational results confirm the single-site nature of the Cu(I) active site. This is further supported by complementary experiments to measure the chemisorption uptake inside our synthesized samples in order to estimate the amount of active Cu sites present. We observed a level of chemisorption that is roughly half the theoretical maximum, which implies that only half of the Cu atoms incorporated into MFU-4l via metal ion exchange are able to act as binding sites. We speculate that the inactive Cu atoms are coordinately saturated Cu(II) sites. Our work suggests that the performance of Cu(I)-MFU-4l could be significantly increased by optimizing the metal exchange and activation processes.

    Copyright © 2019 American Chemical Society

    Subjects

    what are subjects

    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 on the ACS Publications website at DOI: 10.1021/acs.organomet.9b00351.

    • Detailed computational and experimental methodology (PDF)

    • Coordinates of cluster and periodic structures used in calculations (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!

    This article is cited by 14 publications.

    1. Kurtis M. Carsch, Adrian J. Huang, Matthew N. Dods, Surya T. Parker, Rachel C. Rohde, Henry Z. H. Jiang, Yuto Yabuuchi, Sarah L. Karstens, Hyunchul Kwon, Romit Chakraborty, Karen C. Bustillo, Katie R. Meihaus, Hiroyasu Furukawa, Andrew M. Minor, Martin Head-Gordon, Jeffrey R. Long. Selective Adsorption of Oxygen from Humid Air in a Metal–Organic Framework with Trigonal Pyramidal Copper(I) Sites. Journal of the American Chemical Society 2024, 146 (5) , 3160-3170. https://doi.org/10.1021/jacs.3c10753
    2. Qiao Liu, Nicole Hoefer, Grant Berkbigler, Zhihao Cui, Tianyu Liu, Anne C. Co, David W. McComb, Casey R. Wade. Strong CO2 Chemisorption in a Metal–Organic Framework with Proximate Zn–OH Groups. Inorganic Chemistry 2022, 61 (46) , 18710-18718. https://doi.org/10.1021/acs.inorgchem.2c03212
    3. Rachel E. Mow, Lucy J. T. Metzroth, Michael J. Dzara, Glory A. Russell-Parks, Justin C. Johnson, Derek R. Vardon, Svitlana Pylypenko, Shubham Vyas, Thomas Gennett, Wade A. Braunecker. Phototriggered Desorption of Hydrogen, Ethylene, and Carbon Monoxide from a Cu(I)-Modified Covalent Organic Framework. The Journal of Physical Chemistry C 2022, 126 (35) , 14801-14812. https://doi.org/10.1021/acs.jpcc.2c03194
    4. Caitlin E. Bien, Zhongzheng Cai, Casey R. Wade. Using Postsynthetic X-Type Ligand Exchange to Enhance CO2 Adsorption in Metal–Organic Frameworks with Kuratowski-Type Building Units. Inorganic Chemistry 2021, 60 (16) , 11784-11794. https://doi.org/10.1021/acs.inorgchem.1c01077
    5. Mohammad Rasel Mian, Haoyuan Chen, Ran Cao, Kent O. Kirlikovali, Randall Q. Snurr, Timur Islamoglu, Omar K. Farha. Insights into Catalytic Hydrolysis of Organophosphonates at M–OH Sites of Azolate-Based Metal Organic Frameworks. Journal of the American Chemical Society 2021, 143 (26) , 9893-9900. https://doi.org/10.1021/jacs.1c03901
    6. Ashley M. Wright, Chenyue Sun, Mircea Dincă. Thermal Cycling of a MOF-Based NO Disproportionation Catalyst. Journal of the American Chemical Society 2021, 143 (2) , 681-686. https://doi.org/10.1021/jacs.0c12134
    7. Subratanath Koner. Catalytic epoxidation of olefin over metal-organic framework solids: A mini-review. Journal of Organometallic Chemistry 2025, 1025 , 123449. https://doi.org/10.1016/j.jorganchem.2024.123449
    8. Qiao Liu, Jordon S. Hilliard, Zhongzheng Cai, Casey R. Wade. Comparative study of metal–organic frameworks synthesized via imide condensation and coordination assembly. RSC Advances 2024, 14 (38) , 27634-27643. https://doi.org/10.1039/D4RA05563B
    9. Kuiwei Yang, Jianwen Jiang. Highly efficient CO2 conversion on a robust metal-organic framework Cu(I)-MFU-4l: Prediction and mechanistic understanding from DFT calculations. Journal of CO2 Utilization 2022, 63 , 102148. https://doi.org/10.1016/j.jcou.2022.102148
    10. R. Eric Sikma, Krista P. Balto, Joshua S. Figueroa, Seth M. Cohen. Metal–Organic Frameworks with Low‐Valent Metal Nodes. Angewandte Chemie 2022, 134 (33) https://doi.org/10.1002/ange.202206353
    11. R. Eric Sikma, Krista P. Balto, Joshua S. Figueroa, Seth M. Cohen. Metal–Organic Frameworks with Low‐Valent Metal Nodes. Angewandte Chemie International Edition 2022, 61 (33) https://doi.org/10.1002/anie.202206353
    12. Kushantha P. K. Withanage, Kamal Sharkas, J. Karl Johnson, John P. Perdew, Juan E. Peralta, Koblar A. Jackson. Fermi–Löwdin orbital self-interaction correction of adsorption energies on transition metal ions. The Journal of Chemical Physics 2022, 156 (13) https://doi.org/10.1063/5.0078970
    13. Marta Viciano-Chumillas, Xiangyu Liu, Antonio Leyva-Pérez, Donatella Armentano, Jesús Ferrando-Soria, Emilio Pardo. Mixed component metal-organic frameworks: Heterogeneity and complexity at the service of application performances. Coordination Chemistry Reviews 2022, 451 , 214273. https://doi.org/10.1016/j.ccr.2021.214273
    14. Yisi Yang, Libo Li, Rui-Biao Lin, Yingxiang Ye, Zizhu Yao, Ling Yang, Fahui Xiang, Shimin Chen, Zhangjing Zhang, Shengchang Xiang, Banglin Chen. Ethylene/ethane separation in a stable hydrogen-bonded organic framework through a gating mechanism. Nature Chemistry 2021, 13 (10) , 933-939. https://doi.org/10.1038/s41557-021-00740-z
    Download PDF
    Go to Organometallics
    Get e-Alerts
    Get e-Alerts

    Organometallics

    Cite this: Organometallics 2019, 38, 18, 3453–3459
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.9b00351
    Published August 21, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Article Views

    1794

    Altmetric

    -

    Citations

    14
    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.