Observation of an Intermediate to H2 Binding in a Metal–Organic Framework

Barnett, Brandon R.; Evans, Hayden A.; Su, Gregory M.; Jiang, Henry Z. H.; Chakraborty, Romit; Banyeretse, Didier; Hartman, Tyler J.; Martinez, Madison B.; Trump, Benjamin A.; Tarver, Jacob D.; Dods, Matthew N.; Funke, Lena M.; Börgel, Jonas; Reimer, Jeffrey A.; Drisdell, Walter S.; Hurst, Katherine E.; Gennett, Thomas; FitzGerald, Stephen A.; Brown, Craig M.; Head-Gordon, Martin; Long, Jeffrey R.

doi:10.1021/jacs.1c07223

Title: Observation of an Intermediate to H₂ Binding in a Metal–Organic Framework

Journal Article · 30 August 2021 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c07223 · OSTI ID:1820592

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Rochester, NY (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Oberlin College, OH (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)

Coordinatively unsaturated metal sites within certain zeolites and metal–organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H₂ at the trigonal pyramidal Cu⁺ sites in the metal–organic framework Cu^I-MFU-₄l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. Here, the activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu⁺ coordination environment that enhances p-backbonding with H₂. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office

Grant/Contract Number:: AC02-05CH11231; AC36-08GO28308

OSTI ID:: 1820592

Report Number(s):: NREL/JA--5900-80956; MainId:78734; UUID:4bb9a2dd-404d-4867-93a7-93881d7f1731; MainAdminID:61815

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 36 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adsorption
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CCDC 1987754: Experimental Crystal Structure Determination R., Barnett, Brandon; A., Evans, Hayden; M., Su, Gregory https://doi.org/10.5517/ccdc.csd.cc24qf3f The current record is supplemented by this dataset	dataset	January 2021
CCDC 1987755: Experimental Crystal Structure Determination R., Barnett, Brandon; A., Evans, Hayden; M., Su, Gregory https://doi.org/10.5517/ccdc.csd.cc24qf4g The current record is supplemented by this dataset	dataset	January 2021
CCDC 1987756: Experimental Crystal Structure Determination R., Barnett, Brandon; A., Evans, Hayden; M., Su, Gregory https://doi.org/10.5517/ccdc.csd.cc24qf5h The current record is supplemented by this dataset	dataset	January 2021
CCDC 1987757: Experimental Crystal Structure Determination R., Barnett, Brandon; A., Evans, Hayden; M., Su, Gregory https://doi.org/10.5517/ccdc.csd.cc24qf6j The current record is supplemented by this dataset	dataset	January 2021
CCDC 1987758: Experimental Crystal Structure Determination R., Barnett, Brandon; A., Evans, Hayden; M., Su, Gregory https://doi.org/10.5517/ccdc.csd.cc24qf7k The current record is supplemented by this dataset	dataset	January 2021

Title: Observation of an Intermediate to H2 Binding in a Metal–Organic Framework

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Title: Observation of an Intermediate to H₂ Binding in a Metal–Organic Framework