Revisiting Competitive Adsorption of Small Molecules in the Metal–Organic Framework Ni-MOF-74

Pandey, Haardik; Wang, Hao; Feng, Liang; Wang, Kun-Yu; Zhou, Hong-Cai; Li, Jing; Thonhauser, Timo; Tan, Kui

doi:10.1021/acs.inorgchem.2c03751

Title: Revisiting Competitive Adsorption of Small Molecules in the Metal–Organic Framework Ni-MOF-74

Journal Article · Sat Dec 31 00:00:00 EST 2022 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c03751· OSTI ID:2294071

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Wake Forest University, Winston-Salem, NC (United States)
Rutgers University, Piscataway, NJ (United States)
Texas A&M University, College Station, TX (United States)
University of Texas at Dallas, Richardson, TX (United States)

To precisely evaluate the potential of metal-organic frameworks (MOFs) for gas separation and purification applications, it is crucial to understand how various molecules competitively adsorb inside MOFs. In this paper, we combine in situ infrared spectroscopy with ab initio calculations to investigate the mechanisms associated with co-adsorption of a number of small molecules including CO, NO, and CO₂ inside the prototypical framework Ni-MOF-74. Surprisingly, we find that the displacement of CO bound inside Ni-MOF-74 (binding energy of 53 kJ/mol) is readily driven by CO₂ exposure, even though CO₂ has a noticeably weaker binding energy of only 41 kJ/mol; meanwhile, the significantly more strongly binding NO molecule (90 kJ/mol) is not able to easily displace bound CO inside Ni-MOF74. These results show that single-phase binding energies of a molecule inside the MOF cannot completely describe their interaction with the MOF in the presence of other guest molecules. Here, we unveil a number of crucial factors such as the kinetic barrier, partial pressure, secondary binding sites, and guest-host/lateral interactions that control the co-adsorption process and combined with the binding energy are better descriptors of the behavior and adsorption of gas mixtures inside MOFs.

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Research Organization:: Univ. of North Texas, Denton, TX (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0019902

OSTI ID:: 2294071

Journal Information:: Inorganic Chemistry, Vol. 62, Issue 2; ISSN 0020-1669

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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Metal organic frameworks
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Title: Revisiting Competitive Adsorption of Small Molecules in the Metal–Organic Framework Ni-MOF-74

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