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DOE OSTI · 3015926

Multigas Adsorption with Single-Site Cooperativity in a Metal-Organic Framework

Carsch, Kurtis [University of California, Berkeley]·Jiang, Henry [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Klein, Ryan [National Laboratory of the Rockies, Golden, CO (United States)] (ORCID:0000000268076701)·Rosen, Andrew [Lawrence Berkeley National Laboratory; Princeton University; University of California, Berkeley]·Summerhill, Peyton [Montana State University]·Peltier, Jesse [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Huang, Adrian [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Murphy, Ryan [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Dods, Matthew [University of California, Berkeley]·Silva, Hope [University of California, Berkeley]·Hasanbasri, Zikri [University of California, Davis]·Kwon, Hyunchul [University of California, Berkeley]·Karstens, Sarah [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Yabuuchi, Yuto [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Borgel, Jonas [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Taylor, Jordan [University of California, Berkeley]·Meihaus, Katie [University of California, Berkeley]·Bustillo, Karen [Lawrence Berkeley National Laboratory]·Minor, Andrew [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Persson, Kristin [Lawrence Berkeley National Laboratory; University of California, Berkeley]·Brown, Craig [United States Department of Commerce; University of Delaware]·Britt, R. David [University of California, Berkeley; University of California, Davis]·Stadie, Nicholas [Montana State University]·Long, Jeffrey [Lawrence Berkeley National Laboratory; University of California, Berkeley]
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Abstract

Cooperative gas adsorption in metal-organic frameworks (MOFs) is a rare phenomenon that generally involves long-range communication between multiple binding sites. We demonstrate a MOF containing cobalt(II)-methyl sites that selectively and reversibly capture two carbon monoxide (CO) molecules per site, leading to record-high adsorption capacities at ambient temperatures and pressures. Gas adsorption and structural, spectroscopic, and computational analyses support a mechanism in which binding of one CO molecule triggers a spin transition, followed by binding of a second CO molecule and migratory insertion of the first CO molecule into the cobalt-methyl bond to form an acetyl. The greater binding affinity associated with the second CO results in sigmoidal adsorption isotherms, a hallmark of cooperativity and phase-change materials, despite the absence of long-range interactions within the framework.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY74 ATOMIC AND MOLECULAR PHYSICSCO moleculescobalt-methyl bondcooperative gas adsorption

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Carsch, Kurtis [University of California, Berkeley], Jiang, Henry [Lawrence Berkeley National Laboratory; University of California, Berkeley], Klein, Ryan [National Laboratory of the Rockies, Golden, CO (United States)] (ORCID:0000000268076701), Rosen, Andrew [Lawrence Berkeley National Laboratory; Princeton University; University of California, Berkeley], Summerhill, Peyton [Montana State University], Peltier, Jesse [Lawrence Berkeley National Laboratory; University of California, Berkeley], Huang, Adrian [Lawrence Berkeley National Laboratory; University of California, Berkeley], Murphy, Ryan [Lawrence Berkeley National Laboratory; University of California, Berkeley], Dods, Matthew [University of California, Berkeley], Silva, Hope [University of California, Berkeley], Hasanbasri, Zikri [University of California, Davis], Kwon, Hyunchul [University of California, Berkeley], Karstens, Sarah [Lawrence Berkeley National Laboratory; University of California, Berkeley], Yabuuchi, Yuto [Lawrence Berkeley National Laboratory; University of California, Berkeley], Borgel, Jonas [Lawrence Berkeley National Laboratory; University of California, Berkeley], Taylor, Jordan [University of California, Berkeley], Meihaus, Katie [University of California, Berkeley], Bustillo, Karen [Lawrence Berkeley National Laboratory], Minor, Andrew [Lawrence Berkeley National Laboratory; University of California, Berkeley], Persson, Kristin [Lawrence Berkeley National Laboratory; University of California, Berkeley], Brown, Craig [United States Department of Commerce; University of Delaware], Britt, R. David [University of California, Berkeley; University of California, Davis], Stadie, Nicholas [Montana State University], Long, Jeffrey [Lawrence Berkeley National Laboratory; University of California, Berkeley]. 2025-11-20. Multigas Adsorption with Single-Site Cooperativity in a Metal-Organic Framework. https://doi.org/10.1126/science.ady2607

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