Multigas adsorption with single-site cooperativity in a metal-organic framework

• 成果类型: Article
• 署名作者: Carsch, Kurtis M.; Jiang, Henry Z. H.; Klein, Ryan A.; Rosen, Andrew S.; Summerhill, Peyton S.; Peltier, Jesse L.; Huang, Adrian J.; Murphy, Ryan A.; Dods, Matthew N.; Silva, Hope A.; Hasanbasri, Zikri; Kwon, Hyunchul; Karstens, Sarah L.; Yabuuchi, Yuto; Borgel, Jonas; Taylor, Jordan W.; Meihaus, Katie R.; Bustillo, Karen C.; Minor, Andrew M.; Persson, Kristin A.; Brown, Craig M.; Britt, R. David; Stadie, Nicholas P.; Long, Jeffrey R.
• 署名单位: University of California System; University of California Berkeley; University of California System; University of California Berkeley; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; National Institute of Standards & Technology (NIST) - USA; United States Department of Energy (DOE); National Renewable Energy Laboratory - USA; University of California System; University of California Berkeley; University of California System; University of California Berkeley; Princeton University; Montana State University System; Montana State University Bozeman; University of California System; University of California Berkeley; University of California System; University of California Davis; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; University of Delaware
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8075; 1095-9203
• DOI: 10.1126/science.ady2607
• 发表日期: 2025-11-20
• 页码: 808-812
• 关键词: carbon-monoxide; POWDER-DIFFRACTION; binding; co; exchange; crystal; capture; thermochemistry; COORDINATION; activation

摘要

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.