Multigas adsorption with single-site cooperativity in a metal-organic framework
Kurtis M Carsch1,2, Henry Z H Jiang1,2,3, Ryan A Klein4,5
1Baker Hughes Institute for Decarbonization Materials, University of California, Berkeley, Berkeley, CA, USA.
Science (New York, N.Y.)
|November 20, 2025
Summary
This study showcases a metal-organic framework (MOF) with cobalt(II)-methyl sites that achieve record carbon monoxide (CO) adsorption capacities. The MOF exhibits cooperative CO binding, forming an acetyl group and demonstrating sigmoidal adsorption isotherms.
Area of Science:
- Materials Science
- Chemistry
- Nanotechnology
Background:
- Cooperative gas adsorption in metal-organic frameworks (MOFs) is rare, typically requiring long-range interactions.
- Understanding cooperative adsorption mechanisms is key to designing advanced gas capture materials.
Purpose of the Study:
- To demonstrate a novel MOF with cooperative carbon monoxide (CO) adsorption capabilities.
- To elucidate the mechanism behind the observed cooperative adsorption and high capacities.
Main Methods:
- Synthesis and characterization of a cobalt(II)-methyl functionalized MOF.
- Gas adsorption experiments at ambient conditions.
- Structural, spectroscopic, and computational analyses to probe the adsorption mechanism.
Main Results:
- The MOF selectively captures two CO molecules per cobalt(II)-methyl site, achieving record capacities.
- Adsorption of the first CO triggers a spin transition, facilitating the binding of a second CO.
- The first CO molecule undergoes migratory insertion into the cobalt-methyl bond, forming an acetyl group.
- Sigmoidal adsorption isotherms were observed, indicative of cooperativity.
Conclusions:
- The MOF exhibits unprecedented cooperative CO adsorption without long-range framework interactions.
- The mechanism involves a spin transition and migratory insertion, leading to enhanced binding affinity.
- This work presents a new paradigm for designing MOFs with cooperative gas adsorption properties.
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