近日，美国加州大学伯克利分校Jeffrey R. Long团队研究了金属有机框架中具有单位点协同性的多气体吸附。相关论文于2025年11月20日发表在《科学》杂志上。

金属-有机框架（MOF）中的协同气体吸附是一种罕见现象，通常涉及多个结合位点间的长程相互作用。

研究组报道了一种含钴(II)-甲基位点的MOF材料，其每个位点可选择性可逆地捕获两个一氧化碳（CO）分子，从而在环境温度与压力下实现了创纪录的高吸附容量。气体吸附测试及结构、光谱与计算分析共同证实了其作用机制：第一个CO分子结合引发自旋态转变，随后第二个CO分子结合，同时第一个CO分子迁移插入钴-甲基键形成乙酰基。第二个CO分子更强的结合亲和力导致产生S型吸附等温线——这是协同效应和相变材料的标志性特征，尽管该框架内并不存在长程相互作用。

附：英文原文

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

Author: Kurtis M. Carsch, Henry Z. H. Jiang, Ryan A. Klein, Andrew S. Rosen, Peyton S. Summerhill, Jesse L. Peltier, Adrian J. Huang, Ryan A. Murphy, Matthew N. Dods, Hope A. Silva, Zikri Hasanbasri, Hyunchul Kwon, Sarah L. Karstens, Yuto Yabuuchi, Jonas Brgel, Jordan W. Taylor, Katie R. Meihaus, Karen C. Bustillo, Andrew M. Minor, Kristin A. Persson, Craig M. Brown, R. David Britt, Nicholas P. Stadie, Jeffrey R. Long

Issue&Volume: 2025-11-20

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.

DOI: ady2607

Source: https://www.science.org/doi/10.1126/science.ady2607