期刊
LANGMUIR
卷 36, 期 5, 页码 1345-1356出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.9b03581
关键词
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资金
- UH startup support funds
Metal-organic frameworks (MOFs) have been the focus of extensive research over the past couple of decades owing to their utility in enhancing performance in a range of applications including but not limited to gas separations, heterogeneous catalysis, and sensing. A rigorous understanding of the role of open-metal sites in molecular processes pertinent to these applications is first and foremost reliant on an accurate measure of the quantity of metal atoms that are coordinatively unsaturated under a given set of experimental conditions. Existing methods for quantifying open-metal sites exhibit drawbacks originating from unselective adsorption, use of high pressures and/or low temperatures, or the handling of potentially hazardous reagents. Here we investigate for the first time the use of room-temperature water adsorption isotherms for the quantification of MOF open-metal site density. We report that the quantity of water adsorbed irreversibly at room temperature on MIL-100 represents the open-metal site density under a given set of activation conditions. We use for this purpose a hydroxyl-containing version of MIL-100(Cr) that enables us to track (using in situ Fourier transform infrared spectroscopy) both dehydration and dehydroxylation events leading to open-metal site creation, providing evidence for site counts measured using irreversible water adsorption. Crucially, this approach circumvents the need for assumptions relating to the identity of open-metal sites and the degree of adsorbate saturation, while also obviating risks associated with the use of hazardous reagents. Given the near-universal presence of water as a labile ligand in the first coordination sphere of possible MOF open-metal sites, we envision that the protocols presented here could represent an approach to counting open-metal sites that is broadly applicable within (and maybe even beyond) the field of MOF research.
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