期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 17, 期 40, 页码 26766-26776出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp04474j
关键词
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资金
- U.S. Department of Energy, Energy Efficiency and Renewable Energy program [DE-FG36-08GO18139]
- U.S. Department of Energy, Basic Energy Sciences [DE-FG02-09ER466556, DE-SC0002157]
In situ Fourier-transform infrared (FTIR) spectroscopy is able to probe structural defects via site-specificadsorption of CO to the Cu-BTC (BTC = 1,3,5-benzenetricarboxylate) metal-organic framework (MOF). The temperature-programmed desorption (TPD) of CO chemisorbed to Cu-TDPAT (TDPAT = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine) is virtually identical to Cu-BTC, suggesting CO chemisorbs to the open metal site at the axial position of the copper paddlewheel that is the building unit of both MOFs. Yet, despite an increased gravimetric CO: Cu ratio, CO chemisorbed to Cu-TDPAT is FTIR inactive. We rule out the presence of residual solvent, thermal degradation, adsorption temperature, and ligand-induced electronic effects at the adsorption site. TPD at increased pressure suggests the multiple CO per Cu site rearrange in Cu-TDPAT as a dynamic function of temperature and pressure. Thus, the FTIR inactivity of CO chemisorbed to Cu-TDPAT is attributed to orientation and/or packing of the CO relative to the Cu binding site. The results suggest dynamic chemisorption complicate extension of a site-specific in situ FTIR probe of gas adsorption. For both Cu-BTC and Cu-TDPAT, the in situ FTIR probe is a less sensitive probe of defects than X-ray photoelectron spectroscopy and nitrogen adsorption.
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