期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 12, 期 37, 页码 9182-9187出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.1c02585
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资金
- Nanoscience Foundry and Fine Analysis (NFFA-MIUR Italy Progetti Internazionali) project
- Italian Ministry of University and Research is acknowledged for financial support through the PRIN 2107 program [2017KKP5ZR]
- Universitadegli Studi di Milano
In this study, the location, structural properties, and reactivity of defective sites in the metal-organic framework HKUST-1 were investigated using ambient pressure operando soft X-ray absorption spectroscopy. The formation of Cu+ defective sites and characterization of Cu+/Cu2+ dimeric complexes arising from temperature treatment were reported. Furthermore, reversible adsorption and desorption of CO2 on the surface defective Cu+/Cu2+ sites were demonstrated.
In this work, we apply for the first time ambient pressure operando soft X-ray absorption spectroscopy (XAS) to investigate the location, structural properties, and reactivity of the defective sites present in the prototypical metal-organic framework HKUST-1. We obtained direct evidence that Cu+ defective sites form upon temperature treatment of the powdered form of HKUST-1 at 160 degrees C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu+/Cu2+ dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu2+/Cu2+ paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO2 may be reversibly adsorbed and desorbed from the surface defective Cu+/Cu2+ sites. These findings show that ambient pressure soft-XAS, combined with state-ofthe-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu+/Cu2+ complexes and their reversible restoration upon exposure to gaseous CO2.(.)
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