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Catching the Reversible Formation and Reactivity of Surface Defective Sites in Metal–Organic Frameworks: An Operando Ambient Pressure-NEXAFS Investigation
[Image: see text] 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 evi...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9282676/ https://www.ncbi.nlm.nih.gov/pubmed/34528795 http://dx.doi.org/10.1021/acs.jpclett.1c02585 |
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author | Braglia, Luca Tavani, Francesco Mauri, Silvia Edla, Raju Krizmancic, Damjan Tofoni, Alessandro Colombo, Valentina D’Angelo, Paola Torelli, Piero |
author_facet | Braglia, Luca Tavani, Francesco Mauri, Silvia Edla, Raju Krizmancic, Damjan Tofoni, Alessandro Colombo, Valentina D’Angelo, Paola Torelli, Piero |
author_sort | Braglia, Luca |
collection | PubMed |
description | [Image: see text] 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 °C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu(+)/Cu(2+) dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu(2+)/Cu(2+) paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO(2) may be reversibly adsorbed and desorbed from the surface defective Cu(+)/Cu(2+) sites. These findings show that ambient pressure soft-XAS, combined with state-of-the-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu(+)/Cu(2+) complexes and their reversible restoration upon exposure to gaseous CO(2.) |
format | Online Article Text |
id | pubmed-9282676 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-92826762022-07-15 Catching the Reversible Formation and Reactivity of Surface Defective Sites in Metal–Organic Frameworks: An Operando Ambient Pressure-NEXAFS Investigation Braglia, Luca Tavani, Francesco Mauri, Silvia Edla, Raju Krizmancic, Damjan Tofoni, Alessandro Colombo, Valentina D’Angelo, Paola Torelli, Piero J Phys Chem Lett [Image: see text] 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 °C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu(+)/Cu(2+) dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu(2+)/Cu(2+) paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO(2) may be reversibly adsorbed and desorbed from the surface defective Cu(+)/Cu(2+) sites. These findings show that ambient pressure soft-XAS, combined with state-of-the-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu(+)/Cu(2+) complexes and their reversible restoration upon exposure to gaseous CO(2.) American Chemical Society 2021-09-16 2021-09-23 /pmc/articles/PMC9282676/ /pubmed/34528795 http://dx.doi.org/10.1021/acs.jpclett.1c02585 Text en © 2021 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Braglia, Luca Tavani, Francesco Mauri, Silvia Edla, Raju Krizmancic, Damjan Tofoni, Alessandro Colombo, Valentina D’Angelo, Paola Torelli, Piero Catching the Reversible Formation and Reactivity of Surface Defective Sites in Metal–Organic Frameworks: An Operando Ambient Pressure-NEXAFS Investigation |
title | Catching the Reversible Formation and Reactivity of
Surface Defective Sites in Metal–Organic Frameworks: An Operando
Ambient Pressure-NEXAFS Investigation |
title_full | Catching the Reversible Formation and Reactivity of
Surface Defective Sites in Metal–Organic Frameworks: An Operando
Ambient Pressure-NEXAFS Investigation |
title_fullStr | Catching the Reversible Formation and Reactivity of
Surface Defective Sites in Metal–Organic Frameworks: An Operando
Ambient Pressure-NEXAFS Investigation |
title_full_unstemmed | Catching the Reversible Formation and Reactivity of
Surface Defective Sites in Metal–Organic Frameworks: An Operando
Ambient Pressure-NEXAFS Investigation |
title_short | Catching the Reversible Formation and Reactivity of
Surface Defective Sites in Metal–Organic Frameworks: An Operando
Ambient Pressure-NEXAFS Investigation |
title_sort | catching the reversible formation and reactivity of
surface defective sites in metal–organic frameworks: an operando
ambient pressure-nexafs investigation |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9282676/ https://www.ncbi.nlm.nih.gov/pubmed/34528795 http://dx.doi.org/10.1021/acs.jpclett.1c02585 |
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