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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...

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Autores principales: Braglia, Luca, Tavani, Francesco, Mauri, Silvia, Edla, Raju, Krizmancic, Damjan, Tofoni, Alessandro, Colombo, Valentina, D’Angelo, Paola, Torelli, Piero
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
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.)
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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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