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Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites
The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8171315/ https://www.ncbi.nlm.nih.gov/pubmed/34163822 http://dx.doi.org/10.1039/d1sc00573a |
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author | Heidary, Nina Chartrand, Daniel Guiet, Amandine Kornienko, Nikolay |
author_facet | Heidary, Nina Chartrand, Daniel Guiet, Amandine Kornienko, Nikolay |
author_sort | Heidary, Nina |
collection | PubMed |
description | The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O(4) sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry. |
format | Online Article Text |
id | pubmed-8171315 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81713152021-06-22 Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites Heidary, Nina Chartrand, Daniel Guiet, Amandine Kornienko, Nikolay Chem Sci Chemistry The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O(4) sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry. The Royal Society of Chemistry 2021-04-29 /pmc/articles/PMC8171315/ /pubmed/34163822 http://dx.doi.org/10.1039/d1sc00573a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Heidary, Nina Chartrand, Daniel Guiet, Amandine Kornienko, Nikolay Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title | Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title_full | Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title_fullStr | Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title_full_unstemmed | Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title_short | Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
title_sort | rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8171315/ https://www.ncbi.nlm.nih.gov/pubmed/34163822 http://dx.doi.org/10.1039/d1sc00573a |
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