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Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations

Photoelectrochemical (PEC) organic transformations occurring at anodes are a promising strategy for circumventing the sluggish kinetics of the oxygen evolution reaction. Here, we report a free radical-mediated reaction instead of direct hole transfer occurring at the solid/liquid interface for PEC o...

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Autores principales: Lin, Cheng, Shan, Zhen, Dong, Chaoran, Lu, Yuan, Meng, Weikun, Zhang, Gen, Cai, Bo, Su, Guanyong, Park, Jong Hyeok, Zhang, Kan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10631720/
https://www.ncbi.nlm.nih.gov/pubmed/37939175
http://dx.doi.org/10.1126/sciadv.adi9442
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author Lin, Cheng
Shan, Zhen
Dong, Chaoran
Lu, Yuan
Meng, Weikun
Zhang, Gen
Cai, Bo
Su, Guanyong
Park, Jong Hyeok
Zhang, Kan
author_facet Lin, Cheng
Shan, Zhen
Dong, Chaoran
Lu, Yuan
Meng, Weikun
Zhang, Gen
Cai, Bo
Su, Guanyong
Park, Jong Hyeok
Zhang, Kan
author_sort Lin, Cheng
collection PubMed
description Photoelectrochemical (PEC) organic transformations occurring at anodes are a promising strategy for circumventing the sluggish kinetics of the oxygen evolution reaction. Here, we report a free radical-mediated reaction instead of direct hole transfer occurring at the solid/liquid interface for PEC oxidation of benzyl alcohol (BA) to benzaldehyde (BAD) with high selectivity. A bismuth vanadate (BiVO(4)) photoanode coated with a 2,2′-bipyridine–based covalent organic framework bearing single Ni sites (Ni-TpBpy) was developed to drive the transformation. Experimental studies reveal that the reaction at the Ni-TpBpy/BiVO(4) photoanode followed first-order reaction kinetics, boosting the formation of surface-bound ·OH radicals, which suppressed further BAD oxidation and provided a nearly 100% selectivity and a rate of 80.63 μmol hour(−1) for the BA-to-BAD conversion. Because alcohol-to-aldehyde conversions are involved in the valorizations of biomass and plastics, this work is expected to open distinct avenues for producing key intermediates of great value.
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spelling pubmed-106317202023-11-10 Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations Lin, Cheng Shan, Zhen Dong, Chaoran Lu, Yuan Meng, Weikun Zhang, Gen Cai, Bo Su, Guanyong Park, Jong Hyeok Zhang, Kan Sci Adv Physical and Materials Sciences Photoelectrochemical (PEC) organic transformations occurring at anodes are a promising strategy for circumventing the sluggish kinetics of the oxygen evolution reaction. Here, we report a free radical-mediated reaction instead of direct hole transfer occurring at the solid/liquid interface for PEC oxidation of benzyl alcohol (BA) to benzaldehyde (BAD) with high selectivity. A bismuth vanadate (BiVO(4)) photoanode coated with a 2,2′-bipyridine–based covalent organic framework bearing single Ni sites (Ni-TpBpy) was developed to drive the transformation. Experimental studies reveal that the reaction at the Ni-TpBpy/BiVO(4) photoanode followed first-order reaction kinetics, boosting the formation of surface-bound ·OH radicals, which suppressed further BAD oxidation and provided a nearly 100% selectivity and a rate of 80.63 μmol hour(−1) for the BA-to-BAD conversion. Because alcohol-to-aldehyde conversions are involved in the valorizations of biomass and plastics, this work is expected to open distinct avenues for producing key intermediates of great value. American Association for the Advancement of Science 2023-11-08 /pmc/articles/PMC10631720/ /pubmed/37939175 http://dx.doi.org/10.1126/sciadv.adi9442 Text en Copyright © 2023 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). https://creativecommons.org/licenses/by-nc/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (https://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.
spellingShingle Physical and Materials Sciences
Lin, Cheng
Shan, Zhen
Dong, Chaoran
Lu, Yuan
Meng, Weikun
Zhang, Gen
Cai, Bo
Su, Guanyong
Park, Jong Hyeok
Zhang, Kan
Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title_full Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title_fullStr Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title_full_unstemmed Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title_short Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations
title_sort covalent organic frameworks bearing ni active sites for free radical-mediated photoelectrochemical organic transformations
topic Physical and Materials Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10631720/
https://www.ncbi.nlm.nih.gov/pubmed/37939175
http://dx.doi.org/10.1126/sciadv.adi9442
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