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Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting

[Image: see text] The O–O bond formation process via water nucleophilic attack represents a thermodynamic and kinetic bottleneck in photocatalytic water oxidation because of the considerably high activation free energy barrier. It is therefore of fundamental significance and yet challenging to find...

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Autores principales: Shao, Yang, de Groot, Huub J.M., Buda, Francesco
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6926955/
https://www.ncbi.nlm.nih.gov/pubmed/31763842
http://dx.doi.org/10.1021/acs.jpclett.9b02914
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author Shao, Yang
de Groot, Huub J.M.
Buda, Francesco
author_facet Shao, Yang
de Groot, Huub J.M.
Buda, Francesco
author_sort Shao, Yang
collection PubMed
description [Image: see text] The O–O bond formation process via water nucleophilic attack represents a thermodynamic and kinetic bottleneck in photocatalytic water oxidation because of the considerably high activation free energy barrier. It is therefore of fundamental significance and yet challenging to find strategies to facilitate this reaction. The microscopic details of the photocatalytic water oxidation step involving the O–O bond formation in a catalyst–dye supramolecular complex are here elucidated by density functional theory-based Car–Parrinello molecular dynamics simulations in the presence of an extra proton acceptor. Introducing a proton acceptor group (OH(–)) in the hydration shell near the catalytic active site accelerates the rate-limiting O–O bond formation by inducing a cooperative event proceeding via a concerted proton-coupled electron-transfer mechanism and thus significantly lowering the activation free energy barrier. The in-depth insight provides a strategy for facilitating the photocatalytic water oxidation and for improving the efficiency of dye-sensitized photoelectrochemical cells.
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spelling pubmed-69269552019-12-24 Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting Shao, Yang de Groot, Huub J.M. Buda, Francesco J Phys Chem Lett [Image: see text] The O–O bond formation process via water nucleophilic attack represents a thermodynamic and kinetic bottleneck in photocatalytic water oxidation because of the considerably high activation free energy barrier. It is therefore of fundamental significance and yet challenging to find strategies to facilitate this reaction. The microscopic details of the photocatalytic water oxidation step involving the O–O bond formation in a catalyst–dye supramolecular complex are here elucidated by density functional theory-based Car–Parrinello molecular dynamics simulations in the presence of an extra proton acceptor. Introducing a proton acceptor group (OH(–)) in the hydration shell near the catalytic active site accelerates the rate-limiting O–O bond formation by inducing a cooperative event proceeding via a concerted proton-coupled electron-transfer mechanism and thus significantly lowering the activation free energy barrier. The in-depth insight provides a strategy for facilitating the photocatalytic water oxidation and for improving the efficiency of dye-sensitized photoelectrochemical cells. American Chemical Society 2019-11-25 2019-12-19 /pmc/articles/PMC6926955/ /pubmed/31763842 http://dx.doi.org/10.1021/acs.jpclett.9b02914 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Shao, Yang
de Groot, Huub J.M.
Buda, Francesco
Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title_full Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title_fullStr Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title_full_unstemmed Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title_short Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
title_sort proton acceptor near the active site lowers dramatically the o–o bond formation energy barrier in photocatalytic water splitting
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6926955/
https://www.ncbi.nlm.nih.gov/pubmed/31763842
http://dx.doi.org/10.1021/acs.jpclett.9b02914
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AT budafrancesco protonacceptorneartheactivesitelowersdramaticallytheoobondformationenergybarrierinphotocatalyticwatersplitting