Cargando…

Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation

Strategies that enable the renewable production of storable fuels (i. e. hydrogen or hydrocarbons) through electrocatalysis continue to generate interest in the scientific community. Of central importance to this pursuit is obtaining the requisite chemical (H(+)) and electronic (e(−)) inputs for fue...

Descripción completa

Detalles Bibliográficos
Autores principales: Zhang, Lu‐Hua, Mathew, Simon, Hessels, Joeri, Reek, Joost N. H., Yu, Fengshou
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7820963/
https://www.ncbi.nlm.nih.gov/pubmed/32991076
http://dx.doi.org/10.1002/cssc.202001876
_version_ 1783639321191907328
author Zhang, Lu‐Hua
Mathew, Simon
Hessels, Joeri
Reek, Joost N. H.
Yu, Fengshou
author_facet Zhang, Lu‐Hua
Mathew, Simon
Hessels, Joeri
Reek, Joost N. H.
Yu, Fengshou
author_sort Zhang, Lu‐Hua
collection PubMed
description Strategies that enable the renewable production of storable fuels (i. e. hydrogen or hydrocarbons) through electrocatalysis continue to generate interest in the scientific community. Of central importance to this pursuit is obtaining the requisite chemical (H(+)) and electronic (e(−)) inputs for fuel‐forming reduction reactions, which can be met sustainably by water oxidation catalysis. Further possibility exists to couple these redox transformations to renewable energy sources (i. e. solar), thus creating a carbon neutral solution for long‐term energy storage. Nature uses a Mn−Ca cluster for water oxidation catalysis via multiple proton‐coupled electron‐transfers (PCETs) with a photogenerated bias to perform this process with TOF 100∼300 s(−1). Synthetic molecular catalysts that efficiently perform this conversion commonly utilize rare metals (e. g., Ru, Ir), whose low abundance are associated to higher costs and scalability limitations. Inspired by nature‘s use of 1(st) row transition metal (TM) complexes for water oxidation catalysts (WOCs), attempts to use these abundant metals have been intensively explored but met with limited success. The smaller atomic size of 1(st) row TM ions lowers its ability to accommodate the oxidative equivalents required in the 4e(−)/4H(+) water oxidation catalysis process, unlike noble metal catalysts that perform single‐site electrocatalysis at lower overpotentials (η). Overcoming the limitations of 1(st) row TMs requires developing molecular catalysts that exploit biomimetic phenomena – multiple‐metal redox‐cooperativity, PCET and second‐sphere interactions – to lower the overpotential, preorganize substrates and maintain stability. Thus, the ultimate goal of developing efficient, robust and scalable WOCs remains a challenge. This Review provides a summary of previous research works highlighting 1(st) row TM‐based homogeneous WOCs, catalytic mechanisms, followed by strategies for catalytic activity improvements, before closing with a future outlook for this field.
format Online
Article
Text
id pubmed-7820963
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-78209632021-01-26 Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation Zhang, Lu‐Hua Mathew, Simon Hessels, Joeri Reek, Joost N. H. Yu, Fengshou ChemSusChem Reviews Strategies that enable the renewable production of storable fuels (i. e. hydrogen or hydrocarbons) through electrocatalysis continue to generate interest in the scientific community. Of central importance to this pursuit is obtaining the requisite chemical (H(+)) and electronic (e(−)) inputs for fuel‐forming reduction reactions, which can be met sustainably by water oxidation catalysis. Further possibility exists to couple these redox transformations to renewable energy sources (i. e. solar), thus creating a carbon neutral solution for long‐term energy storage. Nature uses a Mn−Ca cluster for water oxidation catalysis via multiple proton‐coupled electron‐transfers (PCETs) with a photogenerated bias to perform this process with TOF 100∼300 s(−1). Synthetic molecular catalysts that efficiently perform this conversion commonly utilize rare metals (e. g., Ru, Ir), whose low abundance are associated to higher costs and scalability limitations. Inspired by nature‘s use of 1(st) row transition metal (TM) complexes for water oxidation catalysts (WOCs), attempts to use these abundant metals have been intensively explored but met with limited success. The smaller atomic size of 1(st) row TM ions lowers its ability to accommodate the oxidative equivalents required in the 4e(−)/4H(+) water oxidation catalysis process, unlike noble metal catalysts that perform single‐site electrocatalysis at lower overpotentials (η). Overcoming the limitations of 1(st) row TMs requires developing molecular catalysts that exploit biomimetic phenomena – multiple‐metal redox‐cooperativity, PCET and second‐sphere interactions – to lower the overpotential, preorganize substrates and maintain stability. Thus, the ultimate goal of developing efficient, robust and scalable WOCs remains a challenge. This Review provides a summary of previous research works highlighting 1(st) row TM‐based homogeneous WOCs, catalytic mechanisms, followed by strategies for catalytic activity improvements, before closing with a future outlook for this field. John Wiley and Sons Inc. 2020-10-16 2021-01-07 /pmc/articles/PMC7820963/ /pubmed/32991076 http://dx.doi.org/10.1002/cssc.202001876 Text en © 2020 The Authors. ChemSusChem published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Reviews
Zhang, Lu‐Hua
Mathew, Simon
Hessels, Joeri
Reek, Joost N. H.
Yu, Fengshou
Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title_full Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title_fullStr Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title_full_unstemmed Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title_short Homogeneous Catalysts Based on First‐Row Transition‐Metals for Electrochemical Water Oxidation
title_sort homogeneous catalysts based on first‐row transition‐metals for electrochemical water oxidation
topic Reviews
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7820963/
https://www.ncbi.nlm.nih.gov/pubmed/32991076
http://dx.doi.org/10.1002/cssc.202001876
work_keys_str_mv AT zhangluhua homogeneouscatalystsbasedonfirstrowtransitionmetalsforelectrochemicalwateroxidation
AT mathewsimon homogeneouscatalystsbasedonfirstrowtransitionmetalsforelectrochemicalwateroxidation
AT hesselsjoeri homogeneouscatalystsbasedonfirstrowtransitionmetalsforelectrochemicalwateroxidation
AT reekjoostnh homogeneouscatalystsbasedonfirstrowtransitionmetalsforelectrochemicalwateroxidation
AT yufengshou homogeneouscatalystsbasedonfirstrowtransitionmetalsforelectrochemicalwateroxidation