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Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes

The catalytic conversion of CO(2) into valuable chemicals and fuels has attracted increasing attention, providing a promising route for mitigating the greenhouse effect of CO(2) and also meeting the global energy demand. Among many homogeneous and heterogeneous catalysts for CO(2) reduction, this mi...

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Autores principales: Fukuzumi, Shunichi, Lee, Yong-Min, Ahn, Hyun S., Nam, Wonwoo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6053956/
https://www.ncbi.nlm.nih.gov/pubmed/30090295
http://dx.doi.org/10.1039/c8sc02220h
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author Fukuzumi, Shunichi
Lee, Yong-Min
Ahn, Hyun S.
Nam, Wonwoo
author_facet Fukuzumi, Shunichi
Lee, Yong-Min
Ahn, Hyun S.
Nam, Wonwoo
author_sort Fukuzumi, Shunichi
collection PubMed
description The catalytic conversion of CO(2) into valuable chemicals and fuels has attracted increasing attention, providing a promising route for mitigating the greenhouse effect of CO(2) and also meeting the global energy demand. Among many homogeneous and heterogeneous catalysts for CO(2) reduction, this mini-review is focused on heme and nonheme metal complexes that act as effective catalysts for the electrocatalytic and photocatalytic reduction of CO(2). Because metalloporphyrinoids show strong absorption in the visible region, which is sensitive to the oxidation states of the metals and ligands, they are suited for the detection of reactive intermediates in the catalytic CO(2) reduction cycle by electronic absorption spectroscopy. The first part of this review deals with the catalytic mechanism for the one-electron reduction of CO(2) to oxalic acid with heme and nonheme metal complexes, with an emphasis on how the formation of highly energetic CO(2)˙ is avoided. Then, the catalytic mechanism of two-electron reduction of CO(2) to produce CO and H(2)O is compared with that to produce HCOOH. The effect of metals and ligands of the heme and nonheme complexes on the CO or HCOOH product selectivity is also discussed. The catalytic mechanisms of multi-electron reduction of CO(2) to methanol (six-electron reduced product) and methane (eight-electron reduced product) are also discussed for both electrocatalytic and photocatalytic systems.
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spelling pubmed-60539562018-08-08 Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes Fukuzumi, Shunichi Lee, Yong-Min Ahn, Hyun S. Nam, Wonwoo Chem Sci Chemistry The catalytic conversion of CO(2) into valuable chemicals and fuels has attracted increasing attention, providing a promising route for mitigating the greenhouse effect of CO(2) and also meeting the global energy demand. Among many homogeneous and heterogeneous catalysts for CO(2) reduction, this mini-review is focused on heme and nonheme metal complexes that act as effective catalysts for the electrocatalytic and photocatalytic reduction of CO(2). Because metalloporphyrinoids show strong absorption in the visible region, which is sensitive to the oxidation states of the metals and ligands, they are suited for the detection of reactive intermediates in the catalytic CO(2) reduction cycle by electronic absorption spectroscopy. The first part of this review deals with the catalytic mechanism for the one-electron reduction of CO(2) to oxalic acid with heme and nonheme metal complexes, with an emphasis on how the formation of highly energetic CO(2)˙ is avoided. Then, the catalytic mechanism of two-electron reduction of CO(2) to produce CO and H(2)O is compared with that to produce HCOOH. The effect of metals and ligands of the heme and nonheme complexes on the CO or HCOOH product selectivity is also discussed. The catalytic mechanisms of multi-electron reduction of CO(2) to methanol (six-electron reduced product) and methane (eight-electron reduced product) are also discussed for both electrocatalytic and photocatalytic systems. Royal Society of Chemistry 2018-07-02 /pmc/articles/PMC6053956/ /pubmed/30090295 http://dx.doi.org/10.1039/c8sc02220h Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Fukuzumi, Shunichi
Lee, Yong-Min
Ahn, Hyun S.
Nam, Wonwoo
Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title_full Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title_fullStr Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title_full_unstemmed Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title_short Mechanisms of catalytic reduction of CO(2) with heme and nonheme metal complexes
title_sort mechanisms of catalytic reduction of co(2) with heme and nonheme metal complexes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6053956/
https://www.ncbi.nlm.nih.gov/pubmed/30090295
http://dx.doi.org/10.1039/c8sc02220h
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