Cargando…

Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex

[Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear coppe...

Descripción completa

Detalles Bibliográficos
Autores principales: van Langevelde, Phebe H., Kounalis, Errikos, Killian, Lars, Monkcom, Emily C., Broere, Daniël L. J., Hetterscheid, Dennis G. H.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10127274/
https://www.ncbi.nlm.nih.gov/pubmed/37123598
http://dx.doi.org/10.1021/acscatal.3c01143
_version_ 1785030429687939072
author van Langevelde, Phebe H.
Kounalis, Errikos
Killian, Lars
Monkcom, Emily C.
Broere, Daniël L. J.
Hetterscheid, Dennis G. H.
author_facet van Langevelde, Phebe H.
Kounalis, Errikos
Killian, Lars
Monkcom, Emily C.
Broere, Daniël L. J.
Hetterscheid, Dennis G. H.
author_sort van Langevelde, Phebe H.
collection PubMed
description [Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex [Cu(2)L(μ-OH)](3+) (L = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold. We show that the electrochemical reduction of [Cu(2)L(μ-OH)](3+) follows a proton-coupled electron transfer pathway and requires a larger overpotential due to the presence of the Cu-OH-Cu motif. In addition, we provide evidence that metal–metal cooperativity takes place during catalysis that is facilitated by the constraints of the rigid ligand framework, by identification of key intermediates along the catalytic cycle of [Cu(2)L(μ-OH)](3+). Electrochemical studies show that the mechanisms of the ORR and hydrogen peroxide reduction reaction found for [Cu(2)L(μ-OH)](3+) differ from the ones found for analogous mononuclear copper catalysts. In addition, the metal–metal cooperativity results in an improved selectivity for the four-electron ORR of more than 70% because reaction intermediates can be stabilized better between both copper centers. Overall, the mechanism of the [Cu(2)L(μ-OH)](3+)-catalyzed ORR in this work contributes to the understanding of how the cooperative function of multiple metals in close proximity can affect ORR activity and selectivity.
format Online
Article
Text
id pubmed-10127274
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-101272742023-04-26 Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex van Langevelde, Phebe H. Kounalis, Errikos Killian, Lars Monkcom, Emily C. Broere, Daniël L. J. Hetterscheid, Dennis G. H. ACS Catal [Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex [Cu(2)L(μ-OH)](3+) (L = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold. We show that the electrochemical reduction of [Cu(2)L(μ-OH)](3+) follows a proton-coupled electron transfer pathway and requires a larger overpotential due to the presence of the Cu-OH-Cu motif. In addition, we provide evidence that metal–metal cooperativity takes place during catalysis that is facilitated by the constraints of the rigid ligand framework, by identification of key intermediates along the catalytic cycle of [Cu(2)L(μ-OH)](3+). Electrochemical studies show that the mechanisms of the ORR and hydrogen peroxide reduction reaction found for [Cu(2)L(μ-OH)](3+) differ from the ones found for analogous mononuclear copper catalysts. In addition, the metal–metal cooperativity results in an improved selectivity for the four-electron ORR of more than 70% because reaction intermediates can be stabilized better between both copper centers. Overall, the mechanism of the [Cu(2)L(μ-OH)](3+)-catalyzed ORR in this work contributes to the understanding of how the cooperative function of multiple metals in close proximity can affect ORR activity and selectivity. American Chemical Society 2023-04-12 /pmc/articles/PMC10127274/ /pubmed/37123598 http://dx.doi.org/10.1021/acscatal.3c01143 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle van Langevelde, Phebe H.
Kounalis, Errikos
Killian, Lars
Monkcom, Emily C.
Broere, Daniël L. J.
Hetterscheid, Dennis G. H.
Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title_full Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title_fullStr Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title_full_unstemmed Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title_short Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
title_sort mechanistic investigations into the selective reduction of oxygen by a multicopper oxidase t3 site-inspired dicopper complex
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10127274/
https://www.ncbi.nlm.nih.gov/pubmed/37123598
http://dx.doi.org/10.1021/acscatal.3c01143
work_keys_str_mv AT vanlangeveldephebeh mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex
AT kounaliserrikos mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex
AT killianlars mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex
AT monkcomemilyc mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex
AT broeredaniellj mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex
AT hetterscheiddennisgh mechanisticinvestigationsintotheselectivereductionofoxygenbyamulticopperoxidaset3siteinspireddicoppercomplex