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Self-Assembled Liposomes Enhance Electron Transfer for Efficient Photocatalytic CO(2) Reduction
[Image: see text] Light-driven conversion of CO(2) to chemicals provides a sustainable alternative to fossil fuels, but homogeneous systems are typically limited by cross reactivity between different redox half reactions and inefficient charge separation. Herein, we present the bioinspired developme...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9164230/ https://www.ncbi.nlm.nih.gov/pubmed/35594410 http://dx.doi.org/10.1021/jacs.2c01725 |
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author | Rodríguez-Jiménez, Santiago Song, Hongwei Lam, Erwin Wright, Demelza Pannwitz, Andrea Bonke, Shannon A. Baumberg, Jeremy J. Bonnet, Sylvestre Hammarström, Leif Reisner, Erwin |
author_facet | Rodríguez-Jiménez, Santiago Song, Hongwei Lam, Erwin Wright, Demelza Pannwitz, Andrea Bonke, Shannon A. Baumberg, Jeremy J. Bonnet, Sylvestre Hammarström, Leif Reisner, Erwin |
author_sort | Rodríguez-Jiménez, Santiago |
collection | PubMed |
description | [Image: see text] Light-driven conversion of CO(2) to chemicals provides a sustainable alternative to fossil fuels, but homogeneous systems are typically limited by cross reactivity between different redox half reactions and inefficient charge separation. Herein, we present the bioinspired development of amphiphilic photosensitizer and catalyst pairs that self-assemble in lipid membranes to overcome some of these limitations and enable photocatalytic CO(2) reduction in liposomes using precious metal-free catalysts. Using sodium ascorbate as a sacrificial electron source, a membrane-anchored alkylated cobalt porphyrin demonstrates higher catalytic CO production (1456 vs 312 turnovers) and selectivity (77 vs 11%) compared to its water-soluble nonalkylated counterpart. Time-resolved and steady-state spectroscopy revealed that self-assembly facilitates this performance enhancement by enabling a charge-separation state lifetime increase of up to two orders of magnitude in the dye while allowing for a ninefold faster electron transfer to the catalyst. Spectroelectrochemistry and density functional theory calculations of the alkylated Co porphyrin catalyst support a four-electron-charging mechanism that activates the catalyst prior to catalysis, together with key catalytic intermediates. Our molecular liposome system therefore benefits from membrane immobilization and provides a versatile and efficient platform for photocatalysis. |
format | Online Article Text |
id | pubmed-9164230 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-91642302022-06-05 Self-Assembled Liposomes Enhance Electron Transfer for Efficient Photocatalytic CO(2) Reduction Rodríguez-Jiménez, Santiago Song, Hongwei Lam, Erwin Wright, Demelza Pannwitz, Andrea Bonke, Shannon A. Baumberg, Jeremy J. Bonnet, Sylvestre Hammarström, Leif Reisner, Erwin J Am Chem Soc [Image: see text] Light-driven conversion of CO(2) to chemicals provides a sustainable alternative to fossil fuels, but homogeneous systems are typically limited by cross reactivity between different redox half reactions and inefficient charge separation. Herein, we present the bioinspired development of amphiphilic photosensitizer and catalyst pairs that self-assemble in lipid membranes to overcome some of these limitations and enable photocatalytic CO(2) reduction in liposomes using precious metal-free catalysts. Using sodium ascorbate as a sacrificial electron source, a membrane-anchored alkylated cobalt porphyrin demonstrates higher catalytic CO production (1456 vs 312 turnovers) and selectivity (77 vs 11%) compared to its water-soluble nonalkylated counterpart. Time-resolved and steady-state spectroscopy revealed that self-assembly facilitates this performance enhancement by enabling a charge-separation state lifetime increase of up to two orders of magnitude in the dye while allowing for a ninefold faster electron transfer to the catalyst. Spectroelectrochemistry and density functional theory calculations of the alkylated Co porphyrin catalyst support a four-electron-charging mechanism that activates the catalyst prior to catalysis, together with key catalytic intermediates. Our molecular liposome system therefore benefits from membrane immobilization and provides a versatile and efficient platform for photocatalysis. American Chemical Society 2022-05-20 2022-06-01 /pmc/articles/PMC9164230/ /pubmed/35594410 http://dx.doi.org/10.1021/jacs.2c01725 Text en © 2022 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 | Rodríguez-Jiménez, Santiago Song, Hongwei Lam, Erwin Wright, Demelza Pannwitz, Andrea Bonke, Shannon A. Baumberg, Jeremy J. Bonnet, Sylvestre Hammarström, Leif Reisner, Erwin Self-Assembled Liposomes Enhance Electron Transfer for Efficient Photocatalytic CO(2) Reduction |
title | Self-Assembled
Liposomes Enhance Electron Transfer
for Efficient Photocatalytic CO(2) Reduction |
title_full | Self-Assembled
Liposomes Enhance Electron Transfer
for Efficient Photocatalytic CO(2) Reduction |
title_fullStr | Self-Assembled
Liposomes Enhance Electron Transfer
for Efficient Photocatalytic CO(2) Reduction |
title_full_unstemmed | Self-Assembled
Liposomes Enhance Electron Transfer
for Efficient Photocatalytic CO(2) Reduction |
title_short | Self-Assembled
Liposomes Enhance Electron Transfer
for Efficient Photocatalytic CO(2) Reduction |
title_sort | self-assembled
liposomes enhance electron transfer
for efficient photocatalytic co(2) reduction |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9164230/ https://www.ncbi.nlm.nih.gov/pubmed/35594410 http://dx.doi.org/10.1021/jacs.2c01725 |
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