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Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation
The development of systems for photocatalytic CO(2) reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprisin...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8513877/ https://www.ncbi.nlm.nih.gov/pubmed/34745553 http://dx.doi.org/10.1039/d1sc03756k |
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author | Kuttassery, Fazalurahman Kumagai, Hiromu Kamata, Ryutaro Ebato, Yusuke Higashi, Masanobu Suzuki, Hajime Abe, Ryu Ishitani, Osamu |
author_facet | Kuttassery, Fazalurahman Kumagai, Hiromu Kamata, Ryutaro Ebato, Yusuke Higashi, Masanobu Suzuki, Hajime Abe, Ryu Ishitani, Osamu |
author_sort | Kuttassery, Fazalurahman |
collection | PubMed |
description | The development of systems for photocatalytic CO(2) reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprising metal complexes as redox photosensitizers and catalyst units fixed on a p-type semiconductor electrode, the performance of the corresponding photoelectrochemical cells remains low, e.g., their highest incident photon-to-current conversion efficiency (IPCE) equals 1.2%. Herein, we report a novel dye-sensitized molecular photocathode for photocatalytic CO(2) reduction in water featuring a polypyrrole layer, [Ru(diimine)(3)](2+) as a redox photosensitizer unit, and Ru(diimine)(CO)(2)Cl(2) as the catalyst unit and reveal that the incorporation of the polypyrrole network significantly improves reactivity and durability relative to those of previously reported dye-sensitized molecular photocathodes. The irradiation of the novel photocathode with visible light under low applied bias stably induces the photocatalytic reduction of CO(2) to CO and HCOOH with high faradaic efficiency and selectivity (even in aqueous solution), and the highest IPCE is determined as 4.7%. The novel photocathode is coupled with n-type semiconductor photoanodes (CoO(x)/BiVO(4) and RhO(x)/TaON) to construct full cells that photocatalytically reduce CO(2) using water as the reductant upon visible light irradiation as the only energy input at zero bias. The artificial Z-scheme photoelectrochemical cell with the dye-sensitized molecular photocathode achieves the highest energy conversion efficiency of 8.3 × 10(−2)% under the irradiation of both electrodes with visible light, while a solar to chemical conversion efficiency of 4.2 × 10(−2)% is achieved for a tandem-type cell using a solar light simulator (AM 1.5, 100 mW cm(−2)). |
format | Online Article Text |
id | pubmed-8513877 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-85138772021-11-04 Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation Kuttassery, Fazalurahman Kumagai, Hiromu Kamata, Ryutaro Ebato, Yusuke Higashi, Masanobu Suzuki, Hajime Abe, Ryu Ishitani, Osamu Chem Sci Chemistry The development of systems for photocatalytic CO(2) reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprising metal complexes as redox photosensitizers and catalyst units fixed on a p-type semiconductor electrode, the performance of the corresponding photoelectrochemical cells remains low, e.g., their highest incident photon-to-current conversion efficiency (IPCE) equals 1.2%. Herein, we report a novel dye-sensitized molecular photocathode for photocatalytic CO(2) reduction in water featuring a polypyrrole layer, [Ru(diimine)(3)](2+) as a redox photosensitizer unit, and Ru(diimine)(CO)(2)Cl(2) as the catalyst unit and reveal that the incorporation of the polypyrrole network significantly improves reactivity and durability relative to those of previously reported dye-sensitized molecular photocathodes. The irradiation of the novel photocathode with visible light under low applied bias stably induces the photocatalytic reduction of CO(2) to CO and HCOOH with high faradaic efficiency and selectivity (even in aqueous solution), and the highest IPCE is determined as 4.7%. The novel photocathode is coupled with n-type semiconductor photoanodes (CoO(x)/BiVO(4) and RhO(x)/TaON) to construct full cells that photocatalytically reduce CO(2) using water as the reductant upon visible light irradiation as the only energy input at zero bias. The artificial Z-scheme photoelectrochemical cell with the dye-sensitized molecular photocathode achieves the highest energy conversion efficiency of 8.3 × 10(−2)% under the irradiation of both electrodes with visible light, while a solar to chemical conversion efficiency of 4.2 × 10(−2)% is achieved for a tandem-type cell using a solar light simulator (AM 1.5, 100 mW cm(−2)). The Royal Society of Chemistry 2021-09-15 /pmc/articles/PMC8513877/ /pubmed/34745553 http://dx.doi.org/10.1039/d1sc03756k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Kuttassery, Fazalurahman Kumagai, Hiromu Kamata, Ryutaro Ebato, Yusuke Higashi, Masanobu Suzuki, Hajime Abe, Ryu Ishitani, Osamu Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title | Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title_full | Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title_fullStr | Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title_full_unstemmed | Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title_short | Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO(2) reduction coupled with water oxidation |
title_sort | supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic co(2) reduction coupled with water oxidation |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8513877/ https://www.ncbi.nlm.nih.gov/pubmed/34745553 http://dx.doi.org/10.1039/d1sc03756k |
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