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Co-facial π–π Interaction Expedites Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction
[Image: see text] The sunlight-driven reduction of CO(2) into carbonaceous fuels can lower the atmospheric CO(2) concentration and provide renewable energy simultaneously, attracting scientists to design photocatalytic systems for facilitating this process. Significant progress has been made in desi...
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/PMC9241016/ https://www.ncbi.nlm.nih.gov/pubmed/35783182 http://dx.doi.org/10.1021/jacsau.2c00073 |
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author | Wang, Jia-Wei Huang, Hai-Hua Wang, Ping Yang, Guangjun Kupfer, Stephan Huang, Yanjun Li, Zizi Ke, Zhuofeng Ouyang, Gangfeng |
author_facet | Wang, Jia-Wei Huang, Hai-Hua Wang, Ping Yang, Guangjun Kupfer, Stephan Huang, Yanjun Li, Zizi Ke, Zhuofeng Ouyang, Gangfeng |
author_sort | Wang, Jia-Wei |
collection | PubMed |
description | [Image: see text] The sunlight-driven reduction of CO(2) into carbonaceous fuels can lower the atmospheric CO(2) concentration and provide renewable energy simultaneously, attracting scientists to design photocatalytic systems for facilitating this process. Significant progress has been made in designing high-performance photosensitizers and catalysts in this regard, and further improvement can be realized by installing additional interactions between the abovementioned two components, however, the design strategies and mechanistic investigations on such interactions remain challenging. Here, we present the construction of molecular models for intermolecular π–π interactions between the photosensitizer and the catalyst, via the introduction of pyrene groups into both molecular components. The presence, types, and strengths of diverse π–π interactions, as well as their roles in the photocatalytic mechanism, have been examined by (1)H NMR titration, fluorescence quenching measurements, transient absorption spectroscopy, and quantum chemical simulations. We have also explored the rare dual emission behavior of the pyrene-appended iridium photosensitizer, of which the excited state can deliver the photo-excited electron to the pyrene-decorated cobalt catalyst at a fast rate of 2.60 × 10(6) s(–1) via co-facial π–π interaction, enabling a remarkable apparent quantum efficiency of 14.3 ± 0.8% at 425 nm and a high selectivity of 98% for the photocatalytic CO(2)-to-CO conversion. This research demonstrates non-covalent interaction construction as an effective strategy to achieve rapid CO(2) photoreduction besides a conventional photosensitizer/catalyst design. |
format | Online Article Text |
id | pubmed-9241016 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-92410162022-06-30 Co-facial π–π Interaction Expedites Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction Wang, Jia-Wei Huang, Hai-Hua Wang, Ping Yang, Guangjun Kupfer, Stephan Huang, Yanjun Li, Zizi Ke, Zhuofeng Ouyang, Gangfeng JACS Au [Image: see text] The sunlight-driven reduction of CO(2) into carbonaceous fuels can lower the atmospheric CO(2) concentration and provide renewable energy simultaneously, attracting scientists to design photocatalytic systems for facilitating this process. Significant progress has been made in designing high-performance photosensitizers and catalysts in this regard, and further improvement can be realized by installing additional interactions between the abovementioned two components, however, the design strategies and mechanistic investigations on such interactions remain challenging. Here, we present the construction of molecular models for intermolecular π–π interactions between the photosensitizer and the catalyst, via the introduction of pyrene groups into both molecular components. The presence, types, and strengths of diverse π–π interactions, as well as their roles in the photocatalytic mechanism, have been examined by (1)H NMR titration, fluorescence quenching measurements, transient absorption spectroscopy, and quantum chemical simulations. We have also explored the rare dual emission behavior of the pyrene-appended iridium photosensitizer, of which the excited state can deliver the photo-excited electron to the pyrene-decorated cobalt catalyst at a fast rate of 2.60 × 10(6) s(–1) via co-facial π–π interaction, enabling a remarkable apparent quantum efficiency of 14.3 ± 0.8% at 425 nm and a high selectivity of 98% for the photocatalytic CO(2)-to-CO conversion. This research demonstrates non-covalent interaction construction as an effective strategy to achieve rapid CO(2) photoreduction besides a conventional photosensitizer/catalyst design. American Chemical Society 2022-04-07 /pmc/articles/PMC9241016/ /pubmed/35783182 http://dx.doi.org/10.1021/jacsau.2c00073 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 | Wang, Jia-Wei Huang, Hai-Hua Wang, Ping Yang, Guangjun Kupfer, Stephan Huang, Yanjun Li, Zizi Ke, Zhuofeng Ouyang, Gangfeng Co-facial π–π Interaction Expedites Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title | Co-facial π–π Interaction Expedites
Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title_full | Co-facial π–π Interaction Expedites
Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title_fullStr | Co-facial π–π Interaction Expedites
Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title_full_unstemmed | Co-facial π–π Interaction Expedites
Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title_short | Co-facial π–π Interaction Expedites
Sensitizer-to-Catalyst Electron Transfer for High-Performance CO(2) Photoreduction |
title_sort | co-facial π–π interaction expedites
sensitizer-to-catalyst electron transfer for high-performance co(2) photoreduction |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9241016/ https://www.ncbi.nlm.nih.gov/pubmed/35783182 http://dx.doi.org/10.1021/jacsau.2c00073 |
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