Rapid electron transfer via dynamic coordinative interaction boosts quantum efficiency for photocatalytic CO2 reduction
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Abstract
Abstract The fulfillment of a high quantum efficiency for photocatalytic CO 2 reduction presents a key challenge, which can be overcome by developing strategies for dynamic attachment between photosensitizer and catalyst. In this context, we exploit the use of coordinate bond to connect a pyridine-appended iridium photosensitizer and molecular catalysts for CO 2 reduction, which is systematically demonstrated by 1 H nuclear magnetic resonance titration, theoretical calculations, and spectroscopic measurements. The mechanistic investigations reveal that the coordinative interaction between the photosensitizer and an unmodified cobalt phthalocyanine significantly accelerates the electron transfer and thus realizes a remarkable quantum efficiency of 10.2% ± 0.5% at 450 nm for photocatalytic CO 2 -to-CO conversion with a turn-over number of 391 ± 7 and nearly complete selectivity, over 4 times higher than a comparative system with no additional interaction (2.4%±0.2%). Moreover, the decoration of electron-donating amino groups on cobalt phthalocyanine can optimize the quantum efficiency up to 27.9% ± 0.8% at 425 nm, which is more attributable to the enhanced coordinative interaction rather than the intrinsic activity. The control experiments demonstrate that the dynamic feature of coordinative interaction is important to prevent the coordination occupancy of labile sites, also enabling the wide applicability on diverse non-noble-metal catalysts.
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Valuable fuels such as CO, CH4, CH3OH, HCOOH, and C2+ products have been generated through proton-assisted multiple electron-transfer processes.
“Many valuable fuels, such as CO, CH4, CH3OH, HCOOH, and C2+ products have been generated through proton-assisted multiple electron-transfer processes.306, 307, 308, 309, 310”
From Technologies and perspectives for achieving carbon neutrality (2021) · cites this paper as [306]
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Technologies and perspectives for achieving carbon neutrality
Wang, F., Harindintwali, J. D., Yuan, Z., Wang, M., Wang, F., Li, S., Yin, Z., Huang, L., Fu, Y., Li, L., et al. (2021) · The Innovation · doi:10.1016/j.xinn.2021.100180 · Cited by 1,330 · see citing works
- Authors
- Wang, J.-W., Jiang, L., Huang, H.-H., Han, Z., & Ouyang, G.
- Affiliations
- Sun Yat-sen University (CN)
- Corresponding author
- Ouyang, Gangfeng
- Venue
- Nature Communications
- Published
- 2021-07-13
- Volume
- 12
- Issue
- 1
- Pages
- 4276-4276
- ISSN
- 2041-1723 (ISSN-L)
- PMC
- PMC8277789
- OpenAlex
- W3130803308
- Cited by
- 164
- References
- 68
- Citations by year
- 2026: 22 · 2025: 33 · 2024: 41 · 2023: 31 · 2022: 32 · 2021: 5
- FWCI
- 5.11
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Locations
- Nature Communications (publishedVersion, cc-by)
- Research Square (acceptedVersion, cc-by)
- PubMed Central (publishedVersion, cc-by)
- PubMed (publishedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- Funders
- Natural Science Foundation of Guangdong Province (2020A1515110017, 2021A1515012033)
- China Postdoctoral Science Foundation (2020M683020, 2021T140759)
- National Natural Science Foundation of China (22036003, 22076222)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- photocatalytic CO2 reduction, quantum efficiency, electron transfer, iridium photosensitizer, cobalt phthalocyanine, CO selectivity, non-noble metal catalysts
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