Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration
Abstract Cofactors such as nicotinamide adenine dinucleotide (NADH) and its phosphorylated form (NADPH) play a crucial role in natural enzyme‐catalyzed reactions for the synthesis of chemicals. However, the stoichiometric supply of NADH for artificial synthetic processes is uneconomical. Here, inspi...
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Wiley
2025-02-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202413668 |
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| author | Ziqi Zhao Yizhou Wu Chang Liu Yingzheng Li Chen Gong Hongxia Ning Peili Zhang Fei Li Licheng Sun Fusheng Li |
| author_facet | Ziqi Zhao Yizhou Wu Chang Liu Yingzheng Li Chen Gong Hongxia Ning Peili Zhang Fei Li Licheng Sun Fusheng Li |
| author_sort | Ziqi Zhao |
| collection | DOAJ |
| description | Abstract Cofactors such as nicotinamide adenine dinucleotide (NADH) and its phosphorylated form (NADPH) play a crucial role in natural enzyme‐catalyzed reactions for the synthesis of chemicals. However, the stoichiometric supply of NADH for artificial synthetic processes is uneconomical. Here, inspired by the process of cofactor NADPH regeneration in photosystem I (PSI), catalyst‐modified photocathodes are constructed on the surface of polythiophene‐based semiconductors (PTTH) via self‐assembly for photoelectrochemical catalytic NADH regeneration. With the assistance of viologen (vi2+) electron transfer mediators (similar function as Ferredoxin in PSI) linked to the [Rh(Cp*)(bpy)] catalyst, the Rh‐vi2+@PTTH photocathode exhibits higher photocurrent density (−665 µA cm−2) with a high apparent turnover frequency (TOF, 168.4 h−1) under a relatively positive potential (0.0 V vs RHE). In addition, through holistic functional mimics of the photosystem, a tandem photoelectrochemical cell is constructed by assembling a CoPi@BiVO4 photoanode (artificial photosystem II, PSII) with the Rh‐vi2+@PTTH photocathode. This system achieves a production rate of 42.5 µm h−1 cm−2 and a TOF of 179.3 h−1 without an externally applied bias for NADH regeneration. The photo‐generated NADH is directly employed to assist glutamate dehydrogenase (GDH) in the catalytic conversion of α‐ketoglutarate to L‐glutamate. This study presents a novel strategic approach for constructing bias‐free photoelectrochemical NADH regeneration systems. |
| format | Article |
| id | doaj-art-acea00cdae8045008033ee96067ec0cf |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-acea00cdae8045008033ee96067ec0cf2025-08-20T02:30:35ZengWileyAdvanced Science2198-38442025-02-01128n/an/a10.1002/advs.202413668Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH RegenerationZiqi Zhao0Yizhou Wu1Chang Liu2Yingzheng Li3Chen Gong4Hongxia Ning5Peili Zhang6Fei Li7Licheng Sun8Fusheng Li9State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaCenter of Artificial Photosynthesis for Solar Fuels, School of Science Westlake University Hangzhou 310024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaState Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Dalian University of Technology Dalian Liaoning 116024 ChinaAbstract Cofactors such as nicotinamide adenine dinucleotide (NADH) and its phosphorylated form (NADPH) play a crucial role in natural enzyme‐catalyzed reactions for the synthesis of chemicals. However, the stoichiometric supply of NADH for artificial synthetic processes is uneconomical. Here, inspired by the process of cofactor NADPH regeneration in photosystem I (PSI), catalyst‐modified photocathodes are constructed on the surface of polythiophene‐based semiconductors (PTTH) via self‐assembly for photoelectrochemical catalytic NADH regeneration. With the assistance of viologen (vi2+) electron transfer mediators (similar function as Ferredoxin in PSI) linked to the [Rh(Cp*)(bpy)] catalyst, the Rh‐vi2+@PTTH photocathode exhibits higher photocurrent density (−665 µA cm−2) with a high apparent turnover frequency (TOF, 168.4 h−1) under a relatively positive potential (0.0 V vs RHE). In addition, through holistic functional mimics of the photosystem, a tandem photoelectrochemical cell is constructed by assembling a CoPi@BiVO4 photoanode (artificial photosystem II, PSII) with the Rh‐vi2+@PTTH photocathode. This system achieves a production rate of 42.5 µm h−1 cm−2 and a TOF of 179.3 h−1 without an externally applied bias for NADH regeneration. The photo‐generated NADH is directly employed to assist glutamate dehydrogenase (GDH) in the catalytic conversion of α‐ketoglutarate to L‐glutamate. This study presents a novel strategic approach for constructing bias‐free photoelectrochemical NADH regeneration systems.https://doi.org/10.1002/advs.202413668photosynthesisNADH regenerationphotocathodebio‐inspiredcatalyst‐modification |
| spellingShingle | Ziqi Zhao Yizhou Wu Chang Liu Yingzheng Li Chen Gong Hongxia Ning Peili Zhang Fei Li Licheng Sun Fusheng Li Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration Advanced Science photosynthesis NADH regeneration photocathode bio‐inspired catalyst‐modification |
| title | Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration |
| title_full | Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration |
| title_fullStr | Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration |
| title_full_unstemmed | Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration |
| title_short | Bio‐inspired Catalyst‐Modified Photocathode for Bias‐Free Photoelectrochemical NADH Regeneration |
| title_sort | bio inspired catalyst modified photocathode for bias free photoelectrochemical nadh regeneration |
| topic | photosynthesis NADH regeneration photocathode bio‐inspired catalyst‐modification |
| url | https://doi.org/10.1002/advs.202413668 |
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