Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight

Abstract It remains a great challenge to explore redox mediators with multi-electron, suitable redox potential, and stable pH buffer ability to simulate the natural solar-to-fuel process. In this work, we present a defect engineering strategy to design soluble multi-electron redox polyoxometalates m...

Full description

Saved in:
Bibliographic Details
Main Authors: Li-Ping Cui, Shu Zhang, Yue Zhao, Xin-Yue Ge, Le Yang, Ke Li, Liu-Bin Feng, Ren-Gui Li, Jia-Jia Chen
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58622-8
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849699759601745920
author Li-Ping Cui
Shu Zhang
Yue Zhao
Xin-Yue Ge
Le Yang
Ke Li
Liu-Bin Feng
Ren-Gui Li
Jia-Jia Chen
author_facet Li-Ping Cui
Shu Zhang
Yue Zhao
Xin-Yue Ge
Le Yang
Ke Li
Liu-Bin Feng
Ren-Gui Li
Jia-Jia Chen
author_sort Li-Ping Cui
collection DOAJ
description Abstract It remains a great challenge to explore redox mediators with multi-electron, suitable redox potential, and stable pH buffer ability to simulate the natural solar-to-fuel process. In this work, we present a defect engineering strategy to design soluble multi-electron redox polyoxometalates mediators to construct a photocatalysis-electrolysis relay system to decouple H2 and O2 evolution in solar-driven water splitting. The appropriate use of vanadium atoms to replace tungsten in the Dawson-type phosphotungstate successfully regulated the redox properties of the molecular clusters. Specifically, the single vanadium substitution structure ({P2W17V}) possesses 1-electron redox active and sequential proton-electron transfer behavior, while the tri-vanadium substituted cluster ({P2W15V3}) exhibits 3-electron redox active and cooperative proton electron transfer behavior. Based on the developed multi-electronic redox mediator with pH buffering capacity, suitable redox potential (0.6 V), and fast electron exchange rate, we build a photocatalysis-electrolysis relay water splitting system. This system allows for high capacity of solar energy storage through photocatalytic O2 evolution using BiVO4 photocatalyst and stable H2 production with a high Faraday efficiency of over 98.5% in the electrolysis subsystem.
format Article
id doaj-art-1d1adf8ca4a44e19a1deccb16b4d11af
institution DOAJ
issn 2041-1723
language English
publishDate 2025-04-01
publisher Nature Portfolio
record_format Article
series Nature Communications
spelling doaj-art-1d1adf8ca4a44e19a1deccb16b4d11af2025-08-20T03:18:28ZengNature PortfolioNature Communications2041-17232025-04-0116111210.1038/s41467-025-58622-8Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlightLi-Ping Cui0Shu Zhang1Yue Zhao2Xin-Yue Ge3Le Yang4Ke Li5Liu-Bin Feng6Ren-Gui Li7Jia-Jia Chen8State Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory for Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen UniversityAbstract It remains a great challenge to explore redox mediators with multi-electron, suitable redox potential, and stable pH buffer ability to simulate the natural solar-to-fuel process. In this work, we present a defect engineering strategy to design soluble multi-electron redox polyoxometalates mediators to construct a photocatalysis-electrolysis relay system to decouple H2 and O2 evolution in solar-driven water splitting. The appropriate use of vanadium atoms to replace tungsten in the Dawson-type phosphotungstate successfully regulated the redox properties of the molecular clusters. Specifically, the single vanadium substitution structure ({P2W17V}) possesses 1-electron redox active and sequential proton-electron transfer behavior, while the tri-vanadium substituted cluster ({P2W15V3}) exhibits 3-electron redox active and cooperative proton electron transfer behavior. Based on the developed multi-electronic redox mediator with pH buffering capacity, suitable redox potential (0.6 V), and fast electron exchange rate, we build a photocatalysis-electrolysis relay water splitting system. This system allows for high capacity of solar energy storage through photocatalytic O2 evolution using BiVO4 photocatalyst and stable H2 production with a high Faraday efficiency of over 98.5% in the electrolysis subsystem.https://doi.org/10.1038/s41467-025-58622-8
spellingShingle Li-Ping Cui
Shu Zhang
Yue Zhao
Xin-Yue Ge
Le Yang
Ke Li
Liu-Bin Feng
Ren-Gui Li
Jia-Jia Chen
Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
Nature Communications
title Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
title_full Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
title_fullStr Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
title_full_unstemmed Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
title_short Tunable multi-electron redox polyoxometalates for decoupled water splitting driven by sunlight
title_sort tunable multi electron redox polyoxometalates for decoupled water splitting driven by sunlight
url https://doi.org/10.1038/s41467-025-58622-8
work_keys_str_mv AT lipingcui tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT shuzhang tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT yuezhao tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT xinyuege tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT leyang tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT keli tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT liubinfeng tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT renguili tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight
AT jiajiachen tunablemultielectronredoxpolyoxometalatesfordecoupledwatersplittingdrivenbysunlight