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...

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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
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Summary: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.
ISSN:2041-1723