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Published on: October 5, 2019
Boosting Both Chemical and Electrochemical Tandem Steps in Low-Potential Aldehyde Oxidation for Solar-Driven Bipolar
Yuelong Zhou1, Guanping Wei1, Bing Wu2
1College of Chemistry and Materials, Gannan Normal University, Ganzhou, China.
Abstract:
Low-potential aldehyde oxidation offers an energy-efficient anodic alternative to oxygen evolution for bipolar hydrogen production coupled with biomass valorization, yet the tandem non-Faradaic/Faradaic mechanism remains poorly understood. Here, we report PtCu3-coated Cu nanowire arrays supported on Cu foam (PtCu3@Cu/CF) fabricated via galvanic replacement and electrochemical reduction. In situ ATR-FTIR and DFT calculations indicate the PtCu3 shell enhances adsorption of the gem-diolate intermediate while weakens binding of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), accelerating both non-Faradaic C-H cleavage and Faradaic oxidation. This enables selective 5-hydroxymethylfurfural upgrading with anodic hydrogen evolution at 300 mA cm-2 at ∼0.21 V in a two-electrode flow electrolyzer. Additionally, the electrolyzer also achieves 100 mA cm-2 at 0.16 V with 200% combined Faradaic efficiency for bipolar hydrogen production. Integration of a six-cell stack with perovskite photovoltaic module yields a bias-free solar-to-hydrogen efficiency of 16.9% alongside gram-scale HMFCA production. This noble-metal-lean platform establishes scalable solar reforming for co-generating green hydrogen and value-added chemicals.
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