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Unlocking Thermodynamic-Kinetic Synergy via Rh/Co Dual Sites and Ordered Interfacial Hydrogen-Bond Network for Efficient Biomass Electrooxidation
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DOI:10.1002/cey2.70310.png)
Abstract
En 中文
Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) offers a sustainable route to bio-based polymer monomers, yet its efficiency is constrained by sluggish adsorption and proton-coupled electron transfer (PCET) kinetics. Herein, we report a composite catalyst comprising amorphous RhOx anchored on cobalt-deficient Co3O4 (RhOx-Vco) that synergistically optimizes both thermodynamics and kinetics. Combined experiments and theoretical calculations unveil that RhOx and Co defects collaboratively upshift the d-band center of Co and create Rh/Co dual sites, cooperatively enhancing HMF and OH− adsorption. Concurrently, this strengthened OH− adsorption guides preferential parallel alignment of interfacial water molecules, fostering a highly connected hydrogen-bond network that accelerates PCET kinetics. Benefiting from this multi-level synergy, RhOx-Vco achieves a seven-fold higher current density at 1.40 V than pristine Co3O4, along with a high FDCA yield of 95.8% in three-electrode system. Remarkably, when integrated into a membrane electrode assembly flow electrolyzer, the system maintains excellent performance with 93.4% FDCA yield, 85.6% Faradaic efficiency, and robust cycling stability, demonstrating its practical viability. This work establishes a design paradigm integrating defect and interface engineering to coordinately regulate multi-step reaction processes, offering broad insights for advancing biomass and PCET-related electrocatalysis.
Keywords:
adsorption regulation
biomass
electrocatalysis
hydrogen bond network
synergy
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