Oxygen vacancies enhance non-Faradaic deprotonation in furfural electro-oxidation

作者：Jiayi Wu, Shu-Wen Wu, Xiaoxiao Wei, Peng‐Xia Lei, Qi‐Rui Wen, Xiaodong Guo, Xian‐Zhu Fu, Shaoqing Liu, Jing‐Li Luo · 发表于：Applied Catalysis B: Environmental · 年份：2025 · DOI：10.1016/j.apcatb.2025.125802 · 被引用次数：7 · 研究领域：Electrocatalysts for Energy Conversion、Ammonia Synthesis and Nitrogen Reduction、Advanced battery technologies research

Electrochemical oxidation of biomass-derived furfural enables simultaneous production of furoic acid and hydrogen evolution, providing a sustainable strategy for integrated chemical synthesis and clean energy generation. However, its efficiency is limited by a non-Faradaic deprotonation process, which requires hydroxide (OH⁻) participation, as these ions become depleted at the catalyst interface under high reaction rates. Herein, we introduce oxygen vacancy (V O )-rich copper catalysts that enhance local OH⁻ concentration and accelerate key deprotonation steps. Theoretical simulations reveal that enhance the local OH⁻ concentration and accelerate the key deprotonation steps. Theoretical simulations reveal that high OH⁻ coverage lowers the energy barrier for gem-diolate anion (GDA) formation, and V Os increase the interfacial OH⁻ concentration by 1.76-fold at 100 mA cm −2 . Guided by these insights, we synthesized the Cu nanowires with tunable V O densities via controlled reduction. The V O-rich Cu catalyst achieves a current density of 208.1 mA cm −2 at 0.5 V vs. RHE, 4.8 times higher than V O-poor Cu, while maintaining a furoic acid Faradaic Efficiency of 99 %. Operando infrared spectroscopy confirms that V Os facilitate OH⁻ enrichment and enable efficient adsorption of FF on Cu 0 /Cu + active sites, synergistically promoting GDA formation and accelerating C–H bond cleavage. When integrated into a flow reactor, the V O-rich Cu enables bipolar hydrogen production at a cell vo...