The alternative anodic-oxidation-coupled cathodic hydrogen evolution offers substantial potential for reducing energy consumption in hydrogen production. However, the fabrication of catalysts that maintain high activity and stability in integrated systems remains a significant challenge. Herein, we have developed an amorphous metal-metalloid alloy catalyst (NiCoB_x) as anode for alkaline 5-hydroxymethylfurfural oxidation reaction (HMFOR) in integrated biomass electrooxidation-coupled hydrogen production system, which achieves a high current density of 400 mA cm⁻² with a low cell voltage of 1.62 V. It saves ∼1.03 kWh/m³ of H₂ produced and maintains excellent stability (>100 h). Operando/in situ spectroscopic characterization and theoretical analysis unveiled a “reactant-induced activation strategy” for NiCoB_x: organic substrates with aldehyde groups preferentially adsorb on Co sites, reducing dehydrogenation adsorption energy and promoting the generation of Co³⁺ active sites. These insightful results present an inspiring outlook for the industrial application of biomass-coupled hydrogen production strategies.

替代性阳极氧化耦合阴极析氢为降低氢气生产中的能耗提供了巨大的潜力。然而，在集成系统中保持高活性和稳定性的催化剂的制造仍然是一个重大挑战。在此，我们开发了一种非晶金属-类金属合金催化剂（NiCoB _x）作为集成生物质电氧化耦合制氢系统中碱性5-羟甲基糠醛氧化反应（HMFOR）的阳极，实现了400 mA cm ^-2的高电流密度电池电压低至 1.62 V。可节省约 1.03 kWh/m ³产生的H ₂并保持出色的稳定性（>100 小时）。原位/原位光谱表征和理论分析揭示了NiCoB _x的“反应物诱导活化策略” ：具有醛基的有机底物优先吸附在Co位点上，降低脱氢吸附能并促进Co ³⁺活性位点的生成。这些富有洞察力的结果为生物质耦合制氢策略的工业应用提供了鼓舞人心的前景。