Decoupling hydrogen production from water oxidation by integrating a triphase interfacial bioelectrochemical cascade reaction

Water electrolysis to produce H₂ is a promising strategy for generating a renewable fuel. However, the sluggish-kinetics and low value-added anodic oxygen evolution reaction (OER) restricts the overall energy conversion efficiency. Herein we report a strategy of boosting H₂ production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode. In the presence of oxygen, oxidase enzymes can convert biomass into valuable products, and concurrently generate H₂O₂ that can be further electrooxidized at the bioanode. Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H₂O₂ oxidation than that of OER, the cell voltage and energy consumption are reduced by ~0.70 V and ~36%, respectively, relative to regular water electrolysis. This leads to an efficient H₂ production at the cathode and valuable product generation at the bioanode. Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.