An Overall Reaction Integrated with Highly Selective Oxidation of 5‐Hydroxymethylfurfural and Efficient Hydrogen Evolution

Abstract Thermodynamically favorable electrooxidation reactions of biomass derivatives integrated with hydrogen evolution reaction (HER) can simultaneously provide value‐added chemicals and hydrogen, and eventually meeting the need for clean and sustainable energy development. Herein, the integration of a six‐electron involved anodic half‐reaction‐selective electrooxidation of 5‐hydroxymethylfurfural into 2,5‐furandicarboxylic acid (FDCA) on a hierarchically layered double hydroxide (CoFe@NiFe) with a cathodic HER in a two‐chamber system is reported. The overall reaction reaches 38 mA cm −2 at 1.40 V and exhibits 100% selectivity to yield FDCA and a nearly 100% Faraday efficiency with hydrogen production of 901 µmol cm −2 . Several operando techniques confirm that the trivalent nickel species in the CoFe@NiFe catalyst are mainly responsible for this 100%‐selective oxidation reaction. This integrated overall reaction is thus a new strategy to utilize cheap catalysts and biomass derivatives to simultaneously produce value‐added chemicals and sustainable energy materials, and eventually to solve current challenges of energy depletion and environmental pollution.