General Formation of Interfacial Assembled Hierarchical Micro‐Nano Arrays for Biomass Upgrading‐Coupled Hydrogen Production

Construction of efficient catalysts to couple biomass upgrading with hydrogen production is significant for improving energy efficiency, which remains a challenge. Herein, a general method for manufacturing 3D hierarchical micro‐nano arrays consisting of template framework and nanoparticle‐decorated nanosheets is reported. This strategy provides an opportunity to controllably tailor the interfacial assembly of nanosheets on precursor template materials. The obtained Co@NiMoO‐Ni/NF exhibits enhanced electrocatalytic performance for biomass oxidation and hydrogen production. It only needs 1.21 V to achieve 10 mA cm −2 for 5‐hydroxymethylfurfural electrooxidation reaction (HMFOR) assisted H 2 evolution reaction (HER). The good catalytic performance is ascribed to the intense interaction between template (Co) and nanoparticle‐decorated nanosheets (NiMoO‐Ni), which tunes the electron structure of the catalyst to optimize the adsorption behavior of HMFOR/HER intermediates and promote the bonds breakage of key intermediates in the HMFOR/HER process. This work thus provides a strategy for designing ideal catalysts for biomass upgrading‐coupled H 2 production.