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Developing efficient electrooxidation 5‐hydroxymethylfurfural (HMF) catalysts with high selectivity and fast reaction kinetic is challenging. The HMF oxidation reaction (HMFOR) involves the adsorption of HMF and OH− on the catalyst, thus understanding the adsorption behavior between the catalyst surface and reactants is vital. In this work, by studying the relationship between HMFOR performance and the adsorption behavior of reactants on different transition metal oxides (TMOs), it is discovered that the catalytic performance of TMOs is related to the adsorption capacity of OH− and HMF simultaneously. Subsequently, TMOs with different HMF and OH− adsorption abilities are coupled to further optimize the catalytic performance of HMFOR. Experimental and theoretical calculation results indicate that the electronic interactions between different TMOs can regulate the substrate adsorption behavior and electron transfer ability of the catalysts, which is beneficial for HMFOR. Among them, due to the strong interaction between the three components optimizes the adsorption capacity for HMF and OH−, NiO/CuO/Co3O4 exhibits the best HMFOR performance with FDCA selectivity of 99.6 % and formation rate of 16.45 mmol gcat−1 h−1. This work provides a design principle for HMFOR catalysts by modulating the adsorption behavior of reaction molecules. [ABSTRACT FROM AUTHOR]

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 H2 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 H2 production. [ABSTRACT FROM AUTHOR]

An amorphous-crystalline heterostructure (Ni/NiMoO 4 /NiCo(OH) x) is prepared by wet chemical etching method for HMFOR and HER. The interaction between NiCo(OH) x and Ni/NiMoO 4 heterointerface regulates the electronic structure of catalyst to facilitate the adsorption behavior of reaction intermediates, thereby showing good performance for HMFOR-assisted H 2 production. [Display omitted] • Coupling of crystalline and amorphous materials provides abundant active sites. • Interactions between heterointerfaces optimize the adsorption of intermediates. • High FDCA selectivity (99.8%) and stability (40 cycles) for HMF oxidation. • Only 1.34 V is required to reach 10 mA cm−2 for HMFOR-assisted H 2 production. The development of catalysts with high activity, selectivity, and stability is critical for biomass upgrading coupled with hydrogen evolution. In this study, we present a simple method for fabricating crystalline-amorphous phase heterostructures using the etching effect of the acidic medium generated during cobalt salt hydrolysis, resulting in the formation of NiCo(OH) x -modified Ni/NiMoO 4 nanosheets electrode (NiCo(OH) x /Ni/NiMoO 4 /NF). The nanosheets array formed during the synthesis process enlarges the surface area of the prepared catalyst, which facilitates the exposure of electrochemically active sites and improves mass transfer. Unexpectedly, the strong coupling interactions between the amorphous-crystalline heterointerface optimize the adsorption of reaction molecules and the corresponding charge transfer process, consequently boosting the catalytic activity for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) and hydrogen evolution reaction (HER). Specifically, NiCo(OH) x /Ni/NiMoO 4 /NF catalyst requires only 1.34 V to obtain a current density of 10 mA cm−2 for HMFOR-coupled H 2 evolution, and operates stably for 13 consecutive cycles with good product selectivity. This work thus provides insights into the design of efficient and robust catalysts for HMFOR-assisted H 2 evolution. [ABSTRACT FROM AUTHOR]