Interfacial Engineering of MoO2‐FeP Heterojunction for Highly Efficient Hydrogen Evolution Coupled with Biomass Electrooxidation

Simultaneous highly efficient production of hydrogen and conversion of biomass into value‐added products is meaningful but challenging. Herein, a porous nanospindle composed of carbon‐encapsulated MoO2‐FeP heterojunction (MoO2‐FeP@C) is proposed as a robust bifunctional electrocatalyst for hydrogen evolution reaction (HER) and biomass electrooxidation reaction (BEOR). X‐ray photoelectron spectroscopy analysis and theoretical calculations confirm the electron transfer from MoO2 to FeP at the interfaces, where electron accumulation on FeP favors the optimization of H2O and H* absorption energies for HER, whereas hole accumulation on MoO2 is responsible for improving the BEOR activity. Thanks to its interfacial electronic structure, MoO2‐FeP@C exhibits excellent HER activity with an overpotential of 103 mV at 10 mA cm−2 and a Tafel slope of 48 mV dec−1. Meanwhile, when 5‐hydroxymethylfurfural is chosen as the biomass for BEOR, the conversion is almost 100%, and 2,5‐furandicarboxylic acid (FDCA) is obtained with the selectivity of 98.6%. The electrolyzer employing MoO2‐FeP@C for cathodic H2 and anodic FDCA production requires only a low voltage of 1.486 V at 10 mA cm−2 and can be powered by a solar cell (output voltage: 1.45 V). Additionally, other BEORs coupled with HER catalyzed by MoO2‐FeP@C also have excellent catalytic performance, implying their good versatility. A porous MoO2‐FeP@C nanospindle is proposed as a robust bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and biomass electrooxidation reaction. The MoO2‐FeP@C not only exhibits excellent HER activity, but also catalyzes the electrooxidation of biomass into value‐added products. The electrolyzer assembled by MoO2‐FeP@C for cathodic H2 and anodic 2,5‐furandicarboxylic acid production requires a low voltage of 1.486 V at 10 mA cm−2.