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

Abstract 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 MoO 2 ‐FeP heterojunction (MoO 2 ‐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 MoO 2 to FeP at the interfaces, where electron accumulation on FeP favors the optimization of H 2 O and H* absorption energies for HER, whereas hole accumulation on MoO 2 is responsible for improving the BEOR activity. Thanks to its interfacial electronic structure, MoO 2 ‐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 MoO 2 ‐FeP@C for cathodic H 2 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 MoO 2 ‐FeP@C also have excellent catalytic performance, implying their good versatility.