Regulating the electronic structure of nickel phosphides via interface engineering and molybdenum doping boosts benzyl alcohol oxidation coupled with hydrogen production

Coupling the electrocatalytic benzyl alcohol oxidation reaction (BAOR) with hydrogen evolution reaction (HER) presents a favorable energy conversion method. However, the development of highly efficient bifunctional electrocatalysts poses significant challenges. In this study, a Mo doped biphasic Ni 2 P-Ni 12 P 5 heterostructure (Mo-Ni 2 P/Ni 12 P 5 @NF) has been developed to serve as the efficient bifunctional electrocatalyst. The Mo-Ni 2 P/Ni 12 P 5 @NF resulted in exceptional activities for both the BAOR and HER. The electrolyzer cell using Mo-Ni 2 P/Ni 12 P 5 @NF as anode and cathode operates at an impressively low cell voltage of merely 1.38 V to achieve the current density of 10 mA cm −2 in a benzyl alcohol-containing aqueous solution. Experimental results and density functional theory (DFT) calculations indicate that the introduction of Mo can significantly modulate the electronic structure of Ni-based phosphide catalysts and adjust for the d-band center of the active Ni sites. This modulation significantly optimizes the adsorption capabilities for both benzyl alkoxide (Ph-CH 2 O-) and the H* intermediates on Mo-Ni 2 P/Ni 12 P 5 @NF, thereby increasing electrocatalytic activity toward BAOR and HER respectively. Our work offers a valuable insight into designing bifunctional electrocatalysts and highlights the potential of Mo doping systems to produce hydrogen and value-added products efficiently.