Interfacial Engineering to Construct Antioxidative Pd4S/Pd3P0.95 Heterostructure for Robust Hydrogen Production at High Current Density

Abstract The design of highly efficient and stable electrocatalysts for large‐current‐density hydrogen evolution reactions (HER) is an urgent need for commercial industrial electrolyzers. Herein, a novel heterostructure in the form of Pd 4 S/Pd 3 P 0.95 is constructed through interfacial engineering, which inherits the intrinsic merits of individual components and exposes active sites. Density functional theory (DFT) calculations indicate that the optimized heterostructure not only possesses the largest conductivity and adsorption energy for an oxygen atom, but also can significantly lower the kinetic energy barrier of water molecular dissociation. Accordingly, the optimized Pd 4 S/Pd 3 P 0.95 heterostructure catalyst is promising for large‐current‐density HERs, requiring an overpotential of merely 284 and 387 mV to deliver an HER current density as high as 500 mA cm −2 in 0.5 m H 2 SO 4 and 1 m KOH, respectively, which is superior to the benchmark 20% Pt/C (378 and 482 mV, respectively). Notably, the heterostructure catalyst runs smoothly to the current density of 1000 mA cm −2 with an overpotential of merely 538 and 486 mV in 0.5 m H 2 SO 4 and 1 m KOH, respectively. Significantly, the heterostructure catalyst also exhibits fast reaction kinetics and remarkable long‐term durability. Moreover, the strong surface antioxidative ability is retained after a stability test in alkaline solution.