Synergistic Effect of Dual-Doped Carbon on Mo2C Nanocrystals Facilitates Alkaline Hydrogen Evolution

Highlights The B and N dual-doped carbon layer that encapsulated on Mo 2 C nanocrystals (Mo 2 C@BNC) were fabricated for accelerating HER under alkaline condition. Theoretical calculations reveal that the H 2 O could be decomposed spontaneously over the introduced B sites, and the defective C atoms in the dual-doped carbon layer provide the best H binding sites. The optimized dual doped Mo 2 C catalyst with synergistic effect of non-metal sites delivers superior HER performances. Molybdenum carbide (Mo 2 C) materials are promising electrocatalysts with potential applications in hydrogen evolution reaction (HER) due to low cost and Pt-like electronic structures. Nevertheless, their HER activity is usually hindered by the strong hydrogen binding energy. Moreover, the lack of water-cleaving sites makes it difficult for the catalysts to work in alkaline solutions. Here, we designed and synthesized a B and N dual-doped carbon layer that encapsulated on Mo 2 C nanocrystals (Mo 2 C@BNC) for accelerating HER under alkaline condition. The electronic interactions between the Mo 2 C nanocrystals and the multiple-doped carbon layer endow a near-zero H adsorption Gibbs free energy on the defective C atoms over the carbon shell. Meanwhile, the introduced B atoms afford optimal H 2 O adsorption sites for the water-cleaving step. Accordingly, the dual-doped Mo 2 C catalyst with synergistic effect of non-metal sites delivers superior HER performances of a low overpotential (99 mV@10 mA cm −2 ) and a small Tafel slope (58.1 mV dec −1 ) in 1 M KOH solution. Furthermore, it presents a remarkable activity that outperforming the commercial 10% Pt/C catalyst at large current density, demonstrating its applicability in industrial water splitting. This study provides a reasonable design strategy towards noble-metal-free HER catalysts with high activity.