In Situ Synthesis of MoS₂ on C₃N₄ To Form MoS₂/C₃N₄ with Interfacial Mo–N Coordination for Electrocatalytic Reduction of N₂ to NH₃

Abstract

Electrocatalytic nitrogen reduction reaction (NRR), as an alternative to synthetic ammonia under mild condition, provides a promising method for storage and sustainable utilization of ammonia. However, the catalytic performance of the NRR electrocatalyst still requires a systematical investigation and improvement. Herein, this paper reports that MoS2/C3N4 is prepared by in situ controllable synthesis through a one-step pyrolysis process of thiourea and ammonium molybdate. A thorough characterization reveals that the strong interactions between MoS2 and C3N4 of MoS2/C3N4 lead to the formation of an interface with Mo–N coordination, which promotes electron transfer across the MoS2/C3N4 interface. Meanwhile, it is clarified that the formation of interfacial Mo–N coordination is beneficial to improve the catalytic activity and acts as the main active sites for catalyzing NRR. As a result, the as-prepared electrocatalyst exhibits an excellent NH3 yield rate of 19.86 μg h–1 mgcat.–1 and an enhanced faradaic efficiency of 6.87% at −0.5 V (vs reversible hydrogen electrode) in 0.1 M Na2SO4, placing it as one of the most promising NRR electrocatalysts.