Roles of Heterojunction and Cu Vacancies in the Au@Cu 2- x Se for the Enhancement of Electrochemical Nitrogen Reduction Performance.

The utilization of hydrogen (H2 ) as a fuel source is hindered by the limited infrastructure and storage requirements. In contrast, ammonia (NH3 ) offers a promising solution as a hydrogen carrier due to its high energy density, liquid storage capacity, low cost, and sustainable manufacturing. NH3 has garnered significant attention as a key component in the development of next-generation refueling stations, aligning with the goal of a carbon-free economy. The electrochemical nitrogen reduction reaction (ENRR) enables the production of NH3 from nitrogen (N2 ) under ambient conditions. However, the low efficiency of the ENRR is limited by challenges such as the electron-stealing hydrogen evolution reaction (HER) and the breaking of the stable N2 triple bond. To address these limitations and enhance ENRR performance, we prepared Au@Cu2- x Se electrocatalysts with a core@shell structure using a seed-mediated growth method and a facile hot-injection method. The catalytic activity was evaluated using both an aqueous electrolyte of KOH solution and a nonaqueous electrolyte consisting of tetrahydrofuran (THF) solvent with lithium perchlorate and ethanol as proton donors. ENRR in both aqueous and nonaqueous electrolytes was facilitated by the synergistic interaction between Au and Cu2- x Se (copper selenide), forming an Ohmic junction between the metal and p-type semiconductor that effectively suppressed the HER. Furthermore, in nonaqueous conditions, the Cu vacancies in the Cu2- x Se layer of Au@Cu2- x Se promoted the formation of lithium nitride (Li3 N), leading to improved NH3 production. The synergistic effect of Ohmic junctions and Cu vacancies in Au@Cu2- x Se led to significantly higher ammonia yield and faradaic efficiency (FE) in nonaqueous systems compared to those in aqueous conditions. The maximum NH3 yields were approximately 1.10 and 3.64 μg h-1 cm-2 , with the corresponding FE of 2.24 and 67.52% for aqueous and nonaqueous electrolytes, respectively. This study demonstrates an attractive strategy for designing catalysts with increased ENRR activity by effectively engineering vacancies and heterojunctions in Cu-based electrocatalysts in both aqueous and nonaqueous media.