Ammonia occupies a significant standing in the global economy. As a promising alternative to the energy-intensive Haber-Bosch process, electrochemical nitrogen reduction could achieve sustainable ammonia synthesis. However, the attractive alternative suffers from the bottleneck of insufficient activity and low electron selectivity. Here, we report an efficient electrocatalyst using phosphotungstic acid as platforms to anchor bismuth species on the 4-fold hollow site and anchor lithium species on the 3-fold hollow site, which reaches high ammonia yield rates of 61 ± 1 μg h⁻¹ mg_cat.⁻¹ and Faradaic efficiencies of 85% ± 2% at −0.1 V versus reversible hydrogen electrode (RHE). Experiments and theoretical calculations reveal that the Bi^δ+ species can promote the activation and hydrogenation of nitrogen at adjacent unsaturated tungsten active sites, and the incorporated lithium species reduce the hydrogen reduction rate in undesired water splitting. This synergistic functionalization of bismuth and lithium species contributes to the high-efficient catalyst.

氨在全球经济中占有重要地位。作为能源密集型 Haber-Bosch 工艺的有前景的替代方案，电化学氮还原可以实现可持续的氨合成。然而，有吸引力的替代品存在活性不足和电子选择性低的瓶颈。在这里，我们报告了一种使用磷钨酸作为平台的高效电催化剂，将铋物种锚定在 4 倍空心位点上，并将锂物种锚定在 3 倍空心位点上，达到 61 ± 1 μg h ^-1 mg 的高氨产率_猫。^-1和法拉第效率在 -0.1 V 时为 85% ± 2%，与可逆氢电极 (RHE) 相比。实验和理论计算表明，Bi ^δ+物种可以促进相邻不饱和钨活性位点处氮的活化和氢化，并且掺入的锂物种降低了不希望的水分解中的氢还原速率。铋和锂物质的这种协同功能化有助于高效催化剂。