ABSTRACT The inherent high activation energy barrier of the N 2 molecule severely impedes the practical application of electrocatalytic nitrogen reduction reaction (NRR). To overcome this bottleneck, this study employs a Ni 2+ doping strategy to precisely modulate the electronic structure of bismuth molybdate, inducing the formation of electron‐rich sites on adjacent Bi 3+ ions and transforming them into efficient π‐backdonation donor centers. This significantly accelerates electron transfer into the N 2 antibonding orbitals, promoting N 2 activation. Consequently, under 0.1 M HCl electrolyte and an applied potential of −0.2 V versus RHE, the catalyst achieves an exceptional ammonia yield of 92.3 µg mg −1 h −1 and a Faradaic efficiency of 72.6%, surpassing the performance of most reported NRR catalysts. In situ diffuse reflectance Fourier transform infrared spectroscopy confirms the π‐backdonation mechanism is crucial for efficient N≡N bond activation, while cycling tests highlight the material's outstanding stability. This work lays the groundwork for developing highly efficient and selective NRR catalysts and significantly advances sustainable ammonia synthesis technologies.
Zhao et al. (Wed,) studied this question.