Hydrogenated Bismuth Molybdate Nanoframe for Efficient Sunlight-Driven Nitrogen Fixation from Air

Sunlight‐driven dinitrogen fixation can lead to a novel concept for the production of ammonia under mild conditions. However, the efficient artificial photosynthesis of ammonia from ordinary air (instead of high pure N2) has never been implemented. Here, we report for the first time the intrinsic catalytic activity of Bi2MoO6 catalyst for direct ammonia synthesis under light irradiation. The edge‐exposed coordinatively unsaturated Mo atoms in an Mo−O coordination polyhedron can act as activation centers to achieve the chemisorption, activation, and photoreduction of dinitrogen efficiently. Using that insight as a starting point, through rational structure and defect engineering, the optimized Bi2MoO6 sunlight‐driven nitrogen fixation system, which simultaneously possesses robust nitrogen activation ability, excellent light‐harvesting performance, and efficient charge transmission was successfully constructed. As a surprising achievement, this photocatalytic system demonstrated for the first time ultra‐efficient (1.3 mmol g−1 h−1) and stable sunlight‐driven nitrogen fixation from air in the absence of any organic scavengers. Nitrogen‐fixing nano‐style: Nanostructured Bi2MoO6 crystal was confirmed for the first time to possess an intrinsic activation ability for dinitrogen splitting, enabling effective energy coupling between photons, excitons, and dinitrogen, thereby exhibiting exceptional performance (1.3 mmol g−1 h−1; AQE=2.42 % for λ=420 nm) for N2 photo‐reduction from air.