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

Abstract 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 N 2 ) has never been implemented. Here, we report for the first time the intrinsic catalytic activity of Bi 2 MoO 6 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 Bi 2 MoO 6 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.