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Abstract The rational design of single‐atom catalysts with precise coordination environment and high separation efficiency of photogenerated carriers is critical yet challenging to achieve efficient photocatalytic nitrogen reduction. Herein, we design and construct a defective photocatalyst featuring Fe single atoms immobilized in hollow BiOBr microtube using a plasma‐assisted synthesis strategy, where the Bi‐based metal–organic framework is used as sacrificial template. The dual vacancies of oxygen (V O ) and bromine (V Br ) are created in the BiOBr microtube and induce the formation of coordinatively unsaturated FeO 5 configuration, where four oxygen atoms are from Bi 2 O 2 2+ units and one oxygen atom is located in the V Br . Specially, the hollow catalyst with dual defects and FeO 5 moiety exhibits 1.4 and 2.2 times higher ammonia production activity than another two V Br ‐featuring catalysts with coordinatively saturated FeO 6 configuration and unsaturated FeO 4 configuration, respectively. As revealed by experimental and theoretical calculation results, the optimized catalyst with the FeO 5 configuration reduces the energy barrier of electron transfer from Fe 3d orbitals to antibonding orbitals of N 2 molecules, which favors the formation of a key *NNH intermediate in the N 2 fixation reaction and the resultant efficient ammonia production.
Wang et al. (Tue,) studied this question.