Introduction of element Bi in the P-block promotes N2 activation for efficient electrocatalytic nitrogen reduction to produce ammonia

The synthesis of ammonia through electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is a presumable strategy. However, it still faces the problems of poor activity and low Faradic efficiency, so the development of efficient, stable and highly selective catalysts is of the importance. Molybdenum disulfide (MoS 2 ) materials are widely used in NRR reactions owing to good electrical conductivity and abundant active sites, but the edge active site is the dual active site of NRR and competitive hydrogen evolution reaction (HER). Encouragingly, the strong interaction between elements in the P-block and N 2p orbitals results in excellent performance in adsorbing and activating nitrogen. Meanwhile, the partial occupation of p-orbitals by elements in the P-block also leads to poor HER activity. Herein, we introduced the P-block element Bi into 1 T-MoS 2 and prepared Bi 2 S 3 /MoS 2 composite. Taking advantage of the high conductivity of 1 T-MoS 2 and the N 2 adsorption and activation advantages of Bi element, an ammonia yield rate of 54.64 µg h −1 mg −1 cat. and a high Faradic efficiency of 58.56 % were obtained. In addition, the active site and the evolution pathway of N 2 reduction were investigated by in-situ infrared spectroscopy measurements and density functional theory (DFT). The in-situ infrared spectroscopy measurement results manifested the presence of the main intermediate transition state during the reduction of N 2 to NH 3 . The calculation results indicated that N 2 had the best adsorption on the introduced P-block element Bi, and the entire NRR reaction process followed an alternating pathway. This study reveals the synergistic effect of P-block elements and transition metal-based electrocatalytic materials on nitrogen reduction to ammonia synthesis .