Synergistic promotion of N2 activation and water dissociation on Pt single atom and nanocluster modified FeVO4 for photocatalytic ammonia production

Photocatalytic nitrogen reduction reaction (PNRR) is an important tool for advancing carbon neutrality. However, effective N 2 adsorption and activation, and the subsequent dissociation of water, remain major challenges in the PNRR. In this work, FeVO 4 -based catalysts co-modified with Pt nanoclusters (NCs) and single atoms (SAs) (Pt/FeVO 4 ) are synthesized and applied in the PNRR. The synthesized Pt/FeVO 4 catalyst achieves a NH 3 production rate of 35.14 μmol·g −1 ·h −1 , 3.2 times higher than that of the original FeVO 4 , and the photocatalytic nitrogen fixation performance remains at a high level of 80% after four cycles. Density functional theory (DFT) calculations and various characterization experiments results show that the Pt NCs in the Pt/FeVO 4 catalysts can effectively promote the adsorption and dissociation of water, and the active hydrogen (*H) generated from the dissociation of water can migrate to the neighboring Pt SAs through the spillover effect. The local electron concentration around Fe is altered by the Pt SAs, which enables the activation and hydrogenation of N 2 , and thus enhances the efficiency of PNRR. This research emphasizes the essential effects of the dual active sites of NCs and SAs with hydrogen spillover in PNRR, which provides novel concepts for the design of highly efficient catalysts.