Photo-induced synthesis of heteronuclear dual-atom catalysts

Abstract

Dual-atom catalysts (DACs) have garnered significant interest due to their high atom utilization and synergistic catalysis. However, there is no universal synthetic method to precisely synthesize DACs. Here we propose a ‘navigation and positioning’ strategy for precise and scalable synthesis of a series of heteronuclear M1M2 DACs on polymeric carbon nitride (PCN). The primary nucleation sites, M1-PCN, were created by calcining urea and M1 metal salts. Upon light irradiation, the accumulated photoelectrons at the M1 site can navigate and position the second metal ion, M2, close to the M1 site, enabling the precise synthesis of heteronuclear DACs. Density functional theory calculations demonstrate that the hybridization of the Zn s orbital (M1) and Ru d orbital (M2) benefits the formation of stable ZnRu DAC on PCN. The ZnRu DACs were then investigated for photocatalytic hydrogen evolution. It was shown that the Ru site reduced H+ to H* and the Zn site acted as the H* desorption site, thus synergistically boosting activity. A navigation and positioning strategy is proposed for the scalable synthesis of a series of heteronuclear dual-atom catalysts via irradiation. It is shown that photo-induced electron accumulation at the M1 site can attract an M2 metal cation, forming heteronuclear dimers with high purity.