Constructing asymmetric double-atomic sites for synergistic catalysis of electrochemical CO2 reduction

Abstract

Elucidating the synergistic catalytic mechanism between multiple active centers is of great significance for heterogeneous catalysis; however, finding the corresponding experimental evidence remains challenging owing to the complexity of catalyst structures and interface environment. Here we construct an asymmetric TeN₂–CuN₃ double-atomic site catalyst, which is analyzed via full-range synchrotron pair distribution function. In electrochemical CO₂ reduction, the catalyst features a synergistic mechanism with the double-atomic site activating two key molecules: operando spectroscopy confirms that the Te center activates CO₂, and the Cu center helps to dissociate H₂O. The experimental and theoretical results reveal that the TeN₂–CuN₃ could cooperatively lower the energy barriers for the rate-determining step, promoting proton transfer kinetics. Therefore, the TeN₂–CuN₃ displays a broad potential range with high CO selectivity, improved kinetics and good stability. This work presents synthesis and characterization strategies for double-atomic site catalysts, and experimentally unveils the underpinning mechanism of synergistic catalysis.

Elucidating the synergistic catalytic mechanism involving multiple active centers is of great significance for heterogeneous catalysis. Here the authors construct an asymmetric TeN₂–CuN₃ double atomic site catalyst featuring synergistic CO₂ activation and H₂O dissociation for CO₂ electroreduction.