Unraveling Dynamic Structural Evolution of Single Atom Catalyst Surface-Enhanced Infrared Absorption Spectroscopy.

Metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) have been widely applied in catalyzing electrochemical redox reactions. However, their long-term catalytic stabilities greatly limit their practical applications. This work investigates the dynamic evolution of two model Cu-N-C SACs with different Cu-N coordinations, namely the Cu/N-C and Cu/N-C, in electrochemical CO reduction reaction (CORR), based on a collection of characterizations including attenuated total reflectance surface-enhanced infrared absorption spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy and ultraviolet-visible spectroscopy, complemented by theoretical calculations. Our findings reveal that the Cu nanoparticle formation rate over Cu/N-C is more than 6 times higher than that over Cu/N-C during the electrochemical CORR. electron paramagnetic resonance and UV-vis spectroscopy measurements demonstrate that hydrogen radicals can be produced during electrochemical CORR, which will attack the Cu-N bonds in the Cu-N-C SACs, causing leaching of Cu followed by subsequent reduction to form Cu nanoparticles. Kinetic calculations show that Cu/N-C displays a better catalytic stability than Cu/N-C resulting from the stronger Cu-N bonds. This study deepens the understanding of the deactivation mechanism of SACs in electrochemical reactions and provides guidance for the design of next-generation SACs with enhanced durability.