Unraveling Dynamic Structural Evolution of Single Atom Catalyst via In Situ 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 Cu1/Npyri-C and Cu1/Npyrr-C, in electrochemical CO reduction reaction (CORR), based on a collection of in situ characterizations including in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, in situ X-ray absorption spectroscopy, quasi-in situ electron paramagnetic resonance spectroscopy and in situ ultraviolet-visible spectroscopy, complemented by theoretical calculations. Our findings reveal that the Cu nanoparticle formation rate over Cu1/Npyrr-C is more than 6 times higher than that over Cu1/Npyri-C during the electrochemical CORR. Quasi-in situ electron paramagnetic resonance and in situ UV-vis spectroscopy measurements demonstrate that hydrogen radicals can be in situ produced during electrochemical CORR, which will attack the Cu-N bonds in the Cu-N-C SACs, causing leaching of Cu2+ followed by subsequent reduction to form Cu nanoparticles. Kinetic calculations show that Cu1/Npyri-C displays a better catalytic stability than Cu1/Npyrr-C resulting from the stronger Cu-Npyri 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.