Microstructure Induced Thermodynamic and Kinetic Modulation to Enhance CO2 Photothermal Reduction: A Case of Atomic-Scale Dispersed Co-N Species Anchored Co@C Hybrid

The transformation of CO2 into a single product is a critical scientific challenge due to the difficulty associated with targeted activation and conversion of CO2 by heterogeneous catalysts. Herein, we present an atomic-scale dispersed Co-N species anchored Co@C hybrid structure (entitled as Co@CoN&C) that regulates catalytic properties in thermodynamic and kinetic processes to achieve active and highly-selective CO yield in the photothermal CO2 reduction. An optimal sample delivers the maximum yield rate of 132 mmol gcat.-1 h-1 and the remarkable CO selectivity (91.1%), while the undesirable methanation activity, compared to typical of Co nanoparticles (NPs), was suppressed. Mechanism study suggests that the strong photon-matter interaction over graphitic-carbon and Co NPs can enhance the light-to-heat conversion efficiency and thus induce the high work temperature, which is thermodynamically beneficial for CO2 activation and subsequently promoted the catalytic activity. Furthermore, the carbon layers im...