Targeted electron transfer effect of enzyme-like Co-NX catalysts for enhanced C = O hydrogenation

Abstract

In response to increasing energy and environmental concerns, enzyme-like catalysts (ELC) have been widely and artificially created for the conversion of biomass into alternative chemicals. However, the precise construction of desired ELC and the clarification of their conformational relationships still face great challenges. Here, we report a metal nitrogen-doped carbon-based catalyst with enzyme-like properties for targeted adsorption-selective hydrogenation of biomass molecules containing conjugated double bonds. Density-functional theory (DFT) calculations show that nitrogen doping excites electron-directed transfer effects, which promote the polarization and rearrangement of surface charges. This promotes the target adsorption of C = O bonds and reducing the energy barrier for the hydrogenation of RC(CH3) = CHCHO* to RC(CH3) = CHCHOH*. Kinetic calculations indicate that the decrease in the reaction activation energy 67.1 kJ/mol to Ea = 30.86 kJ/mol was due to the doping of the N. This work lays a theoretical foundation for further clarification of the structure–activity relationship of ELC and provides an important paradigm for realizing the conversion of biomass platform molecules into high value-added chemicals.