Promoting CuO/Cu(OH)2 for electrocatalytic reduction of CO2 to HCOOH: The study on pyridine-modified surface active sites

•Surface catalytic active site modification of Cu-based catalysts using pyridine to improve the selectivity of electrocatalytic CO2 reduction to HCOOH.•Experimental results showed that the pyridine-modified material surface significantly increased the CO2 adsorption reaction rate in the electrocatalytic CO2 process.•Theoretical calculations have demonstrated that the CuO/Cu(OH)2 catalyst synthesized by pyridine significantly reduces the reaction energy barrier for the electrocatalytic reduction of CO2 to HCOOH.•Realization of molecularly modified Cu-based catalysts that synergistically catalyze CO2 to HCOOH expands the application of organic molecules in Cu-based catalysts.