Electrosynthesis of Furanic Biofuel: The Effect of Electrode Surface Orientation and Irregularity on Reaction Pathways

Electrocatalytic conversion of biomass-derived furfural to 2-methylfuran holds significant industrial relevance due to the utility of 2-methylfuran as a biofuel candidate and a chemical intermediate. This conversion involves complex reaction pathways that can be optimized using different catalytic surfaces. In this study, we investigated the electrocatalytic conversion of furfural to 2-methylfuran and furfuryl alcohol on copper surfaces with varying crystallographic orientations and roughnesses, utilizing a combination of experimental findings and density functional theory (DFT) calculations. Theoretical DFT calculations, conducted on Cu surfaces such as Cu(111), Cu(200), and stepped Cu10/Cu(111), reveal distinct reaction pathways involved during the conversion. The surface irregularities on the simulated Cu10/Cu(111) surface demonstrated better performance in terms of lower activation energies, greater thermodynamic preference, and enhanced adsorption of intermediates. This variation underscores the critical role of the surface structure in determining the efficiency and selectivity of the electrocatalytic processes. By combining experimental observations with DFT insights, we elucidate the underlying mechanisms governing these conversions, providing valuable guidance for optimizing electrocatalytic processes in industrial applications.