Correlating binding energies of adsorbed CO and H on model surfaces with CO/H2 selectivity from co-electrolysis of CO2 and H2O over copper–palladium bimetallic catalysts

Abstract

Binding energies of adsorbed CO and H are key descriptors governing the activity and selectivity of the co-electrolysis of CO₂ and H₂O to produce syngas with desired CO/H₂ ratios. Palladium hydride (PdH), which forms in situ at negative overpotentials, has been identified as the active Pd phase for CO₂ reduction to syngas. Herein, binding energies of CO and H are determined using temperature programmed desorption (TPD) of CO and H₂ from Pd(111), PdH/Pd(111), and Cu/PdH/Pd(111) under ultra-high vacuum (UHV) conditions. TPD results reveal that desorption of H₂ from subsurface PdH occurs at 460 K, while desorption from surface PdH is more facile at 320 K. CO desorption temperatures shift 20 K lower on PdH/Pd(111) compared to on Pd(111). The presence of 0.7 ML Cu further increases the desorption temperature of H₂ by 30 K while simultaneously reducing CO desorption temperatures by 70 K. Density functional theory (DFT) calculations show that CO adsorption onto Pd sites is hindered on the 0.7 ML Cu/PdH/Pd(111) surface while the kinetic barrier for H₂ desorption is increased. The trends in the binding energies of CO and H on model surfaces are consistent with electrochemical measurements of CuPd powder catalysts in a membrane electrode assembly (MEA), where H₂ evolution is reduced while CO production is enhanced compared to unmodified Pd catalysts. Overall, the results from model surface studies (TPD and DFT) provide a prediction and explanation for the activity and CO/H₂ ratios observed in electrochemical experiments. This study also demonstrates that CuPd is a promising catalyst with reduced Pd-loading to produce CO-rich syngas.