Speaker
Description
Electrochemical carbon dioxide reduction (CO₂RR) is a promising strategy for converting CO₂ into value-added fuels and chemical feedstocks while contributing to carbon utilisation and the development of sustainable energy technologies. Copper is uniquely critical to this process as the only pristine metal catalyst capable of producing deep reduction products, such as hydrocarbons and oxygenates. However, its efficiency and product selectivity depend strongly on catalyst surface properties and the stability of reaction intermediates.. Adsorption energy is a key descriptor of catalytic behaviour because it quantifies the strength of interaction between an adsorbed species and the catalyst surface, influencing intermediate stabilisation, subsequent reaction steps and potential reaction pathways. This study employs density functional theory (DFT), and the PBE exchange correlation functional incorporating the Grimme dispersion correction, as implemented in the CASTEP code.
The calculated adsorption energies span −6.72 to −0.24 eV, demonstrating substantial variation in adsorbate–surface interactions. Atomic carbon exhibits the strongest adsorption (−6.72 eV), whereas CO₂ is weakly adsorbed (−0.24 eV). Other molecular products, including CH₄, CO, HCOOH, CH₃OH and C₂H₄, also exhibit relatively weak adsorption, while several reaction intermediates, including C, CH, CH2, CH3, HCOO, COOH, CH2O, CH₃O, CHOH, CH₂OH, CHO, OCHO, OCCO, COH, O, H and OH, bind more strongly to Cu (111). These contrasting adsorption trends highlight the balance between intermediate stabilisation and product desorption in understanding competing CO₂RR pathways. These results establish an adsorption-energy baseline for pristine Cu (111), providing a basis for evaluating how transition-metal alloying may modify intermediate binding and potentially influence catalytic activity and product selectivity.