The strong effect of the electrolyte cation on the activity and selectivity of the CO2 reduction reaction (CO2RR) can only be understood and controlled if the cation's effect on the interfacial potential distribution is known. Using CO (the key intermediate in the CO2RR) adsorbed on Pt as a probe molecule, and combining IR spectroscopy, capacitance measurements and ab initio molecular dynamics, we show that the cation size determines the location of the outer Helmholtz plane, whereby smaller cations increase not just the polarisation but, most importantly, the polarizability of adsorbed CO (COad) and the accumulation of electronic density on the oxygen atom of COad. This strongly affects its adsorption energy, the degree of hydrogen bonding of interfacial water to COad and the degree of polarisation of water molecules in the cation's solvation shell, all of which can deeply affect the subsequent steps of the CO2RR.
Understanding the structures of electrochemical interfaces at the atomic level is key to developing efficient electrochemical cells for energy storage and conversion. Spectroscopic techniques have been widely used to investigate the structures and vibrational properties of the interfaces. The interpretation of these spectra is however not straightforward. In this work, density functional theory based molecular dynamics simulations were performed to study the vibrational properties of the Pt(111)- and Au(111)-water interfaces. It was found that the specific adsorption of some surface water on Pt(111) leads to a partial charge transfer to the metal, and strong hydrogen bonding with neighbouring water molecules, which resolves the interpretation of the elusive O-H stretching peak at around 3000 cm-1 observed in some experiments.
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