Direct observation of bicarbonate and water reduction on gold: understanding the potential dependent proton source during hydrogen evolution.

ABSTRACT

The electrochemical conversion of CO2 represents a promising way to simultaneously reduce CO2 emissions and store chemical energy. However, the competition between CO2 reduction (CO2R) and the H2 evolution reaction (HER) hinders the efficient conversion of CO2 in aqueous solution. In water, CO2 is in dynamic equilibrium with H2CO3, HCO3 -, and CO3 2-. While CO2 and its associated carbonate species represent carbon sources for CO2R, recent studies by Koper and co-workers indicate that H2CO3 and HCO3 - also act as proton sources during HER (J. Am. Chem. Soc. 2020, 142, 4154-4161, ACS Catal. 2021, 11, 4936-4945, J. Catal. 2022, 405, 346-354), which can favorably compete with water at certain potentials. However, accurately distinguishing between competing reaction mechanisms as a function of potential requires direct observation of the non-equilibrium product distribution present at the electrode/electrolyte interface. In this study, we employ vibrational sum frequency generation (VSFG) spectroscopy to directly probe the interfacial species produced during competing HER/CO2R on Au electrodes. The vibrational spectra at the Ar-purged Na2SO4 solution/Au interface, where only HER occurs, show a strong peak around 3650 cm-1, which appears at the HER onset potential and is assigned to OH-. Notably, this species is absent for the CO2-purged Na2SO4 solution/gold interface; instead, a peak around 3400 cm-1 appears at catalytic potential, which is assigned to CO3 2- in the electrochemical double layer. These spectral reporters allow us to differentiate between HER mechanisms based on water reduction (OH- product) and HCO3 - reduction (CO3 2- product). Monitoring the relative intensities of these features as a function of potential in NaHCO3 electrolyte reveals that the proton donor switches from HCO3 - at low overpotential to H2O at higher overpotential. This work represents the first direct detection of OH- on a metal electrode produced during HER and provides important insights into the surface reactions that mediate selectivity between HER and CO2R in aqueous solution.