Gold is one of the most selective catalysts for the electrochemical reduction of CO2 (CO2RR) to CO. However, the concomitant hydrogen evolution reaction (HER) remains unavoidable under aqueous conditions. In this work, a rotating ring disk electrode (RRDE) setup has been developed to study quantitatively the role of mass transport in the competition between these two reactions on the Au surface in 0.1 M bicarbonate electrolyte. Interestingly, while the faradaic selectivity for CO formation was found to increase with enhanced mass transport (from 67% to 83%), this effect is not due to an enhancement of the CO2RR rate. Remarkably, the inhibition of the competing HER from water reduction with increasing disk rotation rate is responsible for the enhanced CO2RR selectivity. This can be explained by the observation that, on the Au electrode, water reduction improves with more alkaline pH. As a result, the decrease in the local alkalinity near the electrode surface with enhanced mass transport suppresses HER due to the water reduction. Our study shows that controlling the local pH by mass transport conditions can tune the HER rate, in turn regulating the CO2RR and HER competition in the general operating potential window for CO2RR (−0.4 to −1 V vs RHE).

In this article we investigate the electrochemical reduction of CO2 at gold electrodes under mildly acidic conditions. Differential electrochemical mass spectroscopy (DEMS) is used to quantify the amounts of formed hydrogen and carbon monoxide as well as the consumed amount of CO2. We investigate how the Faradaic efficiency of CO formation is affected by the CO2 partial pressure (0.1–0.5 bar) and the proton concentration (1–0.25 mM). Increasing the former enhances the rate of CO2 reduction and suppresses hydrogen evolution from proton reduction, leading to Faradaic efficiencies close to 100%. Hydrogen evolution is suppressed by CO2 reduction as all protons at the electrode surfaces are used to support the formation of water (CO2 + 2H+ + 2e– → CO + H2O). Under conditions of slow mass transport, this leaves no protons to support hydrogen evolution. On the basis of our results, we derive a general design principle for acid CO2 electrolyzers to suppress hydrogen evolution from proton reduction: the rate of CO/OH– formation must be high enough to match/compensate the mass transfer of protons to the electrode surface.

In this work we study the role of alkali metal cation concentration and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alkaline pH (pH 11), increasing the cation concentration significantly enhances the HER activity on Au electrodes (with ar eaction order % 0.5). Based on these results we suggest that cations playac entral role in stabilizing the transition state of the rate-determining Volmer step by favorably interacting with the dissociating water molecule (*H-OH dÀ -cat + ). Moreover,weshowthat increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near-surface cation concentration. Interestingly,atoo high near-surface cation concentration (at high pH and high cation concentration) leads to al owering of the HER activity,w hich we ascribe to ablockage of the surface by near-surface cations.

The electrochemical reduction of CO 2 aims to be a central technology to store excess electricity generated by wind and solar energy. However, the reaction is hindered by the competition with the hydrogen evolution reaction. In this paper, we present a detailed quantitative study of the Faradaic efficiency (FE) to CO on a gold electrode under well-defined mass-transport conditions using rotating ring-disk electrode voltammetry. Varying the concentration of the bicarbonate and the electrolyte cation employing different rotation rates, we map out how these parameters affect the FE(CO). We identify two different potential regimes for the electrolyte effects, characterized by a different dependence on the cation and bicarbonate concentrations. For hydrogen evolution, we analyze the nature of the proton donor for an increasingly negative potential, showing how it changes from carbonic acid to bicarbonate and to water. Our study gives detailed insights into the role of electrolyte composition and mass transport, and helps defining optimized electrolyte conditions for a high FE(CO).

Conspectus The electrochemical reduction of CO 2 (CO2RR) constitutes an alternative to fossil fuel-based technologies for the production of fuels and commodity chemicals. Yet the application of CO2RR electrolyzers is hampered by low energy and Faradaic efficiencies. Concomitant electrochemical reactions, like hydrogen evolution (HER), lower the selectivity, while the conversion of CO 2 into (bi)carbonate through solution acid–base reactions induces an additional concentration overpotential. During CO2RR in aqueous media, the local pH becomes more alkaline than the bulk causing an additional consumption of CO 2 by the homogeneous reactions. The latter effect, in combination with the low solubility of CO 2 in aqueous electrolytes (33 mM), leads to a significant depletion in CO 2 concentration at the electrode surface. The nature of the electrolyte, in terms of pH and cation identity, has recently emerged as an important factor to tune both the energy and Faradaic efficiency. In this Account, we summarize the recent advances in understanding electrolyte effects on CO2RR to CO in aqueous solutions, which is the first, and crucial, step to further reduced products. To compare literature findings in a meaningful way, we focus on results reported under well-defined mass transport conditions and using online analytical techniques. The discussion covers the molecular-level understanding of the effects of the proton donor, in terms of the suppression of the CO 2 gradient vs enhancement of HER at a given mass transport rate and of the cation, which is crucial in enabling both CO2RR and HER. These mechanistic insights are then translated into possible implications for industrially relevant cell geometries and current densities.