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Carbon dioxide (CO2) reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. CO2 partial pressures (PCO2) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at −0.7, −0.9, and −1.1 VRHE. At a given applied overpotential the total current density increased with increasing PCO2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO2 to carbon monoxide (CO) was found to have first-order behavior with respect to PCO2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H2) evolution reaction decreased with increasing PCO2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on PCO2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32∘C at −0.7, −0.9, and −1.1 VRHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.