The specific identity of electrolyte cations has many implications in various electrochemical reactions. However, the exact mechanism by which cations affect electrochemical reactions is not agreed upon in the literature. In this report, we investigate the role of cations during the electrochemical reduction of CO2 by chelating the cations with cryptands, to change the interaction of the cations with the components of the electric double layer. As previously reported we do see the apparent suppression of CO2 reduction in the absence of cations. However, using in situ-SEIRAS we see that CO2 reduction does indeed take place albeit at very reduced scales. We also observe that cations play a role in tuning the absorption strengths of not only CO2 as has been speculated, but also that of reaction products such as CO.

Electrochemical CO2 electrolysis to produce hydrocarbon fuels or material feedstocks offers a renewable alternative to fossilized carbon sources. Gas-diffusion electrodes (GDEs), composed of solid electrocatalysts on porous supports positioned near the interface of a conducting electrolyte and CO2 gas, have been able to demonstrate the substantial current densities needed for future commercialization. These higher reaction rates have often been ascribed to the presence of a three-phase interface, where solid, liquid, and gas provide electrons, water, and CO2, respectively. Conversely, mechanistic work on electrochemical reactions implicates a fully two-phase reaction interface, where gas molecules reach the electrocatalyst's surface by dissolution and diffusion through the electrolyte. Because the discrepancy between an atomistic three-phase versus two-phase reaction has substantial implications for the design of catalysts, gas-diffusion layers, and cell architectures, the nuances of nomenclatures and governing phenomena surrounding the three-phase-region require clarification. Here we outline the macro, micro, and atomistic phenomena occurring within a gas-diffusion electrode to provide a focused discussion on the architecture of the often-discussed three-phase region for CO2 electrolysis. From this information, we comment on the outlook for the broader CO2 electroreduction GDE cell architecture.

Electrochemical CO₂ reduction has received an increased amount of interest in the last decade as a promising avenue for storing renewable electricity in chemical bonds. Despite considerable progress on catalyst performance using nanostructured electrodes, the sensitivity of the reaction to process conditions has led to debate on the origin of the activity and high selectivity. Additionally, this raises questions on the transferability of the performance and knowledge to other electrochemical systems. At its core, the discrepancy is primarily a result of the highly porous nature of nanostructured electrodes, which are vulnerable to both mass transport effects and structural changes during the electrolysis. Both effects are not straightforward to identify and difficult to decouple. Despite the susceptibility of nanostructured electrodes to mass transfer limitations, we highlight that nanostructured silver electrodes exhibit considerably higher activity when normalized to the electrochemically active surface in contrast to gold and copper electrodes. Alongside, we provide a discussion on how active surface area and thickness of the catalytic layer itself can influence the onset potential, selectivity, stability, activity and mass transfer inside and outside of the three dimensional catalyst layer. Key parameters and potential solutions are highlighted to decouple mass transfer effects from the measured activity in electrochemical cells utilizing CO₂ saturated aqueous solutions.

Electrocatalysis of carbon dioxide can provide a valuable pathway towards the sustainable production of chemicals and fuels from renewable electricity sources. One of the main challenges to enable this technology is to find suitable electrodes that can act as efficient, stable and selective CO₂ reduction catalysts. Modified silver catalysts and in particular, catalysts electrochemically derived from silver-oxides, have shown great promise in this regard. Here, we use operando EXAFS analysis to study the differences in surface composition between a pure silver film and oxide-derived silver catalysts-a nanostructured catalyst with improved CO₂ reduction performance. The EXAFS analysis reveals the presence of trace amounts of oxygen in the oxide-derived silver samples, with the measured oxygen content correlating well with experimental studies showing an increase in CO₂ reduction reactivity towards carbon monoxide. The selectivity towards CO production also partially scales with the increased surface area, showing that the morphology, local composition and electronic structure all play important roles in the improved activity and selectivity of oxide-derived silver electrocatalysts. Earlier studies based on X-ray photoelectron spectroscopy (XPS) were not able to identify this oxygen, most likely because in ultra-high vacuum conditions, silver can self-reduce to Ag⁰, removing existing oxygen species. This operando EXAFS study shows the potential for in situ and operando techniques to probe catalyst surfaces during electrolysis and aid in the overall understanding of electrochemical systems.

CO ₂ electroreduction is a promising technology to produce chemicals and fuels from renewable resources. Polycrystalline and nanostructured metals have been tested extensively while less effort has been spent on understanding the performance of bimetallic alloys. In this work, we study compositionally variant, smooth Au-Pd thin film alloys to discard any morphological or mesoscopic effect on the electrocatalytic performance. We find that the onset potential of CO formation exhibits a strong dependence on the Pd content of the alloys. Strikingly, palladium, a hydrogen evolution catalyst with reasonable exchange current density, suppresses hydrogen evolution when alloyed with gold in the presence of CO ₂ . Cyclic voltammetry, in situ surface enhanced infrared absorption spectroscopy, and potential-dependent online product analysis strongly suggest that by alloying Au with Pd a significant increase in the surface coverage of adsorbed CO occurs with increasing Pd content at low overpotentials (e.g., approximately -0.35 V vs RHE). Such an increase in CO coverage suppresses H ₂ evolution due to the lack of vacant active sites. Moreover, the overall increase in the binding energy with the CO ₂ intermediates gained with the addition of Pd increases the CO production at low overpotentials, where polycrystalline Au suffers from poor CO ₂ adsorption and poor selectivity for CO production. These results show that promising CO ₂ reduction electrode materials (e.g., Au) can be alloyed not only to tune the catalyst's activity but also to deliberately decrease the availability of surface sites for competitive H ₂ evolution.

Author Divya Bohra was mistakenly not marked as co-corresponding author in the author list. This has been corrected in the author list shown above. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO₂ER). Herein, we study the role of the formate (HCOO⁻) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO₂ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO⁻ and H₂ production and a higher selectivity towards CO.