Mesoporous Cu foams formed by a template-assisted electrodeposition process have been identified as CO2 electrocatalysts that are highly selective toward C2 product formation (C2H4 and C2H6) with C2 efficiencies (FEC2) reaching 55%. The partial current of C2 product formation was found to be higher than that of the (parasitic) hydrogen evolution reaction (HER) at any potential studied (−0.4 to −1.0 vs the reversible hydrogen electrode). Moreover, formate production could largely be suppressed at any applied potential down to efficiencies (FEformate) of ≤6%. A key point of the Cu foam catalyst activation is the in operando reduction of a Cu2O phase, thereby creating a large abundance of surface sites active for C–C coupling. The cuprous oxide phase has been formed after the Cu electrodeposition step by exposing the large-surface area catalyst to air at room temperature. The superior selectivity of the Cu foam catalyst studied herein originates from a combination of two effects, the availability of specific surface sites for C–C coupling [dominant (100) surface texture] and the temporal trapping of gaseous intermediates (in particular CO and C2H4) inside the mesoporous catalyst material during CO2 electrolysis. A systematic CO2 electrolysis study reveals a strong dependence of the C2 efficiencies on the particular surface pore size of the mesoporous Cu catalysts with a maximal FEC2 between 50 and 100 μm pore diameters.
A major concern of electrocatalysis research is to assess the structural and chemical changes that a catalyst may itself undergo in the course of the catalyzed process. These changes can influence not only the activity of the studied catalyst but also its selectivity toward the formation of a certain product. An illustrative example is the electroreduction of carbon dioxide on tin oxide nanoparticles, where under the operating conditions of the electrolysis (that is, at cathodic potentials), the catalyst undergoes structural changes which, in an extreme case, involve its reduction to metallic tin. This results in a decreased Faradaic efficiency (FE) for the production of formate (HCOO–) that is otherwise the main product of CO2 reduction on SnO x surfaces. In this study, we utilized potential- and time-dependent in operando Raman spectroscopy in order to monitor the oxidation state changes of SnO2 that accompany CO2 reduction. Investigations were carried out at different alkaline pH levels, and a strong correlation between the oxidation state of the surface and the FE of HCOO– formation was found. At moderately cathodic potentials, SnO2 exhibits a high FE for the production of formate, while at very negative potentials the oxide is reduced to metallic Sn, and the efficiency of formate production is significantly decreased. Interestingly, the highest FE of formate production is measured at potentials where SnO2 is thermodynamically unstable; however, its reduction is kinetically hindered.
Ag-foam catalysts have been developed for the electrochemical CO2 reduction reaction (ec-CO2RR) based on a concerted additive- and template-assisted metal-deposition process. In aqueous media (CO2-saturated 0.5 M KHCO3 electrolyte), these Ag foams show high activity and selectivity toward CO production at low and moderate over-potentials. Faradaic efficiencies for CO (FECO) never fell below 90% within an extremely broad potential window of ∼900 mV, starting at −0.3 V and reaching up to −1.2 V versus a reversible hydrogen electrode (RHE). An increased adsorption energy of CO on the Ag foam is discussed as the origin of the efficient suppression of the competing hydrogen-evolution reaction (HER) in this potential range. At potentials of <−1.1 V versus RHE, the FEH2 values significantly increase at the expense of FECO. Superimposed on this anti-correlated change in the CO and H2 efficiencies is the rise in the CH4 efficiency to the maximum of FECH4 = 51% at −1.5 V versus RHE. As a minor byproduct, even C–C-coupled ethylene could be detected reaching a maximum Faradaic efficiency of FEC2H4 = 8.6% at −1.5 V versus RHE. Extended ec-CO2RR reveals the extremely high long-term stability of the Ag foam catalysts, with CO efficiencies never falling below 90% for more than 70 h of electrolysis at −0.8 V versus RHE (potential regime of predominant CO production). However, a more-rapid degradation is observed for extended ec-CO2RR at −1.5 V versus RHE (potential regime of predominant CH4 production), in which the FECH4 values drop to 32% within 5 h of electrolysis. The degradation behavior of the Ag-foam catalyst is correlated to time-resolved identical-location scanning electron microscopy investigations that show severe morphological changes, particularly at higher applied over-potentials (current densities) at −1.5 V versus RHE. This study reports on the first ec-CO2RR catalyst beyond copper that demonstrates a remarkably high selectivity toward hydrocarbon formation, reaching a maximum of ∼60% at −1.5 V versus RHE. The experimental observations presented herein strongly suggest that this newly designed Ag-foam catalyst shares, in part, mechanistic features with common Cu catalysts in terms of ec-CO2RR product selectivity and catalyst degradation behavior.
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