Recent advances in copper chalcogenides for CO2 electroreduction.

Transforming CO2 through electrochemical methods into useful chemicals and energy sources may contribute to solutions for global energy and ecological challenges. Copper chalcogenides exhibit unique properties that make them potential catalysts for CO2 electroreduction. In this review, we provide an overview and comment on the latest advances made in the synthesis, characterization, and performance of copper chalcogenide materials for CO2 electroreduction, focusing on the work of the last five years. Strategies to boost their performance can be classified in three groups: (1) structural and compositional tuning, (2) leveraging on heterostructures and hybrid materials, and (3) optimizing size and morphology. Despite overall progress, concerns about selectivity and stability persist and require further investigation. This review outlines future directions for developing the next-generation of copper chalcogenide materials, emphasizing on rational design and advanced characterization techniques for efficient and selective CO2 electroreduction.

Integration of aprotic CO2 reduction to oxalate at a Pb catalyst into a GDE flow cell configuration.

Electrochemical CO2 reduction to oxalic acid in aprotic solvents could be a potential pathway to produce carbon-neutral oxalic acid. One of the challenges in aprotic CO2 reduction are the limited achievable current densities under standard conditions, despite the increased CO2 solubility compared to aqueous applications. The application of aprotic solvents can reduce CO2 rather selectively to oxalate, and faradaic efficiencies (FEs) of up to 80% were achieved in this study with a Pb catalyst in acetonitrile, the FE being mainly dictated by the local CO2 concentration at the electrode. This process was integrated into a flow cell employing a two-layered carbon-free lead (Pb) gas diffusion electrode (GDE) and a sacrificial zinc (Zn) anode. With the application of this GDE the applicable current densities could be improved up to a current density of j = 80 mA cm-2 at a FE(oxalate) = 53%, which is within the range of the highest j reported in the literature. In addition, we provide an explanation for the deactivation mechanism of metal catalysts observed in the aprotic CO2 reduction literature. The deactivation is not related to a mass transport limitation but to cathodic corrosion observed at highly negative potential when employing quaternary ammonium supporting electrolyte cations, promoting catalyst leaching.

Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO2.

Different electrolytes applied in the aqueous electrocatalytic CO2 reduction reaction (CO2RR) considerably influence the catalyst performance. Their concentration, species, buffer capacity, and pH value influence the local reaction conditions and impact the product distribution of the electrocatalyst. Relevant properties of prospective solvents include their basicity, CO2 solubility, conductivity, and toxicity, which affect the CO2RR and the applicability of the solvents. The complexity of an electrochemical system impedes the direct correlation between a single parameter and cell performance indicators such as the Faradaic efficiency; thus the effects of different electrolytes are often not fully comprehended. For an industrial application, a deeper understanding of the effects described in this review can help with the prediction of performance, as well as the development of scalable electrolyzers. In this review, the application of supporting electrolytes and different solvents in the CO2RR reported in the literature are summarized and discussed.