Recent Advances of the Confinement Effects Boosting Electrochemical CO₂ Reduction

Abstract

Powered by clean and renewable energy, electrocatalytic CO 2 reduction reaction (CO 2 RR) to chemical feedstocks is an effective way to mitigate the greenhouse effect and artificially close the carbon cycle. However, the performance of electrocatalytic CO 2 RR was impeded by the strong thermodynamic stability of CO 2 molecules and the high susceptibility to hydrogen evolution reaction (HER) in aqueous phase systems. Moreover, the numerous reaction intermediates formed at very near potentials lead to poor selectivity of reaction products, further preventing the industrialization of CO 2 RR. Catalysis in confined space can enrich the reaction intermediates to improve their coverage at the active site, increase local pH to inhibit HER, and accelerate the mass transfer rate of reactants/products and subsequently facilitate CO 2 RR performance. Therefore, we summarize the research progress on the application of the confinement effects in the direction of CO 2 RR in theoretical and experimental directions. We first analyzed the mechanism of the confinement effect. Subsequently, the confinement effect was discussed in various forms, which can be characterized as an abnormal catalytic phenomenon due to the relative limitation of the reaction region. In specific, based on the physical structure of the catalyst, the confinement effect was divided in four categories: pore structure confinement, cavity structure confinement, active center confinement, and other confinement methods. Based on these discussions, we also have summarized the prospects and challenges in this field. This review aims to stimulate greater interests for the development of more efficient confined strategy for CO 2 RR in the future.

Nanoconfinement Effects of Yolk–Shell Cu2O Catalyst for Improved C2+ Selectivity and Cu+ Stability in Electrocatalytic CO2 Reduction

“…Nanoconfinement effects have been shown to play an important role in stabilizing Cu + active sites and promoting C–C coupling in the eCO 2 RR. − Nanoconfinement effects in the eCO 2 RR include (i) enrichment of reaction intermediates for enhancing surface coverage of adsorbed species; (ii) increasing local pH to minimize hydrogen evolution reaction (HER); and (iii) accelerating mass transport of reactants and products . For example, Gao et al showed that nanopores Cu 2 O catalysts can confine important carbon intermediates to enhance surface coverage, thereby stabilizing Cu + species .…”