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[Display omitted] • The submitted work is of great interest for the Journal Applied Energy due to its peculiar theme, the electrochemical CO 2 reduction, and for its approach in the investigation. Indeed, a complete ab initio modelling guided the experimental synthesis and testing of a molecular electrocatalyst which shows great performances for the CO2RR. • This work elucidate the possibility to activate the CO 2 through organic molecules and, moreover, shows the feasibility of this approach to be completely integrated inside a TRL 3–4 electrolysis cell. The electrochemical reduction of CO 2 to value-added products is hindered by its thermodynamic stability and by the large energy required to chemically activate the molecule. With this respect, forcing CO 2 in a non-linear geometry would induce an internal electron charge rearrangement which would facilitate further electrochemical transformations. In this work, we achieved this goal through the design of a dual function electro-organocatalyst, which exploits the ability of the imidazolate (Im-) lone pair to bind CO 2 via nucleophilic attack and then electrochemically reduce it. To give structural stability to the Im- based catalyst, the imidazoles species are incorporated into a solid structure, namely ZIF-8. Once activated by the organic Im- ligand, CO 2 is electrochemically reduced to CO when a bias is applied to ZIF-8. The catalyst proposed in our study was first devised by computer aided design based on Density functional Theory simulations and then realized in laboratory. Our results demonstrate that ZIF-8 supported on conductive CNTs presents surface Im- active sites which convert CO 2 into CO with a high faradaic efficiency (70.4 %) at −1.2 V vs reversible hydrogen electrode, by combining chemical activation with electrochemical catalysis. [ABSTRACT FROM AUTHOR]

Catalysts play a vital role in electrochemical reduction of CO 2 to valuable products. Only based on effective catalysts, CO 2 electrolysis process can be advanced toward industrial application. In this work, we present a Sb-Cu 2 O material synthesized via one-pot microwave-assisted solvothermal route. The Sb-Cu 2 O derived bimetallic catalyst achieves a highest CO selectivity of 96% and good CO partial current densities of 37.3 and 74.0 mA cm−2 at − 0.8 and − 1.2 V vs. reversible hydrogen electrode (RHE), respectively. The Sb-Cu catalyst also displays good stability at current densities ranging from 5.6 to 100 mA cm−2. Additionally, for the first time, a complete theoretical study reveals the critical roles of Sb in selective CO 2 conversion to CO on this bimetallic material, including stabilizing stepped Cu surfaces selective for the reaction, lowering energy barriers for the formation of key intermediate and favouring CO desorption. [Display omitted] • Sb-Cu 2 O material is synthesized via a one-pot microwave-assisted route. • Sb is uniformly distributed and promotes the formation of nanocrystalline Cu 2 O. • The derived Sb-Cu shows outstanding performance for the CO 2 RR to CO. • Enhancing local CO 2 concentration is demonstrated to boost CO formation rate. • Theoretical study reveals the critical roles of Sb in CO formation on Sb-Cu. [ABSTRACT FROM AUTHOR]