Catalytic CO₂/CO Reduction: Gas, Aqueous, and Aprotic Phases

Abstract

The catalytic reduction of CO 2 /CO is key to reducing the carbon footprint and producing the chemical building blocks needed for society. In this work, we performed a theoretical investigation of the differences and similarities of the CO 2 /CO catalytic reduction reactions in gas, aqueous solution, and aprotic solution. We demonstrate that the binding energy serves as a good descriptor for the gaseous and aqueous phases and allows catalysts to be categorized by reduction products. The CO* vs O* and CO* vs H* binding energies for these phases give a convenient mapping of catalysts regarding their main product for the CO 2 /CO reduction reactions. However, for the aprotic phase, descriptors alone are insufficient for the mapping. We show that a microkinetic model (including the CO* and H* binding energies) allows spanning and interpreting the reaction space for the aprotic phase.

The importance of a charge transfer descriptor for screening potential CO2 reduction electrocatalysts

“…However, a large part of the metals presented in the figures so far is not actually selectively forming CO during CO 2 RR, but instead formate/formic acid, C 1 - or C 2 - products or even performing the HER. The construction of a kinetic model for all of these processes has been recently attempted including suggestions of descriptors like the *CO, *OH, *C and *H adsorption energies 37 , 38 , 78 , 79 , but these models still lack in their ability to explain all selectivity trends 78 . An interesting outcome from previous studies was the discovered correlation of the adsorption energies of all intermediates in the CO 2 RR process on Cu to C 1 - or C 2 - products with the CO adsorption energy 80 .…”

Insights into Heterogeneous Catalysts under Reaction Conditions by In Situ/Operando Electron Microscopy

“…The catalytic hydrogenation of CO 2 has gained a surge of interest aiming at reducing the carbon footprints and producing the chemical feedstocks. [ 225 ] Various monometallic or multimetallic and metal oxide catalysts have been exploited for CO 2 hydrogenation under reducing gas atmosphere, but the key challenge is the understanding of the detailed dynamic processes of surface sites and morphology of the catalysts under the reaction conditions, which has also attracted increasing interest in using in‐situ TEM techniques to address the challenge.…”

CO2 Electroreduction in Organic Aprotic Solvents: A Mini Review

“…Still, its importance for understanding the mechanism of CO 2 reduction in aprotic solvent-H 2 O solutions is confirmed by recent work, which considers, for example, microkinetic models of interaction of solution components with the cathode surface depending on its nature [74] and influences the nature of the electrode for the distribution of products in anhydrous and water-containing aprotic solvents (Figure 10). In [75], a systematic analysis of the nature influence of the metal cathode on the selectivity and Faradaic efficiencies of CO 2 reduction reaction products in aqueous solutions and nonaqueous aprotic solvents is presented. However, due to the growing interest in aprotic solvent− H 2 O solutions, studies aimed at establishing the dependence of the distribution of CO 2 conversion products on the nature of the cathode are relevant.…”