Theoretical insight into the selectivities of copper-catalyzing heterogeneous reduction of carbon dioxide

Abstract

The chemical reduction of carbon dioxide (CO 2 ) has always drawn intensive attention as it can not only remove CO 2 which is the primary greenhouse gas but also produce useful fuels. Industrial synthesis of methanol utilizing copper-based catalysts is a commonly used process for CO 2 hydrogenation. Despite extensive efforts on improving its reaction mechanism by identifying the active sites and optimizing the operating temperature and pressure, it is still remains completely unveiled. The selectivities of CO 2 electroreduction at copper electrode could mainly be towards carbon monoxide (CO), formic acid (HCOOH), methane (CH 4 ) or ethylene (C 2 H 4 ), which depends on the chemical potentials of hydrogen controlled by the applied potential. Interestingly, methanol could hardly be produced electrochemically despite utilizing metallic copper as catalysts in both processes. Moreover, the mechanistic researches have also been performed aiming to achieve the higher selectivity towards more desirable higher hydrocarbons. In this work, we review the present proposals of reaction mechanisms of copper catalyzing CO 2 reduction in industrial methanol synthesis and electrochemical environment in terms of density functional theory (DFT) calculations, respectively. In addition, the influences of the simulation methods of solvation and electrochemical model at liquid-solid interface on the selectivity are discussed and compared. methanol synthesis, electrocatalytic reduction of CO 2 , CO 2 hydrogenation, selectivity

Insight into CO Activation over Cu(100) under Electrochemical Conditions

“…In addition, we use a dynamic water/metal interface model with many explicit water molecules, which is more accurate in describing the water effect than the vacuum/metal interface model with several static water molecules. [19,20,52] However, for the favored pathway of the formation of COH ads and that of CHO ads formation, the current data cannot confirm whether it is one of the two contributes the most to the whole catalytic process in reality, or they are both reactive. It depends strongly on the subsequent reactions of the two intermediates and further investigates on the reactions are underway.…”

Formulating the bonding contribution equation in heterogeneous catalysis: a quantitative description between the surface structure and adsorption energy

“…To answer this question, we examined the CO adsorption energies on the one-atom substituted Pt alloy surfaces. This system was chosen due to the following reasons: Firstly, the adsorption of CO is very important in many reactions such as CO oxidation 37,40 , dry reforming 38 , CO 2 reduction 41 , and methane oxidation 42 . Secondly, CO adsorbs on the top site of Pt(111), which can also test the generality of the BCCF.…”

A rational catalyst design of CO oxidation using the bonding contribution equation

“…In the last few decades, many approaches were proposed to solve this problem, such as solar cell 2 , photocatalysis 3 , electrolyser 4,5 , and fuel cell 6 . However, most of these systems are limited by the low activities or high costs of catalytic materials.…”