Customizing the microenvironment of CO₂ electrocatalysis via three‐phase interface engineering

Abstract

Converting CO2 into high‐value fuels and chemicals by renewable‐electricity‐powered electrochemical CO2 reduction reaction (CRR) is a viable approach toward carbon‐emissions‐neutral processes. Unlike the thermocatalytic hydrogenation of CO2 at the solid‐gas interface, the CRR takes place at the three‐phase gas/solid/liquid interface near the electrode surface in aqueous solution, which leads to major challenges including the limited mass diffusion of CO2 reactant, competitive hydrogen evolution reaction, and poor product selectivity. Here we critically examine the various methods of surface and interface engineering of the electrocatalysts to optimize the microenvironment for CRR, which can address the above issues. The effective modification strategies for the gas transport, electrolyte composition, controlling intermediate states, and catalyst engineering are discussed. The key emphasis is made on the diverse atomic‐precision modifications to increase the local CO2 concentration, lower the energy barriers for CO2 activation, decrease the H2O coverage, and stabilize intermediates to effectively control the catalytic activity and selectivity. The perspectives on the challenges and outlook for the future applications of three‐phase interface engineering for CRR and other gas‐involving electrocatalytic reactions conclude the article.

High‐Entropy Alloy Aerogels: A New Platform for Carbon Dioxide Reduction

“…[1][2][3][4] Plenty of value-added chemicals or fuels such as carbon monoxide (CO), formic acid (HCOOH), methane (CH 4 ), multicarbon hydrocarbons, and oxygenates would be obtained via CO 2 RR by properly designing and regulating the electrocatalysts. [5][6][7][8][9][10][11] Based on the recent technoeconomic analysis, it is the most economically viable to electrochemically convert CO 2 to HCOOH or CO via a twoelectron process. [10,12] As we all know, Pd-based electrocatalysts show excellent catalytic activity in electrochemical CO 2 RR to produce HCOOH or CO, but they still suffer from the drawbacks, including high cost, strong susceptibility to CO poisoning, and hydrogen evolution ability.…”

Research progress of asymmetrically coordinated single-atom catalysts for electrocatalytic reactions

“…57 Due to the satisfactory catalytic performance brought abour by the tunable coordination environment, M-N-C catalysts based on asymmetric active sites have attracted widespread interest. [60][61][62][63] Especially, the catalytic activity and stability in electrochemical systems have been extensively studied, which show great application potential. 25,[64][65][66][67] The ORR has been recognized as the most important catalytic reaction related to next-generation energy conversion and storage owing to its broad applications in fuel cells and metalair batteries.…”

“…Due to the satisfactory catalytic performance brought abour by the tunable coordination environment, M–N–C catalysts based on asymmetric active sites have attracted widespread interest. 60–63 Especially, the catalytic activity and stability in electrochemical systems have been extensively studied, which show great application potential. 25,64–67…”

Magnetic Field‐Assisted Construction and Enhancement of Electrocatalysts

“…CO 2 is one of the major factors related to global warming, and the CO 2 RR can provide a new strategy for the energy crisis by turning CO 2 into useful chemicals and fuels [136–139] . The electrocatalytic CO 2 RR can convert CO 2 into a carbon‐based fuel [140–142] . Nevertheless, some obstacles exist, such as low reaction selectivity, energy efficiency, and total conversion, which limit the wide application of the CO 2 RR [6,143,144] …”