Rational‐Designed Principles for Electrochemical and Photoelectrochemical Upgrading of CO₂ to Value‐Added Chemicals

Abstract

The chemical transformation of carbon dioxide (CO2) has been considered as a promising strategy to utilize and further upgrade it to value‐added chemicals, aiming at alleviating global warming. In this regard, sustainable driving forces (i.e., electricity and sunlight) have been introduced to convert CO2 into various chemical feedstocks. Electrocatalytic CO2 reduction reaction (CO2RR) can generate carbonaceous molecules (e.g., formate, CO, hydrocarbons, and alcohols) via multiple‐electron transfer. With the assistance of extra light energy, photoelectrocatalysis effectively improve the kinetics of CO2 conversion, which not only decreases the overpotentials for CO2RR but also enhances the lifespan of photo‐induced carriers for the consecutive catalytic process. Recently, rational‐designed catalysts and advanced characterization techniques have emerged in these fields, which make CO2‐to‐chemicals conversion in a clean and highly‐efficient manner. Herein, this review timely and thoroughly discusses the recent advancements in the practical conversion of CO2 through electro‐ and photoelectrocatalytic technologies in the past 5 years. Furthermore, the recent studies of operando analysis and theoretical calculations are highlighted to gain systematic insights into CO2RR. Finally, the challenges and perspectives in the fields of CO2 (photo)electrocatalysis are outlined for their further development.

Powering the World with Solar Fuels from Photoelectrochemical CO2 Reduction: Basic Principles and Recent Advances

“…[28,29] However, despite the tremendous efforts in the development of PEC CRR cells, the performances remain unsatisfactory. [30] Most of the reported PEC CRR photocathodes suffer from low solar-to-chemical conversion efficiency, uncontrolled product selectivity, poor durability, and fierce competition between CRR and hydrogen evolution reaction (HER). [19,31,32] Therefore, the key topic in the PEC CRR still focuses on photoelectrode fabrication and cell design to achieve high energy conversion efficiencies and high selectivities toward target products.…”

Negative Emissions as the New Frontier of Photoelectrochemical CO2 Reduction

“…[21] Photoelectrochemical CO 2 reduction, where carbon-rich solar fuels are produced, has been intensively studied over the last years. [22][23][24][25] The aim here is to capture CO 2 and convert it into an energy carrier by a photoelectrochemical reduction reaction. If not coupled to carbon capture and storage like in BECCS, the captured CO 2 is, however, released again.…”

Recent Progress in Two-Dimensional Materials for Electrocatalytic CO2 Reduction

“…Zhang et al reviewed recent advances on materials development for CO 2 conversion by thermocatalysis, photocatalysis and photothermocatalysis, highlighting the reaction pathways and mechanism on C=O bond activation and intermediate formation [54]. Very recently, they also summarized CO 2 conversion by electro-and photoelectrocatalysis, emphasizing the importance of operando characterization theoretical simulations [55]. Li et al briefly reviewed bimetallic chalcogenides for ECR application in the past five years [56].…”