Research Progress of Operando Spectroscopy for Electrocatalytic CO2 Reduction
Electrocatalytic CO2 reduction reaction(CO2RR)driven by renewable electricity is able to convert CO2 to valuable fuels or chemicals,so that it is considered to be a key technique to close the carbon cycle,and to achieve the goals of carbon neutrality.The techno-economic analysis suggests that the production of formic acid(HCOOH)via CO2RR could generate higher value while consuming less energy.Thus,the CO2RR to HCOOH has received extensive attention from academia and industry.P-block metals,such as Sn,Bi,In,and Pb,can be used as electrocatalysts for CO2RR to HCOOH with a high Faradaic efficiency.The understanding of reaction mechanisms and active sites facilitates the development of practicable electrocatalysts and the optimization of the reaction environment.This work summarizes the operando techniques,which have been used to investigating the CO2RR on p-block metals.The operando techniques include Raman spectroscopy,infrared absorption spectroscopy,X-ray absorption spectroscopy,and differential electrochemical mass spectroscopy.Utilizing in-situ observation technology,we can not only analyze fingerprint information such as chemical bonding,molecular structure,and crystallinity on the catalyst surface,but also conduct qualitative or quantitative analysis of gaseous or volatile products resulting from electrochemical reactions with millisecond time resolution during the potential dynamic scanning process.Through the experimental data obtained under in-situ conditions,the catalytic components of CO2RR were identified,and the reaction pathway diagram was constructed,laying the groundwork for the further design of high-performance and high-stability catalysts.Additionally,alloying is one of the main strategies to improve the performance of catalysts.In this paper,the effects of p-block metal alloying on electronic structure,surface properties and catalytic effect are briefly discussed.This review emphasizes the importance of operando spectroscopic technology in the research of p-block metal catalysts,and provides a solid foundation and innovative ideas for the engineering development of CO2RR.
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