电催化CO_(2)还原过程中非均相界面的动态行为  

The dynamic behaviors of heterogeneous interfaces in electrocatalytic CO_(2) reduction

作　　者：申珅玉 郭庆丰[2] 武甜甜 苏亚琼 Shenyu Shen;Qingfeng Guo;Tiantian Wu;Yaqiong Su(School of Chemistry,Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education,National Innovation Platform(Center)for Industry‐Education Integration of Energy Storage Technology,Xi'an Jiaotong University,Xi'an 710049,Shaanxi,China;Huanghe Science and Technology College,Zhengzhou 450063,Henan,China)

机构地区：[1]西安交通大学化学学院,储能材料与器件教育部工程研究中心,储能技术产教融合国家创新平台(中心),陕西西安710049 [2]黄河科技学院,河南郑州450063

出　　处：《Chinese Journal of Catalysis》2023年第10期52-71,共20页催化学报（英文）

基　　金：国家自然科学基金(22103059).

摘　　要：自工业革命以来,CO_(2)的过量排放导致了环境污染和气候变化,对人类可持续发展造成了极大的威胁.由可再生电力驱动的电催化CO_(2)还原反应(CO_(2)RR)技术可在较温和的条件下将CO_(2)转化为高附加价值的燃料和化学品,因而是一种有效的CO_(2)转换和利用的方法.尽管电催化CO_(2)RR已经取得了较大的研究进展,但其工业化应用依旧面临着许多挑战:CO_(2)RR的反应路径涉及多步电子-质子转移,其产物组分较复杂(包括C1到C3的产物),并且反应过程伴随着析氢反应(HER)副反应发生.此外,不同电催化剂的使用以及实验操作条件均对CO_(2)RR影响较大,导致目前CO_(2)RR催化剂性能尚不够理想,因而难以获得实际应用.为进一步开发性能良好的电催化CO_(2)RR体系,以及认识实际反应过程中催化体系真正的活性位点,理解电催化剂表面结构演变机制至关重要.本文综述了CO_(2)RR条件下非均相催化界面的动态演变行为.首先,本文讨论了催化界面动态演变的原理和分类.催化剂结构在实时工况下会发生演变,导致活性位点难以确定,因此需要明确催化界面动态演变的机制.动态演变行为主要分为催化剂表面形态演变和性质演变:表面形态演变主要指原子重排或迁移,该过程由热力学和动力学驱动;性质演变主要是化学态发生改变,它是催化剂表面性质和外界环境共同作用的结果.目前,大多数的研究都围绕着催化剂表面和次表面活性位点展开,所讨论的影响催化剂性质的因素主要包括化学组成、晶面和表面形态等.除催化剂内在性质外,还详细讨论了影响动态演变的外界环境因素,包括外加电位、温度、电解质以及杂质等.外加电位是影响催化界面的主要因素,电解质中的阴阳离子也对反应选择性有较大的影响.为了更好地认识反应过程中催化剂表面的活性位点,总结了光谱表征、X射线表征、微观表�The electrocatalytic CO_(2) reduction reaction(CO_(2)RR)is a highly promising renewable energy technology that can convert greenhouse gases into valuable fuels and chemicals.However,under ordinary operating conditions,significant dynamic evolution behavior occurs on the catalyst surface,which is mainly manifested as surface morphology evolution and property changes,eventually leading to changes in the active sites of the reaction,affecting selectivity and efficiency.To develop efficient electrocatalytic systems with excellent performance,an essential prerequisite is to understand the underlying mechanism of surface dynamic evolution.Studying the influence of the external environment on dynamic evolution is as important as studying the intrinsic structural properties of catalysts.In this review,we first introduce the concept of dynamic evolution and then emphasize the influence of the external environment(applied potential,temperature,electrolyte,and impurities)on CO_(2)RR dynamic evolution.We also address the use of operando characterization techniques and pulsed CO_(2) electrolysis methods for monitoring and controlling dynamic evolution behaviors under working conditions,along with theoretical methods,including ab initio calculations and machine learning that can simulate dynamic behavior.Finally,we present several current challenges and prospects for the development of techniques for controlling the CO_(2)RR dynamic evolution.

关 键 词：CO_(2)还原反应 动态行为 活性位点 外界环境 电催化 

分 类 号：O64[理学—物理化学]