《厦门大学学报（自然科学版）》

电化学原位红外光谱的方法和研究进展

(1.厦门大学化学化工学院,固体表面物理化学国家重点实验室,福建厦门 361005; 2.厦门大学能源学院,福建厦门 361102)

关键词：电化学原位红外光谱; 方法; 应用; 表界面过程; 电催化剂; 反应机理

Progress in the methods and research of electrochemical in-situ infrared spectroscopy

JIANG Yanxia¹,LI Guang¹,YE Jinyu¹,LI Juntao²,ZHOU Zhiyou¹,SUN Shigang^1,2*

(1.State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China; 2.College of Energy,Xiamen University,Xiamen 361102,China)

DOI: 10.6043/j.issn.0438-0479.202010013

备注

摘要

全文

图/表

参考文献

研究电化学体系多相界面的精细结构和电化学过程对于发展电化学基础理论、认识电催化反应机理和界面过程,以及指导高效电催化剂的可控构筑具有重要意义.传统电化学方法不具备分子识别能力,局限于对复杂电化学体系的宏观和唯像研究.电化学原位红外光谱将电化学调制和红外光谱方法相结合,利用红外光谱的指纹特征和表面选律实现对电化学反应过程中反应物种的成键方式和浓度变化的特异性识别,获取电极表界面的物理结构和化学变化特征,以及对参与电化学反应的各种物质的实时、定性和定量检测,为研究电化学反应过程和机理,建立电极材料的结构与性能的构效关系,提供分子水平的信息.本文以本课题组的工作为主,从理论和实验两个方面综述外反射电化学原位红外光谱的基础与研究进展.首先介绍电化学原位红外光谱的原理、方法及其新技术,重点综述电化学原位红外光谱在燃料电池、锂离子电池等能量转化与储存领域中的研究进展,最后展望电化学原位红外光谱方法的应用和发展方向.

It is of great significance to study the fine structure and electrochemical process of multi-phase interfaces in the electrochemical system in developing electrochemical basic theory,studying electrocatalytic reaction mechanisms and interfacial processes,and controllable construction of efficient electrocatalysts.Traditional electrochemical methods don't have the recognition ability at molecular level,which limits the understanding of the macroscopic and phenomenological study of complex electrochemical systems.Electrochemical in-situ infrared spectroscopy combines electrochemical modulation with infrared spectroscopic technology,and is powerful in determining the bonding mode and concentration variation in the reaction species involved in electrochemical processes through fingerprint features and the surface selection rule of reflection.It attains the physical structure and chemical change characteristics,as well as real-time qualitative and quantitative information of various substances in the electrochemical reaction.The most commonly developed electrochemical in-situ infrared spectroscopy is widely applied,and could provide molecular information for the study of the process and mechanism of electrochemical reactions and the setup of the structure-activity relationship of electrode materials.In this paper,based mainly on the work done in our research group,the basis progress in research of in-situ infrared spectroscopy of external reflection electrochemistry are reviewed from both theoretical and experimental aspects.Firstly,the principle and methods of electrochemical in-situ infrared spectroscopy and new technologies are introduced.Then,the applications of electrochemical in-situ infrared spectroscopy in energy conversion and storage of fuel cells and lithium-ion batteries are reviewed significantly.Finally,future applications and developments of electrochemical in-situ infrared spectroscopy are prospected.

引言
1 电化学原位红外光谱的仪器和原理
2 电化学原位红外光谱方法的发展
3 电化学原位红外光谱的应用
4 总结和展望

图1 电化学原位红外光谱结构图(A)和FTIRS原理图(B)<br/>Fig.1 Structure diagram of electrochemical in-situ infrared spectroscopy(A)and schematic diagram of FTIRS(B)

图1 电化学原位红外光谱结构图(A)和FTIRS原理图(B)
Fig.1 Structure diagram of electrochemical in-situ infrared spectroscopy(A)and schematic diagram of FTIRS(B)

图2 电极表面红外选律的原理图<br/>Fig.2 Schematic diagram of infrared law selection on electrode surface

图2 电极表面红外选律的原理图
Fig.2 Schematic diagram of infrared law selection on electrode surface

图3 电化学原位反射红外电解池示意图[10]<br/>Fig.3 Schematic diagram of electrochemical in-situ reflection infrared cell[10]

图3 电化学原位反射红外电解池示意图[10]
Fig.3 Schematic diagram of electrochemical in-situ reflection infrared cell[10]

表1 薄层与衰减全反射模式电解池的电化学性能比较<br/>Tab.1 Comparison of electrochemical performance between thin layer and attenuated total reflection cell

表1 薄层与衰减全反射模式电解池的电化学性能比较
Tab.1 Comparison of electrochemical performance between thin layer and attenuated total reflection cell

表2 薄层与衰减全反射模式电解池的红外光谱性能比较<br/>Tab.2 Comparison of infrared spectrum performance between thin layer and attenuated total reflection cell

表2 薄层与衰减全反射模式电解池的红外光谱性能比较
Tab.2 Comparison of infrared spectrum performance between thin layer and attenuated total reflection cell

图4 电化学原位红外光谱方法的电解池结构示意图和应用<br/>Fig.4 Electrolytic cell structure diagram and application of electrochemical in-situ infrared spectroscopy

图4 电化学原位红外光谱方法的电解池结构示意图和应用
Fig.4 Electrolytic cell structure diagram and application of electrochemical in-situ infrared spectroscopy

图5 电化学原位红外光谱采谱方法<br/>Fig.5 Spectrum collection methods of electrochemical in-situ infrared spectroscopy

图5 电化学原位红外光谱采谱方法
Fig.5 Spectrum collection methods of electrochemical in-situ infrared spectroscopy

图6 Pd电极的碱性乙醇电催化氧化的原位红外谱图和产物浓度计算[14]<br/>Fig.6 In-situ infrared spectra and product concentration calculation of alkaline ethanol electrocatalytic oxidation of Pd electrode[14]

图6 Pd电极的碱性乙醇电催化氧化的原位红外谱图和产物浓度计算[14]
Fig.6 In-situ infrared spectra and product concentration calculation of alkaline ethanol electrocatalytic oxidation of Pd electrode[14]

图7 高温电化学原位红外光谱方法及Pt/C的乙醇电催化氧化的高温红外光谱[17]<br/>Fig.7 High temperature electrochemical in-situ infrared spectroscopy and high temperature infrared spectra of Pt/C electrocatalytic oxidation of ethanol[17]

图7 高温电化学原位红外光谱方法及Pt/C的乙醇电催化氧化的高温红外光谱[17]
Fig.7 High temperature electrochemical in-situ infrared spectroscopy and high temperature infrared spectra of Pt/C electrocatalytic oxidation of ethanol[17]

图8 可调谐自由电子激光光源<br/>Fig.8 Tunable free electron laser source

图8 可调谐自由电子激光光源
Fig.8 Tunable free electron laser source

图9 CO探针分子对表面组成、电子结构和活性位的探究<br/>Fig.9 Investigation on the surface composition,electronic structure and active site of CO probe molecules

图9 CO探针分子对表面组成、电子结构和活性位的探究
Fig.9 Investigation on the surface composition,electronic structure and active site of CO probe molecules

图10 异常红外效应机理及其应用<br/>Fig.10 Mechanism and application of abnormal infrared effects

图10 异常红外效应机理及其应用
Fig.10 Mechanism and application of abnormal infrared effects

图11 纳米催化剂对燃料分子的EOR机理<br/>Fig.11 EOR mechanism of fuel molecules by nanocatalysts

图11 纳米催化剂对燃料分子的EOR机理
Fig.11 EOR mechanism of fuel molecules by nanocatalysts

图12 Sn负极放电过程(去合金化)(A)和充电过程(合金化)(B)中电解液还原的原位红外光谱[86]<br/>Fig.12 In-situ infrared spectra of electrolyte reduction with Sn anode in discharge process(alloying)(A)and in charge process of Sn anode(de-alloying)(B)[86]

图12 Sn负极放电过程(去合金化)(A)和充电过程(合金化)(B)中电解液还原的原位红外光谱[86]
Fig.12 In-situ infrared spectra of electrolyte reduction with Sn anode in discharge process(alloying)(A)and in charge process of Sn anode(de-alloying)(B)[86]

pdf格式下载

+分享

导出

学报简介

《厦门大学学报（自然科学版）》于1931年创刊，是由教育部主管，厦门大学主办，国内外公开发行的综合性学术期刊（双月刊），是我国自然科学核心期刊。本刊以印刷版、网络版的方式同时出版。主要刊载自然科学各学科的最新研究成果，包括自然科学基础理论研究、应用基础研究、高新技术方面的学术论文。所刊载的论文分三大类型：（1）“快讯”：报道某前沿领域具有突破性的最新研究成果。（2）“研究论文”：刊载理工科基础理论研究与实验研究学术论文。（3）“研究简报”：刊载内容新颖、实用（或阶段性）的成果。更多>>

备注

引言

1 电化学原位红外光谱的仪器和原理

2 电化学原位红外光谱方法的发展

3 电化学原位红外光谱的应用

4 总结和展望

学报简介