电催化原位红外附件
图1:原理示意图
电化学原位红外光谱分析是红外分析技术的一个重要分支,能够定性分析电催化(如CO2电还原等)反应、各种类型电池(如锂离子、锂硫电池等)充放电过程中电极表面的产物或中间产物随时间(电位)不断变化的趋势,是研究电化学反应机理以及电化学反应动力学的重要手段之一。
一 基本原理:
内反射模式:
(1)在单晶硅(Si)上化学镀或真空镀一层纳米金膜,纳米金属膜具有表面增强效应。
(2)纳米金膜可作为导电基底,在导电基底上滴涂或电沉积上电催化剂,作为工作电极。
(3)表面增强红外,可得到电催化剂吸附态产物以及中间产物信息。
图2:内反射模式基本原理
外反射模式:
(1)在基底电极(如GCE)表面电沉积或滴涂电催化剂作为工作电极。
(2)工作电极距离晶体的距离可以调节。
(3)晶体可选Ge,ZnSe,CaF2,Si等。
图3:外反射模式基本原理
二 附件组成:
(1)红外光谱仪主机适配底板,适配主流红外光谱仪。
(2)平面镜加曲面镜。
(3)入射角度调节系统。
(4)衰减全反射晶体。
(5)玻璃电化学池(单池或H型池)以及PEEK外反射池。
(6)电极(玻碳电极、对电极、参比电极)。
(7)距离调节系统。
三 主要特点:
(1)可变入射角光学台,30-80度连续可调,以保证不同电催化剂处于最大光通量状态。
(2)衰减全反射晶体上具有一层增透膜,光通量增大10%以上
(3)电化学池密封性能好,可通入反应气体。
(4)晶体拆卸简单,方便打磨清洗。
(5)晶体种类可选,如Si,CaF2,ZnSe等。
(6)电化学单池或H型池,切换方便。
(7)提供现场技术服务。
(7)可根据客户需求定制反应池并提供可行性方案。
四 ATR Crystal characteristics for FTIR sampling
Crystal | pH range | Spectrum range(cm-1) |
Diamond | 1-14 | 250/525-4000 |
Ge | 1-14 | 575-5000 |
Silicon | 1-12 | 1200-8900 |
ZnSe | 5-9 | 525-15000 |
CaF2 | 5-8 | 1100-7700 |
应用案例
CO2电还原 J. Am. Chem. Soc.2022, 144, 259−269
氧气析出反应 J. Am. Chem. Soc. 2022, 144, 21, 9271–9279
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