化学
衰减全反射
吸附
电化学
电解质
傅里叶变换红外光谱
反应中间体
红外光谱学
氧化还原
分析化学(期刊)
质谱法
反应机理
反应速率常数
动力学
无机化学
化学工程
电极
物理化学
催化作用
色谱法
有机化学
工程类
物理
量子力学
作者
Martin Heinen,Zenonas Jusys,R. Jürgen Behm
出处
期刊:Handbook of Fuel Cells
日期:2010-12-15
被引量:1
标识
DOI:10.1002/9780470974001.f500012
摘要
Abstract A newly developed hyphenated technique, the combination of in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIRS), on‐line differential electrochemical mass spectrometry (DEMS), and electrochemical flow‐cell measurements, is described and its potential for studies of electrocatalytic reactions relevant for fuel cell operation is outlined. This method allows the simultaneous detection of adsorbed reaction intermediates ( in situ ATR‐FTIRS), volatile reaction products (on‐line DEMS), and the total Faradaic current (electrochemical measurements) at the same time, in a single experiment, under enforced and controlled electrolyte transport conditions. It also allows us to follow the adsorption process in electrolyte‐exchange transients at constant potential, which is important for kinetic studies. The potential of this method is illustrated in different examples. CO uptake transients from the CO‐containing electrolyte show the influence of the potential on the CO adsorption kinetics. Using isotope‐labeled CO, similar information can be obtained on CO ad exchange, demonstrating rapid exchange for CO adsorbed on Pt even at room temperature. Adsorption/oxidation transients and potentiodynamic measurements of the oxidation of C 1 and C 2 molecules are presented and discussed, which illustrate the potential of this method for determining the dynamics, kinetics, and mechanism of the adsorption and oxidation of small organic molecules, by combining parallel information on the contributions of different reaction pathways (product analysis) and adsorbed reaction intermediates at different stages of the adsorption/reaction process and under different reaction conditions. Finally, future developments and prospects of this method are outlined.
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