Effect of mass transfer and solution composition on the quantification of reaction kinetics by differential electrochemical mass spectrometry  

作　　者：Wei Chen Nestor Uwitonze Fan He Matthew MSartin Jun Cai Yan-Xia Chen 

机构地区：[1]Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics,University of Science and Technology of China,Hefei 230026,Anhui,China

出　　处：《Journal of Energy Chemistry》2021年第5期412-419,共8页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(no.21872132,21832004,91545124);the 973 Program from the Ministry of Science and Technology of China(no.2015CB932301)。

摘　　要：Differential electrochemical mass spectrometry(DEMS)is one of the most powerful techniques for both the mechanistic and kinetic study of complicated electrocatalytic reactions.It can provide information on the nature and yields of the products generated,their production rate,and the structure-activity relationship between the electrocatalysts and the target reactions.The precise calibration of the mass signal is a prerequisite for the accurate evaluation of reaction kinetics.In this work,we use the oxidation reactions of CO and HCOOH to demonstrate how certain conditions,such as the flow rate and solution composition,affect the collection efficiency and ionization probability of the species to be detected.These parameters can affect the determination of the mass calibration constant and the accuracy of the subsequent quantitative DEMS analysis.We show the relationship between the mass calibration constant and the flow rate,and provide strategies for eliminating this and the related problems.

关 键 词：Differential electrochemical mass spectrometry Quantitative analysis CALIBRATION Flow rate Background correction 

分 类 号：O657.63[理学—分析化学] O643.1[理学—化学]