Effect of mass transfer and solution composition on the quantification of reaction kinetics by differential electrochemical mass spectrometry |
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作者姓名: | Wei Chen Nestor Uwitonze Fan He Matthew MSartin Jun Cai Yan-Xia Chen |
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作者单位: | Hefei National Laboratory for Physical Sciences at Microscale |
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基金项目: | 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)。 |
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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.
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关 键 词: | Differential electrochemical mass spectrometry Quantitative analysis CALIBRATION Flow rate Background correction |
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