Photoionization Mass Spectrometry for Online Detection of Reactive and Unstable Gas‐Phase Intermediates in Heterogeneous Catalytic Reactions

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Heterogeneous catalytic reactions always involve surface intermediates on catalyst surfaces, and some of them also involve reactive and unstable gas‐phase intermediates such as radicals and alkyl hydroperoxides. Online detection of these gas‐phase intermediates is of great importance for fundamentally understanding reaction mechanisms of relevant heterogeneous catalytic reactions, designing structures of efficient catalysts and optimizing reactors. However, it has remained a long‐time challenge due to the lack of routine characterization techniques. Herein we review recent progress on applications of photoionization mass spectrometry in online detection of reactive and unstable gas‐phase intermediates in heterogeneous catalytic reactions. The development and advantages of photoionization mass spectrometry and the relevant equipment setup for heterogeneous catalysis studies are also described. Finally, a future perspective is given.