Time-resolved in situ monitoring of photocatalytic reactions by probe electrospray ionization mass spectrometry

Probe electrospray ionization mass spectrometry (PESI-MS) has been demonstrated to be a useful in situ and online analytical technique for monitoring of various reactions. In this work, PESI-MS with a surface-modified probe was adopted and applied to in situ monitoring of photocatalytic reactions. Typical reactions of semiconductor photocatalysts, namely TiO2, SnO2, WO3, SiC and ZnS catalyzed methylene blue (MB) and brilliant green (BG) degradation, were selected to demonstrate the potential of PESI-MS to monitor heterogeneous photocatalytic reactions occurring in suspensions. Surface modification of the probe ensures increased wettability during the whole monitoring process. PESI-MS could provide continuous sampling and real-time MS results without time-consuming and cumbersome sample pretreatments. This method has other merits including good reproducibility and stability (time scale > 60 min), convenience of operation, low sample consumption, high time resolution and high tolerance to suspended photocatalyst particles. Time-resolved mass spectra and ion chromatograms of every chemical species e.g. the substrate and reactive intermediates could be obtained, which is helpful for a better understanding of the photocatalytic reaction process. Thus, PESI-MS could be a versatile analytical technique for in situ photocatalytic reaction analysis and could be an alternative means for the evaluation of photocatalyst performance.