Hydrogen-Assisted Photoionization and Its Use in Promoting Mass Spectrometry Analysis of VOCs.

As a simple soft ionization method, photoionization (PI) is often coupled with mass spectrometry (MS) for the direct analysis of volatile organic compounds (VOCs). PI enables selective ionization of analytes, but the ion yield is generally not high due to the limited light intensity of the ultraviolet lamp. Here, a hydrogen-assisted photoionization (HAPI) strategy was developed and integrated into a miniature ion trap mass spectrometer. In particular, hydrogen was introduced as a versatile buffer gas to facilitate both photoionization and ion trap operation. This can increase the ion yields by up to 2 orders of magnitude compared to conventional PI-MS, with a low hydrogen consumption (less than 100 μL) for each analysis. The generation of protonated ions indicates a specific photochemical process in HAPI, which has also been studied and initially revealed. The detection of various VOCs and plant volatile gases confirmed the versatility and practicality of the HAPI technology.