Reaction mechanism of toluene decomposition in non-thermal plasma: How does it compare with benzene?

Non-thermal plasma (NTP) catalysis is considered one of the most promising technologies to address a wide range of energy and environmental needs, such as carbon dioxide (CO₂) conversion, NH₃ synthesis, and volatile organic compounds (VOCs) removal. A systematic approach to optimizing NTP systems benefits from understanding VOCs' fundamental NTP destruction behavior and analyzing the correlations between molecular structures and conversion and selectivity. Herein, the mechanical performance of the toluene destruction in NTP is examined and compared with benzene bearing a similar molecular structure. Different experimental and theoretical techniques are applied, including synchrotron vacuum ultraviolet photoionization mass spectrometry(SVUV-PIMS), thermochemistry, and quantum chemistry. Comparatively, toluene is more readily destroyed under the same NTP conditions than benzene. More intriguingly, the distribution of the decomposition species is significantly different. The theoretical calculations reveal that the abundant methyl radicals generated in toluene decomposition mainly lead to the various species distribution. These radicals promote some reactions, such as the decomposition of o-benzoquinone, one of the key intermediates, thus leading to new reaction pathways and products different from benzene. Finally, the critical mechanistic steps of toluene decomposition under the present non-thermal plasma conditions are established, which include the interactions between toluene and electrons or reactive radicals, the cleavage of the aromatic ring, and the various reaction pathways involving of methyl radicals. This study presents an effective approach to elucidate the distinct fundamental reaction mechanisms arising from subtle structural differences, offering new insights into the underlying plasma chemistry crucial for advancing various promising environmental and energy applications of non-thermal plasma systems.