Effect of calcium addition in plasma catalysis for toluene removal by Ni/ZSM-5 : Acidity/basicity, catalytic activity and reaction mechanism

[Display omitted] •Ca-Ni/ZSM-5 sample shows the best potential for toluene conversion and CO2 selectivity.•The introduction of Ca and Ni reduce the acidity of ZSM-5.•Ca-Ni/ZSM-5 catalyst greatly reduces the production of p-nitrotoluene.•Eleven intermediates are detected and four of them are not previously reported.•The reaction mechanism of toluene decomposition in the plasma has been proposed. The effect of Ca modification on the Ni/ZSM-5 catalyst for efficient toluene oxidation was studied in a plasma-catalytic system. The Ni/ZSM-5 and Ca-Ni/ZSM-5 catalysts were prepared by a wet impregnation method and characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Pyridine-FTIR spectroscopy and temperature programmed desorption of ammonia (NH3-TPD). Among the catalysts tested, the Ca-Ni/ZSM-5 sample showed the best potential for toluene conversion (90.2%) and CO2 selectivity (70.7%). Pyridine-FTIR spectra and NH3-TPD results proved that the introduction of Ca and Ni onto ZSM-5 caused a decrease in the strong and weak acidic sites. In addition, gas chromatography/mass spectrometry (GC-MS) result showed that the Ca-Ni/ZSM-5 catalyst reduced the production of undesirable byproducts (such as p-nitrotoluene and methyl benzoate). Calcium in the Ni/ZSM-5 system influenced the acidity and other surface characteristic of the catalyst, as well as directly impacting the reactive plasma species and the intermediates. Finally, possible reaction mechanisms in the plasma catalysis of toluene were also proposed.