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Graphical abstract Highlights • The catalytic self-sustained combustion of toluene was successfully developed. • CuCeZr/TiO 2 catalyst showed the excellent performance in self-sustained combustion. • TPO in N 2 atmosphere was used to investigate the role of lattice oxygen in toluene combustion. Abstract The catalytic self-sustained combustion of toluene over Cu x Mn 1-x Ce 0.75 Zr 0.25 /TiO 2 catalysts (x = 1, 0.5, 0) was studied in a microscale combustor. The catalytic activity is determined not only by the temperature with toluene conversion of 90% (T co), but also by the corresponding lean-combustion limits. It was found that the self-sustained combustion was achieved successfully over the catalysts, with the toluene concentrations of 0.35 con.%, 0.50 con.% and 1.00 con.%. According to T co, the activity decreased in the order of CuCe 0.75 Zr 0.25 /TiO 2 (234 °C)＞Cu 0.5 Mn 0.5 Ce 0.75 Zr 0.25 /TiO 2 (238 °C) ＞MnCe 0.75 Zr 0.25 /TiO 2 (284 °C). The excellent activity of CuCe 0.75 Zr 0.25 /TiO 2 catalyst could be ascribed to the high content of active lattice oxygen, good low-temperature reducibility and homogeneous dispersion, combined with the results of H 2 -TPR, O 2 -TPD and XPS. Furthermore, the results of in-situ DRIFT and temperature-programmed oxidation (TPO) of toluene in N 2 atmosphere suggested that toluene was adsorbed on the catalyst surface by removing α-H from methyl and combining with active oxygen specie to form benzyl group, which was finally oxidized into CO 2 and H 2 O with lattice oxygen. [ABSTRACT FROM AUTHOR]