A facile procedure for doping copper species into CeO2 lattices to prevent ceria from being deactivated and to offer additional active sites for selective H2S oxidation is reported here. Among the prepared catalysts, porous 10Cu/Ce nanorods with well-defined (100) and (110) reactive planes display excellent catalytic performance, exhibiting H2S conversion and sulfur selectivity of 100% at 220 degrees C, which is higher than those of most reported Ce-based catalysts. More importantly, electron transfer from Cu+ to Ce4+ suppresses the transfer of electrons from SO2 to Ce4+, leading to inhibition of SO2 oxidation to surface sulfate, which could deactivate the catalyst. Overall, the results of systematic experimental and theoretical studies prove that copper doping effectively promotes the formation of oxygen vacancies and resistance against SO2 poisoning. Furthermore, through in situ diffuse reflection infrared Fourier transform spectroscopy investigation and density functional theory calculations, the reaction intermediates in selective H2S oxidation and mechanism of SO2 resistance over the Cu-doped CeO2 catalysts are revealed. (C) 2020 Elsevier Inc. All rights reserved.