Oxidative Dehydrogenation of Cyclohexane Over Halogen‐Decorated Ceria Nanorods with Tuned Electronic Structure and Surface Oxygen Species

Abstract Doping of non‐metallic elements is considered a promising strategy for metal oxide catalysts modification in alkane oxidative dehydrogenation (ODH). It can avoid over‐oxidation of alkane and improve product selectivity. Regulating electronic properties of oxygen species on cerium oxide (CeO 2 ) surface is effective for cyclohexane ODH to cyclohexene. In this work, the catalytic performance of CeO 2 in cyclohexane ODH is regulated by halogens (F, Cl, and I). Halide solution‐etched of CeO 2 nanorods effectively inhibits cyclohexane over‐oxidation while promoting cyclohexene generation. At 350 °C, optimal catalysts have good cyclohexene yields of 11.7%. Halogen modification changes reactive oxygen species distribution and oxygen nucleophilicity over catalysts. Pulsed oxygen isotope exchange experiments show halogen modification limits oxygen doping rate. Active O 2 − and O 2− help convert cyclohexane to cyclohexene, while O 2 2− and O − cause over‐oxidation. Halogen modification is valuable for alkane ODH and helps optimize CeO 2 ‐based catalysts.