A-site defective La_2-CuO₄ perovskite-type oxides for efficient oxidation of cyclohexylbenzene

Phenol production through the oxidation of cyclohexylbenzene (CHB) and the subsequent decomposition of tertiary hydroperoxide has attracted more and more attention. In this study, defective La_2-CuO₄ perovskite-type oxide catalysts with tunable A-site deficient structures and abundant surface oxygen vacancies were developed for the liquid phase oxidation of CHB to produce cyclohexylbenzene-1-hydroperoxide (CHBHP). By tuning the amount of A-site La ions in the perovskite structure, more surface oxygen vacancies and Cu⁺ species were formed in catalysts. The A-site-deficient La_1.9CuO₄ catalyst achieved significant catalytic efficiency along with a high CHBHP yield of 27.6% at 48.6% CHB conversion under reaction conditions (i.e., 120 °C and 12 h), outperforming those of other transition metal-based catalysts previously reported in the literature. A series of structural characterization methods and catalytic reactions highlighted the crucial roles of surface oxygen vacancies and metal La and Cu ions in the oxidation process. It was revealed that metal ions favored CHB adsorption and activation, while surface oxygen vacancies facilitated the creation of active adsorbed oxygen species. The present study offers an opportunity for the future design of new high-efficiency heterogeneous catalyst systems for CHB oxidation to obtain phenol.