Sintering- and oxidation-resistant ultrasmall Cu(I)/(II) oxides supported on defect-rich mesoporous alumina...

Supported copper oxides with well-dispersed metal species, small size, tunable valence and high stability are highly desirable in catalysis. Herein, novel copper oxide (CuO_x) catalysts supported on defect-rich mesoporous alumina microspheres are developed using a spray-drying-assisted evaporation induced self-assembly method. The catalysts possess a special structure composed of a mesoporous outer layer, a mesoporous-nanosphere-stacked under layer and a hollow cavity. Because of this special structure and the defective nature of the alumina support, the CuO_x catalysts are ultrasmall in size (1 ~ 3 nm), bivalent with a very high Cu⁺/Cu²⁺ ratio (0.7), and highly stable against sintering and oxidation at high temperatures (up to 800 °C), while the wet impregnation method results in CuO_x catalysts with much larger sizes (~15 nm) and lower the Cu⁺/Cu²⁺ ratios (~0.29). The catalyst formation mechanism through the spray drying method is proposed and discussed. The catalysts show remarkable performance in catalytic ozonation of phenol wastewaters. With high-concentration phenol (250 ppm) as the model organic pollutant, the optimized catalyst delivers promising catalytic performance with 100% phenol removal and 53% TOC removal in 60 min, and a high cyclic stability. Superoxide anion free radicals (⋅O₂^-), singlet oxygen (¹O₂) and hydroxyl radicals (⋅OH) are the predominant reactive species. A detailed structure-performance study reveals the surface hydroxyl groups and Cu⁺/Cu²⁺ redox couples play cooperatively to accelerate O₃ decomposition generating reactive radicals. The plausible catalytic O₃ decomposition mechanism is proposed and discussed with supportive evidences.