稀土掺杂对氯化氢氧化制氯气CuO-CeO2-SiO2催化剂结构和性能的影响

Effects of Rare-Earth Additives on Structures and Performances of CuO-CeO2-SiO2 Catalysts for Recycling Cl2 from HCl Oxidation

CuO-CeO₂-SiO₂ and rare-earth-doped CuO-Ce_0.9M_0.1O₂-SiO₂ (M=La, Pr, Nd) catalysts for recycling Cl₂ from HCl oxidation were prepared by a template method, using activated carbon as a hard template. The catalyst structures were determined using X-ray diffraction (XRD), N₂ adsorption-desorption, transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and H₂ temperatureprogrammed reduction (H₂-TPR). The catalytic performances were also investigated. The results showed that La, Pr, and Nd cations were incorporated into the CeO₂ lattice and formed nanosized solid solutions; this greatly reduced the catalyst grain sizes, leading to higher surface areas. In addition, the oxygen vacancy concentrations were significantly improved. The changes in the structures and surface properties of the solid solutions significantly affected the HCl catalytic oxidation performances. The order of the activities of various catalysts was CuO-Ce_0.9La_0.1O₂-SiO₂>CuO-Ce_0.9Nd_0.1O₂-SiO₂>CuO-Ce_0.9Pr_0.1O₂-SiO₂>CuO-CeO₂-SiO₂. The oxygen vacancy concentrations of the solid solutions were strongly related to their catalytic activities. However, the structures and performances of the Ce_0.9M_0.1O₂-SiO₂ catalysts showed that an increase in the number of oxygen vacancies resulted in decreased catalytic activities of the solid solutions. Kinetic studies showed that oxygen adsorption could be the rate-determining step for rare-earth-doped catalysts; a higher oxygen vacancy concentration in the solid solution led to a slower reaction rate when the volumetric flow ratio of O₂ to HCl was 1. For the CuOCe_0.9M_0.1O₂-SiO₂ catalysts, spillover of oxygen species in the solid solution into the highly dispersed CuO interfaces was enhanced, which increased the overall reaction rate and gave high activity.