Influence of calcination and pretreatment conditions on the activity of Co3O4 for CO oxidation

The influence of calcination and pretreatment conditions on the structure of Co3O4 and its activity for CO oxidation were studied. TG analysis indicated that the precursor of Co3O4 prepared by a precipitation method was present in the form of cobalt hydroxide carbonate, calcination of which within the temperature range of 150–400 °C in air resulted in the formation of cubic phase Co3O4. N2 adsorption-desorption, powder X-ray diffraction, transmission electron microscopy, and activity test results showed that the prepared Co3O4 samples were comprised of nanoparticles, with the specific surface area and size distribution closely related to the calcination temperature. Over these samples, a size dependence of the catalytic activity for CO oxidation was clearly observed. As identified by positron annihilation lifetime spectrum, low temperature oxygen temperature-programmed desorption, and durability testing for CO oxidation, pretreatment of Co3O4 in N2 within the temperature range 150–250 °C favors the formation of surface oxygen vacancy clusters, the occurrence of which would be beneficial for the adsorption and activation of O2, and also for the catalytic oxidation of CO. Meanwhile, the reconstruction of oxygen vacancies on the surface of Co3O4, induced by the pretreatment process, was also discussed.

摘要采用沉淀法制备了 Co3O4, 考察了焙烧和预处理条件对其结构、低温催化氧化 CO 性能的影响. 热重分析表明, 未经焙烧的样品以 Co(OH)2CO3 的形式存在, 150–400 oC 空气气氛中焙烧后, 样品以立方相 Co3O4 的形式存在. N2 吸附-脱附法、X 射线衍射、透射电镜及活性测试结果表明, 以纳米颗粒物存在的 Co3O4 的比表面积、颗粒尺寸、催化氧化 CO 活性与焙烧温度密切相关. 正电子湮没寿命谱、O2-程序升温脱附与定温条件下 CO 氧化测试结果表明, 合适温度 (150–250 oC) 下 N2 预处理有利于 Co3O4 表面氧空穴团的形成, 它在吸附活化分子氧以及 CO 催化氧化反应中起到关键作用. 同时讨论了预处理作用下 Co3O4 表面氧空穴的再构机制.

Graphical AbstractPretreatment of Co3O4 in N2 at moderate temperatures promotes the formation of oxygen vacancy clusters, favoring the adsorption of oxygen molecules and guaranteeing a long durability for CO oxidation.Figure optionsDownload as PowerPoint slide