以聚甲基丙烯酸甲酯(PMMA)为硬模板,三嵌段共聚物F127、十六烷基三甲基溴化铵(CTAB)或聚乙二醇(PEG)为软模板剂(表面活性剂),柠檬酸为络合剂,硝酸铈为金属前驱体,采用双模板法成功地合成出具有介孔孔壁的三维有序大孔(3DOM)结构的立方相CeO2样品CeO2-F127,CeO2-CTAB和CeO2-PEG,并利用多种分析技术表征了它们的物化性质.结果表明,三个样品均具有3DOM结构和蠕虫状介孔孔壁,表面活性剂的种类对样品的孔结构和比表面积影响较大.在制备过程中引入表面活性剂可提高CeO2样品的比表面积,所得CeO2-F127,CeO2-CTAB和CeO2-PEG样品的比表面积分别为60.5,60.2和51.8m2/g.具有3DOM结构的CeO2样品的低温还原性显著好于无孔的体相CeO2,它们的低温还原性按照CeO2-PEG Three-dimensionally ordered macroporous (3DOM) ceria with mesoporous walls and cubic crystal structures were prepared with polymethyl methacrylate (PMMA) as a hard template and triblock copolymer Pluronic F127 (EO106PO70EO106), cetyltrirnethylamrnonium bromide (CTAB), or poly(ethylene glycol) (PEG) as a soft template. Citric acid was used as a complexing agent and cerium nitrate was used as a metal precursor. The 3 DOM CeO2 samples were characterized by numerous analytical techniques. The as-fabricated CeO2 samples had a 3DOM architecture with polycrystalline wormhole-like mesoporous walls. The nature of the soft template had an important effect on the pore structure and the surface area of the final product. The surface areas of the F127-, CTAB-, and PEG-derived 3D0M CeO2 samples (denoted CeO2-F127, CeO2-CTAB, and CeCVPEG, respectively) were ca. 60.5, 60.2, and 51.8 m2/g, respectively. The low-temperature reduci-bility of the 3DOM-structured CeO2 samples was much better than that of the bulk counterpart and the low-temperature reducibility of the three 3DOM ceria samples increased according to CeO2-PEG < CeO2-CTAB < CeO2-F127, which coincided with the surface oxygen vacancy density sequence. The unproved physicochemical properties associated with the formation of the 3DOM skeleton with wormhole-like mesoporous walls may be useful for applications such as CeO2 materials in heterogeneous catalysis.
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