Mai Hao-Xin, Sun Ling-Dong, Zhang Ya-Wen, Si Rui, Feng Wei, Zhang Hong-Peng, Liu Hai-Chao, Yan Chun-Hua
State Key Lab of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China.
J Phys Chem B. 2005 Dec 29;109(51):24380-5. doi: 10.1021/jp055584b.
Single-crystalline and uniform nanopolyhedra, nanorods, and nanocubes of cubic CeO2 were selectively prepared by a hydrothermal method at temperatures in the range of 100-180 degrees C under different NaOH concentrations, using Ce(NO3)3 as the cerium source. According to high-resolution transmission electron microscopy, they have different exposed crystal planes: {111} and {100} for polyhedra, {110} and {100} for rods, and {100} for cubes. During the synthesis, the formation of hexagonal Ce(OH)3 intermediate species and their transformation into CeO2 at elevated temperature, together with the base concentration, have been demonstrated as the key factors responsible for the shape evolution. Oxygen storage capacity (OSC) measurements at 400 degrees C revealed that the oxygen storage takes place both at the surface and in the bulk for the as-obtained CeO2 nanorods and nanocubes, but is restricted at the surface for the nanopolyhedra just like the bulk one, because the {100}/{110}-dominated surface structures are more reactive for CO oxidation than the {111}-dominated one. This result suggests that high OSC materials might be designed and obtained by shape-selective synthetic strategy.
以硝酸铈(Ce(NO3)3)为铈源,通过水热法在100-180℃、不同氢氧化钠浓度条件下,选择性制备了立方相二氧化铈(CeO2)的单晶且均匀的纳米多面体、纳米棒和纳米立方体。根据高分辨率透射电子显微镜观察,它们具有不同的暴露晶面:多面体为{111}和{100},纳米棒为{110}和{100},纳米立方体为{100}。在合成过程中,已证明六方氢氧化铈(Ce(OH)3)中间物种的形成及其在高温下向CeO2的转变,以及碱浓度,是导致形状演变的关键因素。在400℃下的储氧能力(OSC)测量表明,对于所制备的CeO2纳米棒和纳米立方体,表面和体相中均发生储氧,但对于纳米多面体,储氧仅局限于表面,就像体相CeO2一样,因为{100}/{110}主导的表面结构比{111}主导的表面结构对CO氧化更具反应活性。这一结果表明,高OSC材料可能通过形状选择性合成策略来设计和获得。