Si Rui, Zhang Ya-Wen, You Li-Ping, Yan Chun-Hua
State Key Lab of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China.
J Phys Chem B. 2006 Mar 30;110(12):5994-6000. doi: 10.1021/jp057501x.
Four nanometer colloidal ceria nanocrystals in a fluorite cubic structure have been synthesized via an alcohothermal treatment at 180 degrees C for 24 h from Ce(NO(3))(3)*6H(2)O in ethanol, using various alkylamines including triethylamine, butylamine, and hexadecylamine as the bases and poly(vinylpyrrolidone) (PVP) as the stabilizer. They were characterized by multiple measurements of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), ultraviolet visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and infrared spectroscopy (IR). The introduction of PVP could effectively stabilize the cerium nuclei against self-aggregation and finally lead to the formation of the CeO(2) colloids. As compared with that of their precipitated counterparts, the UV-vis spectra showed a blue-shifted absorption edge for the as-obtained colloidal nanocrystals, revealing that their surfaces were well-passivated by PVP. Four types of self-organized monolayer patterns (i.e., isolated particles, short chainlike (pseudo-1-D aggregated), pearl necklace-like (1-D aggregated), and dendritic (pseudo-2-D aggregated) alignments) appeared for the as-obtained colloidal particles on the copper TEM grids, due to the delicate balance of the attractive and repulsive forces between the PVP-passivated CeO(2) nanocrystals during the irreversible evaporation of the solvent from various colloidal solutions under ambient conditions. The type of alkylamine and the concentration of PVP were confirmed to be the crucial factors determining the oriented-aggregation dimensionality of the CeO(2) colloids. Possible interparticle interaction modes have been suggested to explain such complex self-organization patterns exhibited by the as-obtained CeO(2) nanocrystals.
通过在180℃下用乙醇对硝酸铈(Ce(NO₃)₃·6H₂O)进行24小时的醇热处理,使用包括三乙胺、丁胺和十六胺在内的各种烷基胺作为碱,并使用聚乙烯吡咯烷酮(PVP)作为稳定剂,合成了具有萤石立方结构的4纳米二氧化铈胶体纳米晶体。通过X射线衍射(XRD)、透射电子显微镜(TEM)、高分辨率TEM(HRTEM)、紫外可见(UV-vis)光谱、动态光散射(DLS)和红外光谱(IR)等多种测量手段对其进行了表征。PVP的引入可以有效地稳定铈核,防止其自聚集,最终导致CeO₂胶体的形成。与沉淀的对应物相比,UV-vis光谱显示所获得的胶体纳米晶体的吸收边缘发生了蓝移,这表明它们的表面被PVP很好地钝化了。由于在环境条件下,从各种胶体溶液中不可逆地蒸发溶剂时,PVP钝化的CeO₂纳米晶体之间的吸引力和排斥力之间的微妙平衡,在所获得的铜TEM网格上的胶体颗粒上出现了四种自组装单层图案(即孤立颗粒、短链状(准一维聚集)、珍珠项链状(一维聚集)和树枝状(准二维聚集)排列)。已证实烷基胺的类型和PVP的浓度是决定CeO₂胶体定向聚集维度的关键因素。已经提出了可能的颗粒间相互作用模式来解释所获得的CeO₂纳米晶体所表现出的这种复杂的自组织图案。