离子交换低温水热合成高纯微纳米CeO_2
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摘要
首次采用离子交换低温水热法合成了不同粒径及不同形貌的氧化铈前体。经过离子交换纤维的预交换度、尿素浓度、合成温度、合成时间等因素的调变可获得不同粒径分布的以纳米片和微米棒为特征形貌的氧化铈前体。较小粒径的氧化铈前体可以通过适当降低离子交换纤维的预交换度和适度提高反应温度而获得；一定粒度微米棒组合成的花状团簇结构可通过特征实验条件的控制获得。
离子交换低温水热法中离子交换纤维的加入对棒状结构氧化铈前体的形成和生长具有导向作用。沉淀剂尿素的用量、离子交换纤维的预交换度、合成温度、合成时间对产物形貌和粒度的影响是通过影响离子交换纤维表面Ce(OH)2+基团和CO32-离子的扩散和迁移能力实现的。
离子交换低温水热法合成的氧化铈前体为斜方结构的Ce2O(CO3)2·H20单晶,TG结果显示,离子交换低温水热法合成的氧化铈前体中已经有大量氧化铈生成,其可能以无定型状态高分散于Ce2O(CO3)2·H20晶体中。合成的氧化铈前体经400-500℃焙烧后可得到立方多晶结构的CeO2,其结晶良好,并能够保持前体的基本形貌特征。
离子交换水热法中晶粒的形成、生长速度与预交换度、尿素的浓度、温度等条件有关,离子交换纤维在一定条件下成为晶粒生长的模板,控制成核和生长过程,实现了低温双控合成不同形貌纳米材料：体系中的杂质离子通过交换反应在离子交换纤维上富集,无需对产品进行洗涤。整个合成过程节能并环境友好,为高纯纳米材料的合成开辟了一条新途径。
In this paper, different morphology and different partical size of precursors of cerium oxide were synthesized for the first time by low-temperature hydrothermal and ion exchange method. After modulating factors of the ion exchange fiber pre-exchange degrees, the concentration of urea, synthesis temperature and time, cerium oxide precursors with different particle size distribution and nanometer slice and micron stick for feature morphology were obtained. Smaller diameter of cerium oxide precursor can obtain by appropriately reducing pre-exchange degree of ion exchange fiber and moderately increasing reaction temperature; certain particle size of flower shape clusters self-assembly by micron sticks can be obtained under the feature synthesized condition.
Additive ion exchange fiber plays the leading role in the formation and growth of rodlike cerium oxide precursor in ion exchange and low-temperature hydrothermal method. The influence of the amount of urea, the ion exchange fiber pre-exchange degrees, synthesis temperature and synthesis time on the morphology and size of product realized by affecting the capacity of diffusion and migration of Ce(OH)2+ and CO32- on the surface of ion exchange fiber.
The cerium oxide precursor prepared by ion-exchange and low-temperature hydrothermal is orthorhombic structure mono-crystal Ce2O(CO3)2·H2O, according to the results of TG, abundant cerium oxide consist in cerium oxide precursor, which probable highly dispersed in Ce2O(CO3)2·H2O crystal with no finalize the design condition, after roasting at 400 to 500℃obtained cubic pleomorphic CeO2, well crystallization, and can keep the basic morphological features of precursor.
The formation and growth rate of grains prepared by ion-exchange hydrothermal method are related to the pre-exchange degrees, the concentration of urea, the temperature conditions, ion exchange fiber become grain growth template under certain conditions, controlling the nucleation and growth process, realized synthesizing different morphology nanomaterials at the low-temperature dual control; impurity ions of system enriched in fiber through ion exchange reaction and have no need to wash. The whole synthesis process is environment friendly and energy saving, opening a new way for the synthesis of high purity of nanomaterials.
离子交换低温水热法中离子交换纤维的加入对棒状结构氧化铈前体的形成和生长具有导向作用。沉淀剂尿素的用量、离子交换纤维的预交换度、合成温度、合成时间对产物形貌和粒度的影响是通过影响离子交换纤维表面Ce(OH)2+基团和CO32-离子的扩散和迁移能力实现的。
离子交换低温水热法合成的氧化铈前体为斜方结构的Ce2O(CO3)2·H20单晶,TG结果显示,离子交换低温水热法合成的氧化铈前体中已经有大量氧化铈生成,其可能以无定型状态高分散于Ce2O(CO3)2·H20晶体中。合成的氧化铈前体经400-500℃焙烧后可得到立方多晶结构的CeO2,其结晶良好,并能够保持前体的基本形貌特征。
离子交换水热法中晶粒的形成、生长速度与预交换度、尿素的浓度、温度等条件有关,离子交换纤维在一定条件下成为晶粒生长的模板,控制成核和生长过程,实现了低温双控合成不同形貌纳米材料：体系中的杂质离子通过交换反应在离子交换纤维上富集,无需对产品进行洗涤。整个合成过程节能并环境友好,为高纯纳米材料的合成开辟了一条新途径。
In this paper, different morphology and different partical size of precursors of cerium oxide were synthesized for the first time by low-temperature hydrothermal and ion exchange method. After modulating factors of the ion exchange fiber pre-exchange degrees, the concentration of urea, synthesis temperature and time, cerium oxide precursors with different particle size distribution and nanometer slice and micron stick for feature morphology were obtained. Smaller diameter of cerium oxide precursor can obtain by appropriately reducing pre-exchange degree of ion exchange fiber and moderately increasing reaction temperature; certain particle size of flower shape clusters self-assembly by micron sticks can be obtained under the feature synthesized condition.
Additive ion exchange fiber plays the leading role in the formation and growth of rodlike cerium oxide precursor in ion exchange and low-temperature hydrothermal method. The influence of the amount of urea, the ion exchange fiber pre-exchange degrees, synthesis temperature and synthesis time on the morphology and size of product realized by affecting the capacity of diffusion and migration of Ce(OH)2+ and CO32- on the surface of ion exchange fiber.
The cerium oxide precursor prepared by ion-exchange and low-temperature hydrothermal is orthorhombic structure mono-crystal Ce2O(CO3)2·H2O, according to the results of TG, abundant cerium oxide consist in cerium oxide precursor, which probable highly dispersed in Ce2O(CO3)2·H2O crystal with no finalize the design condition, after roasting at 400 to 500℃obtained cubic pleomorphic CeO2, well crystallization, and can keep the basic morphological features of precursor.
The formation and growth rate of grains prepared by ion-exchange hydrothermal method are related to the pre-exchange degrees, the concentration of urea, the temperature conditions, ion exchange fiber become grain growth template under certain conditions, controlling the nucleation and growth process, realized synthesizing different morphology nanomaterials at the low-temperature dual control; impurity ions of system enriched in fiber through ion exchange reaction and have no need to wash. The whole synthesis process is environment friendly and energy saving, opening a new way for the synthesis of high purity of nanomaterials.
引文
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[13]张万忠,乔学亮,陈建国等.纳米材料的表面修饰与应用.化工进展.2004,23(10)：1067
[14]谢丽英,柳召刚.纳米氧化铈粉体的制备技术研究进展.中国稀土学报.2007,28(2)：70-76
[15]王乾.纳米氧化铈/锌复合材料制备及其性能研究.常州轻工职业技术学院学报.2006,4：10-13、18
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[17]侯文华,徐林,邱金等.采用不同方法制备Ce02超细粒子-Ⅰ：溶胶-凝胶法.南京大学学报(自然科学版).1999,35(4)：486-489
[18]董相廷,胡耀,张伟等.聚乙二醇凝胶法制备CeO2纳米晶.长春光学精密机械学院学报.1999,22(4)：1-4.
[19]董相廷,李铭,张伟等.沉淀法制备CeO2纳米晶与表征.中国稀土学报.2001,19(1)：24-26
[20]高岚,屈一新.共沸精馏法制备氧化铈纳米粉体及其煅烧动力学.硅酸盐学报.2005,33(9)：1157-1160
[21]侯文华,陈立刚.采用不同方法制备CeO2超细粒子-Ⅱ：冻脱水法.南京大学学报(自然科学版).2000,36(1)：100-103
[22]Masanori Hirano, Toshio Miwa, Michio Inagak. Low-temperaturedirect synthesis of nanoparticle of fluorite-type ceria-zirconiasolid solutionsby "forced co-hydrolysis" at 100℃. Journal of Solid State Chemistry.2001,158:112-117
[23]Matina Thammachart, Vissanu Meeyoo. Catalytic activity of CeO2-ZrO2 mixed oxide catalysts prepared via sol-gel technique:CO oxidation. CatalysisToday.2001.68:53-61
[24]Jackie Y Ying, Andreas Tschope. Redox activity of nonstoichio-metric cerium oxide based nanocrystalline catalysts. Journal of catalysis.1995,157:42-50
[25]沈兴海,高宏成.纳米微粒的微乳液制备法.化学通报.1995,(11)：6-9
[26]石硕,鲁润华.W/O微乳液中CeO2超细粒子的制备.化学通报.1998,(12)：51-53.
[27]张丽娟,王国良,索继栓等.氧化铈纳米微粒的制备及其在金属钒钝化中的应用.化学研究.2000,11(4)：24-2
[28]孙晶,董相廷,李昌立等.CeO2纳米粒子的油酸包覆研究.长春光学精密机械学院学报.2001,24(4)：23-26
[29]李欢军,李前树.一种制备均匀的单分散CeO2纳米微粒的新方法.分子群学学报.2000,169(4)：239-241
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