碳化铈水解氧化法制备CeO2纳米粉

doi:10.3724/SP.J.1077.2012.00489

无机材料学报 ›› 2012, Vol. 27 ›› Issue (5): 489-494.DOI: 10.3724/SP.J.1077.2012.00489 CSTR: 32189.14.SP.J.1077.2012.00489

碳化铈水解氧化法制备CeO₂纳米粉

吴移清¹, 倪建森¹, 杜亚男¹, 胡鹏飞¹, 丁伟中², 耿淑华²

(上海大学 1. 微结构重点实验室; 2. 材料工程系, 上海 200072)

收稿日期:2011-07-08 修回日期:2011-09-14 出版日期:2012-05-10 网络出版日期:2012-03-31
作者简介:吴移清(1986-), 女, 硕士研究生. E-mail: woshiwuyiqing@126.com
基金资助:
上海市重点学科建设项目(S30107) Shanghai Leading Academic Discipline Project (S30107);实验过程中得到上海大学微结构重点实验室李强、彭剑超、虞伟钧、褚于良、楼燕燕、鲁波、白琴等同志的帮助, 在此一并致谢

Preparation of CeO₂Nanopowders by Hydrolysis and Oxidation of Cerium Carbide

WU Yi-Qing¹, NI Jian-Sen¹, DU Ya-Nan¹, HU Peng-Fei¹, DING Wei-Zhong², GENG Shu-Hua²

(1. Laboratory for Microstructures, Shanghai University, Shanghai 200072, China; 2. Department of Materials Engineering of Shanghai University, Shanghai 200072, China)

Received:2011-07-08 Revised:2011-09-14 Published:2012-05-10 Online:2012-03-31
About author:WU Yi-Qing. E-mail: woshiwuyiqing@126.com

摘要/Abstract

摘要：

提出了一种可大规模制备CeO₂纳米粉的有效方法. 用碳化铈水解氧化制得颗粒大小为3~5 nm的CeO₂纳米粉. 研究了各种实验参数包括水解温度、反应时间和投料比对CeO₂纳米粉比表面积的影响. 结果表明: 较低的水解温度(室温附近), 较高的投料比(1:20(g/mL))和适当的反应时间(18 h)可得到比表面积为149 m²/g的CeO₂纳米粉. 优化实验参数(水解温度为30℃, 水解时间为18 h, 投料比为1:20(g/mL), 滤饼在空气中80℃烘干4 h)得到中间产物Ce(OH)₃和目标产物CeO₂, 并用XRD、TEM、SAED及紫外-可见光分光光度计进行测试表征. 发现Ce(OH)₃是由大量长为50~100 nm, 直径为5~20 nm的纳米棒组成. CeO₂纳米粉具有较高的紫外吸收性能和较好的催化CO性能.

关键词: 碳化铈, CeO₂纳米粉, CO催化, 水解氧化

Abstract:

An effective route for the synthesis of CeO₂ nanopowders on a large scale was presented. High-quality CeO₂ nanopowders composed of nanoparticles with size of 3-5 nm were prepared by hydrolysis and oxidation of cerium carbide. The experimental variables which can tune the BET surface area of CeO₂ nanopowders, including hydrolysis reaction temperature, reaction time, as well as feed ratio of cerium carbide, were systematically. Experimental results indicate that the lower hydrolysis temperature (around room temperature), higher feed ratio (1:20 (g/mL)), and proper reaction time (18 h) can product CeO₂ nanopowders with higher surface area. The intermediate outcome Ce(OH)₃ and aimed product CeO₂ obtained with the optimized experimental variables (hydrolysis of cerium carbide powder at constant temperature (30℃) for 18 h in the suspension with feed ratio of 1:20 (g/mL) and dried at 80℃ for 4 h in the air) were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), selected area electron diffraction (SAED), and UV-visible absorption spectrometer. It is found that the Ce(OH)₃is composed of a large quantity of rodlike nanostructures with length of 50-100 nm and diameter of 5-20 nm and the CeO₂ nanopowders have higher UV-Vis absorbance property. Furthermore, the CeO₂ nanopowders possess fine CO catalytic performance.

Key words: cerium carbide alloy, CeO₂ nanopowders, CO catalytic performance, hydrolysis and oxidation

中图分类号:

O611

吴移清, 倪建森, 杜亚男, 胡鹏飞, 丁伟中, 耿淑华. 碳化铈水解氧化法制备CeO₂纳米粉[J]. 无机材料学报, 2012, 27(5): 489-494.

WU Yi-Qing, NI Jian-Sen, DU Ya-Nan, HU Peng-Fei, DING Wei-Zhong, GENG Shu-Hua. Preparation of CeO₂Nanopowders by Hydrolysis and Oxidation of Cerium Carbide[J]. Journal of Inorganic Materials, 2012, 27(5): 489-494.

图/表 9

图1 滤饼(a)、CeO2纳米粉(b)和厂售CeO2(c)的XRD图谱

Fig. 1 XRD patterns of filter (a), CeO2 nanopowders (b) and commercial CeO2 (c)

图2 滤饼的TEM照片(a)、HRTEM晶格像(b)和SAED(c)

Fig. 2 TEM (a) and HRTEM (b) images of Ce(OH)3 filters and the corresponding SAED(c)

图3 CeO2纳米粉的TEM照片(a) 和HRTEM晶格像(b)

Fig. 3 TEM (a) and HRTEM (b) images of CeO2 nanopowders

图4 CeO2纳米粉比表面积与反应温度的关系

Fig. 4 Effect of reaction temperature on surface area of CeO2 nanopowders

图5 CeO2纳米粉比表面积与反应时间的关系

Fig. 5 Effect of reaction time on surface area of CeO2 nanopowders

图6 CeO2纳米粉比表面积与投料比的关系

Fig. 6 Effect of feed ratio on surface area of CeO2 nanopowders

图7 CeO2纳米粉的等温吸附-脱附曲线(a)和BJH孔分布曲线(b)

Fig. 7 Nitrogen adsorption-desorption isotherms (a) and pore distribution (b) of CeO2 nanopowders

图8 CeO2纳米粉(a)与厂售CeO2(b)UV吸收性能

Fig. 8 UV-Vis absorption spectra of CeO2 nanopowders (a) and commercial CeO2 (b)

图9 CeO2纳米粉的CO催化性能

Fig. 9 CO catalytic performance of CeO2 nanopowders

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碳化铈水解氧化法制备CeO₂纳米粉

Preparation of CeO₂Nanopowders by Hydrolysis and Oxidation of Cerium Carbide

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