TiO2/α-FeOOH纳米复合材料的微结构及性能研究

doi:10.3724/SP.J.1077.2013.12194

无机材料学报 ›› 2013, Vol. 28 ›› Issue (2): 177-183.DOI: 10.3724/SP.J.1077.2013.12194 CSTR: 32189.14.SP.J.1077.2013.12194

TiO₂/α-FeOOH纳米复合材料的微结构及性能研究

王燕飞^1,2, 王卫³, 郑遗凡^1,4, 李国华⁴

(1. 浙江工业大学分析测试中心, 杭州 310014; 2. 天台县质量技术监督局苍山所, 台州 317200; 3. 台州市环境保护局椒江分局, 台州 318000; 4. 浙江工业大学化学工程与材料学院, 杭州 310014)

收稿日期:2012-03-29 修回日期:2012-07-04 出版日期:2013-02-10 网络出版日期:2013-01-23
作者简介:王燕飞(1985–), 女, 硕士, 助理工程师. E-mail: yanfeiwang2011@163.com
基金资助:
浙江省自然科学基金(Y4080209);浙江省科技计划项目(2007F70039)

Microstrcture Characterization and Properties of TiO₂/α-FeOOH Nanocomposites

WANG Yan-Fei^1,2, WANG Wei³, ZHENG Yi-Fan^1,4, LI Guo-Hua⁴

(1. Research Center of Analysis and Measurement Zhajiang University of Technology, HangZhou 310014, China; 2. The Quality and Technology Supervision Bureau of Tiantai, Taizhou, 317200, China; 3. Sub-bureau of Jiaojiang district of Taizhou environmental Taizhou 318000, China; 4. College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou, 310014, China)

Received:2012-03-29 Revised:2012-07-04 Published:2013-02-10 Online:2013-01-23
About author:WANG Yan-Fei. E-mail: yanfeiwang2011@163.com
Supported by:
Natural Science Foundation of ZheJiang Province (Y4080209);Science and Technology Project of the Zhejiang Province (2007F70039)

摘要/Abstract

摘要：

以TiCl₄为前驱体, 铁黄(α-FeOOH)为载体, 采用水解沉淀法在不同温度下制备了系列TiO₂/α-FeOOH纳米复合材料。应用XRD、HRTEM、STEM等方法对样品的物相、形貌、微结构等进行系统表征, 采用UV-DRS光谱仪检测其光学性能。结果表明: 随着反应温度的升高(30℃→90℃), 两相形成的包覆结构先逐渐变的连续, 然后再逐渐失去连续性, 其中45℃反应合成的TiO₂/α-FeOOH包覆结构连续致密; 包覆外层是由晶粒细小的金红石相TiO₂组成, 内层由晶粒较大的针铁矿相(α-FeOOH)组成, 金红石连续致密地包覆在α-FeOOH外面; TiO₂与α-FeOOH之间形成了稳定的共格结构, 部分TiO₂生长到α-FeOOH外层, 晶格畸变变大, 复合结构良好。光学性能测试结果表明, 包覆结构良好的复合材料吸收峰红移最大, 大大拓宽了光谱响应范围, 从而有效提高了对太阳光的利用率。

关键词: 金红石, 铁黄, 纳米复合材料, 微结构

Abstract:

A series of TiO₂/α-FeOOH nanocomposites were prepared by hydrolysis precipitation method at different temperatures using TiCl₄ as Ti source and α-FeOOH as support. The phase composition, morphology, microstructure and optical properties of the samples were investigated by XRD, HRTEM, STEM and UV-DRS. The results show that with the temperature gradually increasing from 30℃ to 90℃, the core-shell structure first gets better and then worse, and the best core-shell structure is formed at 45℃. The shell is composed of fine grains of rutile TiO₂ and the large grain of α-FeOOH serves as the core, and the nanocomposites coated continuous and dense. The interaction between TiO₂ and α-FeOOH is not only physical adsorption, a coherent lattice structure is formed at the interface between TiO₂ and α-FeOOH, which leads to a large lattice distortion and a good composite structure. UV-DRS results show that the largest red shift of absorption peak is observed for the composite with good core-shell structure, indicating that the TiO₂/α-FeOOH nanocomposites can greatly expand the range of spectral response and thus improve the utilization of sunlight.

Key words: rutile, goethite, nanocomposite, microstructure

中图分类号:

O649

王燕飞, 王卫, 郑遗凡, 李国华. TiO₂/α-FeOOH纳米复合材料的微结构及性能研究[J]. 无机材料学报, 2013, 28(2): 177-183.

WANG Yan-Fei, WANG Wei, ZHENG Yi-Fan, LI Guo-Hua. Microstrcture Characterization and Properties of TiO₂/α-FeOOH Nanocomposites[J]. Journal of Inorganic Materials, 2013, 28(2): 177-183.

图/表 6

图1 不同温度反应合成样品的XRD图谱

Fig. 1 XRD patterns of the samples reacted at different temperatures

图2 三个有代表性样品的XRD图谱的Rietveld全谱拟合分析图

Fig. 2 Rietveld whole patterns of the XRD patterns of three representative samples

Table 1 Maud refinement parameters of the XRD patterns of the samples reacted at different temperatures

Samples	Refinement parameters		Goethite						Rutile
			Cell parameters/nm			D/nm (110)	Microstrain (110)	wt%	Cell parameters/nm		D/nm (110)	Microstrain (110)	wt%
			a	b	c	D/nm (110)	Microstrain (110)	wt%	a=b	c	D/nm (110)	Microstrain (110)	wt%
30℃	Sig	1.52	0.46109	0.99652	0.30225	85.8	5.6350×10^-6	95.70	_	_	_	_	4.30
30℃	Rw%	4.98	0.46109	0.99652	0.30225	85.8	5.6350×10^-6	95.70	_	_	_	_	4.30
45℃	Sig	1.37	0.46118	0.99601	0.30229	80.8	6.5158×10^-4	57.68	0.46132	0.29768	3.56	0.0218	42.32
45℃	Rw%	5.29	0.46118	0.99601	0.30229	80.8	6.5158×10^-4	57.68	0.46132	0.29768	3.56	0.0218	42.32
60℃	Sig	1.34	0.46034	0.99628	0.30237	76.4	4.8678×10^-4	54.68	0.46247	0.29824	2.61	0.0164	45.32
60℃	Rw%	5.33	0.46034	0.99628	0.30237	76.4	4.8678×10^-4	54.68	0.46247	0.29824	2.61	0.0164	45.32
75℃	Sig	1.57	_	_	_	_	_	0.58	0.46129	0.29643	5.19	0.0106	99.42
75℃	Rw%	7.89	_	_	_	_	_	0.58	0.46129	0.29643	5.19	0.0106	99.42
90℃	Sig	1.54	_	_	_	_	_	1.08	0.46154	0.29653	5.37	0.0093	98.92
90℃	Rw%	7.66	_	_	_	_	_	1.08	0.46154	0.29653	5.37	0.0093	98.92

图3 不同温度反应合成样品的TEM和HRTEM照片

Fig. 3 TEM and HRTEM images of the samples reacted at different temperatures

图4 STEM-EDX模式下O、Ti和Fe元素的面扫描分布图

Fig. 4 STEM-EDX elemental mappings showing distributions of O, Ti, Fe elements

图5 样品的紫外-可见漫反射谱图

Fig. 5 UV-Vis diffuse reflectance spectra of samples at different temperatures

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TiO₂/α-FeOOH纳米复合材料的微结构及性能研究

Microstrcture Characterization and Properties of TiO₂/α-FeOOH Nanocomposites

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