氧化石墨烯在水热法制备Sc2W3O12粉体中的应用

doi:10.15541/jim20140357

摘要/Abstract

摘要：

以硝酸钪, 钨酸铵等为原料, 氧化石墨烯为表面活性剂, 采用水热法制备了类十字架状Sc₂W₃O₁₂粉体。利用XRD、TG-DSC、Raman及SEM考察了加入氧化石墨烯对所合成产物结构和形貌的影响, 采用TMA测试了所得Sc₂W₃O₁₂粉体的热膨胀性质。分析表明: 在200℃水热条件下, 氧化石墨烯包裹在Sc₂W₃O₁₂晶粒表面并抑制了原有某些晶面的增长, 使晶粒逐渐长为棒状, 进而纳米棒团聚成类十字架状, 产物经620℃热处理10 min后得到纯净的Sc₂W₃O₁₂粉体, 其在室温~800℃均呈现出负热膨胀特性, 且平均热膨胀系数为-4.75×10^-6/K。

关键词: 氧化石墨烯, 表面活性剂, Sc2W3O12, 负热膨胀

Abstract:

Cross-like Sc₂W₃O₁₂ powder was synthesized via hydrothermal method by using scandium nitrate, ammonium tungstate hydrate as raw materials and graphene oxide as surfactant. XRD, TG-DSC, Raman and SEM were used to study the influence of graphene oxide on structures and morphologies of the as-prepared product, and the negative thermal expansion properties were detected by TMA. Results show that graphene oxide wraps the grain of Sc₂W₃O₁₂ and inhibits the growth of some of the original crystal faces, which makes the grain grow to nanorods, then the nanorods assemble into cross-like structure. The pure cross-like Sc₂W₃O₁₂ powder is obtained by hydrothermal method at 200℃ followed by heat treatment at 620℃ for 10 min. The TMA data indicate that the thermal expansion coefficient of Sc₂W₃O₁₂ is -4.75×10^-6/K from room temperature to 800℃.

Key words: graphene oxide, surfactant, scandium tungstate, negative thermal expansion

中图分类号:

TQ174

居相文, 吴日民, 周亚洲, 马双彪, 杨娟, 程晓农. 氧化石墨烯在水热法制备Sc₂W₃O₁₂粉体中的应用[J]. 无机材料学报, 2015, 30(4): 374-378.

JU Xiang-Wen, WU Ri-Min, ZHOU Ya-Zhou, MA Shuang-Biao, YANG Juan, CHENG Xiao-Nong. Application of Graphene Oxide in Synthesis of Sc₂W₃O₁₂ Powder[J]. Journal of Inorganic Materials, 2015, 30(4): 374-378.

图/表 8

图1 不同反应条件下制得产物的XRD图谱

Fig. 1 XRD patterns of products reacted under different conditions (a) Without GO, 200℃, 20 h; (b) GO assisted, 200℃, 10 h; (c) GO assisted, 200℃, 15 h; (d) GO assisted, 200℃, 20 h

图2 Sc2W3O12/GO(a)与Sc2W3O12(b)粉体的XRD图谱和正交相Sc2W3O12标准XRD图谱

Fig. 2 XRD patterns of Sc2W3O12/GO(a) and Sc2W3O12(b), standard XRD pattern of typical orthorhombic phase of Sc2W3O12

表1 Sc2W3O12, Sc2W3O12/GO的晶格常数与晶胞体积

Table 1 Lattice parameters and cell volume of Sc2W3O12 and Sc2W3O12/GO

Sample	Lattice parameters/nm			Cellvolume/nm³
Sample	a-axis	b-axis	c-axis	Cellvolume/nm³
Sc₂W₃O₁₂	0.9593	0.9695	1.3333	1.2401
Sc₂W₃O₁₂/GO	0.9623	0.9713	1.3358	1.2485

图3 Sc2W3O12/GO(a)与Sc2W3O12(b)的TG-DSC曲线

Fig. 3 TG-DSC curves of Sc2W3O12/GO (a) and Sc2W3O12 (b)

图4 Sc2W3O12(a)、Sc2W3O12/GO(b)及GO(c)的拉曼光谱图

Fig. 4 Raman spectra of Sc2W3O12 (a), Sc2W3O12/GO (b) and GO (c)

表2 Sc2W3O12、Sc2W3O12/GO与所用GO的拉曼光谱参数

Table 2 Raman parameters for GO, Sc2W3O12/GO and Sc2W3O12

Sample	Absorption band of [WO₄] /cm^-1			D-band/cm^-1	G-band/cm^-1	R	L_a/nm
Sample	Raman shift			Raman shift	Raman shift	I_D/I_G	4.4/R
Sc₂W₃O₁₂	353	828	1022	—	—	—	—
Sc₂W₃O₁₂/GO	350	827	1017	1354	1599	1.0886	4.042
GO	—	—	—	1347	1584	0.9522	4.621

图5 不同反应条件获得产物的SEM照片

Fig. 5 SEM images of the samples prepared at different conditions (a)Without GO, 200℃, 20 h; (b) GO assisted, 200℃, 10 h; (c) GO assisted, 200℃, 15 h; (d) GO assisted, 200℃, 20 h; (e) High-dispersion Sc2W3O12/GO products; (f) Sc2W3O12 powder

图6 Sc2W3O12的热膨胀曲线

Fig. 6 Thermal expansion curves of Sc2W3O12

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氧化石墨烯在水热法制备Sc₂W₃O₁₂粉体中的应用

Application of Graphene Oxide in Synthesis of Sc₂W₃O₁₂ Powder

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