石墨/TinO2n-1复合材料的制备及性能

doi:10.16085/j.issn.1000-6613.2020-0805

摘要/Abstract

摘要：

在常压下，以钛白粉为原料，石墨为还原剂，采用碳热还原法制备了石墨/Ti_nO₂_n-₁复合材料。采用XRD系统分析了碳热还原过程中钛的价态变化规律；采用XPS、SEM、TEM分析了特定样品的形貌、结构和元素组成。XRD分析结果表明，控制不同的还原条件，可以得到不同n值的石墨/Ti_nO₂_n-₁复合材料，且还原过程的物相转变顺序为：TiO₂（锐钛型）、TiO₂（金红石型）、Ti₉O₁₇、Ti₈O₁₅、Ti₆O₁₁、Ti₅O₉和Ti₄O₇。在还原温度为1250℃，还原时间为20min，碳钛比为5∶10的条件下所制备的石墨/Ti_nO₂_n-₁复合材料的电阻率最低，其值为0.1465Ω·cm。吸附/光降解实验表明，石墨/Ti_nO₂_n-₁复合材料对亚甲基蓝的吸附能力比纯石墨显著增强，吸附去除率为纯石墨的1.40~3.20倍；石墨/Ti_nO₂_n-₁复合材料对亚甲基蓝具有光催化降解活性，但是其光降解能力低于锐钛型TiO₂；复合材料的催化降解速率常数最大值为0.0047min^-1。

关键词: Ti_nO₂_n-₁, 复合材料, 还原, 制备, 吸附, 降解

Abstract:

Under atmospheric pressure, the graphite/Ti_nO₂_n-₁ composites were prepared by an carbothermal reduction process of anatase titanium dioxide powders using graphite reductant. The variation of valence state of titanium was investigated by X-ray diffractometer (XRD) in the carbothermal reduction process, and morphology, structure and element composition of the specific reduced sample was analyzed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The XRD results indicated that the graphite/Ti_nO₂_n-₁ composites with different n value could be obtained with controlling different reduction conditions, and the order of phase transition was TiO₂(anatase), TiO₂(rutile), Ti₉O₁₇, Ti₈O₁₅, Ti₆O₁₁, Ti₅O₉ and Ti₄O₇. The minimum resistivity of the reduced samples was 0.1465Ω·cm, which was prepared at 1250℃ for 20min with the graphite/TiO₂ mass ratio of 5∶10. The adsorption capacity of graphite/Ti_nO₂_n-₁ composites in methylene blue (MB) bleaching was enhanced in comparison with graphite powers, and the removal efficiency was 1.40～3.20 times of graphite. Under visible light irradiation, the graphite/Ti_nO₂_n-₁ composites were confirmed to have photocatalytic activity for the degradation of methylene blue (MB) though a little lower than that of anatase TiO₂. The maximum apparent rate constant k of the graphite/Ti_nO₂_n-₁ composites was 0.0047min^-1.

Key words: Ti_nO₂_n-₁, composites, reduction, preparation, adsorption, degradation

中图分类号:

TQ134.1

吴恩辉, 李军, 侯静, 黄平, 徐众, 蒋燕, 罗彬杨. 石墨/Ti_nO₂_n-₁复合材料的制备及性能[J]. 化工进展, 2021, 40(3): 1517-1526.

WU En’hui, LI Jun, HOU Jing, HUANG Ping, XU Zhong, JIANG Yan, LUO Binyang. Preparation and properties of graphite/Ti_nO₂_n-₁ composites[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1517-1526.

图/表 9

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还原温度/℃	石墨∶TiO₂	还原时间/min	物相组成	k/min^-1	R²
还原样品
1150	3∶10	20	金红石型TiO₂	0.0060±0.0002	0.99433
1200	3∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0042±0.0002	0.98848
1250	3∶10	20	Ti₉O₁₇	0.0036±0.0001	0.99152
1300	3∶10	20	Ti₅O₉	0.0033±0.0001	0.99044
1350	3∶10	20	Ti₄O₇	0.0047±0.0007	0.99804
1250	1∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0040±0.0002	0.98857
1250	2∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0036±0.0001	0.98948
1250	4∶10	20	Ti₈O₁₅	0.0029±0.0009	0.99279
1250	5∶10	20	Ti₆O₁₁	0.0035±0.0001	0.99096
1250	3∶10	5	金红石型TiO₂	0.0070±0.0001	0.99763
1250	3∶10	10	金红石型TiO₂+Ti₉O₁₇	0.0041±0.0001	0.99448
1250	3∶10	40	Ti₄O₇	0.0035±0.0001	0.98597
1250	3∶10	60	Ti₄O₇	0.0035±0.0001	0.98635
锐钛型 TiO₂			锐钛型TiO₂	0.0056±0.0005	0.96879
石墨粉			石墨	0.0019±0.0001	0.99823

还原温度/℃	石墨∶TiO₂	还原时间/min	物相组成	k/min^-1	R²
还原样品
1150	3∶10	20	金红石型TiO₂	0.0060±0.0002	0.99433
1200	3∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0042±0.0002	0.98848
1250	3∶10	20	Ti₉O₁₇	0.0036±0.0001	0.99152
1300	3∶10	20	Ti₅O₉	0.0033±0.0001	0.99044
1350	3∶10	20	Ti₄O₇	0.0047±0.0007	0.99804
1250	1∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0040±0.0002	0.98857
1250	2∶10	20	金红石型TiO₂+Ti₉O₁₇	0.0036±0.0001	0.98948
1250	4∶10	20	Ti₈O₁₅	0.0029±0.0009	0.99279
1250	5∶10	20	Ti₆O₁₁	0.0035±0.0001	0.99096
1250	3∶10	5	金红石型TiO₂	0.0070±0.0001	0.99763
1250	3∶10	10	金红石型TiO₂+Ti₉O₁₇	0.0041±0.0001	0.99448
1250	3∶10	40	Ti₄O₇	0.0035±0.0001	0.98597
1250	3∶10	60	Ti₄O₇	0.0035±0.0001	0.98635
锐钛型 TiO₂			锐钛型TiO₂	0.0056±0.0005	0.96879
石墨粉			石墨	0.0019±0.0001	0.99823

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石墨/Ti_nO₂_n-₁复合材料的制备及性能

Preparation and properties of graphite/Ti_nO₂_n-₁ composites

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