模拟太阳光下锗掺杂纳米TiO2对化学毒剂的降解性能

doi:10.15541/jim20150450

摘要/Abstract

摘要：

采用均匀沉淀法制备不同锗掺杂浓度的纳米二氧化钛(TiO₂); 为了研究掺杂浓度与粉体活性之间的关系, 针对化学毒剂(CWAs)模拟剂2-氯乙基乙基硫醚(2-CEES)和甲基膦酸二甲酯(DMMP)开展光催化消毒实验, 并用动力学方程拟合实验结果; 通过XRD、UV-Vis、BET、BJH、SEM和TEM等技术对样品进行表征, 分析锗掺杂对TiO₂结构及性能的影响; 综合考虑溶剂的毒性、挥发性、可燃性和溶解性等因素, 以氢氟醚(HFE)作为分散溶剂, 研究模拟太阳光下Ge-TiO₂和HFE混合体系对芥子气(HD)、梭曼(GD)和维埃克斯(VX)的消毒性能。结果表明: 适量锗掺杂不会改变纳米TiO₂的晶型结构, 可以减小晶粒尺寸, 增大比表面积, 增强光利用率, 提高消毒活性; 相较于直接使用粉体消毒, 混合体系的消毒效率明显提高; 在模拟太阳光下, 最佳锗掺杂浓度(6.24wt%)样品与HFE-458 (HCF₂CF₂CH₂OCF₂CF₂H)组成的混合体系与三种化学毒剂反应60 min的降解率分别为: HD 98.73%、GD 100%、VX 100%。

关键词: 化学毒剂, 洗消, 锗掺杂, 二氧化钛, 氢氟醚, 模拟太阳光

Abstract:

Titanium dioxide (TiO₂) nanoparticles doped with varying amounts of germanium were prepared by homogeneous precipitation method. To investigate the relationship between doping content and photocatalytic activity, the photocatalytic degradation efficiency of 2-chloroethyl ethyl sulphide (2-CEES) and dimethyl methylphosphonate (DMMP) on the prepared samples were examined, and the data were fitted by a kinetic equation. After that, physical properties of the samples were determined by XRD, UV-Vis, BET, BJH, SEM, and TEM. For consideration of toxicity, volatility, flammability, and solubility, hydrofluoroether (HFE) was first used as dispersion solvent. Ge-TiO₂ was dispersed in HFE-458 (HCF₂CF₂CH₂OCF₂CF₂H), and the disinfection efficiency of sulphur mustard (HD), soman (GD) and S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothiolate (VX) were studied under the simulated sunlight irradiation. These results show that Ge (6.24wt%)-TiO₂ exhibits the best photocatalytic performance. Appropriate amount of Ge dopant doesn’t change the crystal structure of TiO₂, but reduces the grain size, increases the surface area, improves the light utilization, and improves the photocatalytic disinfection activity of TiO₂. After reacting with Ge(6.24wt%)-TiO₂ and HFE-458 suspension for 60 min, the degradation efficiency of HD, GD and VX is 98.73%, 100% and 100%, respectively.

Key words: chemical warfare agents, decontamination, germanium-doped, titanium dioxide, hydrofluoroether, simulated sunlight irradiation

中图分类号:

TF123

沈忠, 钟近艺, 赵渊中, 崔燕, 陈立坤, 郑禾. 模拟太阳光下锗掺杂纳米TiO₂对化学毒剂的降解性能[J]. 无机材料学报, 2016, 31(4): 427-433.

SHEN Zhong, ZHONG Jin-Yi, ZHAO Yuan-Zhong, CUI Yan, CHEN Li-Kun, ZHENG He. Degradation of Chemical Warfare Agents by Germanium-doped Nanosized TiO₂ under Simulated Sunlight Irradiation[J]. Journal of Inorganic Materials, 2016, 31(4): 427-433.

图/表 8

图1 模拟太阳光下样品降解2-CEES和DMMP的动力学曲线

Fig. 1 Degradation kinetic curves of 2-CEES and DMMP on the samples under simulated sunlight irradiation (a) 2-CEES; (b) DMMP

表1 动力学方程拟合结果

Table 1 Fitting results of the kinetic equation

Sample	2-CEES			DMMP
Sample	k₁/h^-1	k₂/h^-1	R²	k₁/h^-1	k₂/h^-1	R²
GT-0	2.40	1.21×10^-1	0.9997	1.31	1.17×10^-1	0.9995
GT-1	0.64	1.21×10^-2	0.9937	0.38	7.65×10^-3	0.9886
GT-2	1.08	4.00×10^-2	0.9954	1.37	1.06×10^-1	0.9952
GT-3	4.80	1.82×10^-1	0.9999	1.58	1.07×10^-1	0.9952
GT-4	1.67	5.09×10^-2	0.9984	0.78	3.81×10^-2	0.9878
GT-5	2.82	1.83×10^-1	0.9999	1.32	1.20×10^-1	0.9990
GT-6	4.66	3.56×10^-1	0.9999	3.91	2.23×10^-1	0.9999
GT-7	3.41	4.86×10^-1	0.9999	2.73	4.62×10^-1	0.9999
GT-8	3.95	3.12×10^-1	0.9999	2.60	1.85×10^-1	0.9997
GT-9	3.56	2.27×10^-1	0.9999	1.64	1.34×10^-1	0.9993

图2 GT-0、GT-4、GT-7和GT-9样品的XRD谱图

Fig. 2 XRD patterns of samples GT-0, GT-4, GT-7 and GT-9

图3 GT-0、GT-4 和GT-7样品的紫外-可见吸收光谱

Fig. 3 UV-Vis absorption spectra of GT-0, GT-4 and GT-7

图4 样品(a) GT-0和(b) GT-7的N2吸附-脱附等温线和孔径微分分布曲线

Fig. 4 Nitrogen adsorption-desorption isotherms and pore width differential distribution curves of sample (a) GT-0 and (b) GT-7

图5 样品(a) GT-0、(b) GT-4和(c) GT-7的SEM照片

Fig. 5 SEM images of sample (a) GT-0, (b) GT-4 and (c) GT-7

图6 样品(a, b)GT-0、(c, d)GT-4和(e, f)GT-7的TEM及HRTEM照片

Fig. 6 TEM and HRTEM images of sample (a, b) GT-0, (c, d) GT-4 and (e, f) GT-7

图7 模拟太阳光下混合体系对HD、GD、VX、2-CEES和DMMP的消毒性能

Fig. 7 Degradation of HD, GD, VX, 2-CEES, and DMMP on Ge-TiO2 (6.24wt%)&HFE-458 suspension under simulated sunlight irradiation

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模拟太阳光下锗掺杂纳米TiO₂对化学毒剂的降解性能

Degradation of Chemical Warfare Agents by Germanium-doped Nanosized TiO₂ under Simulated Sunlight Irradiation

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