TiO2@SiO2复合材料的制备及其光催化与抗菌性能的研究

doi:10.15541/jim20190039

摘要/Abstract

摘要：

采用溶胶-凝胶法制备载体SiO₂, 并通过水解法制备出负载型TiO₂@SiO₂复合光催化抗菌材料, 采用SEM、XRD、BET、FT-IR、XPS和粒度仪对材料进行表征和分析。在UVA紫外光照下, 通过降解甲基橙溶液考察了复合材料的光催化性能, 在照射3 h后, 不同钛掺杂量复合材料的光催化降解率均能达到99.9%, 钛掺比为0.58时催化效率最高。通过平板涂布法检测了复合材料对大肠杆菌的抗菌效果, 发现抗菌性能随着钛含量的增加而提高, 在紫外照射条件下最高可达92%以上, 同时在可见光照射下也能表现出良好的抗菌性能。通过细菌荧光检测, 可以有效证明复合材料所产生的活性氧迁移到了细胞内部, 造成细胞体氧化损伤, 这是光催化材料抗菌机理研究的重要依据。

关键词: TiO₂@SiO₂复合材料, 光催化, 抗菌, 活性氧

Abstract:

Carrier SiO₂ was synthesized through Sol-Gel method, and the photocatalytic antibacterial material of TiO₂@SiO₂ composite was prepared by hydrolysis method. The synthesized composites were characterized. The photocatalytic properties of the composites were investigated by degrading methyl orange with UVA irradiation. After 3 h irradiation, all of composites with different amount of titanium doping can reach 99.9%. And the optimal catalytic efficiency of the composite is obtained when the titanium doping ratio (molar ratio) is 0.58. Antibacterial effect of composites on Escherichia coli, measured by plate coating method, shows that the antibacterial properties are improved with the increase of titanium content, which reach up to 92% under UVA irradiation. Moreover, the composites also exhibit favourable antibacterial properties under visible irradiation. Though fluorescence detection of bacterium, it is proved that the reactive oxygen species (ROS) produced by the composites migrate into the cells and cause the oxidative damage of the cells, which is a significant basis for the antibacterial mechanism of photocatalytic materials.

Key words: TiO₂@SiO₂ composites, photocatalysis, antibacterial, reactive oxygen species (ROS)

中图分类号:

TB332

陈一凡, 唐晓宁, 张彬, 罗勇, 李阳. TiO₂@SiO₂复合材料的制备及其光催化与抗菌性能的研究[J]. 无机材料学报, 2019, 34(12): 1325-1333.

CHEN Yi-Fan, TANG Xiao-Ning, ZHANG Bin, LUO Yong, LI Yang. TiO₂@SiO₂ Composites: Preparation and Photocatalytic Antimicrobial Performance[J]. Journal of Inorganic Materials, 2019, 34(12): 1325-1333.

图/表 15

图1 纯载体材料和复合材料的SEM照片

Fig. 1 SEM images of support and composites (a) SiO2; (b) TiO2-doped SiO2

图2 TiO2@SiO2复合材料的EDS能谱分析

Fig. 2 EDS analysis of TiO2-doped SiO2 composites

表1 TiO2@SiO2复合材料元素含量分析结果

Table 1 Analysis of element content about TiO2-doped SiO2 composites

Element	wt %	at %
Ti	28.40	13.57
Si	25.90	21.10
O	45.70	65.33

图3 SiO2、TiO2和TiO2@SiO2的XRD图谱

Fig. 3 XRD patterns of SiO2, TiO2 and TiO2-doped SiO2

图4 TiO2、SiO2和TiO2@SiO2的红外光谱图

Fig. 4 FT-IR transmission spectra of TiO2, SiO2 and TiO2- doped SiO2

图5 SiO2和TiO2@SiO2的XPS图谱

Fig. 5 XPS spectra of SiO2 and TiO2-doped SiO2

图6 SiO2和TiO2@SiO2(b)的粒径分布图

Fig. 6 Particle size distributions of SiO2 (a) and TiO2-doped SiO2 (b)

图7 不同样品的吸附-脱附曲线

Fig. 7 N2 adsorption-desorption isotherms with inserts showing pore size distributions of different samples by applying the BJH model

表2 SiO2、TiO2和TiO2@SiO2的比表面积和BJH吸附平均孔径

Table 2 BET analysis and BJH adsorption pore size of SiO2, TiO2 and TiO2-doped SiO2 composites

Sample	BET/(m²·g^-1)	BJH Pore size/nm
0.58-TiO₂@SiO₂	177	12.4
SiO₂	83	20.6
TiO₂	115	4.4

图8 不同Ti掺杂量TiO2@SiO2样品的光催化降解曲线

Fig. 8 Photocatalytic degradation of methyl orange by using TiO2-doped SiO2 with different Ti contents (1) 0.3-TiO2@SiO2; (2) 0.44-TiO2@SiO2; (3) 0.58-TiO2@SiO2; (4) 0.74-TiO2@SiO2; (5) 0.88-TiO2@SiO2

图9 UVA条件下SiO2、TiO2和不同钛掺杂量的TiO2@SiO2复合材料抗菌效果照片

Fig. 9 Antimicrobial effect of SiO2, TiO2 and TiO2-doped SiO2 composites with different Ti contents on E.coli under UVA irradiation

图10 UVA条件下不同钛掺杂量对TiO2@SiO2材料抗菌性能的影响

Fig. 10 Effect of the antimicrobial property using TiO2-doped SiO2 composites with different Ti contents under UVA irradiation

表3 不同光照条件下的抗菌性能结果

Table 3 Results of antibacterial activity with different irradiations

Lamp-house	Material	E.coli-BL21
Lamp-house	Material	Number (after 24 h)	Reduction of bacteria/%
UVA	Blank	833	-
	SiO₂	788	5.4
	0.58-TiO₂@SiO₂	163	80.5
	TiO₂	586	29.6
Visible light	Blank	808	-
Visible light	0.58-TiO₂@SiO₂	198	65.5

图11 TiO2@SiO2复合材料的抗菌机制

Fig. 11 Probable antimicrobial mechanism of TiO2-doped SiO2 composites

图12 TiO2、SiO2和0.58-TiO2@SiO2材料的荧光图谱

Fig. 12 Fluorescence spectra of TiO2, SiO2 and 0.58- TiO2@SiO2 Right diagram shows the values of fluorescence with an excitation wavelength of 492 nm and an emission wavelength of 504 nm

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TiO₂@SiO₂复合材料的制备及其光催化与抗菌性能的研究

TiO₂@SiO₂ Composites: Preparation and Photocatalytic Antimicrobial Performance

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