纳米银/伊利石复合材料的制备及其性能研究

doi:10.15541/jim20170253

摘要/Abstract

摘要：

采用水热合成法对伊利石进行改性, 再通过微波辅助和紫外灯还原法制备了高载银量的纳米银/伊利石复合材料。利用X射线衍射(XRD)、红外(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和抑菌圈试验等方法研究了复合材料的结构、形貌及抑菌性能。结果表明, 改性后伊利石具有较高的载银量, 最高可达27.66%, 而且还原的纳米银在伊利石表面分布均匀。抑菌圈试验结果显示, 这种复合材料对金黄色葡萄球菌和大肠杆菌均有良好的抑菌效果, 最大抑菌尺寸分别达到5.68 mm和6.84 mm。

关键词: 纳米银, 伊利石, 水热合成法, 改性, 抑菌圈

Abstract:

High-content nano-Ag/illite composite was prepared through procedure of hydrothermal modification of illite, microwave-assisted upload and ultraviolet lamp irradiation reduction of Ag. Its structure, morphology, particle size, and affinity of Ag and illite were characterized by X-ray diffraction (XRD), infrared spectra (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM), and laser particle size distribution analyzer. The results showed that the modified illite became thicker due to the distracted layers, showing flower-like shape. In the meantime, the adsorption performance and ion-exchange capacity of modified illite obviously are enhanced. Through microwave-assisted upload and ultraviolet reduction of Ag, the uniformed Ag nano-particles were dispersed highly on the surface of illite and interacted closely to illite. Ag content in nano-Ag/illite composite is up to 27.66%. The antibacterial activities of nano-Ag/illite composites against Staphylococcus Aureus and Escherichia Coli were investigated by the inhibition zone test. The results showed that this composite material had excellent antibacterial activity against both Staphylococcus Aureus and Escherichia Coli, and the maximum antibacterial sizes were up to 5.68 mm and 6.84 mm, respectively. Furthermore, the unique lamellar structure and significant adsorption capacities of illite helped a lot to immobilize more bacteria and improved the antibacterial activity.

Key words: nano-Ag, illite, hydrothermal synthesis, modified, inhibition zone

中图分类号:

王树江, 杨永恒, 温春阳, 张国馗, 苑春晖. 纳米银/伊利石复合材料的制备及其性能研究[J]. 无机材料学报, 2018, 33(5): 570-576.

WANG Shu-Jiang, YANG Yong-Heng, WEN Chun-Yang, ZHANG Guo-Kui, YUAN Chun-Hui. Preparation and Property of Nano-Ag/illite Composite Material[J]. Journal of Inorganic Materials, 2018, 33(5): 570-576.

图/表 10

图1 伊利石/改性伊利石的XRD图谱

Fig. 1 XRD patterns of (I) raw illite and (N) modified illite

图2 伊利石/改性伊利石红外谱图

Fig. 2 FT-IR spectra of (I) raw illite and (N) modified illite

图3 伊利石原样(I)和改性伊利石(N)的SEM照片

Fig. 3 SEM images of (I) raw illite and (N) modified illite

图4 纳米银/伊利石复合材料的载银量

Fig. 4 Silver loading of nano-Ag/illite composite

图5 纳米银/伊利石复合材料的XRD图谱

Fig. 5 XRD patterns of nano-Ag/illite composite

图6 纳米银/伊利石复合材料的TEM照片

Fig. 6 TEM images of nano-Ag/illite composite(a) Ag-I; (b) Ag-N; (c) Ag-P-N; (d) Ag-C-N

表1 复合材料的粒径

Table 1 Particle size of the composite

No.	Sample	Average particle size/nm	D₅₀/nm
1	I	1068.3	877.7
2	N	884.8	630.7
3	Ag-I	1043.6	851.1
4	Ag-N	875.7	642.7
5	Ag-P-N	873.2	649.3
6	Ag-C-N	857.8	648.3

图7 纳米银/伊利石复合材料对金黄色葡萄球菌的抑菌效果照片

Fig. 7 Typical photographs of nano-Ag/illite composite re-cultivated Staphylococcus aureus colonies on agar(a) I; (b) Ag-I; (c) Ag-N; (d) Ag-P-N; (e) Ag-C-N; (f) AgNO3

图8 纳米银/伊利石复合材料对大肠杆菌的抑菌效果照片

Fig. 8 Typical photographs of nano-Ag/illite composite re-cultivated Escherichia coli colonies on agar(a) I; (b) Ag-I; (c) Ag-N; (d) Ag-P-N; (e) Ag-C-N; (f) AgNO3

表2 抑菌圈试验结果

Table 2 Result of inhibition zone test

No.	Sample	Staphylococcus aureus			Escherichia coli
No.	Sample	D₁/mm	D₂/mm	D₃/mm	D₁/mm	D₂/mm	D₃/mm
1	I	8.00	8.32	0.32	8.00	8.52	0.52
2	Ag-I	8.00	10.14	2.14	8.00	10.06	2.06
3	Ag-N	8.00	11.44	3.44	8.00	11.28	3.28
4	Ag-P-N	8.00	12.48	4.48	8.00	12.38	4.38
5	Ag-C-N	8.00	13.68	5.68	8.00	14.84	6.84
6	AgNO₃	8.00	12.80	4.80	8.00	11.48	3.48

参考文献 28

[1]	LIU XIN-HAI, LI YI-BO.Study on surface modification of illite. Industrial Minerals & Processing, 2004, 33(2): 8-10.
[2]	SHI JUN, YU ZHI-WEI, ZHENG JU-GONG,et al. Research of the modified illite on reinforcing mechanical properties of flexible PVC. Journal of East China Institute of Technology (Natural Science), 2014, 37(1): 84-87.
[3]	HUANG JI-TAI, DAI JIN-CAO, BEI YI-LING,et al. Modification of illite fines and its application to rubber. China Mining Magazine, 1995, 4(6): 52-55.
[4]	ÖZTOP B, SHAHWAN T.Modification of a montmorillonite-illite clay using alkaline hydrothermal treatment and its application for the removal of aqueous Cs+ ions.Journal of Colloid and Interface Science, 2006, 295(2): 303-309.
[5]	WANG L, LI L.Illite spatial distribution patterns dictate Cr(VI) sorption macrocapacity and macrokinetics.Environmental Science & Technology, 2015, 49(3): 1374-1383.
[6]	BANIK N, MARSAC R, Lützenkirchen J,et al. Sorption and redox speciation of plutonium at the illite surface. Environmental Science&Technology, 2016, 50(4): 2092-2098.
[7]	LI XIAO-MIN, KOU XIAO-WEI.Illite: a new potential clay mineral material.World Geology, 2000, 19(4): 346-349.
[8]	RAI M, YADAV A, GADE A.Silver nanoparticles as a new generation of antimicrobials. Biotechnology Advances, 2009, 27(1): 76-83.
[9]	WANG HUI-LEI, LIU XIAO-HENG.Preparation of silver nanoparticle loaded mesoporous TiO2 and its photocatalytic property.Journal of Inorganic Materials, 2016, 31(5): 555-560.
[10]	TAN YING, TAN GUO-XIN, NING CHENG-YUN,et al. Bioinspired polydopamine functionalization of titanium surface for silver nanoparticles immobilization with antibacterial property. Journal of Inorganic Materials, 2014, 29(12): 1320-1326.
[11]	LI F, WEIR M D, CHEN J,et al. Comparison of quaternary ammonium-containing with nano-silver-containing adhesive in antibacterial properties and cytotoxicity. Dental Materials, 2013, 29(4): 450-461.
[12]	SPADARO D, BARLETTA E, BARRECA F,et al. Synthesis of PMA stabilized silver nanoparticles by chemical reduction process under a two-step UV irradiation. Applied Surface Science, 2010, 256(12): 3812-3816.
[13]	PAL A, SHAH S, DEVI S.Microwave-assisted synthesis of silver nanoparticles using ethanol as a reducing agent.Materials Chemistry and Physics, 2009, 114(2): 530-532.
[14]	HE B, TAN J J, KONG Y L,et al. Synthesis of size controlled Ag nanoparticles. Journal of Molecular Catalysis A Chemical, 2004, 221(1/2): 121-126.
[15]	YAO BAO-HUI, XU GUO-CAI, ZHANG HONG-YAN,et al. Synthesis of nanosilver with polyvinylpyrrolidone(PVP) by microwave method. Chinese Journal of Inorganic Chemistry, 2010, 26(9): 1629-1632.
[16]	VODNIK V V, BOŽANIĆ D K, DŽUNUZOVIĆ E,et al. Thermal and optical properties of silver-poly(methylmethacrylate) nanocomposites prepared by in-situ radical polymerization. European Polymer Journal, 2010, 46(2): 137-144.
[17]	SHI ZHEN-WU, GUO SHAO-BO, XUE QUN-HU.Preparation, photocatalytic property and antibacterial property of Ag@TiO2@SiO2 composite nanomaterials.Journal of Inorganic Materials, 2016, 31(5): 466-472.
[18]	SÁNCHEZ F G, LOON L R V, GIMMI T,et al. Self-diffusion of water and its dependence on temperature and ionic strength in highly compacted montmorillonite, illite and kaolinite. Applied Geochemistry, 2008, 23(12): 3840-3851.
[19]	季桂娟, 张培萍, 姜桂兰. 膨润土加工与应用, 2版. 北京: 化学工业出版社, 2013: 15-19.
[20]	HU XIAO-XIA, ZHAO LIN, ZHAO SHU-YU,et al. Microwave- assisted preparation of copper hydroxyphosphate and characterization of Photocatalysis under visible light. Journal of Inorganic Materials, 2016, 31(4): 421-426.
[21]	HUANG XIANG-DONG, LI JIAN-BAO, XIE ZHI-PENG,et al. Microwave interaction with inorganic nonmetallic substance, Journal of Inorganic Materials, 1998, 13(3): 282-290.
[22]	ZENG XIANG-FENG, ZHANG KAI, YU XIAO-MAN,et al. Adsorption behaviors of Cd on montmorillonite/illite in alkaline saline conditions. Journal of Agro-Environment Science, 2008, 27(6): 2251-2257.
[23]	FOX B S, BEYER M K, BONDYBEY V E.Coordination chemistry of silver cations.Journal of the American Chemical Society, 2002, 124(45): 13613-13623.
[24]	PEARSON R G.Hard and soft acids and bases.Journal of The American Chemical Society. 1963, 85(22): 3533-3539.
[25]	SUN XIAO-FEI, WEI CHANG-PING, LI QI-YUAN,et al. Ag/SiO2 composite thin films: preparation by UV radiation deoxidation and optical properties. Chinese Journal of Inorganic Chemistry, 2008, 24(11): 1895-1899.
[26]	SONDI I, SALOPEK-SONDI B.Silver nanoparticles as antimicrobial agent: a case study onE. coli as a model for gram-negative bacteria. Journal of Colloid and Interface Science, 2004, 275(1): 177-182.
[27]	GUZMAN M, DILLE J, GODET S.Synthesis and antibacterial activity of silver nanoparticles against gram-positive and gram-negative bacteria.Nanomedicine: Nanotechnology, Biology and Medicine, 2012, 8(1): 37-45.
[28]	SADEGHI B, GARMAROUDI F S, HASHEMI M,et al. Comparison of the anti-bacterial activity on the nanosilver shapes: nanoparticles, nanorods and nanoplates. Advanced Powder Technology, 2012, 23(1): 22-26.