CN108746663B - 一种香芹酚微乳体系制备纳米银的方法 - Google Patents
一种香芹酚微乳体系制备纳米银的方法 Download PDFInfo
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Abstract
本发明公开了一种香芹酚微乳体系制备纳米银的方法,利用高压均质技术制备香芹酚微乳液,将银氨溶液添加至微乳液体系中,在40℃~60℃的温度下反应一段时间,直至溶液的颜色变为黑褐色不再加深为止,得到含有纳米银的悬浮液,将该悬浮液在离心机中离心后,经过去离子水、乙醇洗涤后,在80℃~100℃下干燥得到纳米银粉体。本发明提供的制备方法绿色、环保,反应过程中银离子被微乳液中香芹酚的活性基团吸附在油水界面,进而被还原为纳米银,在微乳滴表面效应与香芹酚中活性基团络合的共同作用下纳米银被稳定在微乳液表面,并且纳米银表面被大分子物质络合,从而得到分散性好、稳定存在的粒径为10~50nm的球形纳米银粒子。
Description
技术领域
本发明属于纳米技术领域,涉及一种香芹酚微乳体系制备纳米银的方法。
背景技术
银纳米颗粒具有纳米材料的表面效应、小尺寸效应,量子尺寸效应和宏观量子隧道效应,因此在医学、食品等领域具有广泛的应用。纳米银合成方法有液相化学还原法,光化学还原法、电化学法等。专利申请号201710359697.5采用聚乙烯醇吡咯烷酮或者聚乙二醇作为保护剂,以N,N-二甲基乙醇胺、三乙醇胺或甲基二乙醇胺作为还原剂来制备纳米银溶胶;专利申请号CN201510236822.4采用聚乙烯醇水溶液为保护剂,以硼氢化钠为还原剂制备了纳米银溶胶,并利用该溶胶制备出抗静电及抗菌功能的纳米银天然纤维素纤维;专利申请号CN201611245866.4公开了一种在硝酸银水溶液中加入表面活性剂,并利用紫外线进行照射的方式制备纳米银溶胶。
但这些合成体系中所用的化合物大部分是有毒的,其合成过程会带来一定环境污染。因此,近年来“绿色”合成纳米银引起了广大学者的关注,一些学者采用水溶性的植物提取液制备纳米银,利用。利用刺桐根(P.R.Rathi Sre,M.Reka,R.Poovazhagi,etal.Spectrochim.Acta A.135(2015)1137.)、黄连木种子(B.Sadeghi,A.Rostami,S.S.Momeni,Spectrochim.Acta A.134(2015)326.)、菊花叶子(S.Ashokkumar,S.Ravi,V.Kathiravan,S.Velmurugan,Spectrochim.Acta A.134(2015)34.)和夜花叶子(N.Gogoi,P.J.Babu,C.Mahanta,U.Bora,Mater.Sci.Eng.C Mater.Biol.Appl.46(2015)463.)制备纳米银粒子。申请号CN201810157516.5利用燕水溶液作为还原剂制备纳米银粒子,申请号CN201711487249.X利用黑心菊花制备了粒径为2~3nm的纳米银颗粒。申请号CN201410540760.1用芦荟胶水溶液制备纳米银粒子。
但以上这些提取物作为纳米银的还原剂都是水溶性的,而研究表明对植物中多酚、黄酮等物质的高效提取更为普遍的是采用有机萃取剂,得到的是水不溶性的植物精油,其中含有的还原络合性物质更纯、浓度更高,理论分析其合成效率应更高。同时,本发明所使用的绿色还原剂为植物精油香芹酚,其成分单一,纯度高,稳定性好,在实际生产应用时,可避免利用水植物提取液作为还原剂时由于提取液成分不稳定所带来的产品不稳定现象。
发明内容
为了遵循绿色环保理念,最大程度避免使用有机溶剂和具有还原、分散作用的化学试剂,本发明提供了一种香芹酚微乳体系制备纳米银的方法,该方法构建非水溶性植物提取液的微乳液制备体系制备纳米银粒子,开拓了绿色还原法制备纳米银粒子的新思路。所制备的纳米银粒子为球形或者近球形,粒径为10~50nm,具有较强的抗菌性。
为达到上述目的,本发明采用以下技术手段:
一种香芹酚微乳体系制备纳米银的方法,包括以下步骤:
1)将香芹酚加入去离子水中,然后加入表面活性剂,常温下搅拌,使其混合均匀得到混合液;
2)采用高压均质机均质上述混合液,得到丁香酚微乳液;
3)向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将银氨溶液逐滴加入香芹酚微乳液中,搅拌直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液;
5)将悬浮液离心后采用倾析法分离上层清液,将所得沉淀洗涤后干燥,得到纳米银粒子。
作为本发明的进一步改进,步骤1)中的表面活性剂为Tween80,表面活性剂的添加量为香芹酚质量的20%。
作为本发明的进一步改进,步骤2)中均质压力为500MPa,均质次数为2~4次。
作为本发明的进一步改进,步骤2)微乳液中香芹酚的质量浓度为0.5%。
作为本发明的进一步改进,步骤4)中银与香芹酚的摩尔比为:(1:8)~(1:4)。
作为本发明的进一步改进,步骤5)中采用离心机离心,离心机的转速为5000~10000r/min,离心时间为5~15min。
作为本发明的进一步改进,步骤5)中沉淀分别用无水乙醇与去离子水依次洗涤。
作为本发明的进一步改进,步骤5)中干燥温度为80℃~100℃。
作为本发明的进一步改进,步骤5)中的纳米银为球形,粒径大小为10~50nm。
与现有技术相比,本发明具有以下有益的技术效果:
本发明的纳米银粒子的制备方法,采用香芹酚微乳体系还原纳米银粒子,香芹酚作为一种成分明确的植物精油,原料绿色环保,制备过程不造成污染;将香芹酚制备为水包油的微乳体系,解决了香芹酚不溶于水的问题,提高了微乳液中香芹酚与银氨溶液中银离子接触,使该还原反应更加充分。在还原过程中,银离子先被微乳液中香芹酚的活性基团吸附在油水界面,被还原为纳米银,银离子经历了微乳液表面吸附、还原、络合分散以及进入油相稳定的过程,纳米尺度的乳液表面为水相中银离子富集提供了保障,纳米银与微乳液表面的络合吸附作用是其均匀分散的化学基础。本发明提供的制备方法绿色、环保,反应过程中银离子被微乳液中香芹酚的活性基团吸附在油水界面,进而被还原为纳米银,在微乳滴表面效应与香芹酚中活性基团络合的共同作用下纳米银被稳定在微乳液表面,并且纳米银表面被大分子物质络合,从而得到分散性好、稳定存在的粒径为10~50nm的球形纳米银粒子。
附图说明
图1为本发明实例1制备的纳米银复合溶胶的UV-Vis吸收光谱图;
图2为本发明实施例1制备的纳米银的XRD衍射图谱;
图3为本发明实施例1制备的纳米银的TEM图;
图4为本发明实施例1制备的纳米银的抗菌效果图。
具体实施方式
本发明一种纳米银的制备方法,包括以下步骤:
(1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚质量的20%。
(2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为2~4次,得到香芹酚微乳;
(3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
(4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为:1:8~1:4。
(5)将悬浮液在5000~10000r/min的离心机中离心,离心时间为5~15min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤2~4次,在80℃~100℃干燥后得到纳米银粒子。
以下结合附图和具体实施例对本发明进行详细说明:
实施例1:
1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚质量的20%。
2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为4次,得到水包油型香芹酚微乳;
3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为1:8。
5)将悬浮液在10000r/min的离心机中离心,离心时间为10min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤3次,在80℃干燥后得到纳米银粒子。
图1是本实例制备的肉桂醛-聚乙烯醇-Ag复合溶胶的UV-Vis光谱图,在434nm左右的可见光区处有一个最大吸收峰,而且峰型比较尖锐、对称,此为纳米银颗粒其表面等离子体特征吸收峰(SPR)。
图2为本实例所制备的纳米银的XRD图谱,结果表明,在2θ为38.18°、44.37°、64.48°、77.37°附近出现了明显的衍射峰,这些不同的衍射峰分别归属为立方相金属银的(111),(200)(220)(311)(222)五个晶面的衍射峰(JCPDS(4-0781)),说明生成的纳米银粒子是面心立方结构晶系的单质银。而且没有发现氧化银(Ag2O)的衍射峰,说明制备过程中银离子还原为单质银,且没有发生其他氧化反应,得到的是纯净的纳米银。
图3为本实例所制备的纳米银的TEM图谱,所制备的纳米粒子为球形,分散性好,粒径大小分布在10~20nm。
图4为在不同浓度下的抗菌效果图。图4A,4B为本实例所制备的纳米银粒子分散液浓度为0.05mg/mL时分别对大肠杆菌(E.coli)和金黄色葡萄球菌(S.aureus)的抑菌效果图,抑菌圈直径分别为16.13mm和17.52mm,表现出良好的抗菌性。
实施例2
1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚质量的20%。
2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为3次,得到水包油型香芹酚微乳;
3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为1:5。
5)将悬浮液在10000r/min的离心机中离心,离心时间为5min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤3次,在80℃干燥后得到纳米银粒子。
实施例3
1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚质量的20%。
2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为5次,得到水包油型香芹酚微乳;
3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为1:6。
5)将悬浮液在10000r/min的离心机中离心,离心时间为15min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤4次,在100℃干燥后得到纳米银粒子。
实施例4
1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚质量的20%。
2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为3次,得到水包油型香芹酚微乳;
3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为1:8。
5)将悬浮液在80000r/min的离心机中离心,离心时间为10min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤2次,在100℃干燥后得到纳米银粒子。
实施例5
1)将香芹酚加入去离子水中,然后加入表面活性剂吐温80,常温下搅拌,使其混合均匀,香芹酚的质量浓度为0.5%,吐温的添加量为香芹酚总量的20%。
2)采用高压均质机对步骤(1)得到的混合液进行均质,均质压力为500MPa,均质次数为3次,得到水包油型香芹酚微乳;
3)称取一定量的固体硝酸银,向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将一定量银氨溶液逐滴加入100mL香芹酚微乳液中,封口,在磁力搅拌器上搅拌,直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液。银与香芹酚的摩尔比为1:5。
5)将悬浮液在80000r/min的离心机中离心,离心时间为12min,离心后倾析法分离上层清液,将所得沉淀分别用无水乙醇与去离子水依次洗涤3次,在80℃干燥后得到纳米银粒子。
因此本发明的一种纳米银粒子的制备方法,利用高压均质技术制备香芹酚微乳液,将银氨溶液添加至微乳液体系中,在40℃~60℃的温度下反应一段时间,直至溶液的颜色变为黑褐色不再加深为止,得到含有纳米银的悬浮液,将该悬浮液在离心机中离心后,经过去离子水、乙醇洗涤后,在80℃~100℃下干燥得到纳米银粉体。本发明提供的制备方法绿色、环保,反应过程中银离子被微乳液中香芹酚的活性基团吸附在油水界面,进而被还原为纳米银,在微乳滴表面效应与香芹酚中活性基团络合的共同作用下纳米银被稳定在微乳液表面,并且纳米银表面被大分子物质络合,从而得到分散性好、稳定存在的粒径为10~50nm的球形纳米银粒子,该纳米银对革兰氏阴性大肠杆菌(E.coli)和革兰氏阳性金黄色葡萄球菌(S.aureus)具有良好的抗菌性。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不隔离本发明构思的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定专利保护范围。
Claims (6)
1.一种香芹酚微乳体系制备纳米银的方法,其特征在于,包括以下步骤:
1)将香芹酚加入去离子水中,然后加入表面活性剂,常温下搅拌,使其混合均匀得到混合液;
表面活性剂为Tween80,表面活性剂的添加量为香芹酚质量的20%;
2)采用高压均质机均质上述混合液,得到香芹酚微乳液;
微乳液中香芹酚的质量浓度为0.5%;
3)向硝酸银中逐渐滴加稀氨水,边滴加边摇动,直到生成的沉淀全部溶解,得到银氨溶液;
4)将银氨溶液逐滴加入香芹酚微乳液中,搅拌直到颜色为黑褐色不再加深为止,得到含有银粒子的悬浮液;
5)将悬浮液离心后采用倾析法分离上层清液,将所得沉淀洗涤后干燥,得到纳米银粒子;
纳米银为球形,粒径大小为10~50nm。
2.根据权利要求1所述的一种香芹酚微乳体系制备纳米银的方法,其特征在于:步骤2)中均质压力为500MPa,均质次数为2~4次。
3.根据权利要求1所述的一种香芹酚微乳体系制备纳米银的方法,其特征在于:步骤4)中银与香芹酚的摩尔比为:(1:8)~(1:4)。
4.根据权利要求1所述的一种香芹酚微乳体系制备纳米银的方法,其特征在于:步骤5)中采用离心机离心,离心机的转速为5000~10000r/min,离心时间为5~15min。
5.根据权利要求1所述的一种香芹酚微乳体系制备纳米银的方法,其特征在于:步骤5)中沉淀分别用无水乙醇与去离子水依次洗涤。
6.根据权利要求1所述的一种香芹酚微乳体系制备纳米银的方法,其特征在于:步骤5)中干燥温度为80℃~100℃。
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