CN111617747B - 一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用 - Google Patents
一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用。以含有巯基或硫醚的壳聚糖水凝胶为基体,在基体内均匀分散粒径为0.1‑100nm的金属纳米颗粒。可用于催化、水处理、制药和抗菌领域。本发明具有金属纳米颗粒负载稳定性好、分散性高的特点,此外,还具有制备工艺简单,操作方便,成本低廉,应用范围广的特点。
Description
技术领域
本发明涉及一种水凝胶及其制备方法和应用,特别是一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用。
背景技术
高分子水凝胶是具有三维网络结构的材料。聚合物成为水凝胶材料必须具备两个条件:高分子主链或侧链上具有大量的亲水基团和具备适当的交联网络结构。制备高分子水凝胶的起始材料可以是单体(水溶性或油溶性单体)、聚合物(天然或合成聚合物)或者是单体和聚合物的混合体(功能材料,2003(4):382-385)。水凝胶在水中能够产生十分明显的溶胀行为,并且能保持一定的形状,不会发生溶解。水凝胶具的吸水能力和保水能力通常依赖于通过共价键、氢键、离子键、物理缠结等构成的三维网络结构(Soft Matter,2010,6(11),2364-2371)。水凝胶以各种物理形式存在,包括膜、球、微凝胶和纳米凝胶等。
以海洋生物质为原料的水凝胶有助于缓解石油资源紧张以及防止地球变暖,引起了国内外广泛的关注。壳聚糖作为一种典型的海洋生物质材料,是自然界中唯一大量存在的碱性多糖,具有良好的吸湿性、保湿性、生物可降解性、生物相容性以及抗菌性等,充分利用纤维素资源对全人类社会的可持续发展具有重要的意义(Progress in PolymerScience,2011,36(8),981-1014)。壳聚糖不溶于水和碱性溶液,能够溶于甲酸、醋酸等有机酸溶液以及稀磷酸、稀盐酸等无机酸;壳聚糖分子结构上的氨基在酸性溶液中能发生质子化形成-NH3+,稀酸的羧基去质子化形成-COO-。二元酸的加入则可以在壳聚糖的分子链间引入交联结构。
尺寸小于100nm的纳米金属具有表面效应和量子尺寸效应,显示出与宏观块状金属不同的催化、光学、电学等特性,在催化、传感器、光电器件和生物医学等领域具有潜在的用途(Applied Catalysis B-Environmental,241,415-423)。一般来说,纳米金属的制备需要将高价的金属离子还原为零价。但是,单纯的纳米金属具有很高的表面能,极易发生聚集形成大尺寸的金属颗粒,同时失去纳米金属的独特性能。因此,将纳米金属固定在合适的载体上是解决这一问题的一种有效途径。
虽然目前已有利用水凝胶、石墨烯和二氧化硅微球等作为载体来负载金属纳米颗粒的研究,但是,现目前的负载方式或多或少都存在负载稳定性差、分散性不高的缺陷。
发明内容
本发明的目的在于,提供一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用。本发明具有金属纳米颗粒负载稳定性好、分散性高的特点,此外,还具有制备工艺简单,操作方便,成本低廉,应用范围广的特点。
本发明的技术方案:一种壳聚糖/纳米金属复合水凝胶,以含有巯基或硫醚的壳聚糖水凝胶为基体,在基体内均匀分散粒径为0.1-100nm的金属纳米颗粒。
一种前述的壳聚糖/纳米金属复合水凝胶的制备方法,包括如下步骤:
(1)选取壳聚糖为原料;
(2)将壳聚糖、巯基酸或硫醚酸、水混合;
(3)将混合物置于20-80℃下反应1-8h,得到均相壳聚糖溶液;
(4)将均相壳聚糖溶液离心脱泡后滴入乙醇,形成球状壳聚糖凝胶;
(5)将球状壳聚糖凝胶置于含有目标金属离子的溶液中,常温震荡1-48h,吸附目标金属离子;
(6)将吸附有目标金属离子的凝胶置于硼氢化钠溶液中常温震荡1-48h,得到壳聚糖/纳米金属复合水凝胶。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(1)所述的壳聚糖是以蟹壳、虾壳、昆虫或微生物等生物质资源提取的壳聚糖的一种或任意几种的组合;所述壳聚糖的脱乙酰度为50%-100%。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(2)所述的巯基酸或硫醚酸具有水溶性,且巯基酸或硫醚酸具有以下结构特征:
其中:
A系列为含有巯基的一元酸;
B系列含有巯基或硫醚的二元酸。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(2)所述的混合体系中,壳聚糖的质量浓度为0.1-10%,巯基酸或硫醚酸的质量浓度为0.1%-30%。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(4)所述乙醇与壳聚糖溶液的体积比为5-10:1。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,所述的壳聚糖具有如下结构:
其中,50<n<1000;R为-NH2或质子化氨基-NH3 +;其中,为质子化氨基时,巯基酸或硫醚酸去质子化形成如下结构的一种或一种以上的混合物:
其中:
A系列为含有巯基的一元酸;
B系列含有巯基或硫醚的二元酸。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(5)所述的含有目标金属离子的溶液中的金属离子浓度为0.01-100mg/mL,球状壳聚糖凝胶与含有目标金属离子的溶液的体积比为1:10-100。
前述的壳聚糖/纳米金属复合水凝胶的制备方法,步骤(6)所述的硼氢化钠溶液浓度为0.01-10mol/L,吸附有目标金属离子的凝胶与硼氢化钠溶液的体积比为1:10-100。
一种前述的壳聚糖/纳米金属复合水凝胶在催化、水处理、制药和抗菌领域的应用。
本发明的有益效果
本发明基于壳聚糖溶解于含有巯基或硫醚的一元羧酸和二元羧酸的水溶液中,壳聚糖分子链的氨基发生质子化破坏壳聚糖的氢键网络结构促使其溶解,并且二元羧酸对壳聚糖分子链具备交联作用,经过反溶剂的再生制备了含有巯基或硫醚的壳聚糖水凝胶,再将纳米金属颗粒负载到凝胶上,从而制备出壳聚糖/纳米金属复合水凝胶材料。
本发明的明显优点是制备的复合水凝胶材料以含巯基或硫醚的壳聚糖水凝胶为基体,纳米金属在其内部均匀分散,粒径约0.1-100nm,具有独特的结构优势;所使用的壳聚糖水凝胶制备方便快捷且大小形貌可控,分子结构上具有含硫的巯基或硫醚基团以及氨基和羟基,能够稳定的负载大量的纳米金属,且可有效避免纳米金属制备过程中的团聚问题。
本发明所制备的壳聚糖/纳米金属复合水凝胶材料可以应用于催化、水处理、制药和抗菌等诸多领域,例如可用于催化降解硝基苯衍生物,可用于吸附水体中的汞离子,可用于4-氨基苯酚等医药中间体的生产。
本发明还具有工艺简单、操作方便、成本低廉等优点。
附图说明
图1:本发明专利步骤流程图;
图2:壳聚糖/纳米金复合水凝胶的扫描电子显微镜(SEM)照片;
图3:壳聚糖/纳米金复合水凝胶的透射电子显微镜(TEM)照片和XRD谱图;
图4:紫外-可见光分光光度计监控4-硝基苯酚还原过程。
具体实施方式
下面结合实施例对本发明作进一步的说明,但并不作为对本发明限制的依据。
本发明的实施例
实施例1
本发明制备方法的步骤如下:
(1)选取脱乙酰度为50%的壳聚糖为原料;
(2)将0.1wt%壳聚糖、巯基酸或硫醚酸0.1wt%和余量的水混合;
(3)将混合物置于20℃下反应8h,得到均相壳聚糖溶液;
(4)将均相壳聚糖溶液离心脱泡后按体积比1:5滴入乙醇,形成球状壳聚糖凝胶;
(5)将球状壳聚糖凝胶置于含有目标金属离子的溶液中,金属离子浓度为0.01mg/mL,常温震荡48h,吸附目标金属离子;
(6)将吸附有目标金属离子的凝胶按体积比1:10置于浓度为0.01mol/L的硼氢化钠溶液中常温震荡48h,得到壳聚糖/纳米金属复合水凝胶。
实施例2
本发明制备方法的步骤如下:
(1)选取脱乙酰度为100%的壳聚糖为原料;
(2)将10wt%壳聚糖、巯基酸或硫醚酸30wt%和余量的水混合;
(3)将混合物置于80℃下反应1h,得到均相壳聚糖溶液;
(4)将均相壳聚糖溶液离心脱泡后按体积比1:10滴入乙醇,形成球状壳聚糖凝胶;
(5)将球状壳聚糖凝胶置于含有目标金属离子的溶液中,金属离子浓度为100mg/mL,常温震荡1h,吸附目标金属离子;
(6)将吸附有目标金属离子的凝胶按体积比1:100置于浓度为10mol/L的硼氢化钠溶液中常温震荡1h,得到壳聚糖/纳米金属复合水凝胶。
实施例3
按实施例1的步骤,称取蟹壳壳聚糖1.25克、3-巯基丙酸0.394克、硫代苹果酸0.279克和去离子水20mL,一起加入到圆底烧瓶中,温度为80℃,机械搅拌6h,得到壳聚糖的均相溶液。将壳聚糖溶液通过10,000rpm的转速进行离心脱泡,使用一次性注射器将壳聚糖溶液逐滴滴入3倍量的无水乙醇中,形成直径为3mm的壳聚糖凝胶珠。将此水凝胶珠在无水乙醇中浸泡2h老化。将300颗壳聚糖凝胶珠转移至50mL,1.5mM的氯金酸钠水溶液中在25℃下震荡24h,随后将壳聚糖凝胶柱转移至30mL,0.1M的硼氢化钠水溶液中在保持25℃下震荡2h,将负载的Au(III)还原为纳米金,即可得到壳聚糖/纳米金复合水凝胶。
实施例4
壳聚糖/纳米金复合水凝胶的应用,催化4-硝基苯酚的还原反应制取4-氨基苯酚实验步骤:
1)配制0.1mM 4-硝基苯酚的水溶液;
2)配制0.1M硼氢化钠的水溶液;
3)取3ml NaBH4溶液和3ml 4-硝基苯酚溶液于烧杯,加入30颗实施例2制备的壳聚糖/纳米金复合水凝胶材料,在室温下进行反应,使用紫外-可见光分光光度计对反应过程进行了监控。
实施例5
按实施例1的步骤,称取虾壳壳聚糖1.25克、3-巯基丙酸0.71克、硫代苹果酸0.5克和去离子水20mL,一起加入到圆底烧瓶中,温度为60℃,机械搅拌4h,得到壳聚糖的均相溶液。将壳聚糖溶液通过10,000rpm的转速进行离心脱泡,使用一次性注射器将壳聚糖溶液逐滴滴入3倍量的无水乙醇中,形成直径为3mm的壳聚糖凝胶珠。将此水凝胶珠在无水乙醇中浸泡4h老化。将300颗壳聚糖凝胶珠转移至50mL,1.5mM的氯金酸钠水溶液中在25℃下震荡24h,随后将壳聚糖凝胶珠转移至30mL,0.1M的硼氢化钠水溶液中在保持25℃下震荡2h,将负载的Au(III)还原为纳米金,即可得到壳聚糖/纳米金复合水凝胶。
实施例6
按实施例1的步骤,称取虾壳壳聚糖1.25克、巯基乙酸0.71克、硫代苹果酸0.5克和去离子水20mL,一起加入到圆底烧瓶中,温度为60℃,机械搅拌4h,得到壳聚糖的均相溶液。将壳聚糖溶液通过10,000rpm的转速进行离心脱泡,使用一次性注射器将壳聚糖溶液逐滴滴入3倍量的无水乙醇中,形成直径为3mm的壳聚糖凝胶珠。将此水凝胶珠在无水乙醇中浸泡4h老化。将300颗壳聚糖凝胶珠转移至50mL,1.5mM的氯金酸钠水溶液中在25℃下震荡24h,随后将壳聚糖凝胶柱转移至30mL,0.1M的硼氢化钠水溶液中在保持25℃下震荡2h,将负载的Au(III)还原为纳米金,即可得到壳聚糖/纳米金复合水凝胶。
实施例7
按实施例1的步骤,称取平菇菌丝体提取的壳聚糖1.25克、4-巯基丁酸0.284克、硫代苹果酸0.803克和去离子水20mL,一起加入到圆底烧瓶中,温度为40℃,机械搅拌4h,得到壳聚糖的均相溶液。将壳聚糖溶液通过10,000rpm的转速进行离心脱泡,使用一次性注射器将壳聚糖溶液逐滴滴入3倍量的无水乙醇中,形成直径为3mm的壳聚糖凝胶珠。将此水凝胶珠在无水乙醇中浸泡4h老化。将300颗壳聚糖凝胶珠转移至50mL,1.5mM的氯金酸钠水溶液中在25℃下震荡24h,随后将壳聚糖凝胶柱转移至30mL,0.1M的硼氢化钠水溶液中在保持25℃下震荡2h,将负载的Au(III)还原为纳米金,即可得到壳聚糖/纳米金复合水凝胶。
实施例8
按实施例1的步骤,称取从蚕蛹提取的壳聚糖1.25克、3-巯基丙酸0.284克、内消旋-2,3-二巯基丁二酸0.803克和去离子水20mL,一起加入到圆底烧瓶中,温度为40℃,机械搅拌4h,得到壳聚糖的均相溶液。将壳聚糖溶液通过10,000rpm的转速进行离心脱泡,使用一次性注射器将壳聚糖溶液逐滴滴入3倍量的无水乙醇中,形成直径为3mm的壳聚糖凝胶珠。将此水凝胶珠在无水乙醇中浸泡4h老化。将300颗壳聚糖凝胶珠转移至50mL,1.5mM的氯金酸钠水溶液中在25℃下震荡24h,随后将壳聚糖凝胶柱转移至30mL,0.1M的硼氢化钠水溶液中在保持25℃下震荡2h,将负载的Au(III)还原为纳米金,即可得到壳聚糖/纳米金复合水凝胶。
以上所述,仅为本发明创造较佳的具体实施方式,但本发明创造的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明创造揭露的技术范围内,根据本发明创造的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明创造的保护范围之内。
Claims (9)
1.一种壳聚糖/纳米金属复合水凝胶,其特征在于:以含有巯基或硫醚的壳聚糖水凝胶为基体,在基体内均匀分散粒径为0.1-100nm的金属纳米颗粒;所述的壳聚糖/纳米金属复合水凝胶的制备方法包括如下步骤:
(1)选取壳聚糖为原料;
(2)将壳聚糖、巯基酸或硫醚酸、水混合;
(3)将混合物置于20-80oC下反应1-8h,得到均相壳聚糖溶液;
(4)将均相壳聚糖溶液离心脱泡后滴入乙醇,形成球状壳聚糖凝胶;
(5)将球状壳聚糖凝胶置于含有目标金属离子的溶液中,常温震荡1-48h,吸附目标金属离子;
(6)将吸附有目标金属离子的凝胶置于硼氢化钠溶液中常温震荡1-48h,得到壳聚糖/纳米金属复合水凝胶。
2.根据权利要求1所述的壳聚糖/纳米金属复合水凝胶,其特征在于:制备方法中,所述步骤(1)的壳聚糖是以蟹壳、虾壳、昆虫或微生物等生物质资源提取的壳聚糖的一种或任意几种的组合;所述壳聚糖的脱乙酰度为50-100%。
4.根据权利要求1所述的壳聚糖/纳米金属复合水凝胶,其特征在于:制备方法中,所述步骤(2)的混合体系中,壳聚糖的质量浓度为0.1-10%,巯基酸或硫醚酸的质量浓度为0.1-30%。
5.根据权利要求1所述的壳聚糖/纳米金属复合水凝胶,其特征在于:制备方法中,所述步骤(4)乙醇与壳聚糖溶液的体积比为5-10:1。
7.根据权利要求1所述的壳聚糖/纳米金属复合水凝胶,其特征在于:制备方法中,所述步骤(5)的含有目标金属离子的溶液中的金属离子浓度为0.01-100mg/mL,球状壳聚糖凝胶与含有目标金属离子的溶液的体积比为1:10-100。
8.根据权利要求1所述的壳聚糖/纳米金属复合水凝胶,其特征在于:制备方法中,所述步骤(6)的硼氢化钠溶液浓度为0.01-10mol/L,吸附有目标金属离子的凝胶与硼氢化钠溶液的体积比为1:10-100。
9.一种根据权利要求1所述的壳聚糖/纳米金属复合水凝胶在催化、水处理、制药和抗菌领域的应用。
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