CN107008456A - 一种具有抑菌性能光催化剂的生物辅助合成方法 - Google Patents
一种具有抑菌性能光催化剂的生物辅助合成方法 Download PDFInfo
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Abstract
本发明公开了一种具有抑菌性能光催化剂的生物辅助合成方法，具体步骤为：将氧化石墨烯和六水合三氯化铁固体按一定质量比配成水溶液，加入尿素和海藻酸钠，随后转移至反应釜中200℃加热，反应结束后冷却至室温，所得产物离心，经水和无水乙醇清洗后于60℃真空干燥7h得到RGO/Fe3O4。利用硅烷偶联剂APTES对所得RGO/Fe3O4进行改性。纳米银的负载方法如下，将改性后的RGO/Fe3O4和AgNO3按一定质量比配成水溶液，加入尿素和海藻酸钠，随后转移至反应釜中，置于烘箱中120℃下加热，磁性分离所得产品，洗涤并干燥。所得RGO/Fe3O4/Ag表现出良好的抑菌性能，和优异的催化性能。
Description
技术领域
本发明属于光催化剂技术领域，具体涉及一种生物分子辅助合成纳米复合材料的方法。
背景技术
水是生命之源，与人类的生存和发展息息相关，在全球工业飞速发展的今天，工业废水对环境的污染也日益加剧。已被用于工业废水降解的技术有很多种，包括化学方法、物理化学方法、生物方法或者多种联合的方法，例如，活性炭吸附和微生物降解等。以均相Fenton反应为代表的传统废水治理办法存在着催化剂难分离等缺点。在此基础上发展起来的Fe3O4作催化剂的非均相Fenton氧化虽利用Fe3O4优异的磁性能很好的解决了分离难、二次污染等问题，但因材料的单一性，依然存在催化效率低、适用pH范围窄等弊端。同时，污水中存在的大量细菌病毒等微生物可成为各类疾病的传播媒介，这一问题在传统的水处理方法中并未得到妥善解决。研究发现，近紫外光和可见光的引入可大大提高Fenton反应的速率，因此Photo-Fenton法得到了广泛的研究，尤其是以碳基磁性纳米抑菌材料为催化剂的非均相Photo-Fenton反应不但能高效剔除废液中的有机染料不造成二次污染，而且低能耗适用pH范围广，同时也能抑制水中各类细菌的生长，有着良好的应用前景和极高的应用价值。虽然，催化剂使用中所产生的环境问题虽已得到有效解决，但催化剂合成过程中因有毒试剂，例如水合肼的使用而带来的环境污染仍不容忽视，同时目前市场上常见的光催化剂作为催化剂降解有机污染物的效力较低，合成出高效的光催化剂，是具有重大意义和挑战性。
发明内容
本发明解决的技术问题是在生物分子海藻酸钠的辅助下，得到了形貌均一的碳基磁性纳米抑菌材料(MWCNTs/Fe3O4/Ag)纳米材料，该材料在合成过程中没有采用有毒试剂，有效的避免了对环境的污染，并将所得材料进行了抑菌和催化的应用。
本发明为达到上述目的，本发明采用的技术方案为：
(1)取多壁碳纳米管加入浓硫酸与浓硝酸的混酸中，室温下搅拌，进行酸化；
(2)将酸化后的多壁碳纳米管和六水合三氯化铁固体配成水溶液，加入尿素和海藻酸钠，随后转移至反应釜中200℃加热20h，反应结束后冷却至室温，所得产物离心、清洗、干燥后得到黑色粉末状产物MWCNTs/Fe3O4；
(3)利用硅烷偶联剂对所得MWCNTs/Fe3O4进行改性，取MWCNTs/Fe3O4于水和无水乙醇的混合溶液中超声分散，并加入APTES，搅拌干燥；
(4)将改性后的MWCNTs/Fe3O4和AgNO3配成水溶液，进行纳米银的负载，加入尿素和海藻酸钠，转移至反应釜中，置于烘箱中120℃下加热20h。
所述进行酸化时，取1g多壁碳纳米管加入50mL体积比为3∶1的浓硫酸与浓硝酸的混酸，室温下搅拌8h。
所述制备MWCNTs/Fe3O4，酸化后的多壁碳纳米管和六水合三氯化铁质量比为1∶15-20，尿素和海藻酸钠的质量比为2-4∶1。
所述制备MWCNTs/Fe3O4，所述的水的用量为20-40mL，反应釜为20-80mL的聚四氟乙烯不锈钢反应釜，所述的清洗为将离心的产物经水和无水乙醇交替清洗6次，所述的干燥为于60℃真空干燥7h。
所述对所得MWCNTs/Fe3O4进行改性，所述的水和无水乙醇体积比为1∶1，室温下搅拌7h，所述的干燥为于60℃真空干燥7h。
所述进行纳米银的负载时，MWCNTs/Fe3O4和AgNO3的比例为8∶8-13，尿素和海藻酸钠的质量比为2-4∶1，所述的水的用量为20-40mL，反应釜为20-80mL的聚四氟乙烯不锈钢反应釜。
本发明合成条件易控，操作方便，环境友好，具有合成设备简单，原料常见易得，反应快速高效和产品的催化效率较高，具有很强的光催化活性。
附图说明
图1是本发明实施例1制得的酸化改性后的多壁碳纳米管(MWCNTs)，Fe3O4，MWCNTs/Fe3O4和MWCNTs/Fe3O4/Ag比的XRD图谱。
图2是本发明实施例1制得MWCNTs/Fe3O4/Ag的透射电镜图谱。
图3是本发明在抑菌应用中的效果图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
图1是本实施例制得纳米复合材料的XRD图谱，从上到下依次是酸化改性后的多壁碳纳米管(MWCNTs)，Fe3O4，MWCNTs/Fe3O4和MWCNTs/Fe3O4/Ag的XRD图谱，最下方为Fe3O4标准图谱(JCPDS card No.65-3107)和Ag的标准图谱(JCPDS card No.65-2871)。其中酸化后碳纳米管在2θ＝25.8°和42.9°处出现的衍射峰分别对应JCPDS card No.26-1080标准图谱中(002)和(100)晶面，由此看出，碳纳米管的晶面结构并未因酸化而破坏。MWCNTs/Fe3O4和Fe3O4拥有相同位置的衍射峰，并且能准确对应图中最下方的Fe3O4标准图谱(JCPDS cardNo.65-3107)，Fe3O4的粒径略小于MWCNTs/Fe3O4造成特征峰略低，说明碳纳米管的存在对Fe3O4的生长有一定的抑制作用。而MWCNTs在MWCNTs/Fe3O4和MWCNTs/Fe3O4/Ag图谱中并没有出现明显的特征峰，可能是由于其质量含量低而造成的。MWCNTs/Fe3O4/Ag图谱中在角度为38°和44°左右出现的衍射峰对应Ag的标准图谱(JCPDS card No.65-2871)中的(111)晶面和(200)晶面，其余的衍射峰均能与Fe3O4标准图谱(JCPDS card No.65-3107)准确照应，说明无论是Fe3O4还是Ag都是独立存在的并未生成合金，且Ag的负载并未使Fe3O4因氧化而改变晶相。
图2是本实施例制得MWCNTs/Fe3O4/Ag的透射电镜图，其中由(a)、(b)可以看出，碳纳米管的结构清晰可见，Fe3O4和Ag纳米颗粒的形状较为规则，分散性良好，颗粒的尺寸在10nm～20nm之间，这与场发射扫描电镜的表征结果相互印证。此外，少个颗粒聚集的原因是由于一部分银纳米颗粒与四氧化三铁相连所导致的。关于这一点在上文的合成路线中也给出过相应的解释。(c)和(d)图分别是样品MWCNTs/Fe3O4/Ag的选区衍射与晶格条纹。根据此样品XRD图谱，在衍射图中找到了Fe3O4的(311)、(200)、(111)晶面和Ag的(200)、(111)晶面，在图中找出了四种晶格条纹，晶格间距分别为0.210nm、0.253nm、0.480nm和0.200nm，对应Fe3O4的(400)、(311)、(111)晶面和Ag的(200)晶面。
应用在抑菌实验中，在样品中放入50μL细菌后，在37℃环境中培养24h。取100μL培养后的细菌放入到900μL无菌生理盐水(试管1)中，混合均匀，取管1中100μL菌液再次放入到另一支900μL无菌生理盐水(试管2)中，重复操作一直到试管6，也就意味着稀释106倍，取稀释后菌悬液20μL置于固体培养基上，均匀涂抹一直到其表面干燥，把它在37℃环境中存放24h后，查看菌落生长情况。
图3是本发明所得纳米复合材料的抑菌效果图，以苏云金芽孢杆菌为例，(a)为空白，有223个菌落；(b)是0.7mg/mL实验所得纳米Ag溶液涂抹后的效果，有56个菌落，抑菌率74.8％；(c)为0.7mg/mL所得MWCNTs/Fe3O4/Ag溶液涂抹后的效果，菌落数2，抑菌率99.1％；(d)为0.8mg/mL所得MWCNTs/Fe3O4/Ag溶液涂抹后的效果，没有菌落生长，抑菌率100％，由此推测MWCNTs/Fe3O4/Ag对苏云金芽孢杆菌的最小抑菌浓度为0.8mg/mL。由于碳纳米管能让纳米颗粒有效分散且复合材料中存在协同作用，因此所得复合材料有着比纳米银更突出的抑菌性能。
应用在室温25℃，控制时间为60min，双氧水起始浓度为10.0mmol·L-1，亚甲基蓝的起始浓度为20mg·L-1，MWCNTs/Fe3O4/Ag投加量为0.25g·L-1的条件下，调节溶液起始pH为6的实验条件下探究所得材料在Photo-Fenton体系催化降解亚甲基蓝实验中的催化性能。实验结果表明，60min后最高能达到93％的降解率，且多次循环使用降解率并无明显下降，在实际水样中使用时也同样能保持良好的催化性能，有着很高的应用价值和优秀的应用前景。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (6)
1.一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于，包括以下步骤：
(1)取多壁碳纳米管加入浓硫酸与浓硝酸的混酸中，室温下搅拌，进行酸化；
(2)将酸化后的多壁碳纳米管和六水合三氯化铁固体配成水溶液，加入尿素和海藻酸钠，随后转移至反应釜中200℃加热20h，反应结束后冷却至室温，所得产物离心、清洗、干燥后得到黑色粉末状产物MWCNTs/Fe3O4；
(3)利用硅烷偶联剂对所得MWCNTs/Fe3O4进行改性，取MWCNTs/Fe3O4于水和无水乙醇的混合溶液中超声分散，并加入APTES，搅拌干燥；
(4)将改性后的MWCNTs/Fe3O4和AgNO3配成水溶液，进行纳米银的负载，加入尿素和海藻酸钠，转移至反应釜中，置于烘箱中120℃下加热20h。
2.根据权利要求1所述的一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于：进行酸化时，取1g多壁碳纳米管加入50mL体积比为3∶1的浓硫酸与浓硝酸的混酸，室温下搅拌8h。
3.根据权利要求1所述的一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于：制备MWCNTs/Fe3O4，酸化后的多壁碳纳米管和六水合三氯化铁质量比为1∶15-20，尿素和海藻酸钠的质量比为2-4∶1。
4.根据权利要求1所述的一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于：制备MWCNTs/Fe3O4，所述的水的用量为20-40mL，反应釜为20-80mL的聚四氟乙烯不锈钢反应釜，所述的清洗为将离心的产物经水和无水乙醇交替清洗6次，所述的干燥为于60℃真空干燥7h。
5.根据权利要求1所述的一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于：对所得MWCNTs/Fe3O4进行改性，所述的水和无水乙醇体积比为1∶1，室温下搅拌7h，所述的干燥为于60℃真空干燥7h。
6.根据权利要求1所述的一种具有抑菌性能光催化剂的生物辅助合成方法，其特征在于：进行纳米银的负载时，MWCNTs/Fe3O4和AgNO3的比例为8∶8-13，尿素和海藻酸钠的质量比为2-4∶1，所述的水的用量为20-40mL，反应釜为20-80mL的聚四氟乙烯不锈钢反应釜。
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