CN115226724B - 一种纳米光催化杀菌材料及其制备方法 - Google Patents
一种纳米光催化杀菌材料及其制备方法 Download PDFInfo
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Abstract
本发明属于光催化杀菌材料技术领域，涉及一种纳米光催化杀菌材料及其制备方法。所述的纳米光催化杀菌材料为Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，所述的制备方法包括如下步骤：(1)将四氯化钛缓慢滴加至溶剂中，获得透明液体；(2)将锌加入到所述的透明液体中，使之渐渐变为蓝色液体；(3)将所述的蓝色液体在一定温度下反应一段时间；(4)在反应产物中加入壳聚糖、二硫化钼粉末，超声处理一段时间；(5)将含银离子的盐在搅拌的条件下加入超声处理后的液体中，干燥得到所述的纳米材料。利用本发明的制备方法，能够操作简单方便、易于实现、消耗低、产率高、可重复性好、适合大规模生产、对环境无二次污染的制备所述的纳米材料。
Description
技术领域
本发明属于光催化杀菌材料技术领域，涉及一种纳米光催化杀菌材料及其制备方法。
背景技术
光催化技术是一种高效的解决环境污染和改善公共卫生的技术。二氧化钛(TiO2)是一种稳定、廉价的高效无机光催化材料，由于其高光催化性、高稳定性、低毒性、廉价、绿色环保等优势，TiO2能在紫外线的激发下发生光催化反应，将有机物无差别的最终分解为二氧化碳和水。因此，TiO2光催化材料可用于清除有机物、杀菌、消毒、污水处理等领域。
然而，太阳光中仅有4-5％的紫外光成分，极大地限制了TiO2的光催化应用。为了更好的实现TiO2在自然条件下的应用，通过对其进行金属/非金属离子掺杂、贵金属负载、构造异质结半导体等改性手段，使其能够实现太阳光响应。其中，通过与其他半导体纳米材料构造异质结结构能够有效的提高TiO2的光催化效率，是一种廉价环保的工艺。而作为一种类石墨烯的二维半导体纳米材料，少层二硫化钼(MoS2)纳米片的独特带隙结构使其对可见光具有强烈的吸收作用，在光催化领域得到广泛的应用。由于其强烈的量子限域效应，MoS2纳米片能够高效的将电子转移至TiO2，展现优良的光催化效果。在太阳光激发下，光生载流子从MoS2纳米片上转移到TiO2上，实现可见光响应的光催化；同时，MoS2纳米片的负载有利于电子空穴的分离，提高光催化的量子产率。此外，对TiO2本身进行改性，也可以实现可见光催化。黑色纳米二氧化钛是利用氢将部分Ti4+离子还原为Ti3+离子，使其吸收光谱延伸到可见光区，实现可见光响应。因此，在可见光照射下，MoS2纳米片复合黑色TiO2纳米光催化材料能够实现高效的光催化杀菌的功效。
金属离子(如银、铜、锌等)自古就应用于杀菌消毒。银是一种古老的杀菌剂，相比而言，银离子具有更高的安全性、更好的杀灭效果、广谱的消杀性、无耐药性，对于超级细菌也具有强烈的杀灭效果。然而，银离子易被氯离子等消耗、易流失、见光易分解、被细胞吸收量有限，这极大地限制着含银离子消毒剂的杀灭效果；若仅通过提高银离子剂量来达到杀灭效果，又会对人体和环境造成不可估量的伤害，且不符合环保的排放标准。因此，如何制备安全稳定的含银杀菌消毒剂一直是研究的重点。
锌离子是一种优秀的防霉剂，却也面临着和银离子相似的困境。纳米二氧化钛作为一种优异的金属离子的载体，不仅可以增强离子的稳定性，而且还能增强其杀菌效率；同时，金属离子的添加也使纳米二氧化钛在无光照条件下得到了杀菌的效果，故金属离子负载纳米二氧化钛具有比金属离子和纳米二氧化钛本身更优异的杀菌效果。然而，由于胶体的电荷稳定性，纳米二氧化钛分散液中能够添加的金属离子浓度极为有限，如何提高纳米二氧化钛对金属离子的负载量极为关键。
MoS2纳米材料是一种优良的金属离子载体，其具有极大的比表面积，可以为金属离子提供大量的吸附位点；S元素使金属离子能牢固的吸附在MoS2表面。因此，MoS2纳米片复合黑色纳米TiO2是一种极好的金属离子载体。
发明内容
本发明的首要目的是提供一种纳米光催化杀菌材料的制备方法，以能够操作简单方便、易于实现、消耗低、产率高、可重复性好、适合大规模生产、对环境无二次污染的制备Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料。
为实现此目的，在基础的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，所述的纳米光催化杀菌材料为Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，所述的制备方法包括如下步骤：
(1)将四氯化钛缓慢滴加至溶剂中，获得透明液体；
(2)将锌加入到所述的透明液体中，使之渐渐变为蓝色液体；
(3)将所述的蓝色液体在一定温度下反应一段时间；
(4)在反应产物中加入壳聚糖、二硫化钼(优选平均粒径为2-10微米)粉末，超声处理一段时间(优选制备得到TiO2@MoS2纳米材料为异质结结构)；
(5)将含银离子的盐在搅拌的条件下加入超声处理后的液体中，干燥得到所述的纳米材料(优选制备得到Ag/Zn-TiO2@MoS2纳米材料的平均粒径为100nm)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(1)中，所述的四氯化钛和所述的溶剂的体积比为1:20-30，滴加速度为10-30mL/min。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(1)中，所述的溶剂选自水、无水乙醇、异丙醇中的一种或多种(优选为无水乙醇)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(2)中，所述的锌和所述的透明液体中的钛的摩尔比为1:2-10。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(3)中，所述的一定温度为150-250℃(优选为200℃)，所述的一段时间为6-24h(优选为12h)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(4)中，反应产物中含锌的纳米二氧化钛、壳聚糖、二硫化钼的质量比为(30-75)：(10-25)：(0.5-2)(优选为75：23：2)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(4)中，所述的超声处理的时间为1-4h(优选为2h)，功率为80-300W(优选为300W)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(5)中，所述的含银离子的盐为硝酸银；加入含银离子的盐后Ag离子的浓度为10-1000ppm(优选为100ppm)；所述的含银离子的盐与所述的超声处理后的液体的体积比为1：10-1000；所述的搅拌的速度为100-1000rpm(优选为500rpm)，时间为10-60min(优选为1h)。
在一种优选的实施方案中，本发明提供一种纳米光催化杀菌材料的制备方法，其中步骤(5)中，所述的干燥的温度为40-80℃，时间为3-24h。
本发明的第二个目的是提供一种纳米光催化杀菌材料，即Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，以能够尺寸均匀，分散性、光催化效果和杀菌效果好。
为实现此目的，在基础的实施方案中，本发明提供一种纳米光催化杀菌材料，所述的纳米光催化杀菌材料为Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，由根据前述的制备方法制备得到。
本发明的有益效果在于，利用本发明的纳米光催化杀菌材料及其制备方法，能够操作简单方便、易于实现、消耗低、产率高、可重复性好、适合大规模生产、对环境无二次污染的制备Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，制得纳米材料尺寸均匀，分散性、光催化效果和杀菌效果好。
本发明的有益效果具体体现在：
1)本发明中，可见光响应的黑色纳米二氧化钛代替了常用的紫外光激发的P25纳米二氧化钛用于杀菌。相比而言，黑色纳米二氧化钛可在更广泛的区域实现有效的杀菌，具有更广阔的应用前景。此外，为了改善黑色纳米二氧化钛分散性不佳的问题，壳聚糖作为一种表面修饰物实现了黑色纳米二氧化钛的原位分散；与此同时，壳聚糖还能够阻止剥离开的二硫化钼纳米片重新堆叠团聚。原位分散的黑色纳米二氧化钛负载于少层的二硫化钼纳米片上，得到了黑色纳米TiO2复合MoS2纳米片(TiO2@MoS2)的复合纳米材料。
2)本发明中，Zn作为湿化学制备黑色纳米二氧化钛的还原剂，产生的锌离子镶嵌于二氧化钛表面，一方面可以抑制Ti3+向Ti4+的转变，起到稳定的作用，另一方面还发挥防霉的作用。与单纯的向二氧化钛溶胶中添加锌离子相比，在保持胶体稳定性的前提下，锌离子的负载量能够大大提升。Ag金属离子不仅可以吸附在MoS2纳米片上，还能够有效的吸附在壳聚糖上。壳聚糖不仅能够提高TiO2的可见光活性和抑制纳米TiO2、MoS2纳米片的团聚，还能够增大金属离子在纳米二氧化钛上的吸附量。壳聚糖中富含的活性基团能够有效的捕获游离的金属离子，阻止金属离子的流失，进一步促进金属离子的缓释效果，增强复合材料的长久抗菌效果。此外，由于壳聚糖的存在，直接干燥制备粉体材料得以实现，粉体材料重新分散后，其粒径不增大。另外，上述方法操作简单、方便，易于实现，耗时短，消耗低，成本低，产率高，可重复性好，适合大规模生产或者对环境无二次污染。
3)本发明的制备方法可以实现对纳米二氧化钛进行改性，得到具备可见光催化杀菌能力的二氧化钛，进一步负载银/锌离子极大地增强了其杀菌和防霉能力。本发明公开的制备方法具备大规模产业化的能力，拓展了纳米二氧化钛在空气净化、杀菌、水处理等方面的应用。
附图说明
图1为实施例1制得的Ag/Zn-TiO2@MoS2纳米材料的透射电子显微镜成像图。
图2为实施例1制得的Ag/Zn-TiO2@MoS2纳米材料的金属元素分布图。
图3为实施例1制得的Ag/Zn-TiO2@MoS2纳米材料的光催化降解亚甲基蓝的效率图。
图4为实施例1制得的Ag/Zn-TiO2@MoS2纳米材料对金黄色葡萄球菌杀灭作用的表征图。
图5为实施例1制得的Ag/Zn-TiO2@MoS2纳米材料(银含量为0.5ppm)与Ag/Zn离子混合溶液(银含量5ppm)、黑色TiO2纳米材料(质量浓度与复合材料一致)在30min内的杀菌率图。
具体实施方式
以下通过实施例对本发明的具体实施方式作出进一步的说明。各实施例中使用的四氯化钛、无水乙醇、硝酸银、锌粉和壳聚糖粉末均购买自阿拉丁试剂，二硫化钼粉末(纳米片)购买自南京先锋纳米材料科技有限公司。
实施例1：Ag/Zn-TiO2@MoS2纳米材料的制备
(1)将4mL的TiCl4缓慢滴加到100mL无水乙醇中，保持搅拌直至得到无色透明的溶液；
(2)将0.5g Zn粉加入无色透明溶液中，保持搅拌直至溶液颜色最终变为蓝色；
(3)将蓝色溶液转移至四氟反应釜中，在200℃条件反应12小时；
(4)待反应物冷却至室温后，转移到烧杯中并加入330mg壳聚糖和28mg二硫化钼粉末，在超声功率为300W条件下超声处理2h；
(5)向超声处理后的溶液中加入硝酸银溶液，使溶液中银离子的浓度达到100ppm，持续搅拌1h(500rpm)；
(6)将所得到的分散液在50℃条件下蒸干，得到复合纳米杀菌材料粉体；
(7)将所得到的粉体重新分散于水中，即得杀菌液，该杀菌液可稀释5-20倍使用。
本实施例制备得到的Ag/Zn-TiO2@MoS2纳米材料较稳定，可以在室温下存放1年以上不会出现沉淀现象。将本实施例所得的Ag/Zn-TiO2@MoS2纳米材料进行表征，结果如图1-4所示。其中，图1是Ag/Zn-TiO2@MoS2纳米材料的低倍透射电子显微镜成像图(TEM)；图2是Ag/Zn-TiO2@MoS2纳米材料的金属元素分布图(图1中圆圈标注部分)；图3是Ag/Zn-TiO2@MoS2纳米材料与黑色纳米二氧化钛、MoS2的光催化降解染料对比曲线图(检测方法参见GB/T23762-2020)；图4是Ag/Zn-TiO2@MoS2纳米材料在无光照条件下和可见光光照下对金黄色葡萄球菌的杀灭效果图(检测方法参见GB/T 30706-2014)；图5是Ag/Zn-TiO2@MoS2纳米材料(银含量为0.5ppm)与Ag/Zn离子混合溶液(银含量5ppm)、黑色TiO2纳米材料(质量浓度与复合材料一致)在30min内的杀菌率图(检测方法参见GB/T 30706-2014)。
从图1可以看出，Ag/Zn-TiO2@MoS2纳米材料中TiO2吸附于MoS2纳米片上。
从图2可以看出，制备的纳米材料粉体中同时存在Ag、Mo、Ti和Zn元素，即成功的制备了负载银/锌离子的二氧化钛复合二硫化钼纳米材料。
图3比较了250mg/L的MoS2纳米片分散液、黑色纳米二氧化钛分散液和TiO2@MoS2纳米材料分散液的光催化效率，以浓度为10mg/L的亚甲基蓝为指示剂，在到达液面的光照强度为1500勒克斯的情况下，TiO2@MoS2纳米材料显示了最强的光催化效率(此处使用不含银/锌离子的纳米材料是为了避免光催化下银锌离子被还原为纳米颗粒，干扰光催化效率的测试)。
图4比较了不同浓度的Ag/Zn-TiO2@MoS2纳米材料对金黄色葡萄球菌的杀灭率，可以看出，在可见光光照下，在复合纳米材料中银含量仅为0.5ppm时，对金黄色葡萄球菌的杀灭率达到98％，具有杀菌效果；其浓度提高至5ppm时，杀菌率达到99.9％，具有强烈的杀菌效果。
图5比较了Ag/Zn-TiO2@MoS2纳米材料(银含量为0.5ppm)与Ag/Zn离子混合溶液(银含量5ppm)、黑色TiO2纳米材料(质量浓度与复合材料一致)在30min内的杀菌率，可以明显看出复合纳米材料具有最佳的杀菌效率。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若对本发明的这些修改和变型属于本发明权利要求及其同等技术的范围之内，则本发明也意图包含这些改动和变型在内。上述实施例或实施方式只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。
Claims (7)
1.一种纳米光催化杀菌材料的制备方法，其特征在于，所述的纳米光催化杀菌材料为Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，所述的制备方法包括如下步骤：
(1)将四氯化钛缓慢滴加至溶剂中，获得透明液体；
(2)将锌加入到所述的透明液体中，使之渐渐变为蓝色液体；
(3)将所述的蓝色液体在一定温度下反应一段时间；
(4)在反应产物中加入壳聚糖、二硫化钼粉末，超声处理一段时间；
(5)将含银离子的盐在搅拌的条件下加入超声处理后的液体中，干燥得到所述的纳米材料，
其中：
步骤(1)中，所述的四氯化钛和所述的溶剂的体积比为1:20-30，滴加速度为10-30mL/min；
步骤(1)中，所述的溶剂选自水、无水乙醇、异丙醇中的一种或多种；
步骤(2)中，所述的锌和所述的透明液体中的钛的摩尔比为1:2-10。
2.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，所述的一定温度为150-250℃，所述的一段时间为6-24h。
3.根据权利要求1所述的制备方法，其特征在于：步骤(4)中，反应产物中含锌的纳米二氧化钛、壳聚糖、二硫化钼的质量比为(30-75)：(10-25)：(0.5-2)。
4.根据权利要求1所述的制备方法，其特征在于：步骤(4)中，所述的超声处理的时间为1-4h，功率为80-300W。
5.根据权利要求1所述的制备方法，其特征在于：步骤(5)中，所述的含银离子的盐为硝酸银；加入含银离子的盐后Ag离子的浓度为10-1000ppm；所述的含银离子的盐与所述的超声处理后的液体的体积比为1：10-1000；所述的搅拌的速度为100-1000rpm，时间为10-60min。
6.根据权利要求1所述的制备方法，其特征在于：步骤(5)中，所述的干燥的温度为40-80℃，时间为3-24h。
7.一种纳米光催化杀菌材料，其特征在于：所述的纳米光催化杀菌材料为Ag/Zn离子负载的黑色TiO2复合MoS2纳米片纳米材料，由根据权利要求1-6中任意一项所述的制备方法制备得到。
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