CN112889841B - 一种光催化磷灰石包裹技术专杀病毒喷剂 - Google Patents
一种光催化磷灰石包裹技术专杀病毒喷剂 Download PDFInfo
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Abstract
本发明属于杀毒喷剂技术领域，尤其涉及一种光催化磷灰石包裹技术专杀病毒喷剂，包括杀灭病毒有效成分和溶剂，所述杀灭病毒有效成分为磷灰石‑纳米二氧化钛复合光催化剂，所述磷灰石‑纳米二氧化钛复合光催化剂为两层包覆结构：最内层的芯核为纳米二氧化钛芯球，所述纳米二氧化钛芯球外包覆有羟基磷灰石壳层。本发明所述复合材料。本发明以二氧化钛与磷灰石为材料的复合型光催化剂为主要杀灭病毒作用物，整体提高了二氧化钛的光催化净化和杀灭病毒效率，本发明所述的专杀病毒喷剂经过无毒无害产品检测和试验，达到食品级标准，安全无毒，无二次污染，是真正达到100％的健康环保杀灭病毒产品。
Description
技术领域
本发明属于杀毒喷剂技术领域，尤其涉及一种光催化磷灰石包裹技术专杀病毒喷剂。
背景技术
据世界卫生组织(WHO)统计，在发展中国家内的80％的疾病是源于致病微生物污染，这些微生物包括寄生虫、原生动物、真菌、细菌、B克次氏体、病毒以及肮病毒⑴。这些微生物会对人体引起严重的疾病，如腹泻、肺结核、肺炎、伤寒症等。
目前，传统的消毒方法主要包括氯气、臭氧和紫外光。具中,氯气消毒是被公认为最有效的，但是该工艺会生成致畸、致癌的消毒副产物，包括三卤甲烷，卤乙酸等，从而造成二次污染和水质盐碱化。臭氧消毒同样会生成多种有机消毒副产物，包括乙醛、殁酸、酮类和漠酸盐，而且臭氧还需要复杂的设备和有效的接触系统。紫外消毒则是利用波长V280nm的光辐射,同样需要昂贵的光源和大量的电耗，而且因紫外光在水中的穿透能力有限，处理后的细菌往往还会重新生长。综上所述，现有技术中的这些消毒方法的缺点也使得他们的应用依然具有局限性，因此，研究开发一种能克服现有消毒方法缺点的，有效、低价，同时对环境和人体无害的新型消毒试剂和消毒方法是当前迫切需要的。
PCM是光催化的简称，在国际上称为photocatalyst，是利用光能转化成化学能的一种催化剂。PCM光催化氧化还原技术原理是：在光的照射下，PCM会产生类似光合作用的光催化反应，产生出氧化能力极强的自由氢氧基和活性氧，具有很强的光氧化还原功能，可氧化分解各种有机化合物和部分无机物，能破坏细菌的细胞膜和固化病毒的蛋白质，可杀灭细菌和分解有机污染物，把有机污染物分解成无污染的水(H2O)和二氧化碳(CO2)，因而具有极强的消毒、杀灭病毒、抑菌、抗病毒、除螨、除臭、防霉、净化空气功能。
纳米TiO2是一种新型的无机金属氧化物材料，它是一种N型半导体材料，由于具有较大的比表面积和合适的禁带宽度，因此具有光催化氧化降解一些化合物的能力，纳米TiO2具有优异的光催化活性，并且价格便宜，无毒无害等优点因此被广泛的应用。但由于TiO2光激发产生电子与空穴的表面和体相复合率较高，导致量子利用率低，严重制约着TiO2光催化杀灭病毒消毒效率的提高。
发明内容
为解决上述现有技术中存在的问题，本发明提供了一种光催化磷灰石包裹技术专杀病毒喷剂，本发明以二氧化钛与磷灰石为材料的复合型光催化剂为主要杀灭病毒作用物，整体提高了二氧化钛的光催化净化和杀灭病毒效率，本发明所述的专杀病毒喷剂经过无毒无害产品检测和试验，达到食品级标准，安全无毒，无二次污染，是真正达到100％健康环保的杀灭病毒产品。
为实现上述目的，本发明采用如下技术方案：
一种光催化磷灰石包裹技术专杀病毒喷剂，包括杀灭病毒有效成分和溶剂，所述杀灭病毒有效成分为磷灰石-纳米二氧化钛复合光催化剂，所述磷灰石-纳米二氧化钛复合光催化剂为两层包覆结构：最内层的芯核为纳米二氧化钛芯球，所述纳米二氧化钛芯球外包覆有羟基磷灰石壳层。
优选的，所述纳米二氧化钛芯球为MOFs-纳米二氧化钛复合芯球。MOFs(金属有机骨架化合物，英文名称Metal organic Frameworks)是由有机配体和金属阳离子或簇连接而成的新型多孔纳米结构，具有高比表面积，高孔隙率和分散良好的活性中心。
优选的，所述MOFs为铂-银双金属有机骨架化合物，结合铂-银双金属的协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
优选的，所述铂-银双金属有机骨架化合物由以下方法制备：将硝酸铂、硝酸银和均苯四甲酸在室温下反应，离心、洗涤、干燥、煅烧后即得到所述铂-银双金属有机骨架化合物。
优选的，所述MOFs-纳米二氧化钛复合芯球由以下方法制备：铂-银双金属有机骨架化合物制成溶液，然后在溶液中加入纳米二氧化钛，微波分散，离心、洗涤、干燥、煅烧后即得到所述MOFs-纳米二氧化钛复合芯球。
优选的，所述MOFs-纳米二氧化钛复合芯球的直径为10-30nm。
优选的，所述羟基磷灰石壳层上负载有Pt。Pt起到助催化剂的协同作用，可促进电子的迁移，有效阻止光生载流子的复合，提高量子产率，从而具有良好的光催化活性。
优选的，所述磷灰石-纳米二氧化钛复合光催化剂由以下方法制备：将合成得到的MOFs-纳米二氧化钛复合芯球首先进行Ca(OH)2包覆，得到中间产物，然后将该中间产物直接进行磷化处理以使Ca(OH)2壳层转化为羟基磷灰石壳层，得到TiO2-羟基磷灰石核壳结构的中间产物，最后对该TiO2-羟基磷灰石核壳结构的中间产物负载Pt，即可得到负载Pt的磷灰石-纳米二氧化钛复合光催化剂。
优选的，所述羟基磷灰石壳层的厚度为1-5nm。
本发明所述的专杀病毒喷剂的杀灭病毒原理为：
本发明所述的专杀病毒喷剂通过喷覆在物体表面，可形成更具生物相容性及强吸附力的纳米复合薄膜，纳米复合薄膜内含有的杀灭病毒有效成分——磷灰石-纳米二氧化钛复合光催化剂，其芯核中含有纳米二氧化钛，属N型半导体，在日光紫外线照射作用下，电子由价带(Valence band)跃迁至导带(Conduction band)，产生电子与空穴，电子与空气中的O2-反应生成超氧负离子O2-，空穴与表面吸附的水或OH-反应形成具有强氧化性的羟基自由基·OH，高活性的羟基具有很高的氧化能力，超氧负离子具有杀灭病毒、抗菌作用。
而采用MOFs-纳米二氧化钛复合芯球作为芯核，铂-银双金属有机骨架化合物起到协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
其次，在羟基磷灰石壳层上负载有Pt，Pt起到助催化剂的协同作用，可促进电子的迁移，有效阻止光生载流子的复合，提高量子产率，从而具有良好的光催化活性。
有益效果
本发明公开了一种光催化磷灰石包裹技术专杀病毒喷剂，本发明以二氧化钛与磷灰石为材料的复合型光催化剂为主要杀灭病毒作用物，整体提高了二氧化钛的光催化净化和杀灭病毒效率，添加磷灰石配方的光催化剂，其形成的纳米膜会更具生物相容性及强吸附力，而且具备晚上吸附细菌，白天分解有毒有机物和细菌的独特功效，使复合薄膜在无光的条件下也能产生减少介质中有毒有机物及细菌的效用，净化效果更持久稳定。
本发明所述的专杀病毒喷剂具有良好的抗菌功能，对多种常见菌种(如酵母菌、大肠杆菌和金黄色葡萄球菌等)具有高效的抗菌作用，是一种安全性高，不易挥发，不易分解，耐热性好，对人体无害且能长效抗菌、防霉的专杀病毒喷剂。本发明所述的专杀病毒喷剂经过无毒无害产品检测和试验，达到食品级标准，安全无毒，无二次污染，是100％健康环保杀灭病毒消毒产品。
现有技术中普通的光催化剂材料需要经过紫外线或太阳光照射才能完全发挥作用实现杀灭病毒消毒效果，而本发明所述的光催化剂仅在室内微弱的灯光下，也能高效持久地发挥医疗级的杀灭病毒净化作用。
附图说明
图1为本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂灭螨虫效果检测结果图；
图2为本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂杀灭甲型流感病毒效果检测结果图；
图3为本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂杀灭大肠埃希氏菌效果检测结果图。
具体实施方式
以下，将详细地描述本发明。在进行描述之前，应当理解的是，在本说明书和所附的权利要求书中使用的术语不应解释为限制于一般含义和字典含义，而应当在允许发明人适当定义术语以进行最佳解释的原则的基础上，根据与本发明的技术方面相应的含义和概念进行解释。因此，这里提出的描述仅仅是出于举例说明目的的优选实例，并非意图限制本发明的范围，从而应当理解的是，在不偏离本发明的精神和范围的情况下，可以由其获得其他等价方式或改进方式。
以下实施例仅是作为本发明的实施方案的例子列举，并不对本发明构成任何限制，本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。除非特别说明，以下实施例中使用的试剂和仪器均为市售可得产品。
实施例1
一种光催化磷灰石包裹技术专杀病毒喷剂，包括杀灭病毒有效成分和溶剂，所述杀灭病毒有效成分为磷灰石-纳米二氧化钛复合光催化剂，所述磷灰石-纳米二氧化钛复合光催化剂为两层包覆结构：最内层的芯核为纳米二氧化钛芯球，所述纳米二氧化钛芯球外包覆有羟基磷灰石壳层。
所述纳米二氧化钛芯球为MOFs-纳米二氧化钛复合芯球。MOFs(金属有机骨架化合物，英文名称Metal organic Frameworks)是由有机配体和金属阳离子或簇连接而成的新型多孔纳米结构，具有高比表面积，高孔隙率和分散良好的活性中心。
所述MOFs为铂-银双金属有机骨架化合物，结合铂-银双金属的协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
所述MOFs-纳米二氧化钛复合芯球的直径为10-30nm。
本实施例所述的专杀病毒喷剂的杀灭病毒原理为：
本发明所述的专杀病毒喷剂通过喷覆在物体表面，可形成更具生物相容性及强吸附力的纳米复合薄膜，纳米复合薄膜内含有的杀灭病毒有效成分——磷灰石-纳米二氧化钛复合光催化剂，其芯核中含有纳米二氧化钛，属N型半导体，在日光紫外线照射作用下，电子由价带(Valence band)跃迁至导带(Conduction band)，产生电子与空穴，电子与空气中的O2-反应生成超氧负离子O2-，空穴与表面吸附的水或OH-反应形成具有强氧化性的羟基自由基·OH，高活性的羟基具有很高的氧化能力，超氧负离子具有杀灭病毒、抗菌作用。
而采用MOFs-纳米二氧化钛复合芯球作为芯核，铂-银双金属有机骨架化合物起到协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
实施例2
一种光催化磷灰石包裹技术专杀病毒喷剂，包括杀灭病毒有效成分和溶剂，所述杀灭病毒有效成分为磷灰石-纳米二氧化钛复合光催化剂，所述磷灰石-纳米二氧化钛复合光催化剂为两层包覆结构：最内层的芯核为纳米二氧化钛芯球，所述纳米二氧化钛芯球外包覆有羟基磷灰石壳层。
所述纳米二氧化钛芯球为MOFs-纳米二氧化钛复合芯球。MOFs(金属有机骨架化合物，英文名称Metal organic Frameworks)是由有机配体和金属阳离子或簇连接而成的新型多孔纳米结构，具有高比表面积，高孔隙率和分散良好的活性中心。
所述MOFs为铂-银双金属有机骨架化合物，结合铂-银双金属的协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
所述MOFs-纳米二氧化钛复合芯球的直径为10-30nm。
所述羟基磷灰石壳层上负载有Pt。Pt起到助催化剂的协同作用，可促进电子的迁移，有效阻止光生载流子的复合，提高量子产率，从而具有良好的光催化活性。
所述羟基磷灰石壳层的厚度为1-5nm。
本实施例所述的专杀病毒喷剂的杀灭病毒原理为：
本发明所述的专杀病毒喷剂通过喷覆在物体表面，可形成更具生物相容性及强吸附力的纳米复合薄膜，纳米复合薄膜内含有的杀灭病毒有效成分——磷灰石-纳米二氧化钛复合光催化剂，其芯核中含有纳米二氧化钛，属N型半导体，在日光紫外线照射作用下，电子由价带(Valence band)跃迁至导带(Conduction band)，产生电子与空穴，电子与空气中的O2-反应生成超氧负离子O2-，空穴与表面吸附的水或OH-反应形成具有强氧化性的羟基自由基·OH，高活性的羟基具有很高的氧化能力，超氧负离子具有杀灭病毒、抗菌作用。
而采用MOFs-纳米二氧化钛复合芯球作为芯核，铂-银双金属有机骨架化合物起到协同催化效应，增强了金属位点间的电子传递，提高量子产率，从而具有良好的光催化活性，达到高效杀灭病毒的目的。
其次，在羟基磷灰石壳层上负载有Pt，Pt起到助催化剂的协同作用，可促进电子的迁移，有效阻止光生载流子的复合，提高量子产率，从而具有良好的光催化活性。
实施例3
实施例2所述磷灰石-纳米二氧化钛复合光催化剂的制备方法，包括以下步骤：
(1)铂-银双金属有机骨架化合物的制备：将硝酸铂、硝酸银和均苯四甲酸在室温下反应，离心、洗涤、干燥、煅烧后即得到所述铂-银双金属有机骨架化合物；
(2)MOFs-纳米二氧化钛复合芯球的制备：铂-银双金属有机骨架化合物制成溶液，然后在溶液中加入纳米二氧化钛，微波分散，离心、洗涤、干燥、煅烧后即得到所述MOFs-纳米二氧化钛复合芯球；
(3)将合成得到的MOFs-纳米二氧化钛复合芯球首先进行Ca(OH)2包覆，得到中间产物，然后将该中间产物直接进行磷化处理以使Ca(OH)2壳层转化为羟基磷灰石壳层，得到TiO2-羟基磷灰石核壳结构的中间产物，最后对该TiO2-羟基磷灰石核壳结构的中间产物负载Pt，即可得到负载Pt的磷灰石-纳米二氧化钛复合光催化剂。
实验例
为验证本发明所述光催化磷灰石包裹技术专杀病毒喷剂的杀灭病毒效果，将本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂送至广东省微生物分析检测中心进行抗菌、杀灭病毒效果检测，具体检测结果如图1-3所示。
对本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂与现有常用的杀灭病毒消毒液进行对比，具体结果见表1。
表1.本发明所述专杀病毒喷剂与现有杀灭病毒液的对比表
对本发明实施例2所得的光催化磷灰石包裹技术专杀病毒喷剂进行杀灭病毒效果实验，具体结果见表2。
表2.本发明所述专杀病毒喷剂的杀灭病毒种类与成效表
以上实施例仅用以说明本发明的技术方案，而非对其进行限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (5)
1.一种光催化磷灰石包裹技术专杀病毒喷剂，其特征在于：
包括杀灭病毒有效成分和溶剂，所述杀灭病毒有效成分为磷灰石-纳米二氧化钛复合光催化剂，所述磷灰石-纳米二氧化钛复合光催化剂为两层包覆结构：最内层的芯核为纳米二氧化钛芯球，所述纳米二氧化钛芯球外包覆有羟基磷灰石壳层；
所述纳米二氧化钛芯球为MOFs-纳米二氧化钛复合芯球，所述MOFs为铂-银双金属有机骨架化合物；
所述MOFs-纳米二氧化钛复合芯球由以下方法制备：
(1)将硝酸铂、硝酸银和均苯四甲酸在室温下反应，离心、洗涤、干燥、煅烧后即得到所述铂-银双金属有机骨架化合物；
(2)铂-银双金属有机骨架化合物制成溶液，然后在溶液中加入纳米二氧化钛，微波分散，离心、洗涤、干燥、煅烧后即得到所述MOFs-纳米二氧化钛复合芯球。
2.根据权利要求1所述的光催化磷灰石包裹技术专杀病毒喷剂，其特征在于，所述MOFs-纳米二氧化钛复合芯球的直径为10-30nm。
3.根据权利要求1所述的光催化磷灰石包裹技术专杀病毒喷剂，其特征在于，所述羟基磷灰石壳层上负载有Pt。
4.根据权利要求3所述的光催化磷灰石包裹技术专杀病毒喷剂，其特征在于，所述磷灰石-纳米二氧化钛复合光催化剂由以下方法制备：将合成得到的MOFs-纳米二氧化钛复合芯球首先进行Ca(OH)2包覆，得到中间产物，然后将该中间产物直接进行磷化处理以使Ca(OH)2壳层转化为羟基磷灰石壳层，得到TiO2-羟基磷灰石核壳结构的中间产物，最后对该TiO2-羟基磷灰石核壳结构的中间产物负载Pt，即可得到负载Pt的磷灰石-纳米二氧化钛复合光催化剂。
5.根据权利要求4所述的光催化磷灰石包裹技术专杀病毒喷剂，其特征在于，所述羟基磷灰石壳层的厚度为1-5nm。
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