CN108126746A - 一种用于杀菌消毒的玻璃窗光热催化涂膜及其制备和应用 - Google Patents
一种用于杀菌消毒的玻璃窗光热催化涂膜及其制备和应用 Download PDFInfo
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Abstract
本发明公开了一种用于杀菌消毒的玻璃窗光热催化涂膜及其制备和应用,(1)将钨原与有机溶剂按质量比1:300~1000混匀并搅拌反应至溶液澄清,而后通过蒸发得固体物质A;将丙烯酸羟丙酯按按体积比1:6~15滴加至硅溶胶溶液中混匀并搅拌反应,获得杂化溶液B;(2)A和B按质量比1:5000~50000混合均匀即得光热催化铸膜液;(3)光热催化铸膜液喷至玻璃表面,遮光环境下待铸膜液自然流平后,用紫外光照射;(4)固化后的玻璃窗光热催化涂膜在自然光照射下进行杀菌消毒。本发明提高光催化消毒在太阳光作用下的激发效率,可以通过喷雾器喷涂及紫外光固化,在医院现有已安装的玻璃上新构建一层光催化玻璃膜,通过催化材料光热反应,实现对空气杀菌消毒作用。
Description
技术领域
本发明属于光热催化领域,具体涉及一种用于杀菌消毒的玻璃窗光热催化涂膜及其制备方法。
背景技术
空气微生物包括空气中的细菌、真菌和放线菌等生命活体,在空气中以气溶胶的形式存在。其可借助空气流动传播扩散,当其浓度超过一定限制时,会引起各种呼吸道疾病及过敏反应的发生,对人体健康有重大影响。近年来,人们已逐渐认识到医院环境是某些病原菌的储存库,医院环境微生物污染将促进医院感染的发生和传播。医院环境的耐药基因将对医院感染造成另一种威胁,特别是某些耐药致病菌的出现,而医院环境空气介质传播疾病途径占各传染途径首位,因此对医院环境空气进行有效及长期灭菌不应忽视。
光催化氧化技术具有反应条件温和、能耗低、操作简便、可减少二次污染及可望用太阳光为反应光源等突出特点。该材料在光(特别是紫外光)照射下,具有杀灭细菌的作用,其称为光催化杀菌。1998年Kayano等人发表了TiO2薄膜光催化剂抗菌和解毒作用的研究论文,证实了光催化材料不仅可以杀死细菌,而且可以彻底将细菌的残骸分解,避免了细菌残骸分解出的内毒素对人类的二次毒害。光催化杀菌有直接和间接反应两种不同的机理,直接反应机理为光生电子和光生空穴直接和细胞壁、细胞膜或细胞的组成成分反应,导致功能单元失活而致细胞死亡。间接反应机理为光生电子或光生空穴与水分子或氧反应,形成氢氧自由基·OH、超氧离子(·O2 -)和H2O2等强氧化类物质,它们与细胞壁、细胞膜和细胞内组成成分发生链式反应,导致细胞死亡。
基于该机理,大量研究者设计开发了多种光催化杀菌设备及方法。例如专利201010624646.9设计了一种制备纳米二氧化钛光催化杀菌涂料的方法,该发明明具有广谱杀菌功效;专利201710357419.6公开了一种净化空气的光催化涂料,其在纳米二氧化钛表面包覆一层聚吡咯,可以显著提高纳米二氧化钛的光催化效率,并且实现二氧化钛填料的有机无机复合,获得一种光催化效率高、成本低、综合性能好的新型光催化剂。
然而目前这些专利所采用的光催化材料带隙宽度极大,导致这些材料仅对太阳光中的紫外光具有显著的吸收利用作用,导致光催化材料能源利用率低,效果不佳。此外大量设备亦采用人工紫外光对催化材料进行激发,造成了大量的能源消耗。
发明内容
本发明提供了一种适用于医院杀菌消毒的玻璃窗光热催化涂膜,提高光催化消毒在太阳光作用下的激发效率,可以通过喷雾器喷涂及紫外光固化,在医院现有已安装的玻璃上新构建一层光催化玻璃膜,通过催化材料光热反应,实现对空气杀菌消毒作用。
为提高光催化消毒在太阳光作用下的激发效率,本发明开发一种光热催化材料。在紫外光作用下或部分低波长可见光作用下,光催化材料催化产生空穴与电子,用于杀灭空气中的细菌微生物;而在长波长可见光以及红外光的作用下,该材料可以近红外区能产生等离子共振吸收,具有显著的近红外光热转化性质,可以显著提升光催化性能。
一种用于杀菌消毒的玻璃窗光热催化铸膜液的制备方法,包括如下步骤:
(1)将钨原与有机溶剂按质量比1:300~1000混匀并搅拌反应至溶液澄清,而后通过蒸发得固体物质A;将丙烯酸羟丙酯按按体积比1:6~15滴加至硅溶胶溶液中混匀并搅拌反应,获得杂化溶液B;
(2)固体物质A和杂化溶液B按质量比1:5000~50000混合均匀即得光热催化铸膜液。
本发明通过简易化学沉淀法获得光热催化材料,即固体A,而后通过采用酸性硅溶胶与丙烯酸羟丙酯(HPA)反应合成杂化溶胶,然后涂覆在经热加工处理后的普通汽车玻璃上,在紫外光照射条件下固化,得到亲水性玻璃涂膜,及溶液B,而后通过简易混合获得光热催化铸膜液。
步骤(1)所述的钨原与有机溶剂按质量比1:300~1000,当钨原含量过低时,会造成有机溶剂浪费,并降低生产效率,当钨原含量过高时,纳米光热催化材料会产生大量杂质,降低催化材料质量。优选地,钨原与有机溶剂按质量比1:700~900。更进一步优选地,以氯化钨与乙醇质量比1:850~900杀毒效果更好,最优选以氯化钨与乙醇质量比1:900杀毒效果最好。
优选地,固体物质A和杂化溶液B按质量比1:10000~30000配比;更进一步优选地,固体物质A和杂化溶液B按质量比1:25000~30000配比;更进一步优选地,固体物质A和杂化溶液B按质量比1:28000~30000配比。
优选地,步骤(1)中所述钨原为氯化钨、硝酸钨或硫酸钨,所述有机溶剂为冰醋酸、乙醇或三乙胺。在实验过程中,不同试剂并不会显著影响催化剂性能,但从成本角度考虑,钨原可进一步优选为硫酸钨,有机溶剂进一步优选为乙醇。
优选地,步骤(1)中制备固体物质A和杂化溶液B的搅拌反应时间均为0.5~2小时,制备杂化溶液B的搅拌反应过程在旋转蒸发仪器中进行,恒定温度为30~40℃。制备杂化溶液B的搅拌反应过程在旋转蒸发仪器中进行,恒定温度为30~40℃,升温目的在于出去反应体系中多余的水分。当温度过高时,会导致溶液B中产生大量颗粒物质,导致膜无法涂布均匀,温度过低则导致水分驱散不完全。恒定温度可进一步优选为35℃。
优选地,制备固体物质A的蒸发过程在减压环境中进行,真空度低于0.1Mpa,温度为40~60℃。温度过低会导致蒸发过程缓慢,温度过高则会导致催化材料晶体形态受到影响,也会导致能源大量浪费。
优选地,制备杂化溶液B时丙烯酸羟丙酯的滴加速度为10~30ml/L(溶胶)/min。
优选地,丙烯酸羟丙酯和硅溶胶溶液的体积比为1:8~12,最优选为1:10。
本发明还提供一种用于杀菌消毒的玻璃窗光热催化涂膜,将所述制备方法所制备得到的光热催化铸膜液喷至玻璃表面,遮光环境下,静等5~10分钟,待铸膜液自然流平后,用紫外光照射固化即得。
本发明还提供一种玻璃窗光热催化杀菌消毒的方法,包括如下步骤:
(1)将所述制备方法所制备得到的光热催化铸膜液喷至玻璃表面,遮光环境下,静等5~10分钟,待铸膜液自然流平后,用紫外光照射固化;
(2)固化后的玻璃窗光热催化涂膜在自然光照射下对室内空气进行杀菌消毒。
铸膜液喷涂后需要静等一段时间,当时间过短时,铸膜液无法自然流平,导致玻璃膜分布不均,当时间过长时,会导致铸膜液厚度过低,催化效果变差,因此作为优选,铸膜液喷至玻璃表面后需要静置5~10分钟,进一步优选为5~6分钟。
作为优选,用于固化的紫外光功率为0.5-1kW,功率过低会导致铸膜液固化缓慢,且部分深层铸膜液无法固化,功率过高则会在操作过程中对人体造成危害。从效果及安全性角度考虑,紫外光功率进一步优选为1kW。
作为优选,紫外光照射固化时间为2-5分钟,进一步优选为2.5~3.5min。时间过短会导致铸膜液固化不完全,但由于催化材料会在紫外光照射下激发,从而降低光催化使用寿命。
与现有技术相比,本发明具有如下有益效果:
(1)本发明能够在现有已安装的窗户玻璃上直接喷涂敷膜,操作简单快捷,成本低廉,安装过程不影响室内原住居民;
(2)本发明无需任何人工维护及能源输入,仅通过外界自然光照射即可实现杀菌消毒作用。
(3)本发明相比普通光催化材料,可以同时利用太阳光中的紫外光,可见光和红外光,光转化效率高。
附图说明
图1是实施例1所对应实验结果图。
图2是实施例3所对应实验结果图。
具体实施方式
实施例1
将氯化钨与乙醇按质量比1~1000混匀并搅拌2小时至溶液澄清,而后通过减压蒸发得固体物质A;2)将丙烯酸羟丙酯(HPA)按体积比1:10,以20ml/L(溶胶)/min的速度滴加至硅溶胶溶液中,旋转蒸发仪器中混匀搅拌1小时,恒定温度为35℃,获得杂化溶液B;3)将A固体与溶液B以质量比1:30000均匀混合,即得光热催化铸膜液;4)而后通过喷雾器将铸膜液喷至玻璃表面,遮光环境下,静等5分钟;5)等铸膜液自然流平后,用1kW紫外光照射3分钟固化。
对4*4*5m单房间的窗户进行喷膜处理,窗户面积为4.5m2,实验在5月进行。每隔两天在下午17点是对房间进行通过空气微生物样品采集采用Anderson-6级撞击式采样器,该采样器共有6级,各级捕获粒径从上往下逐渐减小,依次为≥7.0μm,4.7~7.0μm,3.3~4.7μm,2.1~3.3μm,1.1~2.1μm,0.65~1.1μm。采样流量为28.3L/min,采样时间根据不同的采样环境和不同的培养基质采集10min不等。细菌培养基的配制方法选用营养琼脂法,称取33g营养琼脂粉于锥形瓶中,加蒸馏水1000mL加热溶解后于灭菌锅中高压灭菌(130Kpa,30min)。而后通过平板计数法计算微生物浓度。实验结果如图1所示,在光热催化膜作用下,空气中微生物的含量下降约30%。
实施例2
保持其他条件与实施例1完全一致,调节氯化钨与乙醇质量比从1:300~1000,结果如表1所示,在光热催化膜作用下,空气中微生物的含量下降约20%~45%,其中在氯化钨与乙醇质量比为1:750时效果最好。
表1
比例 | 室内原菌浓度 | 催化灭菌后室内菌浓度 |
1:300 | 490±32 | 402±41 |
1:450 | 543±19 | 392±11 |
1:600 | 521±34 | 350±25 |
1:750 | 562±77 | 320±33 |
1:900 | 487±34 | 331±51 |
1:1000 | 512±21 | 376±21 |
实施例3
将氯化钨与乙醇按质量比1~1000混匀并搅拌2小时至溶液澄清,而后通过减压蒸发得固体物质A;2)将丙烯酸羟丙酯(HPA)按体积比1:10,以10ml/L(溶胶)/min的速度滴加至硅溶胶溶液中,旋转蒸发仪器中混匀搅拌1小时,恒定温度为35℃,获得杂化溶液B;3)将A固体与溶液B以质量比1:10000均匀混合,即得光热催化铸膜液:4)而后通过喷雾器将铸膜液喷至玻璃表面,遮光环境下,静等5分钟;5)等铸膜液自然流平后,用紫外光照射3分钟固化。
测定方法同实施例2,不同之处在于本研究中的催化剂浓度为实施例3倍。实验结果如图2所示,在光热催化膜作用下,空气中微生物的含量下降约50%。
实施例4
保持其他条件与实施例3完全一致,调节氯化钨与乙醇质量比从1:300~1000,结果如表2所示,在光热催化膜作用下,空气中微生物的含量下降约32%~57%,其中在氯化钨与乙醇质量比为1:900时效果最好。
表2
比例 | 室内原菌浓度 | 催化灭菌后室内菌浓度 |
1:300 | 531±62 | 362±22 |
1:450 | 503±9 | 342±21 |
1:600 | 552±19 | 290±42 |
1:750 | 531±57 | 255±32 |
1:900 | 588±34 | 254±61 |
1:1000 | 532±33 | 276±44 |
以上所述仅为本发明专利的具体实施案例,但本发明专利的技术特征并不局限于此,任何相关领域的技术人员在本发明的领域内,所作的变化或修饰皆涵盖在本发明的专利范围之中。
Claims (9)
1.一种用于杀菌消毒的玻璃窗光热催化铸膜液的制备方法,其特征在于,包括如下步骤:
(1)将钨原与有机溶剂按质量比1:300~1000混匀并搅拌反应至溶液澄清,而后通过蒸发得固体物质A;将丙烯酸羟丙酯按按体积比1:6~15滴加至硅溶胶溶液中混匀并搅拌反应,获得杂化溶液B;
(2)固体物质A和杂化溶液B按质量比1:5000~50000混合均匀即得光热催化铸膜液。
2.根据权利要求1所述制备方法,其特征在于,步骤(1)中所述钨原为氯化钨、硝酸钨或硫酸钨,所述有机溶剂为冰醋酸、乙醇或三乙胺。
3.根据权利要求1所述制备方法,其特征在于,步骤(1)中制备固体物质A和杂化溶液B的搅拌反应时间均为0.5~2小时,制备杂化溶液B的搅拌反应过程在旋转蒸发仪器中进行,恒定温度为30~40℃。
4.根据权利要求1所述制备方法,其特征在于,制备固体物质A的蒸发过程在减压环境中进行,真空度低于0.1Mpa,温度为40~60℃。
5.根据权利要求1所述制备方法,其特征在于,制备杂化溶液B时丙烯酸羟丙酯的滴加速度为10~30ml/L溶胶/min。
6.一种用于杀菌消毒的玻璃窗光热催化涂膜,其特征在于,将如权利要求1~5任一权利要求所述制备方法制备得到的光热催化铸膜液喷至玻璃表面,遮光环境下,静等5~10分钟,待铸膜液自然流平后,用紫外光照射固化即得。
7.一种玻璃窗光热催化杀菌消毒的方法,其特征在于,包括如下步骤:
(1)将如权利要求1~5任一权利要求述制备方法所制备得到的光热催化铸膜液喷至玻璃表面,遮光环境下,静等5~10分钟,待铸膜液自然流平后,用紫外光照射固化;
(2)固化后的玻璃窗光热催化涂膜在自然光照射下对空气进行杀菌消毒。
8.根据权利要求7所述方法,其特征在于,紫外光的功率为0.5-1kW。
9.根据权利要求7所述方法,其特征在于,紫外光照射固化时间为2-5分钟。
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