CN113231053A - 自消毒光催化剂片 - Google Patents
自消毒光催化剂片 Download PDFInfo
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- CN113231053A CN113231053A CN202110314284.1A CN202110314284A CN113231053A CN 113231053 A CN113231053 A CN 113231053A CN 202110314284 A CN202110314284 A CN 202110314284A CN 113231053 A CN113231053 A CN 113231053A
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- photocatalyst
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- disinfecting
- sheet
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Abstract
本申请公开了自消毒光催化剂片,其包括:具有第一侧及与第一侧相对的第二侧的基底材料;及包括主要光催化剂和次要光催化剂的光催化剂层;其中,主要光催化剂包括金属氧化物光催化剂,次要光催化剂包括金属光催化剂,主要光催化剂与次要光催化剂的质量比在10:1到100:1之间,主要光催化剂在基底材料的第一侧上在分子水平与基底材料形成共价键。该自消毒光催化剂片可由可见光激活并针对细菌和病毒进行自消毒。本申请还公开了自消毒光催化剂片的生产方法。
Description
技术领域
本发明属于抗菌光催化剂装置领域,尤其涉及自消毒光催化剂片。
背景技术
COVID-19全球大流行已触发对消毒设施的强烈需求,包括空气和表面消毒。对于空气消毒,有可持续的解决方案,如房间上方的杀菌UV设备或者美国专利申请US 16/995,588中公开的空气消毒光催化设备,其可对空气持续进行消毒而没有任何健康问题。然而,没有提供持续表面消毒的解决方案。目前,对于表面消毒,有两种一般的方法。第一种方法是向表面喷化学消毒剂,及第二种方法是向表面照射具有254nm的中心波长的UVC光。两种方法对于表面消毒均有效。然而,它们仅可在空间中没有用户时使用,因为当人直接暴露于化学消毒剂或UVC光时,有副作用或健康问题,如导致皮肤或呼吸过敏(化学消毒剂)或者导致皮肤和眼睛损伤(UVC光)。因此,化学消毒剂和UVC设备仅可在下班时间定期施加。在施加化学消毒剂和UVC光的时间之间,由于用户物理接触表面或者从人带菌者发出的空气传播的小滴着落在表面上,细菌和病毒将在表面上生长。更好的表面消毒解决方案需要能够持续对表面消毒且对用户不会引起任何副作用。
已知光催化剂在紫外光下变得有效并通过破坏细菌的细胞壁而灭杀细菌。Soma,R.等在美国专利6,242,752中教导了在照明设备的透镜上使用由锐钛型二氧化钛(TiO2)制成的光催化薄膜,使得随着源自照明设备的光照射透过二氧化钛薄膜,光的UV射线激活光催化剂,使得其破坏细菌的细胞壁并导致细菌的灭杀。那么,基于该专利的教导,用基础材料和光催化剂层产生光催化剂片是可行的。然而,这样的光催化剂片仅对UV光源具有光催化反应,而UV光源不应在用户附近使用。因此,这样的光催化剂片不能用于提供持续的表面消毒。
在美国专利9,522,384中,Liu L.等介绍了菱形锐钛矿型二氧化钛(TiO2)的应用,使得该新型的TiO2可由可见光波长激活并变得杀菌活跃。当用该专利介绍的这种新型TiO2制作光催化剂片时,这样的光催化剂片将对具有可见光波长的常规室内照明源有光催化反应。该光催化剂片因而可一直使用并提供持续的表面消毒。然而,这种可见光反应光催化剂片存在几个问题。新型TiO2直接喷雾沉积在基础材料上在该TiO2光催化剂层与基础材料之间不能提供足够强的结合。因此,该TiO2光催化剂层不能经受正常使用的力并可能从基础材料快速剥离。这种光催化剂片的持续表面消毒的寿命短。因而,需要解决光催化剂层与基础材料的牢固结合,从而经受正常的损耗。其次,即使在该光催化剂层与基础层之间有强结合,该光催化剂层由于正常使用的损耗仍可能磨损。在这种情况发生时,光催化消毒将变得不太有效。如果不知道光催化剂层磨损,用户将在表面消毒保护的错误感觉下使用光催化剂片,这甚至比没有任何表面消毒保护更糟。
发明内容
本发明提出一种自消毒光催化剂片,其可针对细菌和病毒提供持续的表面消毒,同时解决上面提及的问题并确保有效的表面消毒。
在一方面,自消毒光催化剂片包括基底材料和光催化剂层。基底材料具有第一侧和第二侧。光催化剂层包含主要光催化剂和次要光催化剂。主要光催化剂为金属氧化物光催化剂,次要光催化剂为金属光催化剂。主要光催化剂与次要光催化剂的质量比为10:1-100:1。由于该质量比,金属光催化剂被适当地分类为次要光催化剂,不应被视为主要光催化剂的联合光催化剂,因为其对光催化活动的贡献与主要光催化剂并不处于同一水平。
自消毒光催化剂片的一个新颖特征在于,在基底材料的第一侧,主要光催化剂与基底材料在分子水平形成共价键。共价键为化学键的一种。与(例如使用粘合剂的)物理结合(连在一起的两种材料仍然可区分并可通过力分开)不同,共价键涉及的两种材料在分子水平缠结在一起因而不可分。主要光催化剂层与基底材料之间的共价键比物理结合强,能经受住正常使用的力量。因此,本发明的光催化剂层不会从基底材料剥离。金属氧化物光催化剂被选择为本发明的主要光催化剂,因为其可与基底材料形成共价键。作为金属光催化剂的次要光催化剂不能与基底材料形成价键合。非必须地,粘合剂层被涂覆在基底材料的第二侧上,使得本发明产品可粘附到一表面从而对该表面提供自消毒保护。
在一些实施例中,主要金属氧化物光催化剂包括锐钛矿二氧化钛(TiO2),因为锐钛矿型钛(IV)的二氧化物(TiO2)已知在TiO2材料家族中具有最好的光催化特性。在一些实施例中,主要光催化剂包括菱形锐钛矿二氧化钛(TiO2)并具有10-15nm的长轴和3-6nm的短轴。该菱形锐钛矿TiO2具有比标准球形锐钛矿TiO2高得多的体积密度。因此,当菱形锐钛矿TiO2被激活时,其可产生比球形锐钛矿TiO2多得多的激活的光催化粒子,从而导致更有效的针对病原体的消毒。
在一些实施例中,次要金属光催化剂可包括银、金、铜、锌、镍、铈或其组合。可以预见,可使用其它金属元素作为次要光催化剂。金属光催化剂不仅贡献于光催化活动本身,而且使主要金属氧化物光催化剂能吸收可见光波长的光谱能量并变得光催化活跃。在一些实施例中,光催化剂层可由大于400nm的波长范围的可见光激活。由于该特征,当自消毒光催化剂片在室内环境中使用时,其可用从室内光源发出的可见光而使得光催化活跃,并可针对微生物持续对表面进行自消毒。
次要金属光催化剂可包含一种、两种或更多种金属光催化剂材料。在一些实施例中,次要光催化剂仅包括两种金属光催化剂材料即第三金属光催化剂和第四金属光催化剂。在一些实施例中,第三金属光催化剂包括银纳米颗粒(NP),第三金属光催化剂包括铈纳米颗粒。银纳米颗粒和铈纳米颗粒均有助于在锐钛矿TiO2用可见光照射时提高其光催化活性。已发现银纳米颗粒自身在可见光下对抑制细菌有效,而铈纳米颗粒在可见光下对抑制病毒有效。使银纳米颗粒和铈纳米颗粒用作次要金属光催化剂将提高本发明产品在可见光下的自消毒效力。
在一些实施例中,基底材料包括玻璃。一些移动电话屏幕保护贴由钠钙玻璃或者碱性-矽酸铝玻璃制成,及它们可被制成为非常薄的片。它们是本发明的基底材料的很好的候选材料。具有自消毒光催化表面的屏幕保护贴向移动电话的用户提供针对屏幕保护贴上的任何病菌的持续抗菌保护。
在一些实施例中,基底材料包括树脂。树脂已广泛用于屏幕保护帖、包装和表面覆盖。一些广泛使用的树脂包括聚氯乙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚氨酯、热塑性聚氨酯、聚丙烯、聚苯乙烯、硅酮、及其它热塑性和热固性树脂。一旦树脂与所提出的主要光催化剂形成共价键,树脂产品的表面将变得抗菌和自消毒。这样的树脂则可用于覆盖任何表面,无论平坦与否,并对该表面提供持续消毒保护。
在一些实施例中,非必需的粘合剂层包括压敏粘合剂(PSA)材料。PSA,尤其是基于丙烯酸的PSA,可被调整以提供多种需要的属性如弹性、粘着性、透明性、抗氧化和日光性,且对于不同应用具有必要的粘附和粘合度。由于PSA层,本发明产品可附着到表面、从表面取下及再次附着到表面,并对该表面提供自消毒保护。
在一些其它实施例中,非必需的粘合剂层包括静电增强剂,用于附着到由能够经静电进行附着的材料制成的表面上。塑料、陶瓷和玻璃为可经静电附着的材料。静电增强剂可以是环氧树脂、聚环氧化物或石墨烯。可以预见,基底材料可包含静电增强剂如石墨烯,在该情形下,则不必向基底材料添加静电增强剂。
主要光催化剂与基底材料之间的共价键强,使得光催化剂层不会从基底材料剥离。然而,光催化剂层仍然可能因正常损耗而磨损。当光催化剂层正被磨损或者当光催化剂层的自消毒功能将要丧失时,有必要提醒用户。在一些实施例中,本发明还包括变色染料,其被涂覆在光催化剂层的至少一部分上,用于通过其颜色变化提醒用户自消毒光催化剂片将到期。在一些实施例中,变色染料包括酚红。酚红在未检测到细菌时为红色。当检测到细菌时,其颜色变为橙色。在将酚红涂覆在光催化剂层上之后,如果光催化剂层仍然光催化有效且保持表面无细菌,酚红因而将保持为红色。当光催化剂层在针对细菌消毒方面变得无效果时,酚红的颜色将变为橙色。通过观察涂覆在本发明产品上的酚红的颜色,用户能够知道是否需要更换自消毒光催化剂片。在一些其它实施例中,变色染料包括银纳米颗粒。银纳米颗粒在首次暴露于空气时为棕色。由于氧化,其将逐渐变为紫色。通过控制银纳米颗粒的量,其颜色变化特征因而可用作计时器。当其变为深紫色时,用户可得到直观提示并更换自消毒光催化剂片。
光催化剂层的光催化特性在本发明的光催化剂层因正常损耗而磨损时将下降。使用同样可因正常损耗而磨损或消失的染料将合理,染料的磨损或消失可用作光催化剂层磨损的指示物。因此,通过观察自消毒光催化剂片上的染料的磨损或消失,用户可知道是否到了需更换自消毒光催化剂片的时间。在一些实施例中,自消毒光催化剂片还包括涂覆在光催化剂层的至少一部分上的染料,其中染料的磨损或消失代表光催化剂层的磨损。
在一些实施例中,本发明产品透明并具有大于90%的可见光透射率。可以预见,对于不同的应用,另外的材料可添加到基底材料,或者另外的涂层可添加到基底材料的第二侧,例如滤掉UV光或蓝光,或者添加淡色以降低可见光的光谱穿透率。
用于生产本发明产品的方法包括下述步骤。步骤1为表面激活步骤。在步骤1,将低温大气等离子体施加到基底材料的第一侧以提高基底材料的亲水特性。基底材料如玻璃或树脂本来具有低亲水特性。很难将基于水的溶液涂覆到玻璃或树脂表面。通过向基底材料施加低温大气等离子体,基底材料的亲水特性可短时间大幅提高,从而便于随后涂覆基于水的溶液。低温大气等离子体可以是氧等离子体或氮等离子体。施加大气等离子体的时间和温度将取决于基底材料。例如,当对表面激活树脂基底材料使用大气等离子体时,时间较短及温度较低,而当对表面激活玻璃基底材料使用大气等离子体时,时间较长及温度较高。步骤2为表面涂覆步骤。在步骤2,基于水的光催化剂溶液被均匀喷在基底材料的第一侧上。基于水的溶液包括大于98wt%的水及小于2wt%的主要光催化剂和次要光催化剂。主要光催化剂与次要光催化剂的质量比为10:1-100:1。步骤3为固化步骤。热固化应用于喷有基于水的光催化剂溶液的基底材料。热使得从主要光催化剂产生羟基,其适于与基底材料的第一侧上的基底材料形成共价键。温度越高及热固化过程越长,越多的主要光催化剂分子将产生羟基,这导致更多主要光催化剂分子与基底材料第一侧上的更多基底材料分子之间的共价键。步骤4为可选步骤,用于将粘合剂层涂覆在基底材料的第二侧上。粘合剂层可包括压敏粘合剂(PSA)材料或者静电增强剂。
附图说明
包括附图以帮助进一步理解本发明,及附图构成本发明的一部分。附图示出了本发明的经选择的多个实施例,连同下面的详细描述一起,用于阐释本发明的原理。应意识到,为清楚地图示本发明的概念,附图并不必然按比例绘制,一些元件可能与实际实施中的大小不成比例。
图1示意性地示出了本发明的一实施例,在基底材料的第二侧具有粘合层;
图2示意性地示出了本发明的另一实施例,在光催化剂层上涂覆有染料。
具体实施方式
概述
本发明的多种不同的实施方式及有关发明概念在下面描述。然而,应当承认,本发明不限于任何特定的实施方式,在此明确描述的多个不同实施例主要用于说明目的。例如,在此描述的多个不同的概念可以主要光催化剂、次要光催化剂、基底材料和染料的变化适当地实施。
本发明公开了一种自消毒光催化剂片,其包括基底材料和具有主要光催化剂和次要光催化剂层的光催化剂层。主要光催化剂为金属氧化物光催化剂,而次要光催化剂为金属光催化剂。主要光催化剂与基底材料形成共价键。自消毒光催化剂片可由可见光激活并可针对细菌和病毒自消毒。
实施例
在图1中,示出了本发明的实施例100。光催化剂层102被涂覆在基底材料聚氯乙烯(PVC)101上。光催化剂层包含一种主要金属氧化物光催化剂TiO2 104和两种次要金属光催化剂即银纳米颗粒(NP)105和铈纳米颗粒106。主要光催化剂TiO2 104沿光催化剂层102与基底材料101相遇处的边界103与PVC基底材料101形成共价键。由于存在两种次要光催化剂,光催化剂层102可由具有大于400nm波长的可见光激活。PVC基底材料的第二侧被涂覆粘合层107,其包括压(压力)敏粘合剂(PSA)材料。由于PSA层,该实施例可用作自消毒窗户膜,及其可附着到玻璃窗户、从玻璃窗户取下、甚至再次附着到玻璃窗户并对玻璃窗户提供自消毒保护。
该实施例通过下述处理形成:首先,在50℃用氧等离子体处理PVC基底材料101。然后,向经等离子体处理的基底材料PVC的一侧喷基于水的TiO2溶液,该溶液还包含银纳米颗粒和铈纳米颗粒。TiO2、银纳米颗粒和铈纳米颗粒一起具有该溶液的小于2wt%,水具有该溶液的98wt%。次要光催化剂即银纳米颗粒和铈纳米颗粒与主要光催化剂TiO2的质量比为30:1。之后,喷了基于水的TiO2溶液的基底材料在150℃经受热固化处理30分钟。最后,PVC基底材料的第二侧被涂覆包括压敏粘合剂(PSA)材料的粘合剂层。
在图2中,示出了本发明的另一实施例200。基底材料即钠钙玻璃201被涂覆光催化剂层202,其包含一种主要金属氧化物光催化剂TiO2 204和两种次要金属光催化剂即银纳米颗粒205和铈纳米颗粒206。主要光催化剂TiO2 204沿光催化剂层202与基底材料201相遇处的边界203与基底材料201形成共价键。一层酚红208被涂覆在光催化剂层202的一部分上。当该实施例在可见光下首次使用时,酚红层为红色,由于光催化剂层202可由可见光激活并针对细菌进行自消毒,因此,酚红层未检测到细菌。随着光催化剂层202因正常的损耗而磨损,其光催化效力开始下降并在表面上留下一些细菌。当足够的细菌积累在光催化剂层202的表面上时,它们将被酚红层208检测到,导致酚红的颜色变成橙色。通过观察酚红层208的颜色变化,用户可决定是否需要更换自消毒光催化剂片。
钠钙玻璃基底材料的第二侧被涂覆包括静电增强剂207的粘合剂层,该实施例200具有大于90%的可见光透光率。该实施例可用作移动电话屏幕保护膜,因为其可经静电增强层207粘附到移动电话屏幕,而不会阻挡移动电话屏幕的内容,更重要地,对移动电话屏幕提供自消毒保护。
另外及备选的实施注意事项
尽管相应技术已按某些应用特定的语言进行描述,应当理解,所附权利要求并不必然限于在此描述的具体特征或应用。而是,这些具体特征和例子作为实施相应技术的非限制性的示例性形式公开。
如本申请中使用的,术语“或”意为包括“或”而不是排除“或”。也就是说,除非指明或者可从上下文明显看出,“X采用A或B”意为任何自然包括的变化组合。即,如果X采用A、X采用B、或者X采用A和B,则在任何前述具体情况下满足“X采用A或B”。此外,本申请中使用的“一”应一般地解释为意为“一个或多个”,除非明确指明或者从上下文可明显看出其就是指单数形式。
Claims (18)
1.一种自消毒光催化剂片,包括:
具有第一侧及与第一侧相对的第二侧的基底材料;及
包括主要光催化剂和次要光催化剂的光催化剂层;
其中,
主要光催化剂包括金属氧化物光催化剂;
次要光催化剂包括金属光催化剂;
主要光催化剂与次要光催化剂的质量比在10:1到100:1之间;
主要光催化剂在基底材料的第一侧上在分子水平与基底材料形成共价键。
2.根据权利要求1所述的自消毒光催化剂片,其中,基底材料的第二侧上涂覆有粘合剂层。
3.根据权利要求1所述的自消毒光催化剂片,其中,主要光催化剂包括锐钛矿二氧化钛。
4.根据权利要求3所述的自消毒光催化剂片,其中,主要光催化剂包括菱形锐钛矿二氧化钛并具有10-15nm的长轴及3-6nm的短轴。
5.根据权利要求1所述的自消毒光催化剂片,其中,次要光催化剂包括银、金、铜、锌、镍、铈或其组合。
6.根据权利要求5所述的自消毒光催化剂片,其中,次要光催化剂还包括第三金属光催化剂和第四金属光催化剂,而没有其它金属光催化剂。
7.根据权利要求6所述的自消毒光催化剂片,其中,第三金属光催化剂包括银纳米颗粒,及第三金属光催化剂包括铈纳米颗粒。
8.根据权利要求1所述的自消毒光催化剂片,其中,光催化剂层可由大于400nm波长范围的可见光激活。
9.根据权利要求1所述的自消毒光催化剂片,其中,基底材料包括玻璃。
10.根据权利要求1所述的自消毒光催化剂片,其中,基底材料包括树脂。
11.根据权利要求2所述的自消毒光催化剂片,其中,粘合剂层包括压敏粘合剂材料。
12.根据权利要求2所述的自消毒光催化剂片,其中,粘合剂层包括静电增强剂。
13.根据权利要求1所述的自消毒光催化剂片,还包括:
涂覆在光催化剂层的至少一部分上的变色染料,所述变色染料配置成通过其颜色变化提示用户所述自消毒光催化剂片的使用期满。
14.根据权利要求13所述的自消毒光催化剂片,其中,变色染料包括酚红。
15.根据权利要求13所述的自消毒光催化剂片,其中,变色染料包括银纳米颗粒。
16.根据权利要求1所述的自消毒光催化剂片,还包括:
涂覆在光催化剂层的至少一部分上的染料,其中,该染料的磨损或消失代表光催化剂层的损耗。
17.根据权利要求1所述的自消毒光催化剂片,其中,所述自消毒光催化剂片具有大于90%的可见光透射率。
18.用于生产自消毒光催化剂片的方法,包括:
形成具有基底材料和光催化剂层的自消毒光催化剂片,所述基底材料具有第一侧和与第一侧相对的第二侧,所述光催化剂层包括主要光催化剂和次要光催化剂;所述形成包括
-向基底材料的第一侧施加低温大气等离子体;
-在基底材料的第一侧上喷基于水的光催化剂溶液,其中基于水的光催化剂溶液包括大于98wt%的水及小于2wt%的主要光催化剂和次要光催化剂,及主要光催化剂与次要光催化剂的质量比在10:1到100:1之间;
-进行热固化处理以从主要光催化剂产生羟基从而与基底材料第一侧上的基底材料形成共价键;及
-在基底材料的第二侧上涂覆粘合剂层。
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US17/027,535 US20220089912A1 (en) | 2020-09-21 | 2020-09-21 | Self-Disinfecting Photocatalyst Sheet |
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