CN106223009B - 一种可见光催化剂自清洁抗菌织物及其制备和应用 - Google Patents
一种可见光催化剂自清洁抗菌织物及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种可见光催化剂自清洁抗菌织物及其制备和应用，织物表面形成由TiO2、C3N4与Cu2O组成的复合催化颗粒膜。室温条件下，将TiO2、含氮化合物、蒸馏水混合，超声震荡，烘干，研磨，煅烧，得到物质A；在涂层剂中加入物质A分散均匀，然后直接涂布在织物表面，烘干；室温下，将织物浸渍混合液中，调节pH值，浸渍处理，然后在70～90℃下加入葡萄糖溶液，处理30～60min，取出后室温晾干，即得。本发明利用在不同波长下具有光催化性能的催化剂复合与混合的形式，制备了催化波长范围宽、催化效率高的可见光催化剂。
Description
技术领域
本发明属于光催化剂及其制备和应用领域，特别涉及一种可见光催化剂自清洁抗菌织物及其制备和应用。
背景技术
环保性能较差的室内装饰材料和家具会挥发二甲苯等多种有害化合物，这些物质与人体接触时间越长，隐形危害越大。随着人们生活水平的提高，内饰织物在室内使用得越来越多。通过后整理加工，使织物能较好地降解有害气体，可明显改善人们的居住环境。
通过纳米TiO2的光催化作用来净化挥发性较强的氨，采用纳米纤维材料去除甲醛等方法均有报道。由于纳米TiO2具有光催化适用范围广、催化条件低、无二次污染等优点，所以纳米TiO2在室内环境治理技术的发展中发挥着越来越重要的作用。同时TiO2具有化学性质稳定、无毒、光催化活性高和成本低等优点，被公认为应用最为广泛的光催化剂。然而就实际而言，其存在着禁带宽度较宽，对太阳能的利用率较低，以及光生电子和空穴对容易复合，量子利用效率比较低等问题，因此目前大多集中在如何拓宽其催化范围与提高催化效率的研究上，特别是经过复合或掺杂手段获得具有可见光响应的TiO2复合催化剂已成为国内外的研究热点。
在制造工艺上，纳米光催化材料和纺织纤维坚牢结合，能作为一种高效和持久性的光催化多功能纺织品，降解或分解环境中的挥发性有机物，可应用于日常生活中和某些特殊场合，达到“净化空气”的作用；同时该光催化功能纺织品还具有防紫外线、抗菌除臭等多种功能，然而，要实现催化剂粒子在织物表面的均匀分散并与纤维坚牢结合成为了制备光催化功能纺织品的主要难点，织物去除空气中的有害气体的效果与其附着量也密切相关。
发明内容
本发明所要解决的技术问题是提供一种可见光催化剂自清洁抗菌织物及其制备和应用，本发明利用在不同波长下具有光催化性能的催化剂复合与混合的形式，制备了催化波长范围宽、催化效率高的可见光催化剂，该催化剂具有在可见光下光催化自清洁、净化空气、杀菌的效果，其制备方法简单，制备的织物可应用于医院、室内装饰、汽车内部装饰等领域。
本发明的一种可见光催化剂自清洁抗菌织物，所述织物表面形成由TiO2、C3N4与Cu2O组成的复合催化颗粒膜；其中TiO2、C3N4与Cu2O的摩尔比为1:0.5～1:1。
本发明的一种可见光催化剂自清洁抗菌织物的制备方法，包括：
(1)室温条件下，将TiO2、含氮化合物、蒸馏水混合，超声震荡，烘干，研磨，煅烧，得到物质A；其中TiO2和含氮化合物的质量比为1:1～1:3；
(2)在涂层剂中加入物质A分散均匀，然后直接涂布在织物表面，烘干；
(3)室温下，将步骤(2)所得织物浸渍在含有物质A、CuSO4、水溶性壳聚糖和水的混合液中，调节pH值为5.0～7.0，浸渍处理30～60min，然后在70～90℃下加入葡萄糖溶液，处理30～60min，取出后室温晾干，即得可见光催化剂自清洁抗菌织物；其中混合液组分包括：物质A、CuSO4、水溶性壳聚糖和水。
所述步骤(1)中含氮化合物为尿素、单氰胺中的一种或两种。
所述步骤(1)中烘干温度为60-70℃；煅烧为：在马弗炉中煅烧，10～15℃/min升温至450～550℃，保温1～2h后自然降温至室温。
所述步骤(2)织物纤维为尼龙(锦纶)、聚丙烯(丙纶)、聚丙烯腈(腈纶)、聚酯(涤纶)中一种或两种。
所述步骤(2)中涂层剂和物质A的比例为5～6kg:1g。
所述步骤(2)中涂层剂组分包括：水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂；其中水与水溶性聚丙烯酸酯的质量比为9:1～8:2，六偏磷酸钠与硅烷偶联剂的质量比为10:1～5:1。
所述表面活性剂为十二烷基苯磺酸盐、十二烷基硫酸盐、十二烷基甘油醚羧酸盐中的一种或几种。
步骤(2)中涂布量为50～150g/m2；烘干为110～120℃下烘干3～5min。
所述步骤(3)中织物浸渍混合液的浴比为1:40～50。
所述步骤(3)中葡萄糖溶液和混合液的体积比为1:2～3。
所述步骤(3)中混合液中物质A浓度为5～10g/L，CuSO4浓度为1～2g/L，水溶性壳聚糖浓度为1～3g/L。
所述步骤(3)中葡萄糖碱性溶液为：葡萄糖溶液的浓度为5～10g/L，用NaOH溶液调节其pH值为10～11。
本发明的一种可见光催化剂自清洁抗菌织物的应用，所述织物作为光催化剂分解细菌、降解空气有害气体的应用；用于医院、室内装饰、汽车内部装饰领域。
本发明采用分步涂层方式与原位生成方式在织物表面形成由TiO2、C3N4与Cu2O组成的复合催化颗粒膜，利用不同催化剂在不同波长范围内的催化性能，拓宽织物的光催化范围，满足在可见光条件下的自清洁要求，同时利用氮化碳材料的吸附性能，加快有害气体在织物表面的接触，提高催化效率。在涂层步骤充分考虑到催化剂与化学纤维结合不牢固的问题，通过原位生成Cu2O步骤添加水溶性壳聚糖，作为Cu2+的螯合剂以及与织物基体结合的成膜剂，提高Cu2O在C3N4、TiO2和织物表面的形成量。该方法步骤简单，成本低廉，催化剂与织物结合牢固，有效催化成分与空气的接触面较大，催化效率较高，制备的织物能利用自然光催化分解细菌和降解空气中的有害气体，达到自清洁与抗菌的目的，可应用于医院、室内装饰、汽车内部装饰等领域，具有广阔的应用前景。
参照行业标准《室内空气净化功能涂覆材料净化性能》(JC/T1074-2008)测定本发明制备的织物(500mm×500mm)对甲醛的净化效率，24小时甲醛净化效率均超过45％。
有益效果
(1)本发明的可见光催化自清洁抗菌织物具有高催化活性和良好稳定性、无二次污染、在可见光照的条件下具有良好的自清洁效果；
(2)本发明的制备方法简单，便于实验室操作，反应液组成简单且成本低，对设备要求性能低，可用于工业化生产。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
室温下将一定量的TiO2、尿素和适量去离子水混合均匀后，在60℃下烘干4小时，研磨成粉末状，放置马弗炉中以15℃/min升温速率升至450℃保温1小时，自然降温，形成物质A；
其中TiO2与尿素质量比为1:1.5；
将物质A添加到涂层剂中,直接涂覆在织物上,涂覆量为50～150g/m2,110℃下烘干5min；
其中基布主要成分为聚酯纤维，涂层剂为水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂的混合物，水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂的质量比为8:2:5:1,表面活性剂为十二烷基丙磺酸钠；
室温下将织物浸在含有物质A、CuSO4、水溶性壳聚糖和水的混合液中，调节pH值6.0，将织物浸渍其中处理30min；浴比为1:50。
其中物质A浓度为5g/L，CuSO4浓度为1g/L，水溶性壳聚糖浓度为1g/L；
在70℃下加入葡萄糖溶液，处理60min取出后室温晾干，即得可见光催化自清洁抗菌织物；
其中葡萄糖溶液的浓度为5g/L，用NaOH溶液调节pH值为10～11。
参照行业标准《室内空气净化功能涂覆材料净化性能》(JC/T1074-2008)测定制备织物(500mm×500mm)对甲醛的净化效率，24小时甲醛净化效率达到50％。
实施例2
室温下将一定量的TiO2和单氰胺混合均匀后，在80℃下烘干,研磨成粉末状,放置马弗炉中以10℃/min升温速率升至550℃保温2小时，自然降温，形成物质A；
其中TiO2跟单氰胺的质量比为1:1；
将物质A添加到涂层剂中,直接涂覆在织物上，涂覆量50～150g/m2,115℃下烘干3min；
其中基布主要成分为聚丙烯纤维，涂层剂为水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂的混合物，水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂的质量比为6:1:7:1,表面活性剂为十二烷基丙磺酸钠；
室温下将织物浸在含有物质A、CuSO4、水溶性壳聚糖和水的混合液中，调节pH值6.0，将织物浸渍其中处理50min；浴比为1:40；
其中物质A浓度为7g/L，CuSO4浓度为1.5g/L，水溶性壳聚糖浓度为2g/L；
在80℃下加入葡萄糖溶液，处理60min取出后室温晾干，即得可见光催化自清洁抗菌织物；
其中葡萄糖碱性溶液的葡萄糖浓度为8g/L，用NaOH溶液调节pH值为10～11。
参照行业标准JC/T1074-2008《室内空气净化功能涂覆材料净化性能》测定制备织物(500mm×500mm)对甲醛的净化效率，24小时甲醛净化效率达到55％。
实施例3
室温下将一定量的TiO2和单氰胺混合均匀后，在在80℃下烘干,研磨成粉末状,放置马弗炉中以10℃/min升温速率升至550℃保温2小时，自然降温，形成物质A；
其中TiO2跟单氰胺的质量比为1:1.5；
将物质A添加到涂层剂中,直接涂覆在织物上,涂覆量50～150g/m2,115℃下烘干3min。
其中基布主要成分为聚丙烯腈纤维，涂层剂为水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂的混合物，水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂的质量比为9:1:1:10,表面活性剂为十二烷基丙磺酸钠；
室温下将织物浸在含有物质A、CuSO4、水溶性壳聚糖和水的混合液中，调节pH值6.0，将织物浸渍其中处理60min；浴比为1:50。
其中物质A浓度为10g/L，CuSO4浓度为2g/L，水溶性壳聚糖浓度为3g/L；
在90℃下加入葡萄糖溶液，处理60min取出后室温晾干，即得可见光催化自清洁抗菌织物；
其中葡萄糖碱性溶液的葡萄糖浓度为10g/L，用NaOH溶液调节pH值为10～11。
参照行业标准JC/T1074-2008《室内空气净化功能涂覆材料净化性能》测定制备织物(500mm×500mm)对甲醛的净化效率，24小时甲醛净化效率达到65％。
Claims (5)
1.一种可见光催化剂自清洁抗菌织物，其特征在于：所述织物表面形成由TiO2、C3N4与Cu2O组成的复合催化颗粒膜；其中TiO2、C3N4与Cu2O的摩尔比为1:0.5~1:1；由下列方法制备，包括：
（1）室温条件下，将TiO2、含氮化合物、蒸馏水混合，超声震荡，烘干，研磨，煅烧，得到物质A；其中TiO2和含氮化合物的质量比为1:1~1:3；烘干温度为60-70℃；煅烧为：在马弗炉中煅烧，10~15℃/min升温至450~550℃，保温1~2h后自然降温至室温；所述含氮化合物为尿素、单氰胺中的一种或两种；
（2）在涂层剂中加入物质A分散均匀，然后直接涂布在织物表面，烘干；其中涂层剂组分包括：水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂；其中水与水溶性聚丙烯酸酯的质量比为9:1~8:2，六偏磷酸钠与硅烷偶联剂的质量比为10:1~5:1；
（3）室温下，将步骤（2）所得织物浸渍在混合液中，调节pH值为5.0-7.0，浸渍处理30~60min，然后在70~90℃下加入葡萄糖溶液，处理30~60min，取出后室温晾干，即得可见光催化剂自清洁抗菌织物；所述混合液组分包括：物质A、CuSO4、水溶性壳聚糖和水；所述混合液中物质A浓度为5~10g/L，CuSO4浓度为1~2g/L，水溶性壳聚糖浓度为1~3g /L；所述葡萄糖溶液为：葡萄糖溶液的浓度为5~10g/L，用NaOH溶液调节其pH值为10~11。
2.一种如权利要求1所述的可见光催化剂自清洁抗菌织物的制备方法，包括：
（1）室温条件下，将TiO2、含氮化合物、蒸馏水混合，超声震荡，烘干，研磨，煅烧，得到物质A；其中TiO2和含氮化合物的质量比为1:1~1:3；烘干温度为60-70℃；煅烧为：在马弗炉中煅烧，10~15℃/min升温至450~550℃，保温1~2h后自然降温至室温；所述含氮化合物为尿素、单氰胺中的一种或两种；
（2）在涂层剂中加入物质A分散均匀，然后直接涂布在织物表面，烘干；其中涂层剂组分包括：水、水溶性聚丙烯酸酯、六偏磷酸钠、硅烷偶联剂和表面活性剂；其中水与水溶性聚丙烯酸酯的质量比为9:1~8:2，六偏磷酸钠与硅烷偶联剂的质量比为10:1~5:1；
（3）室温下，将步骤（2）所得织物浸渍在混合液中，调节pH值为5.0-7.0，浸渍处理30~60min，然后在70~90℃下加入葡萄糖溶液，处理30~60min，取出后室温晾干，即得可见光催化剂自清洁抗菌织物；其中混合液组分包括：物质A、CuSO4、水溶性壳聚糖和水；所述混合液中物质A浓度为5~10g/L，CuSO4浓度为1~2g/L，水溶性壳聚糖浓度为1~3g /L；所述葡萄糖溶液为：葡萄糖溶液的浓度为5~10g/L，用NaOH溶液调节其pH值为10~11。
3.根据权利要求2所述的一种可见光催化剂自清洁抗菌织物的制备方法，其特征在于：所述表面活性剂为十二烷基苯磺酸盐、十二烷基硫酸盐、十二烷基甘油醚羧酸盐中的一种或几种。
4.根据权利要求2所述的一种可见光催化剂自清洁抗菌织物的制备方法，其特征在于：步骤（2）中涂布量为50~150g/m2；烘干为110~120℃下烘干3~5min。
5.一种如权利要求1所述的可见光催化剂自清洁抗菌织物的应用，其特征在于：所述织物作为光催化剂分解细菌、降解空气有害气体的应用；用于医院、室内装饰、汽车内部装饰领域。
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| KR20050119532A (ko) * | 2004-06-16 | 2005-12-21 | (주)선한엠엔티 | 이산화티탄 광촉매가 코팅된 섬유 및 그 제조방법 |
| CN1757444A (zh) * | 2004-10-08 | 2006-04-12 | 香港理工大学 | 一种在物品表面形成二氧化钛涂层的方法 |
| CN104588110A (zh) * | 2014-12-23 | 2015-05-06 | 郑州轻工业学院 | 一种石墨烯/壳聚糖/氧化亚铜复合材料及其制备方法和应用 |
| CN104846623A (zh) * | 2015-05-20 | 2015-08-19 | 江苏腾盛纺织科技集团有限公司 | 一种具有甲醛净化功能的遮光窗帘布及其制备方法 |
| CN105032468A (zh) * | 2015-08-03 | 2015-11-11 | 中南大学 | 一种Cu2O-TiO2/g-C3N4三元复合物及其制备和应用方法 |
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