CN108654674A - 一种光响应多功能纤维材料及其制备方法和应用 - Google Patents
一种光响应多功能纤维材料及其制备方法和应用 Download PDFInfo
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- CN108654674A CN108654674A CN201810440246.9A CN201810440246A CN108654674A CN 108654674 A CN108654674 A CN 108654674A CN 201810440246 A CN201810440246 A CN 201810440246A CN 108654674 A CN108654674 A CN 108654674A
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- fibrous material
- photoresponse
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- fiber
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Abstract
本发明公开了一种光响应多功能纤维材料及其制备方法和应用。本发明的光催化材料为二维超薄氮化碳纳米片胶体悬浮液,纤维材料为棉、麻、毛、植物纤维、化纤等成分的织物或无纺布。纤维材料无需前处理,直接将氮化碳纳米片通过喷瓶喷涂于纤维材料表面,通过纳米片表面的羟基和氨基与纤维材料表面的相关基团的氢键作用,获得稳定的光响应多功能纤维材料。本发明的光响应多功能纤维材料,其涂层可见光透过性好,不掩盖织物本身颜色,可在阳光下降解多种常见染料及生物质色素,保护纤维,并且可以催化降解甲醛气体,具有极佳的应用前景。本发明方法工艺简单,易控制,可操作性强,生产成本较低,易于工业化生产,具有良好的经济效益和广阔的应用前景。
Description
技术领域
本发明涉及光催化自清洁纤维材料的制备领域,具体涉及一种光响应多功能纤维材料及其制备方法和应用。
背景技术
伴随着人们生活水平的提高,环保理念的提升,以及生活节奏的加速和自然环境的破坏,人们对服装、家用纤维材料的功能性有了新的需求。自清洁功能是纤维材料众多功能性中的一种,近年来用于纺织领域的自清洁功能纤维迅速发展,具有自清洁功能的纤维材料不仅可以缓解洗涤带来的环境和能源问题,还能有效保护人体不受环境污染物的伤害。因此,自清洁纤维材料的研究与产业化具有十分重要的意义。在当前全世界对环境和能源问题异常重视的前提下,自清洁纤维的功能改良与拓展研究成为了备受关注的热点问题之一。
传统自清洁纤维纺织技术主要分为超疏水表面涂层技术和基于纳米TiO2的光催化自清洁技术。其中,超疏水表面涂层技术采用仿生学原理和纳米技术在纤维表面构建类似超疏水材料的表面结构,或使用低表面能的含氟、硅基团的物质进行修饰和涂层,使纤维材料表面产生“荷叶效应”,疏水化的纤维织物就会具有一定程度的自清洁能力,但是疏水化并不能降解处理污染物,是一种不完全的自清洁方法;1997年,Wang等在Nature上首次报道了纳米TiO2薄膜的双亲性,并研发出具有防雾和自清洁功能的玻璃后,光催化自清洁技术开始在纺织领域迅速发展。相比于超疏水涂层,光催化技术能够将有机污染物在自然光的作用下直接降解为无毒无害的小分子H2O、CO2等,而不会造成二次污染,并且直接利用太阳光,成本低廉,具有较好的实用价值。但是通过静电纺丝等技术将纳米TiO2结合于纤维结构中,需要消耗大量电能,且对纳米TiO2的需求量较大,实际具有光催化活性的TiO2则较少,而且纳米TiO2带隙较宽,对可见光的利用率低,结合纤维材料的光催化效率有待提高,实际应用中效果并不理想。
发明内容
本发明通过一种新型的改性方法将性能优于纳米TiO2的氮化碳纳米片(CNNS)稳定结合到各类常见纤维材料上,得到一种具有光响应性的高性能自清洁纤维材料,并拓展开发了多种功能,比传统自清洁纤维材料具有更广泛的实用价值。
本发明提供了一种简单的喷涂法,将石墨相氮化碳(g-C3N4)通过不同方法剥离得到的CNNS胶体结合于不同种类的纤维基体表面,通过对喷涂法制备的多种光响应纤维材料进行性能测试,根据结合稳定性和光催化性能筛选出最优的CNNS胶体。
本发明的喷涂法包括以下步骤:将CNNS胶体装入喷雾瓶,均匀喷涂于纤维材料表面,烘干后用去离子水洗涤,烘干后再次喷涂,重复以上步骤3-5次,通过差量法测定纤维材料的质量变化,直至质量不再变化,此时CNNS负载量饱和,多次洗涤,除去纤维材料表面结合牢固度较低的CNNS,测定洗涤液的紫外吸收光谱,直至CNNS的特征吸收峰消失,烘干后即可得到稳定的具有光催化性能的自清洁纤维材料。通过对自清洁纤维材料再次测定质量,即可得到该纤维材料上CNNS的负载量。
石墨相氮化碳为三均三嗪环结构,通常为淡黄色固体,可通过热聚合法制得,包括以下步骤:准确称取25g三聚氰胺置于坩埚中并盖上坩埚盖。然后将坩埚放入马弗炉中并设置升温-保温-降温程序。马弗炉设定以6℃min-1的升温速率加热到520℃并保温4h后使其自然冷却。最后,取出坩埚并研磨块状产物得到黄色块体g-C3N4。
g-C3N4的剥离方法主要包括硫酸插层剥离法、碱剥离法、水剥离法、石墨烯量子点辅助超声剥离法、化学吹制法等。剥离步骤可参照文献(X.Dong,et al.Recentdevelopment in exfoliated two-dimensional g-C3N4 nanosheets for photocatalyticapplications.J.Mater.Chem.A,2015,3,23642和F.Cheng,et al.An alkali treatingstrategy for the colloidization of graphitic carbon nitride and its excellentphotocatalytic performance.J.Colloid.Interf.Sci)执行。
经过发明人对不同的剥离方法及所用的酸(碱)浓度、量子点类型、超声频率及时间等因素进行调整和实验,得到了不同厚度、表面携带不同官能团、不同带电性的氮化碳纳米片胶体,它们与纤维材料的结合稳定性受这些因素影响,可通过这些CNNS胶体在不同纤维材料上的负载量及牢固度筛选出较优的CNNS胶体。
本发明中提供的最优剥离方法为:通过0.2M的NaOH溶液在100℃条件下剥离12小时,静置澄清后取下层固体,用蒸馏水洗涤至上层出现胶体,通过8000r min-1离心分离,上层胶体即为最优的CNNS胶体。该胶体浓度较高,光催化性能较好,且表面带有大量羟基和氨基,可通过喷涂法将这种CNNS胶体以最高的负载量负载于上述各种材质的纤维材料上。
在一些实施方式中,不同种类的纤维材料为棉、麻、毛、丝、植物纤维、化学纤维成分的纺织面料或无纺布,均为市售的衣物、毛巾、墙纸及湿巾材料。
CNNS与纤维材料的结合稳定性测试步骤为:在酸(碱)溶液、无水乙醇中浸泡并通过去离子水多次洗涤,测定洗涤前后的CNNS负载量的变化,可通过差量法进行确定,当负载量大于0.8g m-2时可视为稳定性良好。
光催化性能测试步骤为:取10cm×10cm的光响应纤维材料、量取100mL浓度为10mgL-1的罗丹明B(RhB)加入到石英反应器中;反应器置于暗箱中均匀搅拌60min使染料吸附达到平衡,之后打开光源并每隔20min吸取3.5mL液体,使用紫外-可见分光光谱仪进行测试,并记录样品在554nm处的吸光度。
本发明中对喷涂了CNNS后纤维材料的光催化性能进行了测试,包括对不同染料(罗丹明B、中性红、甲基蓝、活性紫)和各类生物质色素(深色果汁、有色饮料、酱油)的降解、对室内污染气体VOC(甲醛、甲苯)的降解以及抑制大肠杆菌破坏纤维结构的性能测试。
所制备的光响应纤维材料的结构表征包括:扫描/透射电子显微镜(SEM/TEM)观察纤维表面的负载情况,紫外分析仪(365nm)测定纤维材料的荧光发射情况,紫外漫反射谱测定纤维材料表面负载情况。
与现有技术相比,本发明具有如下优点:
本发明采用简单喷涂法,可使CNNS能通过氢键作用稳定结合在纤维材料的表面,简单的物理化学处理不会使其脱附。该纤维材料具有自清洁能力,可降解粘附于其表面的有机染料、生物质色素,抑制表面附着的细菌生长,甚至降解空气中的甲醛等有害人体健康的小分子。而粉体CNNS由于有了稳定的载体,也解决了难以回收利用的难题。本发明的具有自清洁能力的纤维材料可以再加工成免洗衣物、除甲醛墙纸、耐菌型毛巾等用品;投放到水体吸附、降解污染物;投放到新装修的室内降解甲醛、VOC并回收再利用。其次,剥离得到的CNNS胶体具有极高的可见光透过率,喷涂于纤维材料表面不会对其颜色造成影响,是一种“隐形”涂料。与传统的二氧化钛光催化剂相比,氮化碳能够充分利用可见光,且热稳定性和化学稳定性良好,作为无机非金属材料,其环境友好性、对生物体无毒无害的特点也是本发明能够实施的关键。最后,喷涂法的操作简易性是本发明最为核心的一点,这意味着通过简单喷涂就可直接得到自清洁纤维材料,无需机械化生产即可有效应用到人们的实际生活中。
相比于传统超疏水表面涂层,本发明制得的新型自清洁纤维材料的手感与一般纤维材料无异,不会出现僵硬、粗糙等问题,不破坏纤维结构,不会影响纤维本身的颜色。且喷涂的方法极为简单,明显优于需要覆盖多层才能保证牢固度及自清洁性能的超疏水表面。此外,超疏水表面自清洁材料的原理在于污染物难以附着,并不能从根本上降解污染物,而CNNS强大的光催化降解能力可以解决这个关键问题。
而相比于通过静电纺丝技术将TiO2附着于材料表面的传统光催化自清洁纤维材料,喷涂法的优势不仅在于操作简单、绿色节能、对纤维影响小,还可将CNNS表面官能团的氢键结合能力发挥出来,喷涂法的结合牢固度可与静电纺丝技术相当。传统静电纺丝法需要消耗大量电能,生产速度较慢,产率较低,对光催化剂的消耗较大、利用率较低,实际应用中存在诸多问题,喷涂法则可从源头解决这些问题:零耗能、加工快、产率高、对光催化剂的利用率也较高。并且通过实验对比,传统光催化自清洁纤维材料完全降解染料通常需24h以上(参照文献N.M.Bedford,et al.Photocatalytic Self Cleaning Textile Fibers byCoaxial Electrospinning.ACS Appl.Mater.Inter.2010,2448-2455数据),而本发明制得的新型光响应多功能纤维材料降解多种常见染料均只需2-3h,在性能上有了极大的提升。
此外,喷涂法对于纤维基体材料的要求较低,棉、麻、毛、丝、植物纤维、化学纤维成分的织物、纸类或无纺布均可作为CNNS的载体,这意味着通过喷涂法,人们日常生活中用到的纤维材料均可获得光催化能力。综上所述,本发明开发的由喷涂法制备的新型光响应多功能纤维材料相比于传统自清洁纤维材料,在实用性上具有巨大的优势。
附图说明
图1中(a)是实施例1中氮化碳纳米片CNNS的制备方法示意图;(b)是实施例2中喷涂法示意图;(c)为实施例3中纤维材料在喷涂改性前后的荧光发射能力(Tyndall效应)对比示意图;
图2是实施例3中的棉无纺布在改性处理前后的扫描电子显微镜(SEM)照片,图(a)、(b)和(c)为棉无纺布改性后在不同放大倍数下的SEM照片,(d)为棉无纺布在改性前的SEM照片;
图3是实施例3制备的光催化自清洁纤维材料的稳定性测试图,图(a)为洗涤5次时,每次洗涤后洗涤液的紫外吸收光谱,(b)为洗涤液颜色对比图,(c)和(d)依次为喷涂-洗涤前和喷涂-洗涤5次后的棉无纺布Tyndall效应照片对比;
图4是应用例1和应用例2制备的光催化自清洁无纺布在阳光下降解各种有色物质的照片,从(a)至(f)依次为罗丹明B、中性红、甲基蓝、活性紫、红肉火龙果汁、杨梅汁,每隔10min记录一次;图(g1)-(g4)为应用例2的白色T恤经喷涂CNNS胶体后的自清洁能力测试照片,使用的染料为①罗丹明B、②甲基蓝、③中性红、④活性紫,每隔20min记录一次;
图5是应用例1制备的光催化自清洁无纺布在氙灯下降解罗丹明B的结果图,其中(a)为每隔5分钟罗丹明B的吸收曲线,554nm处为罗丹明B的特征吸收峰,可知,随时间增加,峰强度不断下降;(b)为液相中罗丹明B含量百分比随时间的变化曲线;(c)为其对罗丹明B进行降解的重复性对比图;
图6是应用例2制备的自清洁棉无纺布降解甲醛的装置示意图,甲醛的含量由甲醛检测仪实时监测。(a)为容积10L的密封玻璃反应器;(b)为经喷涂后纤维材料表面的扫描电镜照片;(c)为材料表面负载的氮化碳纳米片的结构示意图;(d)为反应器内置的甲醛挥发装置(福尔马林溶液及加热装置);(e)为高精度室内甲醛检测仪(产品型号LZY-301);
图7是应用例2制备的自清洁棉无纺布降解甲醛的浓度-时间图及重复性测试图。(a)为氙灯下降解甲醛的三组降解曲线和无光照对照组;(b)为氙灯下降解甲醛的重复性测试图;(c)为LED灯模拟室内环境下降解甲醛的三组降解曲线和无光照对照组;(d)为LED灯模拟室内环境下降解甲醛的重复性测试图。
具体实施方式
下面结合附图对本发明作进一步详细的说明。
实施例1
如图1所示通过热聚合制备石墨相氮化碳g-C3N4,包括以下步骤:准确称取25g三聚氰胺置于坩埚中并盖上坩埚盖。然后将坩埚放入马弗炉中并设置升温-保温-降温程序。马弗炉设定以6℃ min-1的升温速率加热到520℃并保温4h后使其自然冷却。最后,取出坩埚并研磨块状产物得到黄色块体g-C3N4。
将g-C3N4分散于0.2M的NaOH溶液中,在100℃条件下剥离12小时,静置澄清后取下层固体,用蒸馏水洗涤至pH值呈中性,通过8000转/min离心分离,上层胶体即为CNNS胶体。
得到CNNS胶体500mL,通过差量法测定其浓度为0.88g/L。通过X射线粉末衍射仪得到X-射线衍射(XRD)图谱,样品在13.1°和27.6°有两个显著衍射峰,分别对应CN面内(100)衍射和层间(002)衍射,结果表明,样品为三均三嗪环结构的石墨相氮化碳纳米片。
将所制得的CNNS胶体平均分为8份,每份100mL,加水稀释或水浴加热浓缩配制成0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0g/L浓度梯度的CNNS胶体以备用。
实施例2
如图1(b)所示,取实施例1制备的不同浓度的CNNS各20mL,超声分散0.5h后装入8个相同的喷雾瓶(市售)中,分别对相同面积的不同纤维材料,如定性滤纸、商业用墙纸、市售湿巾、毛巾、纯棉衣物、麻制衣物、蚕丝衣物、毛衣等进行喷涂,重复喷涂-烘干-洗涤操作5次后用差量法测定各种纤维材料的吸附量;风干样品,静置24h后,将各组纤维材料分别浸泡于稀盐酸溶液、稀氢氧化钠溶液、乙醇水溶液中30min,再用去离子水洗涤3次,烘干后用差量法测定CNNS的损失量,测定浓度对喷涂法的影响,筛选出最优的CNNS浓度,评估喷涂法对于各类纤维材料的牢固度。结果显示,CNNS在棉质纤维材料上的负载稳定性最佳,吸附量为0.8-1.5g m-2之间,酸处理、碱处理、乙醇洗涤、表面活性剂洗涤均不能使其脱附;CNNS胶体浓度在1.5-2.5g L-1之间效果最佳,浓度较低时需较大的喷涂量才能达到纤维材料的饱和吸附量,浓度较高时胶体易发生絮凝作用,形成较大粒径的团聚体,不利于其均匀负载于纤维表面,喷涂稳定性下降。
实施例3
取实施例2筛选出的0.2M的CNNS胶体50mL,通过喷涂法以喷雾的形式将CNNS胶体分散于10cm×10cm的洁净棉无纺布(市售湿巾)表面,放入烘箱70℃烘干后,通过去离子水洗涤,70℃烘干后再次喷涂,重复以上步骤5次,得到表面稳定结合CNNS的棉无纺布,即光响应多功能纤维材料。
通过SEM观察无纺布纤维表面氮化碳纳米片的负载情况,如图2(a)、(b)、(c)所示,可观察到大量的氮化碳纳米片通过氢键作用附着在纤维表面照片,对比图2(d),发现通过喷涂法可将大量CNNS附着于纤维材料表面,与原纤维表面明显不同,实现了纤维层面的改性。
通过ZF-1三用紫外分析仪观察无纺布表面的荧光发射性质,如图3(c)和图3(d)所示,喷涂后的纤维材料在紫外分析仪365nm处呈现出明显的荧光发射能力。
通过差量法测定棉无纺布通过喷涂改性后表面CNNS的负载量,由图3可知洗涤五次后基本无CNNS纳米片从纤维材料表面脱落。如表一所示,经多次洗涤后依然有大量CNNS纳米片负载于纤维材料表面,平均负载量为0.9805g/cm2,可见CNNS能够稳定负载于棉无纺布表面。
表一、纤维材料洗涤五次后差量法测定的CNNS负载量表
实施例4
取实施例2筛选出的最优浓度的CNNS胶体50mL,通过喷涂法以喷雾的形式将CNNS胶体分散于日常使用的纯棉白色T恤(市售)表面,置于阳光下晒干后通过去离子水洗涤,晒干后干后再次喷涂,重复以上步骤5次,得到表面稳定结合CNNS的白色T恤。通过ZF-1三用紫外分析仪观察其表面的负载情况,并通过差量法测定负载量为1.275g。
实施例5
取实施例2筛选出的最优浓度的CNNS胶体50mL,通过喷涂法以喷雾的形式将CNNS胶体分散于10×10cm的白色墙纸(市售)表面,自然风干后将其浸没于去离子水进行漂洗,多次洗涤后风干,然后再次喷涂,重复以上步骤3次,得到表面稳定结合CNNS的自清洁墙纸。通过差量法测定负载量在0.975-1.731g m-2之间。筛选出褶皱程度较低的自清洁墙纸进行实用性测试。
实施例6
取实施例2筛选出的最优浓度的CNNS胶体50mL,通过喷涂法以喷雾的形式将CNNS胶体分散于10cm×10cm的白色毛巾(市售)表面,自然风干后将其浸没于去离子水进行漂洗,多次洗涤后风干,然后再次喷涂,重复以上步骤3次,得到表面稳定结合CNNS的毛巾。通过差量法测定负载量在0.815-1.349g m-2之间。取同样材质和大小的毛巾作为对比样进行下一步测试。
实施例7
取实施例2筛选出的最优浓度的CNNS胶体50mL,通过喷涂法以喷雾的形式将CNNS胶体分散于多种棉布、麻质衣物、毛衣、化纤布料等纤维材料的表面,自然风干后将其浸没于去离子水进行漂洗,多次洗涤后风干,然后再次喷涂,重复以上步骤5次,得到表面稳定结合CNNS的各类纤维材料。通过差量法测定负载量,通过负载量分析喷涂法的普适性,并通过归一化对比筛选出喷涂法的最优纤维载体。结果表明,喷涂法普遍适用于各类纤维材料,其中纯棉织物为最优载体。
对比例1
取实施例1制备的块体石墨相氮化碳g-C3N4,充分研磨1h磨细后,采用浓硫酸插层剥离法剥离得到CNNS-1胶体,具体步骤为:量取40mL 98wt%的H2SO4于100mL烧杯中,称取2g块体g-C3N4缓慢倒入其中,室温下搅拌10h,接着将混合物倒入200mL去离子水中超声8h,然后将悬浮液于10000rmp下离心至上层出现CNNS胶体。将所得的CNNS-1胶体平均分为5份,每份100mL,加水稀释或水浴加热浓缩配制成0.5、1.O、1.5、2.0、2.5g/L浓度梯度的CNNS-1胶体,通过喷涂法对不同纤维材料进行负载实验,通过差量法评估CNNS-1胶体的吸附性能。
对比例2
取实施例1制备的块体石墨相氮化碳g-C3N4,充分研磨1h磨细后,采用水剥离法剥离得到CNNS-2胶体,具体步骤为:取实施例1制备的1g的g-C3N4分散到150mL水中并进一步加热到100℃,搅拌12h。将所得悬浮液在8000rmp下离心4min并收集上层胶体。将所得的CNNS-2胶体平均分为8份,每份100mL,加水稀释或水浴加热浓缩配制成0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0g/L浓度梯度的CNNS-2胶体,通过喷涂法对不同纤维材料进行负载实验,通过差量法评估CNNS-2胶体的吸附性能。
对比例3
取实施例1制备的块体石墨相氮化碳g-C3N4,充分研磨1h磨细后,采用石墨烯量子点辅助超声剥离法剥离得到CNNS-3胶体,具体步骤为:取实施例1制备的1g的g-C3N4均匀分散到GQDs溶液中,将装有样品的试剂瓶放入超声波清洗仪中超声。一段时间后将混合物转移到离心管中在在转速为5000rmp离心机中离心4min,之后用吸管缓慢吸取收集上层的胶体。将所得的CNNS-3胶体平均分为8份,每份20mL,加水稀释或水浴加热浓缩配制成0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0g/L浓度梯度的CNNS-3胶体,通过喷涂法对不同纤维材料进行负载实验,通过差量法评估CNNS-3胶体的吸附性能。
对比例4
取实施例1制备的块体石墨相氮化碳g-C3N4,充分研磨1h磨细后,采用化学吹制法得到CNNS-4粉体,具体步骤为:称取2g实施例1所述的三聚氰胺和一定质量的氯化铵,充分研磨后置于坩埚中,以实施例1的煅烧方法煅烧4h后得到CNNS-4粉体。称取8份0.1g CNNS-4粉体,分别分散于100mL去离子水中,加水稀释或水浴加热浓缩配制成0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0g/L浓度梯度的CNNS-4胶体,通过喷涂法对不同纤维材料进行负载实验,通过差量法评估CNNS-4胶体的吸附性能。
对比例5
通过差量法评估对比例1-4中所述的不同CNNS在棉无纺布表面的负载稳定性,筛选出最优浓度的负载量,与实施例3碱剥离的CNNS负载量进行对比。结果显示,碱剥离的CNNS负载能力明显优于对比例1-4中所述的不同CNNS。
表二、不同CNNS胶体在棉无纺布表面负载量数据对比表
应用例1
可见光下降解各种常见有色物质的光催化活性测试:
取多块实施例3所述的自清洁棉无纺布,分别在其表面滴加罗丹明B、甲基蓝、中性红、活性紫等染料和火龙果汁、杨梅汁等生物质色素(深色),置于阳光下进行降解,每隔十分钟拍照记录无纺布的颜色变化。待自清洁完毕后再次分别滴加同种染料及生物质色素,置于阳光下进行降解,重复上述操作3-5次,测试重复性。结果如图4所示,随着时间的变化,棉无纺布上面的有色物质不断降解淡化,说明改性后的棉无纺布在阳光下展现出高效的自清洁能力。
本实施例制备的光催化自清洁无纺布在氙灯下降解罗丹明B的结果如表三和图5所示,随时间增加,罗丹明B的吸收峰强度不断下降,罗丹明B含量百分比随时间变化而不断降低,说明改性后的无纺布具有较强的光催化性能,对罗丹明B具有较强的降解能力。图5(c)说明改性后的无纺布纤维材料的光催化能力具有良好的重复性,并不会随着光催化次数的增加而退化。可见,本发明的光响应纤维材料能够重复利用,实用性较高,不仅环保,而且节省资源,具有潜在的市场前景。
表三、改性后的棉无纺布对罗丹明B的降解含量百分比数据表
应用例2
喷涂法在纯棉衣物上的实用性测试:
如图4(g1-g4)所示,取实施例4所述的经喷涂法处理过的白色T恤,分别在其表面滴加圆形范围的罗丹明B、甲基蓝、中性红、活性紫等染料和果汁、有色饮料等多种生物质色素,置于阳光下进行降解,每隔二十分钟拍照记录无纺布的颜色变化。待其表面自清洁完毕,再次在同个位置滴加相同量的有色物质,在阳光下进行降解,重复上述操作3-5次,测试其重复性。根据催化速率,选择光强度较弱的LED灯模仿室内环境再次进行实验。
应用例3
可见光下气相催化降解甲醛:
如图6所示,在10L的密封广口瓶中,将实施例5制得的自清洁墙纸平贴于瓶内壁,将甲醛检测仪开启后调零,置于瓶底便于观察读数的位置,密封瓶口,待甲醛检测仪示数稳定,记录数据;打开瓶盖,用气相进样器抽取瓶内空气进行气相色谱表征。将盛有福尔马林溶液的表面皿放入瓶内,待其挥发平衡,记录甲醛检测仪示数。打开瓶盖,用气相进样器抽取瓶内空气进行气相色谱表征。用氙灯模拟阳光照射自清洁无纺布,每个五分钟记录甲醛检测仪示数,直至示数不再下降,用气相进样器抽取瓶内空气进行气相色谱表征。根据降解速率,选择光强度较弱的LED灯模仿室内环境再次进行实验。结果如图7所示,自清洁墙纸使甲醛含量明显降低,且重复性良好,对光强度要求也较低。
应用例4
喷涂法抑制细菌破坏棉纤维结构的性能测试:
准备多组实施例6制备的光响应毛巾样品及对比样品,在稀大肠杆菌培养液中浸泡1h后自然风干,将毛巾置于潮湿且30℃恒温的密闭容器中72h,期间提供模拟自然光间断的氙灯光照,反应完成后通过扫描电子显微镜观察毛巾表面纤维材料的完整度,并进行机械强度测试,验证喷涂法对纤维材料的保护作用。对比两者差异,选择光强度较弱的LED灯模仿室内环境再次进行实验。结果如下表所示,光响应毛巾表面纤维明显比普通毛巾表面纤维保存完整,机械强度远高于后者,部分对照组甚至出现霉烂情况,对比可知CNNS可有效保护纤维。
表四、光响应纤维与普通纤维耐菌强度对比表
应用例5
喷涂法的普适性测试:
取实施例7制得的以棉、麻、毛、植物纤维、化纤等成分的各类织物为载体的自清洁纤维材料,分别在其表面滴加罗丹明B、甲基蓝、中性红、活性紫等染料和果汁、有色饮料、食用酱油等生物质色素(深色),置于阳光下进行降解,每隔十分钟拍照记录颜色变化。通过各类纤维材料的自清洁能力分析喷涂法的普适性。结果类似于图4,各类织物通过喷涂负载CNNS后,均展现出高效且重复性良好的自清洁能力。
以上所述的仅是本发明的一些实施方式。对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (10)
1.一种光响应多功能纤维材料,其中,包括纤维基体和喷涂于所述纤维基体表面的氮化碳纳米片,所述氮化碳纳米片的表面含有羟基和氨基,所述氮化碳纳米片能够透过可见光,所述纤维材料能够吸收365nm波长的紫外光并发射荧光,所述纤维材料能降解附着于纤维材料表面的污染物及挥发性有机化合物、抑制纤维材料表面的微生物对纤维结构的破坏。
2.根据权利要求1所述的光响应多功能纤维材料,其中,所述纤维材料中氮化碳纳米片的负载量为0.8-1.5g·m-2。
3.根据权利要求1所述的光响应多功能纤维材料,其中,所述污染物包括有机染料、生物质色素的一种或多种,所述挥发性有机化合物包括甲醛,所述微生物包括大肠杆菌。
4.如权利要求1-3任一项所述的光响应多功能纤维材料的制备方法,其中,包括采用氮化碳纳米片胶体对纤维基体表面进行喷涂,使氮化碳纳米片通过氢键作用结合于所述纤维基体的表面。
5.根据权利要求4所述的方法,其中,所述氮化碳纳米片胶体的浓度为0.5-4g/L。
6.根据权利要求4所述的方法,其中,所述氮化碳纳米片胶体通过将石墨相氮化碳在浓度为0.1-1.0M的NaOH溶液中,60-150℃下反应5-15小时剥离而成。
7.根据权利要求4所述的方法,其中,喷涂次数1-5次,所述方法还包括在每次喷涂后采用去离子水对所述纤维材料进行1-5次清洗,每次5-10秒。
8.根据权利要求4所述的方法,其中,所述光响应纤维材料中的纤维基体包括各类棉、麻、毛、丝、植物纤维和化学纤维。
9.一种光响应自清洁纺织品,包括根据权利要求4-8任一项所述的方法制备的光响应多功能纤维材料。
10.一种光响应墙纸,包括根据权利要求4-8任一项所述的方法制备的光响应多功能纤维材料。
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CN111790421A (zh) * | 2020-06-18 | 2020-10-20 | 安徽工程大学 | 一种石墨相氮化碳改性织物可见光催化剂及其一步法制备方法和应用 |
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