CN108864463A - 一种自支撑柔性超亲水氧化钛薄膜及其制备方法 - Google Patents
一种自支撑柔性超亲水氧化钛薄膜及其制备方法 Download PDFInfo
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- CN108864463A CN108864463A CN201710322259.1A CN201710322259A CN108864463A CN 108864463 A CN108864463 A CN 108864463A CN 201710322259 A CN201710322259 A CN 201710322259A CN 108864463 A CN108864463 A CN 108864463A
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000010409 thin film Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910003087 TiOx Inorganic materials 0.000 claims abstract description 32
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 21
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- 239000010936 titanium Substances 0.000 claims description 25
- 239000010408 film Substances 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- -1 alkali metal titanate Chemical class 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 15
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及一种自支撑柔性超亲水氧化钛薄膜及其制备方法，在基底表面依次涂覆水溶性牺牲层、柔性衬底和氧化钛纳米片剥离液，经干燥后用水去掉水溶性牺牲层，得到所述自支撑柔性超亲水氧化钛薄膜。本方法可以大规模得到自支撑柔性超亲水氧化钛薄膜，并且大小形状任意可调，在背面涂覆粘性材料，可得到粘贴式自支撑柔性超亲水氧化钛薄膜。
Description
技术领域
本发明涉及一种自支撑柔性超亲水氧化钛薄膜的制备方法，具体涉及将高活性二氧化钛纳米片剥离液负载在柔性衬底上，自然干燥得到高吸附性能高催化性能的二氧化钛柔性薄膜的方法。
背景技术
随着环境污染和能源危机的日益严峻，太阳能作为最有应用前景的清洁能源受到了广泛的关注。二氧化钛作为一种储量丰富而又性能优良的半导体材料，自1972年发现二氧化钛光电极表面持续产氢的现象以来(Fujishima,A.；Honda,K.；Nature 238,37-38)，基于二氧化钛的半导体光催化技术受到了极大关注并取得了巨大的进展。氧化钛可以广泛地应用于降解有机污染物、裂解水产氢、抗菌和防污等方面，是解决目前能源短缺和环境污染等问题的一个理想途径。
但是，常用的材料氧化钛颗粒，吸附性能较差，吸附速率慢，并且难以回收再利用。因此，改性氧化钛催化剂，设计和开发新工艺以应对日益严重的环境污染问题具有十分重大的意义。近年来，有关无机层状化合物剥离分层制备二维单分子层纳米片(nanosheets)的研究越来越受到研究者的青睐。由层状化合物剥离生成的二维纳米片，其结构、组成与母体层状化合物板层相一致。纳米片厚度在分子尺度(1nm左右)，横向尺寸在亚微米至数微米间，表现出极端的二维各向异性。此外，剥离所得纳米片表面通常带有电荷，因此可作为基本单元用来构筑多功能复合薄膜和其它纳米复合材料。由于这些优异的物理化学性质，二维单分子层纳米片材料在能源、环境、传感和计算机芯片等领域具有十分广泛的应用前景。特别地，由于其较好的亲水性能和较高的比表面积，这种材料在降解有机污染物、裂解水产氢、抗菌，重金属离子吸附等方面表现出优异的性能。
但是，二维单分子层纳米片作为一种平面二维材料，片层之间十分容易堆叠，造成比表面积和孔体积大大减少，使得其直接用于吸附材料有许多困难，并且通常难以回收再利用。
发明内容
针对上述问题，本发明从工艺入手构造一种适合的可回收利用的自支撑柔性超亲水氧化钛薄膜及其制备方法和应用。
一方面，本发明提供了一种自支撑柔性超亲水氧化钛薄膜的制备方法，在基底表面依次涂覆水溶性牺牲层、柔性衬底和氧化钛纳米片剥离液，经干燥后用水去掉水溶性牺牲层，得到所述自支撑柔性超亲水氧化钛薄膜。
较佳地，所述水溶性牺牲层的材料选自聚苯乙烯磺酸钠、丙烯酰胺的聚合物、甲基丙烯酰胺的聚合物、丙烯酰胺和甲基丙烯酰胺的共聚物、丙烯酸和甲基丙烯酰胺的共聚物及其盐、丙烯酸和丙烯酰胺的共聚物及其盐、甲基丙烯酸和甲基丙烯酰胺的共聚物及其盐、甲基丙烯酸与丙烯酰胺的共聚物及其盐、海藻酸、瓜尔胶、羧甲基纤维素、淀粉的钠盐中的至少一种。
较佳地，所述涂覆方式为旋涂，所述旋涂的参数包括：转数：800-4000rpm；时间10-30s。
较佳地，所述干燥为在10～80℃下干燥2-24小时。
较佳地，所述基底选自普通玻璃、FTO(掺杂氟的SnO2透明导电玻璃)、ITO(氧化铟锡透明导电膜玻璃)、硅片、陶瓷和塑料中的一种。
较佳地，氧化钛纳米片剥离液的制备方法包括：
将层状碱金属钛酸盐和浓度为0.5-2M的酸溶液按照1～40g/L的液固比混合并搅拌1-3天，每2～12小时更换一次酸溶液，得到质子化相层状碱金属钛酸盐；
将质子化相层状碱金属钛酸盐置于含有小分子有机胺的溶液中，经搅拌后得到氧化钛纳米片剥离液。
又，较佳地，所述含有小分子有机胺的溶液的浓度为0.1～10mmol/L，所述含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐的固液比为1～20g/L。
又，较佳地，所述小分子有机胺选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。
又，较佳地，所述酸溶液选自盐酸、硫酸和硝酸中的至少一种。
另一方面，本发明提供了根据上述方法制备的自支撑柔性超亲水氧化钛薄膜，包括柔性衬底、以及附着于所述柔性衬底表面的具有有序层状堆叠结构的氧化钛纳米片薄膜层。
本发明中所述自支撑柔性超亲水氧化钛薄膜，其微观结构为表层是层状堆叠的氧化钛纳米片，底层为柔性聚氨酯，具有良好的自清洁、亲水、抗氧化性能，是一款适用于外装的材料，例如外装漆，墙面，陶瓷，面板等。
较佳地，所述氧化钛纳米片薄膜层的厚度为0.01～0.5微米。
较佳地，所述柔性衬底的材料为油性聚合物，优选为油性聚氨酯(PU)和聚氨酯丙烯酸酯(PUA)中的至少一种。
较佳地，所述柔性衬底的厚度为0.05～0.5微米。
再一方面，本发明还提供了一种根据上述自支撑柔性超亲水氧化钛薄膜在降解有机污染物、裂解水产氢、抗菌和重金属离子吸附中的应用。
本方法可以大规模得到自支撑柔性超亲水氧化钛薄膜，并且大小形状任意可调，在背面涂覆粘性材料，可得到粘贴式自支撑柔性超亲水氧化钛薄膜。本发明还可在二氧化钛胶体中引入催化活性物质、医学活性成份等，以使得所形成的薄膜含有活性成份分散在表面中。本发明制备得到的氧化钛薄膜在降解污染物，吸附，能源以及医疗等领域中有广阔的应用前景。
附图说明
图1示出本发明实施例1所用到的烘干之后的氧化钛纳米片剥离液实物照片，且该剥离液具有丁达尔现象；
图2示出本发明实施例1制备得到的烘干之后自支撑柔性超亲水氧化钛薄膜实物照片，可以看出其具有优异的柔韧性；
图3示出本发明实施例1制备得到的自支撑柔性超亲水氧化钛薄膜扫描电镜照片；
图4示出本发明实施例2制备得到的自支撑柔性超亲水氧化钛薄膜高倍扫描电镜照片，可以观察到表层是有序层状堆叠的氧化钛纳米片结构；
图5示出本发明实施例2制备得到的自支撑柔性超亲水氧化钛薄膜的XRD图谱，出现了一系列新的低角度衍射峰，可能来源于有序层状堆叠结构；
图6示出本发明实施例3制备得到的自支撑柔性超亲水氧化钛薄膜的接触角测试结果照片，氧化钛薄膜对水的接触角为0°，可以看出所得自支撑柔性超亲水氧化钛薄膜具有很强的亲水性；
图7示出本发明实施例1制备得到的自支撑柔性超亲水氧化钛薄膜的吸附各种金属离子的吸附动力曲线；
图8示出本发明实施例2制备得到的自支撑柔性超亲水氧化钛薄膜在紫外光下降解甲基橙的速率对比图；
图9示出本发明实施例2制备得到的自支撑柔性超亲水氧化钛薄膜在紫外光下降解染料的循环测试图，表明在10个循环中，二氧化钛薄膜降解速率保持稳定，没有发现速率衰减的情况。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
本发明将高活性二氧化钛纳米片剥离液负载在柔性衬底上，自然干燥得到高吸附性能高催化性能的二氧化钛柔性薄膜，包括柔性衬底、以及附着于所述柔性衬底表面的具有有序层状堆叠结构的氧化钛纳米片薄膜层。所述氧化钛纳米片薄膜层的厚度可为0.01～0.5微米。所述柔性衬底的材料为油性聚合物，优选为油性聚氨酯(PU)和聚氨酯丙烯酸酯(PUA)中的至少一种。所述柔性衬底的厚度根据需要可调，一般可为0.05～0.5微米。
本发明提供一种可以简单、快速制备自支撑柔性超亲水氧化钛薄膜的制备方法。这种薄膜具有优异的亲水性、良好的柔韧性，极佳的催化活性，因而在重金属离子吸附，污染物降解中具有较好的应用，可应用于环境净化领域。以下示例性地说明本发明提供的自支撑柔性超亲水氧化钛薄膜的制备方法。
通过酸化、剥离碱金属钛酸盐，得到有机胺修饰的高活性二氧化钛胶体。具体来说，酸化具有层状结构的碱金属钛酸盐，得到相应的质子化相。再利用酸碱中和原理，引入有机胺，中和层间氢离子，同时将层状钛酸盐剥离为高活性的氧化钛纳米片，并且由于有机胺的修饰，得到稳定的氧化钛纳米片剥离液。
制备层状碱金属钛酸盐。层状结构的碱金属钛酸盐(层状碱金属钛酸盐)可通过高温固相法、水热结晶法、溶胶凝胶法中的一种或几种的组合进行制备。其中层状碱金属钛酸盐粉体微观形态包括片、棒、带、管和不规则多边形中的一种或几种的组合。此外，层状碱金属钛酸盐中碱金属元素包括锂，钠，钾和铯中一种或几种的组合。所述层状结构的碱金属钛酸盐可为K2Ti4O9、Na2Ti4O9、CsxTi2-x/4□x/4O4(x＝0.7)(□代表Ti空位)、K0.8Ti1.73Li0.27O4等。
酸化具有层状结构的碱金属钛酸盐，得到相应的质子化相层状碱金属钛酸盐。将层状碱金属钛酸盐和浓度为0.5-2M的酸溶液按照1～40g/L的液固比混合并搅拌1-5天，每2～12小时更换一次酸溶液，得到质子化相层状碱金属钛酸盐。所述酸溶液可选自盐酸、硫酸和硝酸中的至少一种。
再利用酸碱中和原理，引入有机胺，中和层间氢离子，同时将层状钛酸盐剥离为高活性的氧化钛纳米片，并且由于有机胺的修饰，得到稳定的氧化钛纳米片剥离液(所述高活性的氧化钛纳米片为相应的单层或少层的片层结构)。具体来说，将浓度为0.1～10mmol/L的含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐按照1～20g/L的固液比混合并搅拌4～14天，得到氧化钛纳米片剥离液。所述小分子有机胺可选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。其中搅拌一般在10-30℃下搅拌，优选常温(25℃)下搅拌。
在基底上涂覆一层水溶性的牺牲层，然后在表面涂覆一层油性聚合物(柔性衬底)，再涂覆一层氧化钛纳米片剥离液，最后用水去掉牺牲层即可得到自支撑柔性超亲水氧化钛薄膜。所述基底包括普通玻璃、FTO(掺杂氟的SnO2透明导电玻璃)、ITO(氧化铟锡透明导电膜玻璃)、硅片、陶瓷、塑料等。所述水溶性的牺牲层包括聚苯乙烯磺酸钠，丙烯酰胺和/或甲基丙烯酰胺的聚合物、及其共聚物，丙烯酸或甲基丙烯酸与丙烯酰胺或甲基丙烯酰胺的共聚物、及其盐，海藻酸、瓜尔胶、羧甲基纤维素或淀粉的钠盐。所述油性聚合物为商用油性聚氨酯(PU)和聚氨酯丙烯酸酯(PUA)等。作为一个示例，在玻璃或FTO上涂一层水溶性的牺牲层，然后在表面涂覆一层油性聚合物，再涂覆一层氧化钛剥离液，最后用水去掉牺牲层得到独立的超亲水自支撑膜。
上述所述涂覆方式可为旋涂。所述涂覆方式为旋涂，所述旋涂的参数包括：转数：800-4000rpm；时间10-30s。
在本发明中，只需剥离，涂覆(例如旋涂方式等)即可实现自支撑柔性超亲水氧化钛薄膜的大规模制备。
本发明提供上述自支撑柔性超亲水氧化钛薄膜在重金属离子吸附，污染物降解中的应用。本发明采用ICP原子吸收光谱测得测溶液中剩余重金属离子浓度。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1：
固相烧结K2Ti4O9块体，取摩尔比K2CO3和TiO2研磨均匀，与马弗炉中，温度800摄氏度，时间20h。将得到的K2Ti4O9粉末(20g)分散于1M HCl溶液(1L)中，氢离子交换24h，中间换三次酸溶液，抽滤清洗，60摄氏度烘干得到相应的质子化相。再利用酸碱中和原理，将10g质子化相分散于1L四丁基氢氧化铵(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液。在玻璃上旋涂一层聚苯乙烯磺酸钠(1000rpm；时间10s)，自然干燥后，在表面涂覆一层聚氨酯(1000rpm；时间10s)，立即再涂覆一层氧化钛纳米片剥离液(5mg/L，800rpm；时间15s)，放置于60℃热板上烘烤10分钟，冷却后将材料泡入水中，去掉聚苯乙烯磺酸钠层，可将柔性超亲水氧化钛薄膜从玻璃上揭下。所述氧化钛纳米片薄膜层的厚度为0.1微米，聚氨酯厚度0.5微米；
将所得自支撑柔性超亲水氧化钛薄膜，分别放入含有200mmol/L Fe3+、Cr3+、Pb2+、Cu2+离子的溶液，常温(25℃)吸附，于5min、10min、20min、30min、40min、50min、60min分别测溶液中剩余金属离子浓度，如图7所示。
实施例2：
固相烧结CsxTi2-x/4□x/4O4(x＝0.7)(□代表Ti空位)，取Cs2CO3和TiO2(摩尔比为1：5.3)研磨均匀，与马弗炉中，温度800摄氏度，时间20h。将得到的CsxTi2-x/4□x/4O4(x＝0.7)粉末(10g)分散于1M HCl溶液(1L)中，氢离子交换12h，中间换三次酸溶液，抽滤清洗，60摄氏度烘干得到相应的质子化相。再利用酸碱中和原理，将5g质子化相分散于1L乙胺(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；在FTO表面上旋涂一层聚苯烯酸钠(800rpm；时间10s)，自然干燥后，在表面涂覆一层油性聚氨酯(1500rpm；时间10s)，立即再涂覆一层氧化钛纳米片剥离液(4mg/L，800rpm；时间10s)，放置于40℃热板上烘烤30分钟，冷却后将材料泡入水中，去掉聚苯烯酸钠得到自支撑柔性超亲水氧化钛薄膜。所述氧化钛纳米片薄膜层的厚度为0.3微米，聚氨酯厚度0.4微米；
将自支撑氧化钛薄膜用于紫外光降解甲基橙实验，所用光源为500W高压汞灯，亚甲基橙溶液的浓度为10mg/L，如图8所示，可以看到8min后亚甲基橙完全降解。相同测试条件下，由图9的光催化降解甲基橙循环测试可以看到，经过10个循环后，自支撑氧化钛薄膜光催化性能没有衰减。
实施例3：
固相烧结K0.8Ti1.73Li0.27O4，取摩尔比K2CO3，Li2CO3和TiO2研磨均匀，与马弗炉中，温度900摄氏度，时间24h。将得到的K0.8Ti1.73Li0.27O4粉末(40g)分散于1M HCl溶液中，氢离子交换24h，中间换三次酸溶液，抽滤清洗，60摄氏度烘干得到相应的质子化相。再利用酸碱中和原理，将20g质子化相分散于1L四丁基氢氧化铵(4mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；取100mL氧化钛纳米片剥离液(8mg/L)加入5mL琼脂溶液(20g/L)搅拌均匀。在FTO表面上旋涂一层聚苯乙烯磺酸钠(3000rpm；时间10s)，自然干燥后，在表面涂覆一层油性聚氨酯(1000rpm；时间20s)，立即再涂覆一层氧化钛纳米片剥离液(1000rpm；时间10s)，放置于60℃热板上烘烤30分钟，冷却后将材料泡入水中，去掉聚苯乙烯磺酸钠层得到自支撑柔性超亲水氧化钛薄膜。所述氧化钛纳米片薄膜层的厚度为0.4微米，聚氨酯厚度0.5微米；
将所得自支撑柔性超亲水氧化钛薄膜，进行光催化裂解水产氢实验。光催化产氢测试在顶端光源辐射的Pyrex反应容器中进行，光源采用300W氙灯。将氧化钛薄膜置于200mL20％的甲醇水溶液中，加入0.05mL 1g/L的H2PtCl6溶液使得薄膜负载一定的Pt。使用A2排除容器内和溶液中的空气，在光源下进行照射测试光催化裂解水性能，测试过程中保持循环水流动制冷及搅拌。每隔一段时间取密闭系统中的气氛样，利用气相色谱(上海,GC-7900,TCD,N2载气)测试密闭系统中的氢含量。溶液中甲醇作为牺牲剂，避免产生O2，实验表明，氧化钛薄膜的产氢效率达到25.4mmol h-1 g-1。
实施例4：
固相烧结Na2Ti4O9，取摩尔比Na2CO3和TiO2研磨均匀，与马弗炉中，温度700摄氏度，时间16h。将得到的Na2Ti4O9粉末分散于1M HCl溶液中，氢离子交换24h，中间换三次酸溶液，抽滤清洗，60摄氏度烘干得到相应的质子化相。将10g质子化相分散于1L苯胺(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液。在陶瓷表面上旋涂一层聚苯烯酸钠(2000rpm；时间10s)，自然干燥后，在表面涂覆一层油性聚丙烯酰胺(1000rpm；时间20s)，立即再涂覆一层氧化钛纳米片剥离液(6mg/L，2000rpm；时间10s)，放置于50℃热板上烘烤30分钟，冷却后将材料泡入水中，去掉聚苯烯酸钠层得到自支撑柔性超亲水氧化钛薄膜。所述氧化钛纳米片薄膜层的厚度为0.1微米，聚丙烯酰胺厚度0.5微米。将自支撑柔性超亲水氧化钛薄膜用于紫外光降解甲基橙实验，所用光源为500W高压汞灯，亚甲基橙溶液的浓度为10mg/L，10min后亚甲基橙完全降解。
Claims (9)
1.一种自支撑柔性超亲水氧化钛薄膜的制备方法，其特征在于，在基底表面依次涂覆水溶性牺牲层、柔性衬底和氧化钛纳米片剥离液，经干燥后用水去掉水溶性牺牲层，得到所述自支撑柔性超亲水氧化钛薄膜。
2.根据权利要求1所述的制备方法，其特征在于，所述水溶性牺牲层的材料选自聚苯乙烯磺酸钠、丙烯酰胺的聚合物、甲基丙烯酰胺的聚合物、丙烯酰胺和甲基丙烯酰胺的共聚物、丙烯酸和甲基丙烯酰胺的共聚物及其盐、丙烯酸和丙烯酰胺的共聚物及其盐、甲基丙烯酸和甲基丙烯酰胺的共聚物及其盐、甲基丙烯酸与丙烯酰胺的共聚物及其盐、海藻酸、瓜尔胶、羧甲基纤维素、淀粉的钠盐中的至少一种。
3.根据权利要求1或2所述的制备方法，其特征在于，所述涂覆方式为旋涂，所述旋涂的参数包括：转数：800～4000 rpm；时间10～30 秒。
4.根据权利要求1-3中任一项所述的制备方法，其特征在于，氧化钛纳米片剥离液的制备方法包括：
将层状碱金属钛酸盐和浓度为0.5～2M的酸溶液按照1～40 g/L的液固比混合并搅拌，得到质子化相层状碱金属钛酸盐；
将质子化相层状碱金属钛酸盐置于含有小分子有机胺的溶液中，经搅拌后得到氧化钛纳米片剥离液。
5.根据权利要求4所述的制备方法，其特征在于，所述含有小分子有机胺的溶液的浓度为0.1～10 mmol/L，所述含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐的固液比为1～20 g/L。
6.根据权利要求4或5所述的制备方法，其特征在于，所述小分子有机胺选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。
7.一种权利要求1-6中任一项所述的制备方法制备的自支撑柔性超亲水氧化钛薄膜，其特征在于，包括柔性衬底、以及附着于所述柔性衬底表面的具有有序层状堆叠结构的氧化钛纳米片薄膜层。
8.根据权利要求7所述的自支撑柔性超亲水氧化钛薄膜，其特征在于，所述氧化钛纳米片薄膜层的厚度为0.01～0.5微米。
9.根据权利要求7或8所述的自支撑柔性超亲水氧化钛薄膜，其特征在于，所述柔性衬底的材料为油性聚合物，优选为油性聚氨酯PU和聚氨酯丙烯酸酯PUA中的至少一种。
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