CN110252417B - Titanate nanocone/polyacrylonitrile nanofiber composite material and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明公开了一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料及其制备方法。以聚丙烯腈纳米纤维为载体，先在其表面沉积无定型TiO₂作为种子层，然后在含有前驱体及形貌控制剂的溶液中沉积钛酸盐纳米锥。钛酸盐纳米锥的沉积增大了纤维复合材料的比表面积，其对污染物的吸附能力增强，且钛酸盐纳米锥的一维结构能提高光生载流体的传输能力，促进光生电子和空穴的分离，有利于光催化降解能力的增强。本发明提供的纤维复合材料制备过程简单，反应条件温和，耗能低，环境友好，应用广泛。

The invention discloses a titanate nanocone/polyacrylonitrile nanofiber composite material and a preparation method thereof. Using polyacrylonitrile nanofibers as a carrier, amorphous_TiO2 was first deposited on its surface as a seed layer, and then titanate nanocones were deposited in a solution containing precursors and morphology control agents. The deposition of titanate nanocones increases the specific surface area of the fiber composite material, and its adsorption capacity for pollutants is enhanced, and the one-dimensional structure of titanate nanocones can improve the transport capacity of photogenerated carrier fluids, and promote photogenerated electrons and empty space. The separation of the holes is beneficial to the enhancement of the photocatalytic degradation ability. The fiber composite material provided by the invention has the advantages of simple preparation process, mild reaction conditions, low energy consumption, environmental friendliness and wide application.

Description

Translated fromChinese

一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料及其制备方法A titanate nanocone/polyacrylonitrile nanofiber composite material and its preparationmethod

技术领域technical field

本发明涉及一种光催化复合材料及其制备方法，特别涉及一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料及其制备方法，属于光催化材料技术领域。The invention relates to a photocatalytic composite material and a preparation method thereof, in particular to a titanate nanocone/polyacrylonitrile nanofiber composite material and a preparation method thereof, belonging to the technical field of photocatalytic materials.

背景技术Background technique

目前，环境污染问题已经成为影响人类生存和发展的重要问题。太阳能具有廉价、清洁、可再生等优点，半导体光催化材料的制备与应用能够充分开发利用太阳能来帮助解决环境污染难题，被认为是解决环境污染问题的最有应用前景的技术之一。At present, environmental pollution has become an important issue affecting human survival and development. Solar energy has the advantages of being cheap, clean and renewable. The preparation and application of semiconductor photocatalytic materials can fully exploit and utilize solar energy to help solve the problem of environmental pollution. It is considered to be one of the most promising technologies for solving environmental pollution problems.

质子钛酸盐作为一种功能材料在各领域的应用中具有巨大潜力，同时合成具有与质子钛酸盐相同形态的TiO₂也有广泛的应用前景。钛酸盐是一种新型的纳米材料，具有较高的光催化效应和特殊的可见光区吸收，在光催化材料方面有着广泛的应用前景。钛酸盐是目前发现的光催化效果较好的层状半导体，主要是由于较大的比表面积和独特的一维结构，有利于分离光生电子和空穴。As a functional material, proton titanate has great potential for application in various fields, and the synthesis of_TiO2 with the same morphology as proton titanate also has broad application prospects. Titanate is a new type of nanomaterial with high photocatalytic effect and special absorption in the visible light region, and has broad application prospects in photocatalytic materials. Titanate is a layered semiconductor with good photocatalytic effect found so far, mainly due to its large specific surface area and unique one-dimensional structure, which is conducive to the separation of photogenerated electrons and holes.

一维钛酸纳米材料的制备方法主要包括：碱热法（参见文献：Liu, Y.; Shu, W.;Chen, K.; Peng, Z.; Chen, W., Acs Catalysis 2012, 2 (12), 2557-2565.）、微波法（参见文献：Wang, Y. A., Yang, J., Zhang, J., Liu, H., & Zhang, Z. (2005).Chemistry letters, 34(8), 1168-1169.）和熔融法（参见文献：Watts, J. A. (1970).Journal of Solid State Chemistry, 1(3-4), 319-325.）。强碱水热法是目前比较常用的制备各种一维钛酸盐纳米材料的方法。以TiO₂为原料，在水热条件下使用浓碱制得一维钛酸盐，通过离子交换从所得的碱金属层状钛酸盐中获得质子钛酸盐（参见文献：Zhong,L., Liu, Y. L., Shu, W., Song, Y. B., & Chen, W. (2009). In AdvancedMaterials Research (Vol. 79, pp. 433-436). Trans Tech Publications.）。采用强碱水热工艺制备钛酸(盐)材料的特点是晶粒粒度分布均匀，颗粒之间团聚少，具有较高的比表面积。但采用浓碱法在高温高压条件下制备，反应条件不够温和，耗能较高（参见文献：Liu, Y., Zhong, L., Peng, Z., Cai, Y., Song, Y., & Chen, W. (2011).CrystEngComm, 13(17), 5467-5473.），对有机高分子载体不友好，限制了粉末状光催化剂的应用。此外，强碱水热法需要额外处理酸溶液，对环境及生产成本都是比较大的负担。The preparation methods of one-dimensional titanate nanomaterials mainly include: alkaline heat method (refer to the literature: Liu, Y.; Shu, W.; Chen, K.; Peng, Z.; Chen, W., Acs Catalysis 2012, 2 ( 12), 2557-2565.), microwave method (see literature: Wang, YA, Yang, J., Zhang, J., Liu, H., & Zhang, Z. (2005). Chemistry letters, 34(8) , 1168-1169.) and the fusion method (see: Watts, JA (1970). Journal of Solid State Chemistry, 1(3-4), 319-325.). The strong alkali hydrothermal method is a commonly used method to prepare various one-dimensional titanate nanomaterials. One-dimensional titanates were prepared using concentrated alkali under hydrothermal conditions using_TiO as raw material, and proton titanates were obtained from the resulting alkali metal layered titanates by ion exchange (refer to: Zhong, L., Liu, YL, Shu, W., Song, YB, & Chen, W. (2009). In AdvancedMaterials Research (Vol. 79, pp. 433-436). Trans Tech Publications.). The characteristics of titanate (salt) material prepared by strong alkali hydrothermal process are uniform grain size distribution, less agglomeration between particles, and high specific surface area. However, it is prepared by concentrated alkali method under high temperature and high pressure conditions, the reaction conditions are not mild enough, and the energy consumption is high (refer to the literature: Liu, Y., Zhong, L., Peng, Z., Cai, Y., Song, Y., & Chen, W. (2011). CrystEngComm, 13(17), 5467-5473.), unfriendly to organic polymer carriers, which limits the application of powdered photocatalysts. In addition, the strong alkali hydrothermal method requires additional treatment of the acid solution, which is a relatively large burden on the environment and production costs.

粉末状光催化剂存在难回收及易于造成二次污染等问题，而纳米纤维级半导体材料因具备比表面积大、反应活性点多、制备简单、体密度小、不易团聚等优势而得到重视，近年来得到了广泛的应用。而负载有光催化剂的纳米纤维膜不仅在降解污染物方面有潜力，还具有一定的自清洁效果，可以降解吸附在复合材料表面的污染物。迄今，还未见在聚丙烯腈纳米纤维表面负载一维钛酸盐的报道。Powdered photocatalysts are difficult to recycle and easily cause secondary pollution, while nanofiber-grade semiconductor materials have attracted attention due to their advantages of large specific surface area, many reactive sites, simple preparation, low bulk density, and difficulty in agglomeration. to a wide range of applications. The photocatalyst-loaded nanofiber membrane not only has the potential to degrade pollutants, but also has a certain self-cleaning effect, which can degrade the pollutants adsorbed on the surface of the composite material. So far, there is no report of loading one-dimensional titanate on the surface of polyacrylonitrile nanofibers.

发明内容SUMMARY OF THE INVENTION

本发明针对制备钛酸盐现有技术存在的不足，提供一种直接合成质子化钛酸盐，制备工艺简单、温和，对环境更友好的在聚丙烯腈纳米纤维表面负载钛酸盐纳米锥的复合材料及其制备方法。Aiming at the deficiencies in the prior art for preparing titanate, the present invention provides a method for directly synthesizing protonated titanate, the preparation process is simple, mild and more environmentally friendly, a nano-cone of titanate is supported on the surface of polyacrylonitrile nanofibers. Composite materials and methods of making the same.

实现本发明目的的技术方案是提供一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，包括以下步骤：The technical solution to achieve the purpose of the present invention is to provide a preparation method of titanate nanocone/polyacrylonitrile nanofiber composite material, comprising the following steps:

（1）按质量比（0.2～1）：1，将羧基化聚丙烯腈粉末和聚丙烯腈粉末溶解于溶剂N，N-二甲基甲酰胺或二甲亚砜中，得到质量分数为10～20%的纺丝液；采用静电纺丝工艺，制备羧基化聚丙烯腈纳米纤维膜；(1) Dissolve the carboxylated polyacrylonitrile powder and polyacrylonitrile powder in the solvent N,N-dimethylformamide or dimethyl sulfoxide according to the mass ratio (0.2～1):1 to obtain a mass fraction of 10 ~20% spinning solution; using electrospinning process to prepare carboxylated polyacrylonitrile nanofiber membrane;

（2）按摩尔比（0.1～1）：（1～6）：（10～50）：（200～800），将钛酸四丁酯、硝酸、水、乙醇混合均匀，得到混合溶液；将步骤（1）制备的羧基化聚丙烯腈纳米纤维膜浸泡在混合溶液中6～48h， 再经温度为20～60℃的鼓风干燥，得到无定型TiO₂/聚丙烯腈纳米纤维膜；(2) in a molar ratio (0.1-1): (1-6): (10-50): (200-800), mix tetrabutyl titanate, nitric acid, water and ethanol uniformly to obtain a mixed solution; The carboxylated polyacrylonitrile nanofiber membrane prepared in step (1) is soaked in the mixed solution for 6 to 48 hours, and then dried by blasting at a temperature of 20 to 60° C. to obtain an amorphous TiO₂ /polyacrylonitrile nanofiber membrane;

（3）按摩尔比为1：（0.1～2.5）：（4～25）：（5～20）：（500～2000），将钛源、形貌控制剂、浓盐酸、过氧化氢、去离子水混合，得到混合溶液；将制得的无定型TiO₂/聚丙烯腈纳米纤维膜浸泡在混合溶液中，置于恒温摇床上反应，再经水洗、鼓风干燥，得到负载有钛酸盐纳米锥的聚丙烯腈纳米纤维复合材料。(3) The molar ratio is 1: (0.1-2.5): (4-25): (5-20): (500-2000), mix the titanium source, morphology control agent, concentrated hydrochloric acid, hydrogen peroxide, and Ionized water is mixed to obtain a mixed solution; the prepared amorphous TiO₂ /polyacrylonitrile nanofiber membrane is immersed in the mixed solution, placed on a constant temperature shaker to react, washed with water, and dried by blasting to obtain a titanate loaded with titanate Nanocones of polyacrylonitrile nanofiber composites.

本发明所述羧基化聚丙烯腈的制备方法如下：按质量比为（1～3）：10，将衣康酸或丙烯酸与丙烯腈混合，得到的混合物溶解于二甲亚砜和去离子水的体积比为1：（1～3）的溶剂中，得到质量分数为3%～10%的溶液；在氮气气氛中，加入引发剂偶氮二异丁腈，搅拌预处理后在温度为55～85℃的条件下反应；再经抽滤、洗涤、冷冻干燥，得到羧基化聚丙烯腈粉末。The preparation method of the carboxylated polyacrylonitrile of the present invention is as follows: in a mass ratio of (1-3):10, itaconic acid or acrylic acid and acrylonitrile are mixed, and the obtained mixture is dissolved in dimethyl sulfoxide and deionized water In a solvent with a volume ratio of 1:(1~3), a solution with a mass fraction of 3%~10% is obtained; in a nitrogen atmosphere, the initiator azobisisobutyronitrile is added, and after stirring and pretreatment, the temperature is 55 The reaction was carried out under the condition of ~85°C; the carboxylated polyacrylonitrile powder was obtained by suction filtration, washing and freeze-drying.

步骤（1）采用的静电纺丝工艺条件为流速0.1～0.5ml/h，电压6.00～15.00kv，接收距离8～15cm，接收器为铝箔或铜网。The electrospinning process conditions used in step (1) are flow rate 0.1-0.5ml/h, voltage 6.00-15.00kv, receiving distance 8-15cm, and the receiver is aluminum foil or copper mesh.

将步骤（2）得到的无定型TiO₂/聚丙烯腈纳米纤维膜浸泡于质量分数为0.1%～2%的盐酸水溶液中，在温度为20℃～80℃的条件下处理6～12h，再经水洗、鼓风干燥，除去未附着完全的无定型TiO₂。The amorphous TiO₂ /polyacrylonitrile nanofiber membrane obtained in step (2) is soaked in an aqueous hydrochloric acid solution with a mass fraction of 0.1% to 2%, and treated at a temperature of 20 ° C to 80 ° C for 6 to 12 hours, and then After washing with water and air drying, the incompletely attached amorphous TiO₂ was removed.

所述的钛源为四氯化钛、钛酸四丁酯、钛酸四乙酯、钛酸异丙酯、三氯化钛、硫酸氧钛、硫酸钛、氟钛酸铵中的一种，或两种以上的混合物。The titanium source is one of titanium tetrachloride, tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium trichloride, titanium oxysulfate, titanium sulfate, and ammonium fluorotitanate, or a mixture of two or more.

所述的形貌控制剂为三聚氰酸、尿素、三聚氰胺、六甲基四胺中的一种，或两种以上的混合物。The shape control agent is one of cyanuric acid, urea, melamine and hexamethyltetramine, or a mixture of two or more.

步骤（3）中置于恒温摇床上的反应温度为10～60℃，反应时间为12～72h。In step (3), the reaction temperature placed on the constant temperature shaking table is 10-60° C., and the reaction time is 12-72 h.

本发明技术方案还包括一种按上述制备方法得到的钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料。The technical solution of the present invention also includes a titanate nanocone/polyacrylonitrile nanofiber composite material obtained by the above preparation method.

与现有技术相比，本发明的优点如下：Compared with the prior art, the advantages of the present invention are as follows:

1．本发明中所应用的聚丙烯腈纳米纤维经改性，形成羧基化聚丙烯腈，为负载无机物颗粒提供一定的结合力。钛酸四丁酯在纳米纤维表面水解后，会在纳米纤维表面形成稳定的无定型二氧化钛溶胶网络，其作为种子层有利于钛酸盐的沉积，防止无机物从聚丙烯腈纳米纤维表面脱落，更有利于复合材料的回收利用。负载有钛酸盐纳米锥的复合材料也具有一定的自清洁效果，可以降解吸附在复合材料表面的污染物。1. The polyacrylonitrile nanofibers used in the present invention are modified to form carboxylated polyacrylonitrile, which provides a certain binding force for the loaded inorganic particles. After tetrabutyl titanate is hydrolyzed on the surface of nanofibers, a stable amorphous titania sol network will be formed on the surface of nanofibers. As a seed layer, it is conducive to the deposition of titanate and prevents inorganic substances from falling off the surface of polyacrylonitrile nanofibers. It is more conducive to the recycling of composite materials. The composites loaded with titanate nanocones also have a certain self-cleaning effect, which can degrade the pollutants adsorbed on the surface of the composites.

2.常温下在聚丙烯腈纳米纤维表面沉积钛酸盐，避免使用高温高压反应釜，避免使用浓碱，对设备要求低，大大降低了能耗，具有广阔的应用前景。2. Deposition of titanate on the surface of polyacrylonitrile nanofibers at room temperature, avoiding the use of high temperature and high pressure reactors, avoiding the use of concentrated alkali, low equipment requirements, greatly reducing energy consumption, and having broad application prospects.

附图说明Description of drawings

图1为本发明实施例提供的各步骤所得样品的X射线衍射图；其中，曲线(a)为羧基化聚丙烯腈纳米纤维在不添加钛源的条件下，按相同步骤制备的对比样品的X射线衍射图谱，曲线(b)为无定型TiO₂/聚丙烯腈纳米纤维复合材料的X射线衍射图谱，曲线(c)为钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的X射线衍射图谱；Fig. 1 is the X-ray diffraction pattern of the sample obtained in each step provided by the embodiment of the present invention; wherein, curve (a) is the comparison sample prepared by the same steps of the carboxylated polyacrylonitrile nanofiber without adding a titanium source. X-ray diffraction pattern, curve (b) is the X-ray diffraction pattern of amorphous_TiO2 /polyacrylonitrile nanofiber composites, and curve (c) is the X-ray diffraction of titanate nanocones/polyacrylonitrile nanofiber composites atlas;

图2为本发明实施例提供的各步骤所得的样品的SEM扫描电镜图；其中，图(a)、(b)为羧基化聚丙烯腈纳米纤维的扫描电镜图，图(c)、（d）为无定型TiO₂/聚丙烯腈纳米纤维的扫描电镜图，图(e)、(f)为钛酸盐纳米锥/聚丙烯腈纳米纤维的扫描电镜图；Fig. 2 is the SEM scanning electron microscope image of the sample obtained by each step provided in the embodiment of the present invention; wherein, Figs (a), (b) are SEM images of carboxylated polyacrylonitrile nanofibers, Figs (c), (d) ) are SEM images of amorphous TiO₂ /polyacrylonitrile nanofibers, and Figures (e) and (f) are SEM images of titanate nanocones/polyacrylonitrile nanofibers;

图3为本发明实施例所得的样品在暗吸附罗丹明B水溶液（共50ml，浓度为50mg/L）条件下，罗丹明B水溶液的吸光度随时间变化曲线图；3 is a graph showing the change of the absorbance of the Rhodamine B aqueous solution with time under the condition of dark adsorption of the Rhodamine B aqueous solution (50 ml in total, the concentration is 50 mg/L) of the samples obtained in the embodiment of the present invention;

图4为本发明实施例所得的样品在LED光照射罗丹明B水溶液（共100ml，浓度为10mg/L）条件下，罗丹明B水溶液的吸光度随时间变化曲线图；Fig. 4 is a graph showing the change of the absorbance of the Rhodamine B aqueous solution with time under the condition that the samples obtained in the embodiment of the present invention are irradiated with the Rhodamine B aqueous solution (a total of 100 ml, the concentration is 10 mg/L);

图5为本发明实施例所得的样品用罗丹明B染色后所得染色的纤维膜在LED光照射下K/S值随时间变化曲线。FIG. 5 is a curve showing the change of K/S value with time of the dyed fibrous membrane obtained after the sample obtained in the embodiment of the present invention is dyed with rhodamine B under the irradiation of LED light.

具体实施方式Detailed ways

下面结合附图和实施例对本发明技术方案作进一步描述。The technical solutions of the present invention will be further described below with reference to the accompanying drawings and embodiments.

实施例1Example 1

羧基化聚丙烯腈纳米纤维膜的制备：在装有机械搅拌、冷凝管和导气管的三口烧瓶中分别加入第一单体19.95g丙烯腈、第二单体1.05g衣康酸、150ml二甲亚砜和150ml去离子水，开动搅拌并通入氮气20min，将引发剂0.21g偶氮二异丁腈加入到上述体系中，保持氮气氛围，搅拌速度调节至150rpm预处理15min后升温至70℃，反应8h；反应结束后将反应液抽滤，所得的粉末在室温下用去离子水反复洗涤、冷冻干燥即可得到丙烯腈-衣康酸共聚物粉末，聚丙烯腈在衣康酸的改性下形成羧基化聚丙烯腈。称取0.8g丙烯腈-衣康酸共聚物粉末和0.8g市售的聚丙烯腈粉末溶解在12g N，N-二甲基甲酰胺溶液中。用铝箔作为接收器，在流速为0.2ml/h、电压为7.00kv、接收距离为12cm的纺丝条件下静电纺丝，所得羧基化聚丙烯腈纤维膜在鼓风烘箱中干燥。Preparation of carboxylated polyacrylonitrile nanofiber membrane: add the first monomer 19.95g acrylonitrile, the second monomer 1.05g itaconic acid, and 150ml dimethylbenzene to a three-necked flask equipped with a mechanical stirring, a condenser tube and an airway. Sulfoxide and 150ml deionized water, start stirring and pass nitrogen gas for 20min, add 0.21g azobisisobutyronitrile initiator to the above system, keep nitrogen atmosphere, adjust the stirring speed to 150rpm for pretreatment for 15min, and then heat up to 70℃ , and reacted for 8 h; after the reaction, the reaction solution was suction filtered, and the obtained powder was repeatedly washed with deionized water at room temperature and freeze-dried to obtain acrylonitrile-itaconic acid copolymer powder. The modification of polyacrylonitrile in itaconic acid carboxylated polyacrylonitrile is formed under the 0.8 g of acrylonitrile-itaconic acid copolymer powder and 0.8 g of commercially available polyacrylonitrile powder were weighed and dissolved in 12 g of N,N-dimethylformamide solution. Using aluminum foil as a receiver, electrospinning was performed under the spinning conditions of a flow rate of 0.2 ml/h, a voltage of 7.00 kv, and a receiving distance of 12 cm, and the obtained carboxylated polyacrylonitrile fiber membrane was dried in a forced air oven.

参见附图2中的图(a) 、(b)，它们是本实施例提供的羧基化聚丙烯腈纳米纤维的扫描电镜图，通过该图可以看出，纳米纤维较为均匀，无珠结，直径为400～700nm。Referring to Figures (a) and (b) in accompanyingdrawing 2, they are SEM images of the carboxylated polyacrylonitrile nanofibers provided in this example. From this figure, it can be seen that the nanofibers are relatively uniform and have no bead knots. The diameter is 400 to 700 nm.

取上述制备的羧基化聚丙烯腈纤维膜20cm×20cm，在含有钛酸四丁酯（2g）、硝酸（3g）、水（5.76g）和乙醇（200g）的混合溶液中浸泡36h，每隔2h取出并在室温下晾干，再次浸泡到混合溶液中，最后将纤维膜在室温下晾干，水洗后在30℃下鼓风干燥。Take the carboxylated polyacrylonitrile fiber membrane prepared above 20cm×20cm, soak it in a mixed solution containing tetrabutyl titanate (2g), nitric acid (3g), water (5.76g) and ethanol (200g) for 36h, every other After 2 hours, it was taken out and dried at room temperature, and then soaked in the mixed solution again. Finally, the fiber membrane was air-dried at room temperature, washed with water, and air-dried at 30 °C.

将上述处理后的聚丙烯腈纤维膜浸泡在100ml溶有盐酸（0.5g）的去离子水中，在80℃下加热12h以除去未附着完全的无定型TiO₂，水洗后鼓风干燥。The polyacrylonitrile fiber membrane after the above treatment was soaked in 100 ml of deionized water dissolved in hydrochloric acid (0.5 g), heated at 80 °C for 12 h to remove the incompletely attached amorphous TiO₂ , washed with water and dried by blasting.

将沉积有无定型TiO₂的聚丙烯腈纳米纤维膜浸泡在含有四氯化钛（1ml）、三聚氰酸（0.4g）、过氧化氢（5ml）、浓盐酸（1ml）去离子水（120ml）的混合溶液中，在35℃恒温摇床上在50rpm的转速下反应36h。将反应后的纤维膜取出后用去离子水洗涤至溶液为中性，在40℃下鼓风干燥即可制备出一维钛酸盐/聚丙烯腈纳米纤维复合材料。The polyacrylonitrile nanofiber membranes deposited with amorphous_TiO were soaked in deionized water ( 120ml) in the mixed solution, react for 36h at a speed of 50rpm on a constant temperature shaker at 35°C. The reacted fiber membrane is taken out, washed with deionized water until the solution is neutral, and dried by blasting at 40 °C to prepare a one-dimensional titanate/polyacrylonitrile nanofiber composite material.

参见附图1，它是本实施例提供的样品的X射线粉末衍射图，图中，曲线（a）为聚丙烯腈纳米纤维在不添加Ti源的条件下，按相同步骤制备的对比样品的X射线衍射图谱，（b）为无定型TiO₂/聚丙烯腈纳米纤维的X射线衍射图谱，（c）为一维钛酸盐/聚丙烯腈纳米纤维复合材料的X射线衍射图谱。由图可见：2θ=17°处有1个尖锐的结晶峰及2θ=22°处有1个宽的非结晶峰均为聚丙烯腈纳米纤维X射线衍射图的特征峰。一维钛酸盐/聚丙烯腈纳米纤维样品测试结果中包含有聚丙烯腈的特征峰以及钛酸盐的特征峰。Referring to Fig. 1, it is the X-ray powder diffraction pattern of the sample provided in this example. In the figure, curve (a) is the comparison sample prepared by the same steps for polyacrylonitrile nanofibers without adding Ti source. X-ray diffraction pattern, (b) is the X-ray diffraction pattern of amorphous_TiO2 /polyacrylonitrile nanofiber, (c) is the X-ray diffraction pattern of one-dimensional titanate/polyacrylonitrile nanofiber composite. It can be seen from the figure that a sharp crystalline peak at 2θ=17° and a broad amorphous peak at 2θ=22° are characteristic peaks of the X-ray diffraction pattern of polyacrylonitrile nanofibers. The test results of the one-dimensional titanate/polyacrylonitrile nanofiber sample contain the characteristic peaks of polyacrylonitrile and the characteristic peaks of titanate.

参见附图2，它是本实施例提供的样品的SEM图，其中图（c）、（d）是为无定型TiO₂/聚丙烯腈纳米纤维的扫描电镜图，图(e)、（f）是一维钛酸盐/聚丙烯腈纳米纤维的扫描电镜图。如图2所示，无定型二氧化钛水解后吸附在聚丙烯腈纳米纤维表面，沉积的一维钛酸盐均匀附着在聚丙烯腈纳米纤维上。Referring to FIG. 2, it is the SEM image of the sample provided in this example, wherein the images (c) and (d) are the scanning electron microscope images of amorphous TiO₂ /polyacrylonitrile nanofibers, and the images (e) and (f) ) is the SEM image of one-dimensional titanate/polyacrylonitrile nanofibers. As shown in Figure 2, the amorphous titanium dioxide was hydrolyzed and adsorbed on the surface of the polyacrylonitrile nanofibers, and the deposited one-dimensional titanate was uniformly attached to the polyacrylonitrile nanofibers.

参见附图3，它是本实施例所得的样品在暗吸附罗丹明B水溶液（共50ml，浓度为50mg/L）条件下，罗丹明B水溶液的吸光度随时间变化曲线图；经复合材料吸附，罗丹明B水溶液的浓度大大的降低。Referring to Figure 3, it is a graph showing the change of the absorbance of the Rhodamine B aqueous solution with time under the condition of dark adsorption of the Rhodamine B aqueous solution (50 ml in total, with a concentration of 50 mg/L) for the samples obtained in this example; The concentration of Rhodamine B in water was greatly reduced.

参见附图4，它是本发明实施例所得的样品在LED光照射后罗丹明B水溶液（共100ml，浓度为10mg/L）的吸光度随时间变化曲线图。吸附平衡试验后（光照0min）罗丹明B的浓度下降，这得益于复合材料大的比表面积；与纯的罗丹明B水溶液相比，载有一维钛酸盐/聚丙烯腈纳米纤维的罗丹明B水溶液经不同时间的LED光照射后吸收峰逐渐减弱。Referring to FIG. 4 , it is a graph showing the change of absorbance with time of the Rhodamine B aqueous solution (100 ml in total, the concentration is 10 mg/L) of the samples obtained in the embodiment of the present invention after being irradiated with LED light. The concentration of rhodamine B decreased after the adsorption equilibrium test (light 0 min), which benefited from the large specific surface area of the composite; compared with the pure rhodamine B aqueous solution, the rhodamine B loaded with one-dimensional titanate/polyacrylonitrile nanofibers The absorption peak of Ming B aqueous solution gradually weakened after being irradiated with LED light for different time.

参见附图5，它是本发明实施例所得的样品用罗丹明B染色后所得染色的纤维膜在LED光照射下K/S值随时间变化曲线。Referring to FIG. 5, it is a curve of K/S value versus time of the dyed fiber membrane obtained after the sample obtained in the embodiment of the present invention is dyed with rhodamine B under LED light irradiation.

实施例2Example 2

聚丙烯腈纳米纤维膜的制备：在装有机械搅拌、冷凝管和导气管的三口烧瓶中分别加入第一单体19.95g丙烯腈、第二单体1.95g丙烯酸、150ml二甲亚砜和150ml去离子水，开动搅拌并通入氮气20min，将引发剂0.21g偶氮二异丁腈加入到上述体系中，保持氮气氛围，搅拌速度调节至150rpm预处理15min后升温至70℃，反应8h。反应结束后将反应液抽滤，所得的粉末在室温下用去离子水反复洗涤、冷冻干燥即可得到丙烯腈-丙烯酸共聚物粉末，本实施例中，聚丙烯腈在丙烯酸的改性下形成羧基化聚丙烯腈。0.6g丙烯腈-丙烯酸共聚物粉末和1.0g市售的聚丙烯腈粉末溶解在10g N,N-二甲基甲酰胺溶液中。用铜网作为接收器，在流速为0.3ml/h、电压为7.00kv、接收距离为14cm的纺丝条件下进行静电纺丝，所得的纤维膜在鼓风烘箱中干燥。Preparation of polyacrylonitrile nanofiber membrane: In a three-necked flask equipped with a mechanical stirring, a condenser tube and an air-conducting tube, 19.95 g of the first monomer, 1.95 g of acrylic acid, 150 ml of dimethyl sulfoxide and 150 ml of the second monomer were respectively added. Deionized water, start stirring and pass nitrogen gas for 20min, add initiator 0.21g azobisisobutyronitrile to the above system, maintain nitrogen atmosphere, adjust the stirring speed to 150rpm for pretreatment for 15min, heat up to 70℃, and react for 8h. After the reaction, the reaction solution was suction filtered, and the obtained powder was repeatedly washed with deionized water and freeze-dried at room temperature to obtain acrylonitrile-acrylic acid copolymer powder. In this embodiment, polyacrylonitrile was formed under the modification of acrylic acid. Carboxylated polyacrylonitrile. 0.6 g of acrylonitrile-acrylic acid copolymer powder and 1.0 g of commercially available polyacrylonitrile powder were dissolved in 10 g of N,N-dimethylformamide solution. Using a copper mesh as a receiver, electrospinning was performed under the spinning conditions of a flow rate of 0.3 ml/h, a voltage of 7.00 kv, and a receiving distance of 14 cm, and the resulting fiber film was dried in a blast oven.

取上述制备的聚丙烯腈纤维膜20cm×20cm在含有钛酸四丁酯（2g）、硝酸（3g）、水（5.76g）和乙醇（200g）的混合溶液中浸泡48h，每隔2h取出并在室温下晾干，再次浸泡到混合溶液中，最后将纤维膜在室温下晾干，水洗后在30℃下鼓风干燥。Take 20cm × 20cm of the polyacrylonitrile fiber membrane prepared above and soak it in a mixed solution containing tetrabutyl titanate (2g), nitric acid (3g), water (5.76g) and ethanol (200g) for 48h, take it out every 2h Air-dry at room temperature, soak in the mixed solution again, and finally air-dry the fiber membrane at room temperature, wash with water, and blow dry at 30°C.

将上述处理后的聚丙烯腈纤维膜浸泡在100ml溶有盐酸（0.25g）的去离子水中，在60℃下加热12h以除去未附着完全的无定型TiO₂，水洗后鼓风干燥。The polyacrylonitrile fiber membrane after the above treatment was soaked in 100 ml of deionized water dissolved in hydrochloric acid (0.25 g), heated at 60 °C for 12 h to remove the incompletely attached amorphous TiO₂ , washed with water and dried by blasting.

将沉积有无定型TiO₂的聚丙烯腈纳米纤维膜浸泡在含有四氯化钛（0.5ml）、三聚氰酸（0.06g）、过氧化氢（0.56ml）、浓盐酸（0.7ml）去离子水（40ml）的混合溶液中，在25℃恒温摇床上在50rpm的转速下反应72h。将反应后的纤维膜取出后用去离子水洗涤至液体为中性、鼓风干燥即可制备出一维钛酸盐/聚丙烯腈纳米纤维复合材料。The polyacrylonitrile nanofiber membrane deposited with amorphous_TiO2 was soaked in a solution containing titanium tetrachloride (0.5ml), cyanuric acid (0.06g), hydrogen peroxide (0.56ml), concentrated hydrochloric acid (0.7ml) to remove In the mixed solution of ionized water (40ml), the reaction was carried out on a constant temperature shaker at 25°C at a speed of 50rpm for 72h. The one-dimensional titanate/polyacrylonitrile nanofiber composite material is prepared by taking out the reacted fiber membrane, washing it with deionized water until the liquid is neutral, and blowing dry.

本实施例制备的样品及其X射线粉末衍射图、形貌结构、暗吸附条件下染料的吸光度变化曲线图、光催化条件下染料的吸光度变化曲线图、样品染色后所得染色纤维膜在LED光照射下K/S值变化曲线图均与实施例1相类似。The sample prepared in this example and its X-ray powder diffraction pattern, morphological structure, the absorbance change curve of the dye under dark adsorption conditions, the absorbance change curve of the dye under the photocatalytic condition, the dyed fiber film obtained after dyeing the sample in LED light The change curves of K/S value under irradiation are all similar to those in Example 1.

实施例3Example 3

聚丙烯腈纳米纤维膜的制备：在装有机械搅拌、冷凝管和导气管的三口烧瓶中分别加入第一单体19.95g丙烯腈、第二单体1.05g衣康酸、150ml二甲亚砜和150ml去离子水，开动搅拌并通入氮气20min，将引发剂0.21g偶氮二异丁腈加入到上述体系中，保持氮气氛围，搅拌速度调节至150rpm预处理15min后升温至70℃，反应8h。反应结束后将反应液抽滤，所得的粉末在室温下用去离子水反复洗涤、冷冻干燥即可得到丙烯腈-衣康酸共聚物粉末，本实施例中，聚丙烯腈在衣康酸的改性下形成羧基化聚丙烯腈。0.6g丙烯腈-衣康酸共聚物粉末和1.0g市售的聚丙烯腈粉末溶解在10g N，N-二甲基甲酰胺溶液中。用铝箔作为接收器，在流速为0.15ml/h、电压为7.00kv、接收距离为12cm的纺丝条件下进行静电纺丝，所得的纤维膜在鼓风烘箱中干燥。Preparation of polyacrylonitrile nanofiber membrane: add the first monomer 19.95g acrylonitrile, the second monomer 1.05g itaconic acid, and 150ml dimethyl sulfoxide to the three-necked flask equipped with mechanical stirring, condenser tube and airway respectively and 150ml of deionized water, start stirring and introduce nitrogen for 20min, add initiator 0.21g azobisisobutyronitrile to the above system, maintain nitrogen atmosphere, adjust the stirring speed to 150rpm for pretreatment for 15min and then heat up to 70 ° C, the reaction 8h. After the reaction, the reaction solution was suction filtered, and the obtained powder was repeatedly washed with deionized water at room temperature and freeze-dried to obtain acrylonitrile-itaconic acid copolymer powder. In this embodiment, polyacrylonitrile in the itaconic acid solution. Under the modification, carboxylated polyacrylonitrile is formed. 0.6 g of acrylonitrile-itaconic acid copolymer powder and 1.0 g of commercially available polyacrylonitrile powder were dissolved in 10 g of N,N-dimethylformamide solution. Using aluminum foil as a receiver, electrospinning was performed under the spinning conditions of flow rate of 0.15 ml/h, voltage of 7.00 kv, and receiving distance of 12 cm, and the obtained fiber film was dried in a forced air oven.

取上述制备的聚丙烯腈纤维膜20cm×20cm在含有钛酸四丁酯（2g）、硝酸（3g）、水（5.76g）和乙醇（200g）的混合溶液中浸泡36h，每隔2h取出并在室温下晾干，再次浸泡到混合溶液中，最后将纤维膜在室温下晾干，水洗后在30℃下鼓风干燥。Take the polyacrylonitrile fiber membrane prepared above 20cm×20cm and soak it in a mixed solution containing tetrabutyl titanate (2g), nitric acid (3g), water (5.76g) and ethanol (200g) for 36h, take out every 2h Air-dry at room temperature, soak in the mixed solution again, and finally air-dry the fiber membrane at room temperature, wash with water, and blow dry at 30°C.

将上述处理后的聚丙烯腈纤维膜浸泡在100ml溶有盐酸（0.5g）的去离子水中，在60℃下加热12h以除去未附着完全的无定型TiO₂，水洗后鼓风干燥。The polyacrylonitrile fiber membrane after the above treatment was soaked in 100 ml of deionized water dissolved in hydrochloric acid (0.5 g), heated at 60 °C for 12 h to remove the incompletely attached amorphous TiO₂ , washed with water and dried by blasting.

将沉积有无定型TiO₂的聚丙烯腈纳米纤维膜浸泡在含有四氯化钛（0.5ml）、三聚氰酸（1.5g）、过氧化氢（3.5ml）、浓盐酸（2.5ml）去离子水（165ml）的混合溶液中，在60℃恒温摇床上在100rpm的转速下反应12h。将反应后的纤维膜取出后用去离子水洗涤至液体为中性、鼓风干燥即可制备出一维钛酸盐/聚丙烯腈纳米纤维复合材料。The polyacrylonitrile nanofiber membrane deposited with amorphous_TiO2 was soaked in a solution containing titanium tetrachloride (0.5ml), cyanuric acid (1.5g), hydrogen peroxide (3.5ml), concentrated hydrochloric acid (2.5ml) to remove In the mixed solution of ionized water (165ml), the reaction was carried out on a constant temperature shaker at 60°C at a speed of 100rpm for 12h. The one-dimensional titanate/polyacrylonitrile nanofiber composite material is prepared by taking out the reacted fiber membrane, washing it with deionized water until the liquid is neutral, and blowing dry.

本实施例制备的样品及其X射线粉末衍射图、形貌结构、暗吸附条件下染料的吸光度变化曲线图、光催化条件下染料的吸光度变化曲线图、样品染色后所得染色纤维膜在LED光照射下K/S值变化曲线图均与实施例1相似。The sample prepared in this example and its X-ray powder diffraction pattern, morphological structure, the absorbance change curve of the dye under dark adsorption conditions, the absorbance change curve of the dye under the photocatalytic condition, the dyed fiber film obtained after dyeing the sample in LED light The change curves of K/S value under irradiation are all similar to those in Example 1.

Claims (5)

Translated fromChinese

1.一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，其特征在于包括以下步骤：1. a preparation method of titanate nanocone/polyacrylonitrile nanofiber composite material, is characterized in that comprising the following steps:（1）按质量比（0.2～1）：1，将羧基化聚丙烯腈粉末和聚丙烯腈粉末溶解于溶剂N，N-二甲基甲酰胺或二甲亚砜中，得到质量分数为10～20%的纺丝液；采用静电纺丝工艺，制备羧基化聚丙烯腈纳米纤维膜；(1) Dissolve the carboxylated polyacrylonitrile powder and polyacrylonitrile powder in the solvent N,N-dimethylformamide or dimethyl sulfoxide according to the mass ratio (0.2～1):1 to obtain a mass fraction of 10 ~20% spinning solution; using electrospinning process to prepare carboxylated polyacrylonitrile nanofiber membrane;（2）按摩尔比（0.1～1）：（1～6）：（10～50）：（200～800），将钛酸四丁酯、硝酸、水、乙醇混合均匀，得到混合溶液；将步骤（1）制备的羧基化聚丙烯腈纳米纤维膜浸泡在混合溶液中6～48h，再经温度为20～60℃的鼓风干燥，得到无定型TiO₂/聚丙烯腈纳米纤维膜；(2) in a molar ratio (0.1-1): (1-6): (10-50): (200-800), mix tetrabutyl titanate, nitric acid, water and ethanol uniformly to obtain a mixed solution; The carboxylated polyacrylonitrile nanofiber membrane prepared in step (1) is soaked in the mixed solution for 6 to 48 hours, and then dried by blast at a temperature of 20 to 60° C. to obtain an amorphous TiO₂ /polyacrylonitrile nanofiber membrane;（3）按摩尔比为1：（0.1～2.5）：（4～25）：（5～20）：（500～2000），将钛源、形貌控制剂、浓盐酸、过氧化氢、去离子水混合，得到混合溶液；将制得的无定型TiO₂/聚丙烯腈纳米纤维膜浸泡在混合溶液中，置于恒温摇床上反应，再经水洗、鼓风干燥，得到钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料；(3) The molar ratio is 1: (0.1-2.5): (4-25): (5-20): (500-2000), mix the titanium source, morphology control agent, concentrated hydrochloric acid, hydrogen peroxide, and Ionized water is mixed to obtain a mixed solution; the prepared amorphous TiO₂ /polyacrylonitrile nanofiber membrane is immersed in the mixed solution, placed on a constant temperature shaker to react, washed with water and dried by blast to obtain titanate nanocones / polyacrylonitrile nanofiber composites;其中，所述的形貌控制剂为三聚氰酸、尿素、三聚氰胺、六甲基四胺中的一种，或两种以上的混合物；Wherein, the shape control agent is one of cyanuric acid, urea, melamine, and hexamethyltetramine, or a mixture of two or more;置于恒温摇床上的反应温度为10～60℃，反应时间为12～72h。The reaction temperature placed on a constant temperature shaker is 10-60° C., and the reaction time is 12-72 h.2.根据权利要求1所述的一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，其特征在于：所述羧基化聚丙烯腈的制备方法如下：按质量比为（1～3）：10，将衣康酸或丙烯酸与丙烯腈混合，得到的混合物溶解于二甲亚砜和去离子水的体积比为1：（1～3）的溶剂中，得到质量分数为3%～10%的溶液；在氮气气氛中，加入引发剂偶氮二异丁腈，搅拌预处理后在温度为55～85℃的条件下反应；再经抽滤、洗涤、冷冻干燥，得到羧基化聚丙烯腈粉末。2. the preparation method of a kind of titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, is characterized in that: the preparation method of described carboxylated polyacrylonitrile is as follows: by mass ratio is (1 ~3): 10. Mix itaconic acid or acrylic acid with acrylonitrile, and the obtained mixture is dissolved in a solvent with a volume ratio of dimethyl sulfoxide and deionized water of 1: (1 to 3) to obtain a mass fraction of 3 %～10% solution; in nitrogen atmosphere, add initiator azobisisobutyronitrile, stir and pretreat, react under the condition of temperature of 55～85 ℃; then through suction filtration, washing, freeze-drying, obtain carboxyl group Polyacrylonitrile powder.3.根据权利要求1所述的一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，其特征在于：步骤（1）采用的静电纺丝工艺条件为流速0.1～0.5ml/h，电压6.00～15.00kV，接收距离8～15cm，接收器为铝箔或铜网。3 . The method for preparing a titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1 , wherein the electrospinning process condition used in step (1) is a flow rate of 0.1 to 0.5 ml/ h, the voltage is 6.00～15.00kV, the receiving distance is 8～15cm, and the receiver is aluminum foil or copper mesh.4.根据权利要求1所述的一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，其特征在于：将步骤（2）得到的无定型TiO₂/聚丙烯腈纳米纤维膜浸泡于质量分数为0.1%～2%的盐酸水溶液中，在温度为20℃～80℃的条件下处理6～12h，再经水洗、鼓风干燥，除去未附着完全的无定型TiO₂。4. The method for preparing a titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, wherein the amorphous_TiO2 /polyacrylonitrile nanofiber film obtained in step (2) is used Soak in hydrochloric acid aqueous solution with a mass fraction of 0.1% to 2%, treat for 6 to 12 hours at a temperature of 20 ° C to 80 ° C, and then wash with water and blast dry to remove incompletely attached amorphous TiO₂ .5.根据权利要求1中所述的一种钛酸盐纳米锥/聚丙烯腈纳米纤维复合材料的制备方法，其特征在于：所述的钛源为四氯化钛、钛酸四丁酯、钛酸四乙酯、钛酸异丙酯、三氯化钛、硫酸氧钛、硫酸钛、氟钛酸铵中的一种，或两种以上的混合物。5. the preparation method of a kind of titanate nanocone/polyacrylonitrile nanofiber composite material described in claim 1, is characterized in that: described titanium source is titanium tetrachloride, tetrabutyl titanate, One of tetraethyl titanate, isopropyl titanate, titanium trichloride, titanyl sulfate, titanium sulfate, ammonium fluorotitanate, or a mixture of two or more.

Images