技术领域technical field
本发明涉及TiO2中空全介孔纳米纤维在光催化剂中的应用，属于光催化剂材料技术领域。The invention relates to the application ofTiO2 hollow fully mesoporous nanofibers in photocatalysts, belonging to the technical field of photocatalyst materials.
背景技术Background technique
光催化技术因其反应条件温和，无二次污染等优点，可以吸收太阳能产生光电子和空穴直接分解水制氢和降解有机污染物，是现今能源和环境领域研究的热点。光催化技术的应用关键在于光催化剂的研制，几十年的研究积累已经探索发现了数百种光催化剂。其中，TiO2是最具代表性的光催化剂，在光催化领域得到了广泛应用。然而，传统的TiO2光催化剂材料在实际应用中仍然存在一些实际应用中难题有待进一步解决，如比表面积偏低导致光催化效率偏低，以及常见的纳米粉体光催化剂液相体系反应时极易团聚，光催化稳定性较差且难以回收再利用造成催化剂的浪费。针对于TiO2光催化剂存在的问题，最直观有效的方法是对其结构形貌的优化。全介孔结构的TiO2纳米纤维具备独特的高表面积和一维几何构造特性，能够克服传统TiO2光催化剂存在的活性低和稳定性差的缺点，在光催化领域具有潜在的应用前景。此外，近期研究报道也表明，一维中空结构的TiO2纳米材料具有低密度以及较大的空腔体积等新颖特性，亦可有效的提高TiO2光催化剂材料的光催化效率。目前，已有大量的文献报道了关于TiO2介孔纳米纤维光催化剂和TiO2中空纳米纤维光催化剂的制备，但是关于兼具介孔和中空结构TiO2纳米纤维光催化剂还少有文献报道。因此，TiO2中空全介孔纳米纤维光催化剂的制备依然面临着困难和挑战。Due to its mild reaction conditions and no secondary pollution, photocatalytic technology can absorb solar energy to generate photoelectrons and holes to directly decompose water to produce hydrogen and degrade organic pollutants. It is a research hotspot in the field of energy and environment. The key to the application of photocatalytic technology lies in the development of photocatalysts. Hundreds of photocatalysts have been discovered through decades of research. Among them,TiO2 is the most representative photocatalyst and has been widely used in the field of photocatalysis. However, traditional TiO2 photocatalyst materials still have some problems in practical applications that need to be further solved, such as the low specific surface area leading to low photocatalytic efficiency, and the common nano-powder photocatalyst liquid phase system reacts very quickly. It is easy to agglomerate, has poor photocatalytic stability and is difficult to recycle and reuse, resulting in waste of catalyst. For the problems existing in TiO2 photocatalysts, the most intuitive and effective method is to optimize its structure and morphology. The fully mesoporous TiO2 nanofibers have unique high surface area and one-dimensional geometric structure characteristics, which can overcome the shortcomings of low activity and poor stability of traditional TiO2 photocatalysts, and have potential application prospects in the field of photocatalysis. In addition, recent research reports also show that TiO2 nanomaterials with one-dimensional hollow structure have novel characteristics such as low density and large cavity volume, which can also effectively improve the photocatalytic efficiency of TiO2 photocatalyst materials. At present, there have been a large number of literature reports on the preparation of TiO2 mesoporous nanofiber photocatalysts and TiO2 hollow nanofiber photocatalysts, but there are few literature reports on TiO2 nanofiber photocatalysts with both mesoporous and hollow structures. Therefore, the preparation ofTiO2 hollow fully mesoporous nanofiber photocatalysts still faces difficulties and challenges.
发明内容Contents of the invention
本发明的目的是针对现有的技术存在上述问题，提出了一种具有全介孔和中空结构的TiO2纳米纤维在光催化剂中的应用。The purpose of the present invention is to have above-mentioned problems in existing technology, has proposed a kind ofTiO2 nanofiber with full mesopore and hollow structure in photocatalyst application.
本发明的目的可通过下列技术方案来实现：一种TiO2中空全介孔纳米纤维在光催化剂中的应用，所述纳米纤维主要组成元素为Ti、O，主要表现形式为TiO2，所述纳米纤维具有多孔结构，所述多孔结构的孔包括介孔。The purpose of the present invention can be achieved through the following technical solutions: a kind of application of TiO2 hollow fully mesoporous nanofibers in photocatalysts, the main constituent elements of the nanofibers are Ti and O, and the main form of expression is TiO2 . Nanofibers have a porous structure whose pores include mesopores.
作为优选，所述TiO2的主要晶型为锐钛矿型或金红石型。Preferably, the main crystal form of the TiO2 is anatase or rutile.
作为优选，所述纳米纤维具有多孔结构且所述多孔结构的孔均为全介孔。Preferably, the nanofiber has a porous structure and the pores of the porous structure are all mesoporous.
作为优选，所述纳米纤维兼具中空和全介孔结构。Preferably, the nanofiber has both hollow and fully mesoporous structures.
作为优选，所述TiO2中空全介孔纳米纤维的比表面积为25-50m2/g，孔径值为35-45nm。Preferably, the specific surface area of the TiO2 hollow fully mesoporous nanofiber is 25-50 m2 /g, and the pore diameter is 35-45 nm.
TiO2中空全介孔纳米纤维在光催化剂中的应用为将TiO2中空全介孔纳米纤维分散于分解物质中在光照射下发生催化反应，其中分解物质为含水和降解物质的物质。The application of TiO2 hollow fully mesoporous nanofibers in photocatalysts is to disperse TiO2 hollow fully mesoporous nanofibers in decomposed substances to undergo a catalytic reaction under light irradiation, wherein the decomposed substances are substances containing water and degraded substances.
作为优选，所述水与降解物质的体积比为2-5:1。Preferably, the volume ratio of the water to the degradation substance is 2-5:1.
进一步优选，所述降解物质为有机质。Further preferably, the degradation substance is organic matter.
再进一步优选，所述有机质为甲醇。Still further preferably, the organic matter is methanol.
上述TiO2中空全介孔纳米纤维的制备方法包括如下步骤：Above-mentionedTiO The preparation method of hollow fully mesoporous nanofiber comprises the following steps:
配制前驱体纺丝液；Prepare precursor spinning solution;
将前驱体纺丝液进行静电纺丝得到有机前驱体纳米纤维；Electrospinning the precursor spinning solution to obtain organic precursor nanofibers;
将有机前驱体纳米纤维经高温煅烧，即可得TiO2中空全介孔纳米纤维。The organic precursor nanofibers are calcined at high temperature to obtain TiO2 hollow fully mesoporous nanofibers.
在上述TiO2中空全介孔纳米纤维的制备方法中，配制前驱体纺丝液的方法为：将聚乙烯吡咯烷酮(PVP)和钛酸丁酯(TBOT)溶解于溶剂中，搅拌均匀，然后加入发泡剂并继续搅拌，最后加入表面活性剂和石蜡油搅拌得前驱体纺丝液。In the preparation method of the above-mentionedTiO2 hollow fully mesoporous nanofibers, the method of preparing the precursor spinning solution is: dissolving polyvinylpyrrolidone (PVP) and butyl titanate (TBOT) in the solvent, stirring evenly, and then adding Foaming agent and continue to stir, finally add surfactant and paraffin oil and stir to obtain the precursor spinning solution.
前驱体纺丝液的浓度主要是通过影响溶液粘度影响纤维的形貌及直径。若前驱体纺丝液的浓度过低，在静电纺丝中，溶液粘度极低，很难维持喷丝细流的连续性，不能形成稳定的流体，而形成了喷射液滴，因此得到呈不规则块状体纳米纤维，没有纤维出现。若前驱体纺丝液的浓度过高，纤维有粗有细，分布不均匀，甚至出现粘结现象，其原因在于，聚合物分子之间相互作用开始影响聚合物链的运动，聚合物分子链相互缠结，若浓度继续增加，聚合物相互交穿，形成冻胶。高浓度的流体在针头迅速干燥以及聚合物形成冻胶引起的流体在针头流动的不稳定，难于维持喷丝细流，同时造成喷头粘连，使静电纺丝无法进行。因此，在配制前驱体纺丝液中，需要控制好各原料之间的质量关系，从而使前驱体纺丝液达到合适的浓度，进而形成很好纤维形貌，直径分布均匀的纳米纤维。在上述前驱体纺丝液的配制中TBOT提供Ti源供TiO2合成，PVP调控纺丝液的粘度，表面活性剂提高溶液的可纺性，通过发泡剂对纤维基体进行造孔，PVP和表面活性剂在煅烧处理的过程中都将分解完全并挥发，因此两者不会影响纳米纤维最后的结构。前驱体纺丝液的配制中，石蜡油在溶剂中强烈搅拌后形成微乳液，在纺丝过程中，由于静电力的作用被连续相包覆于内部，经煅烧处理后分解挥发形成中空结构，因此石蜡油的含量关系着纳米纤维的内部结构。若石蜡油的含量较少，最后制得的TiO2全介孔纳米纤维为实心结构(非中空结构)；若石蜡油的含量较多，最后制得的TiO2全介孔纳米纤维为多级中空结构。The concentration of the precursor spinning solution mainly affects the shape and diameter of the fiber by affecting the viscosity of the solution. If the concentration of the precursor spinning solution is too low, the viscosity of the solution is extremely low in electrospinning, it is difficult to maintain the continuity of the fine spinneret flow, and a stable fluid cannot be formed, and jet droplets are formed, so the obtained Regular blocks of nanofibers, no fibers appear. If the concentration of the precursor spinning solution is too high, the fibers may be thick or thin, unevenly distributed, or even bonded. The reason is that the interaction between polymer molecules begins to affect the movement of polymer chains, and the polymer molecular chains Intertwined with each other, if the concentration continues to increase, the polymers cross each other to form a jelly. High-concentration fluid dries rapidly at the needle and polymer gel forms unstable fluid flow at the needle, which makes it difficult to maintain a fine spinneret flow, and at the same time causes nozzle adhesion, making electrospinning impossible. Therefore, in preparing the precursor spinning solution, it is necessary to control the quality relationship between the raw materials, so that the precursor spinning solution reaches a suitable concentration, and then form nanofibers with a good fiber shape and uniform diameter distribution. In the preparation of the above-mentioned precursor spinning solution, TBOT provides Ti source forTiO2 synthesis, PVP regulates the viscosity of spinning solution, surfactant improves the spinnability of the solution, and the fiber matrix is made pore by foaming agent, PVP and Both surfactants will be completely decomposed and volatilized during the calcination process, so the two will not affect the final structure of the nanofibers. In the preparation of the precursor spinning solution, the paraffin oil is strongly stirred in the solvent to form a microemulsion. During the spinning process, due to the electrostatic force, the continuous phase is coated inside, and after calcination, it decomposes and volatilizes to form a hollow structure. Therefore, the content of paraffin oil is related to the internal structure of nanofibers. If the content of paraffin oil is less, the finally obtained TiO2 fully mesoporous nanofibers are solid structure (non-hollow structure); if the content of paraffin oil is more, the finally prepared TiO2 fully mesoporous nanofibers are multi-level Hollow structure.
因此，作为优选，配制前驱体纺丝液的方法中所述石蜡油与溶剂的体积比为1.5-2.5:10。Therefore, preferably, the volume ratio of the paraffin oil to the solvent in the method for preparing the precursor spinning solution is 1.5-2.5:10.
作为优选，配制前驱体纺丝液的方法中所述的溶剂为无水乙醇和冰醋酸的混合液。Preferably, the solvent described in the method for preparing the precursor spinning solution is a mixed solution of absolute ethanol and glacial acetic acid.
进一步优选，所述无水乙醇和冰醋酸的体积比为2-3:1。Further preferably, the volume ratio of the absolute ethanol to glacial acetic acid is 2-3:1.
作为优选，配制前驱体纺丝液的方法所述的发泡剂为偶氮二甲酸二异丙酯(DIPA)。本发明纳米纤维采用发泡辅助静电纺丝法制成中空全介孔结构，其中DIPA作为发泡剂加入可实现纤维基体造孔的目的。Preferably, the foaming agent described in the method for preparing the precursor spinning solution is diisopropyl azodicarboxylate (DIPA). The nanofiber of the present invention adopts a foaming-assisted electrospinning method to form a hollow full mesoporous structure, wherein DIPA is added as a foaming agent to realize the purpose of forming pores in the fiber matrix.
作为优选，配制前驱体纺丝液的方法中所述表面活性剂为十六烷基三甲基溴化铵(CTAB)。Preferably, the surfactant in the method for preparing the precursor spinning solution is cetyltrimethylammonium bromide (CTAB).
在上述TiO2中空全介孔纳米纤维的制备方法中，所述静电纺丝的方法为：将前驱体纺丝液注入针管内，并置于静电纺丝机，金属针头作电纺丝阳极，锡箔或铁丝网作接收材料的阴极，在高压下进行静电纺丝，然后从铁丝网上收集得到有机前驱体纳米纤维。In the preparation method of the above-mentionedTiO2 hollow fully mesoporous nanofibers, the electrospinning method is as follows: the precursor spinning solution is injected into the needle tube, and placed in the electrospinning machine, and the metal needle is used as the electrospinning anode, Tin foil or wire mesh is used as the cathode of the receiving material, electrospun under high pressure, and then organic precursor nanofibers are collected from the wire mesh.
静电纺丝是一个简单、灵活的制备纤维技术，其基本原理为：在高压电场的作用下，悬于毛细管出口的前驱体纺丝液滴变形为泰勒锥。随着电场强度的进一步提高，当液滴表面由于所带电荷形成的静电排斥力超过其本身的表面张力时，在泰勒锥的顶端形成液体细流，带有电荷的液体细流在电场中流动，进一步受到拉伸作用，同时溶剂蒸发(或熔体冷却)，成为纤维并沉积在接收装置上，形成有机前驱体纤维材料。在静电纺丝过程中，影响纤维性能的电纺参数主要有：前驱体纺丝液的浓度、纺丝电压、阳极与阴极之间的距离和溶液流速等。Electrospinning is a simple and flexible fiber preparation technology. Its basic principle is: under the action of a high-voltage electric field, the precursor spinning droplet suspended at the capillary outlet is deformed into a Taylor cone. With the further increase of the electric field strength, when the electrostatic repulsion formed by the charge on the surface of the droplet exceeds its own surface tension, a liquid streamlet is formed at the top of the Taylor cone, and the charged liquid streamlet flows in the electric field , further subjected to stretching, while the solvent evaporates (or the melt cools), becomes fibers and deposits on the receiving device, forming an organic precursor fiber material. In the electrospinning process, the electrospinning parameters that affect the fiber performance mainly include: the concentration of the precursor spinning solution, the spinning voltage, the distance between the anode and the cathode, and the solution flow rate.
作为优选，静电纺丝中前驱体纺丝液注入针管内的注射速度为0.8-1.2ml/h。Preferably, the injection speed of the precursor spinning liquid into the needle tube in the electrospinning is 0.8-1.2ml/h.
作为优选，静电纺丝时的条件为：阳极与阴极之间的距离为18cm-22cm，高压为15kV-20kV。随着阳极与阴极之间接收距离的变化，纳米纤维的形态也发生了变化，在不考虑其他因素的情况下，接收距离过小会产生“念珠状”纤维紧贴在阴极，进而影响纳米纤维的性质。电压小于15kV时，大部分前驱体纺丝液滴落在收集的铁丝网上，静电纺丝不能进行；当电压高于20kV时，发生强烈的电晕放电，静电纺丝则不能继续进行。前驱体纺丝液在15kV-20kV高压的静电纺丝中，纤维平均直径随着纺丝电压的增大而增大。Preferably, the conditions during electrospinning are: the distance between the anode and the cathode is 18cm-22cm, and the high voltage is 15kV-20kV. As the receiving distance between the anode and the cathode changes, the morphology of the nanofibers also changes. Without considering other factors, the receiving distance is too small to produce "bead-like" fibers that cling to the cathode, thereby affecting the nanofibers. nature. When the voltage is less than 15kV, most of the precursor spinning liquid drops on the collected wire mesh, and the electrospinning cannot be carried out; when the voltage is higher than 20kV, a strong corona discharge occurs, and the electrospinning cannot continue. Precursor spinning liquid in 15kV-20kV high voltage electrospinning, the average fiber diameter increases with the increase of spinning voltage.
作为优选，静电纺丝中从锡箔或铁丝网上收集得到有机前驱体纳米纤维还需要进行干燥处理。进一步优选，所述干燥的温度为50-70℃。Preferably, the organic precursor nanofibers collected from tin foil or barbed wire during electrospinning also need to be dried. Further preferably, the drying temperature is 50-70°C.
在上述TiO2中空全介孔纳米纤维的制备方法中，所述高温煅烧的温度为480-520℃，保温1-3h，升温速度为1-5℃/min。In the preparation method of the above-mentioned TiO2 hollow fully mesoporous nanofibers, the temperature of the high-temperature calcination is 480-520° C., the temperature is kept for 1-3 hours, and the heating rate is 1-5° C./min.
作为优选，为了提高TiO2材料的结晶度，步骤(2)中的煅烧处理在空气气氛下进行。Preferably, in order to increase the crystallinity of theTiO2 material, the calcination treatment in step (2) is carried out under air atmosphere.
与现有技术中的TiO2纳米纤维相比，本发明具有如下优点：Compared withTiO nanofibers in the prior art, the present invention has the following advantages:
1、本发明TiO2纳米纤维在光催化剂中的应用具有较好的高效性和稳定性。1. The application of TiO2 nanofibers of the present invention in photocatalysts has better efficiency and stability.
2、本发明通过添加适量的石蜡油，在静电力的作用被连续相包覆于内部，有效合成同时兼具中空结构和全介孔的结构的TiO2全介孔纳米纤维。2. In the present invention, by adding an appropriate amount of paraffin oil, the continuous phase is coated inside under the action of electrostatic force, effectively synthesizing TiO2 fully mesoporous nanofibers with both hollow structure and fully mesoporous structure.
3、本发明TiO2中空全介孔纳米纤维的制备方法工艺简单可控。3. The preparation method of the TiO2 hollow fully mesoporous nanofibers of the present invention is simple and controllable.
附图说明Description of drawings
图1为本发明实施例1所制得的有机前驱体纳米纤维的低倍扫描电镜(SEM)图。Figure 1 is a low magnification scanning electron microscope (SEM) image of the organic precursor nanofibers prepared in Example 1 of the present invention.
图2为本发明实施例1所制得的有机前驱体纳米纤维的高倍扫描电镜(SEM)图。FIG. 2 is a high-magnification scanning electron microscope (SEM) image of the organic precursor nanofiber prepared in Example 1 of the present invention.
图3为本发明实施例1所制得的TiO2全介孔纤维的比表面和孔径分析图。Fig. 3 is an analysis diagram of the specific surface and pore size of the TiO2 fully mesoporous fiber prepared in Example 1 of the present invention.
图4为本发明实施例1所制得的TiO2全介孔纤维的扫描电镜(SEM)图。FIG. 4 is a scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Example 1 of the present invention.
图5为本发明实施例1所制得的TiO2全介孔纤维的低倍扫描电镜(SEM)图。Fig. 5 is a low magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Example 1 of the present invention.
图6为本发明实施例1所制得的TiO2全介孔纳米纤维的断面扫描电镜(SEM)图。Fig. 6 is a cross-sectional scanning electron microscope (SEM) image of TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图7为本发明实施例1所制得的TiO2全介孔纳米纤维的高倍扫描电镜(SEM)图。7 is a high-magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图8为本发明实施例1所制得的TiO2全介孔纳米纤维的X射线衍射谱图。Fig. 8 is an X-ray diffraction spectrum of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图9为本发明实施例1所制得的TiO2全介孔纳米纤维的透射电镜(TEM)图。FIG. 9 is a transmission electron microscope (TEM) image of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图10为本发明实施例1所制得的TiO2全介孔纳米纤维的透射电镜(TEM)图。FIG. 10 is a transmission electron microscope (TEM) image of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图11为本发明实施例1所制得的TiO2全介孔纳米纤维的高分辨透射电镜(HRTEM)图。FIG. 11 is a high-resolution transmission electron microscope (HRTEM) image of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图12为本发明实施例1所制得的TiO2全介孔纳米纤维的能谱(EDS)图。12 is an energy spectrum (EDS) diagram of the TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图13为本发明实施例1所制得的TiO2全介孔纳米纤维的选区电子衍射(SAED)图。Fig. 13 is a selected area electron diffraction (SAED) pattern of TiO2 fully mesoporous nanofibers prepared in Example 1 of the present invention.
图14为本发明对比例1所制得的TiO2全介孔纤维的低倍扫描电镜(SEM)图。Fig. 14 is a low magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Comparative Example 1 of the present invention.
图15为本发明对比例1所制得的TiO2全介孔纤维的高倍扫描电镜(SEM)图。FIG. 15 is a high-magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Comparative Example 1 of the present invention.
图16为本发明对比例2所制得的TiO2全介孔纤维的低倍扫描电镜(SEM)图。Fig. 16 is a low magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Comparative Example 2 of the present invention.
图17为本发明对比例2所制得的TiO2全介孔纤维的高倍扫描电镜(SEM)图。FIG. 17 is a high-magnification scanning electron microscope (SEM) image of the TiO2 fully mesoporous fiber prepared in Comparative Example 2 of the present invention.
图18为本发明TiO2中空全介孔纳米纤维作为光催化剂与P25的光催化产氢活性对比图。Fig. 18 is a comparison chart of the photocatalytic hydrogen production activity of TiO2 hollow fully mesoporous nanofibers of the present invention as photocatalysts and P25.
图19为本发明TiO2中空全介孔纳米纤维作为光催化剂与P25的光催化产氢稳定性对比图。Fig. 19 is a comparison chart of photocatalytic hydrogen production stability between TiO2 hollow fully mesoporous nanofibers of the present invention as photocatalysts and P25.
具体实施方式Detailed ways
以下是本发明的具体实施例并结合附图，对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。The following are specific embodiments of the present invention and in conjunction with the accompanying drawings, the technical solutions of the present invention are further described, but the present invention is not limited to these embodiments.
实施例1Example 1
称取聚乙烯吡咯烷酮(PVP)0.6g和钛酸丁酯(TBOT)3.0g溶解于7ml无水乙醇和3ml冰醋酸的混合液中，室温下搅拌混合2小时后加入0.5g偶氮二甲酸二异丙酯(发泡剂，DIPA)并继续搅拌得到橙黄色的透明溶液。然后在上述溶液中加入0.5g十六烷基三甲基溴化铵(CTAB)和2ml石蜡油强烈搅拌得前驱体纺丝液。Weigh 0.6g of polyvinylpyrrolidone (PVP) and 3.0g of butyl titanate (TBOT) and dissolve in a mixture of 7ml of absolute ethanol and 3ml of glacial acetic acid, stir and mix at room temperature for 2 hours, then add 0.5g of azodicarboxylate Isopropyl ester (foaming agent, DIPA) and continued stirring to obtain an orange-yellow transparent solution. Then, 0.5 g of cetyltrimethylammonium bromide (CTAB) and 2 ml of paraffin oil were added to the above solution and vigorously stirred to obtain a precursor spinning solution.
将前驱体纺丝液静置后量取6ml注入塑料针管内，并置于微量注射泵上，设置注射速度为1ml/h。金属针头作电纺丝阳极，铁丝网作接收材料的阴极，阳极与阴极之间的距离为20cm，在18kV高压下进行静电纺丝，从铁丝网上收集得到固体有机前驱体纤维材料并置于60℃的恒温烘干箱内，制得核壳结构的有机前驱体纳米纤维。After the precursor spinning solution was left to stand, 6ml was measured and injected into a plastic needle tube, and placed on a micro-injection pump, and the injection speed was set at 1ml/h. The metal needle is used as the electrospinning anode, and the wire mesh is used as the cathode of the receiving material. The distance between the anode and the cathode is 20cm. Electrospinning is performed under a high voltage of 18kV, and the solid organic precursor fiber material is collected from the wire mesh and placed at 60°C. The organic precursor nanofibers with core-shell structure were prepared in a constant temperature drying box.
最后将有机前驱体纳米纤维置于石英舟中，在空气气氛下，以3℃/min的升温速度升温至500℃煅烧2小时，然后随炉冷却，制得TiO2全介孔纳米纤维。Finally, the organic precursor nanofibers were placed in a quartz boat and calcined at 500 °C for 2 hours at a heating rate of 3 °C/min in an air atmosphere, and then cooled with the furnace to prepare TiO2 fully mesoporous nanofibers.
实施例2Example 2
称取聚乙烯吡咯烷酮(PVP)0.6g和钛酸丁酯(TBOT)3.0g溶解于7ml无水乙醇和3ml冰醋酸的混合液中，室温下搅拌混合2小时后加入0.5g偶氮二甲酸二异丙酯(发泡剂，DIPA)并继续搅拌得到橙黄色的透明溶液。然后在上述溶液中加入0.5g十六烷基三甲基溴化铵(CTAB)和2.2ml石蜡油强烈搅拌得前驱体纺丝液。Weigh 0.6g of polyvinylpyrrolidone (PVP) and 3.0g of butyl titanate (TBOT) and dissolve in a mixture of 7ml of absolute ethanol and 3ml of glacial acetic acid, stir and mix at room temperature for 2 hours, then add 0.5g of azodicarboxylate Isopropyl ester (foaming agent, DIPA) and continued stirring to obtain an orange-yellow transparent solution. Then, 0.5 g of cetyltrimethylammonium bromide (CTAB) and 2.2 ml of paraffin oil were added to the above solution and vigorously stirred to obtain a precursor spinning solution.
将前驱体纺丝液静置后量取6ml注入塑料针管内，并置于微量注射泵上，设置注射速度为1.1ml/h。金属针头作电纺丝阳极，铁丝网作接收材料的阴极，阳极与阴极之间的距离为19cm，在19kV高压下进行静电纺丝，从铁丝网上收集得到固体有机前驱体纤维材料并置于65℃的恒温烘干箱内，制得核壳结构的有机前驱体纳米纤维。After the precursor spinning solution was left to stand, 6ml was measured and injected into a plastic needle tube, and placed on a micro-injection pump, and the injection speed was set to 1.1ml/h. The metal needle is used as the electrospinning anode, and the wire mesh is used as the cathode of the receiving material. The distance between the anode and the cathode is 19cm. Electrospinning is performed under a high voltage of 19kV, and the solid organic precursor fiber material is collected from the wire mesh and placed at 65°C. The organic precursor nanofibers with core-shell structure were prepared in a constant temperature drying box.
最后将有机前驱体纳米纤维置于石英舟中，在空气气氛下，以2℃/min的升温速度升温至510℃煅烧2小时，然后随炉冷却，制得TiO2全介孔纳米纤维。Finally, the organic precursor nanofibers were placed in a quartz boat and calcined at a rate of 2 °C/min to 510 °C for 2 hours in an air atmosphere, and then cooled with the furnace to prepare TiO2 fully mesoporous nanofibers.
实施例3Example 3
称取聚乙烯吡咯烷酮(PVP)0.6g和钛酸丁酯(TBOT)3.0g溶解于8ml无水乙醇和3ml冰醋酸的混合液中，室温下搅拌混合2小时后加入0.5g偶氮二甲酸二异丙酯(发泡剂，DIPA)并继续搅拌得到橙黄色的透明溶液。然后在上述溶液中加入0.5g十六烷基三甲基溴化铵(CTAB)和1.8ml石蜡油强烈搅拌得前驱体纺丝液。Weigh 0.6g of polyvinylpyrrolidone (PVP) and 3.0g of butyl titanate (TBOT) and dissolve them in a mixture of 8ml of absolute ethanol and 3ml of glacial acetic acid, stir and mix at room temperature for 2 hours, then add 0.5g of azodicarboxylate Isopropyl ester (foaming agent, DIPA) and continued stirring to obtain an orange-yellow transparent solution. Then, 0.5 g of cetyltrimethylammonium bromide (CTAB) and 1.8 ml of paraffin oil were added to the above solution and vigorously stirred to obtain a precursor spinning solution.
将前驱体纺丝液静置后量取6ml注入塑料针管内，并置于微量注射泵上，设置注射速度为0.9ml/h。金属针头作电纺丝阳极，铁丝网作接收材料的阴极，阳极与阴极之间的距离为21cm，在16kV高压下进行静电纺丝，从铁丝网上收集得到固体有机前驱体纤维材料并置于68℃的恒温烘干箱内，制得核壳结构的有机前驱体纳米纤维。After the precursor spinning liquid is left to stand, measure 6ml and inject it into a plastic needle tube, and place it on a micro-injection pump, and set the injection speed to 0.9ml/h. The metal needle is used as the electrospinning anode, and the wire mesh is used as the cathode of the receiving material. The distance between the anode and the cathode is 21cm. Electrospinning is performed under a high voltage of 16kV, and the solid organic precursor fiber material is collected from the wire mesh and placed at 68°C. The organic precursor nanofibers with core-shell structure were prepared in a constant temperature drying box.
最后将有机前驱体纳米纤维置于石英舟中，在空气气氛下，以4℃/min的升温速度升温至490℃煅烧2小时，然后随炉冷却，制得TiO2全介孔纳米纤维。Finally, the organic precursor nanofibers were placed in a quartz boat and calcined at 490 °C for 2 hours at a heating rate of 4 °C/min in an air atmosphere, and then cooled with the furnace to prepare TiO2 fully mesoporous nanofibers.
实施例4Example 4
称取聚乙烯吡咯烷酮(PVP)0.6g和钛酸丁酯(TBOT)3.0g溶解于8ml无水乙醇和3ml冰醋酸的混合液中，室温下搅拌混合2小时后加入0.5g偶氮二甲酸二异丙酯(发泡剂，DIPA)并继续搅拌得到橙黄色的透明溶液。然后在上述溶液中加入0.5g十六烷基三甲基溴化铵(CTAB)和2.5ml石蜡油强烈搅拌得前驱体纺丝液。Weigh 0.6g of polyvinylpyrrolidone (PVP) and 3.0g of butyl titanate (TBOT) and dissolve them in a mixture of 8ml of absolute ethanol and 3ml of glacial acetic acid, stir and mix at room temperature for 2 hours, then add 0.5g of azodicarboxylate Isopropyl ester (foaming agent, DIPA) and continued stirring to obtain an orange-yellow transparent solution. Then, 0.5 g of cetyltrimethylammonium bromide (CTAB) and 2.5 ml of paraffin oil were added to the above solution and vigorously stirred to obtain a precursor spinning solution.
将前驱体纺丝液静置后量取6ml注入塑料针管内，并置于微量注射泵上，设置注射速度为0.8ml/h。金属针头作电纺丝阳极，铁丝网作接收材料的阴极，阳极与阴极之间的距离为22cm，在15kV高压下进行静电纺丝，从铁丝网上收集得到固体有机前驱体纤维材料并置于70℃的恒温烘干箱内，制得核壳结构的有机前驱体纳米纤维。After the precursor spinning solution was left to stand, 6ml was measured and injected into a plastic needle tube, and placed on a micro-injection pump, and the injection speed was set to 0.8ml/h. The metal needle is used as the electrospinning anode, and the wire mesh is used as the cathode of the receiving material. The distance between the anode and the cathode is 22cm. Electrospinning is performed under a high voltage of 15kV, and the solid organic precursor fiber material is collected from the wire mesh and placed at 70°C. The organic precursor nanofibers with core-shell structure were prepared in a constant temperature drying box.
最后将有机前驱体纳米纤维置于石英舟中，在空气气氛下，以5℃/min的升温速度升温至500℃煅烧2小时，然后随炉冷却，制得TiO2全介孔纳米纤维。Finally, the organic precursor nanofibers were placed in a quartz boat and calcined at 500 °C for 2 hours at a heating rate of 5 °C/min in an air atmosphere, and then cooled with the furnace to prepare TiO2 fully mesoporous nanofibers.
实施例5Example 5
称取聚乙烯吡咯烷酮(PVP)0.6g和钛酸丁酯(TBOT)3.0g溶解于7.5ml无水乙醇和2.5ml冰醋酸的混合液中，室温下搅拌混合2小时后加入0.5g偶氮二甲酸二异丙酯(发泡剂，DIPA)并继续搅拌得到橙黄色的透明溶液。然后在上述溶液中加入0.5g十六烷基三甲基溴化铵(CTAB)和1.5ml石蜡油强烈搅拌得前驱体纺丝液。Weigh 0.6g of polyvinylpyrrolidone (PVP) and 3.0g of butyl titanate (TBOT) and dissolve them in a mixture of 7.5ml of absolute ethanol and 2.5ml of glacial acetic acid, stir and mix at room temperature for 2 hours, then add 0.5g of azobis diisopropyl formate (foaming agent, DIPA) and continued stirring to obtain an orange-yellow transparent solution. Then, 0.5 g of cetyltrimethylammonium bromide (CTAB) and 1.5 ml of paraffin oil were added to the above solution and vigorously stirred to obtain a precursor spinning solution.
将前驱体纺丝液静置后量取6ml注入塑料针管内，并置于微量注射泵上，设置注射速度为1.2ml/h。金属针头作电纺丝阳极，铁丝网作接收材料的阴极，阳极与阴极之间的距离为18cm，在20kV高压下进行静电纺丝，从铁丝网上收集得到固体有机前驱体纤维材料并置于62℃的恒温烘干箱内，制得核壳结构的有机前驱体纳米纤维。After the precursor spinning solution was left to stand, 6ml was measured and injected into a plastic needle tube, and placed on a micro-injection pump, and the injection speed was set at 1.2ml/h. The metal needle is used as the electrospinning anode, and the wire mesh is used as the cathode of the receiving material. The distance between the anode and the cathode is 18cm. Electrospinning is performed at a high voltage of 20kV, and the solid organic precursor fiber material is collected from the wire mesh and placed at 62°C. The organic precursor nanofibers with core-shell structure were prepared in a constant temperature drying box.
最后将有机前驱体纳米纤维置于石英舟中，在空气气氛下，以1℃/min的升温速度升温至480℃煅烧2小时，然后随炉冷却，制得TiO2全介孔纳米纤维。Finally, the organic precursor nanofibers were placed in a quartz boat and calcined at 480 °C for 2 hours at a heating rate of 1 °C/min in an air atmosphere, and then cooled with the furnace to prepare TiO2 fully mesoporous nanofibers.
对比例1Comparative example 1
与实施例1仅区别在只添加1ml石蜡油，其他工艺与实施例1相同，此处不再累述。The only difference from Example 1 is that only 1ml of paraffin oil is added, and other processes are the same as in Example 1, and will not be repeated here.
对比例2Comparative example 2
与实施例1仅区别在添加3ml石蜡油，其他工艺与实施例1相同，此处不再累述。Only difference with embodiment 1 is that 3ml paraffin oil is added, other processes are identical with embodiment 1, repeat no more here.
图1、图2分别为实施例1中制得的核壳结构的有机前驱体纳米纤维的低倍电镜(SEM)图和高倍电镜(SEM)图。Fig. 1, Fig. 2 are respectively the low magnification electron microscope (SEM) figure and the high magnification electron microscope (SEM) figure of the organic precursor nanofiber of core-shell structure prepared in embodiment 1.
图3为实施例1中制得的TiO2全介孔纳米纤维的比表面和孔径分析图，从其相应的氮吸附曲线和孔径分布曲线说明该纳米纤维存在介孔，其比表面积为27.2m2/g，孔径值为38.1nm。Fig. 3 is the specific surface and pore size analysis figure of the TiO2 prepared in embodiment1 fully mesoporous nanofiber, shows that this nanofiber has mesopore from its corresponding nitrogen adsorption curve and pore size distribution curve, and its specific surface area is 27.2m2 /g, and the pore size is 38.1nm.
图4为实施例1中值得的TiO2全介孔纤维的扫描电镜(SEM)图，具体的，图5、图6、图7分别为实施例1中制得的TiO2全介孔纳米纤维在不同放大倍数下电镜(SEM)扫描得到的低倍扫描电镜(SEM)图、断面扫描电镜(SEM)图、高倍扫描电镜(SEM)图，从图中表明所制备得到的TiO2全介孔纳米纤维同时兼具全介孔和中空结构，为TiO2中空全介孔纳米纤维。Fig. 4 is the scanning electron microscope (SEM) figure ofTiO fully mesoporous fiber worth in embodiment 1, specifically, Fig. 5, Fig. 6, Fig. 7 are TiO obtained in embodiment1 respectively Full mesoporous nanofiber The low-magnification scanning electron microscope (SEM) images, cross-sectional scanning electron microscope (SEM) images, and high-magnification scanning electron microscope (SEM) images obtained by scanning electron microscopy (SEM) at different magnifications show that the preparedTiO2 full mesoporous The nanofibers have both fully mesoporous and hollow structures, and are TiO2 hollow fully mesoporous nanofibers.
图8为实施例1中制得的TiO2全介孔纳米纤维的X射线衍射谱图(XRD)，表明所制备的TiO2纳米纤维的主要晶型为锐钛矿型或金红石型。Figure 8 is the X-ray diffraction spectrum (XRD) of the TiO2 fully mesoporous nanofibers prepared in Example 1, indicating that the main crystal form of the prepared TiO2 nanofibers is anatase or rutile.
图9和图10分布为本发明实施例中制得的TiO2全介孔纳米纤维的单根纳米纤维100nm和800nm的透射电镜(TEM)图，进一步显示了所合成的材料具有典型的全介孔和中空结构。Fig. 9 and Fig. 10 distribution are the transmission electron microscope (TEM) picture of the single nanofiber 100nm and 800nm ofTiO2 fully mesoporous nanofiber made in the embodiment of the present invention, further show that the synthesized material has a typical mesoporous Holes and hollow structures.
图11为实施例1中制得的TiO2全介孔纳米纤维晶体相应的高分辨透射电镜(HRTEM)，进一步证实了本发明的纳米纤维为锐钛矿或金红石型组成的复合晶体相。Figure 11 is the corresponding high-resolution transmission electron microscope (HRTEM) of the TiO2 fully mesoporous nanofiber crystal prepared in Example 1, which further confirms that the nanofiber of the present invention is a composite crystal phase composed of anatase or rutile.
图12为实施例1中制得的TiO2中空全介孔纳米纤维的能谱图(EDS)，从图可见，该纳米纤维主要由Ti和O元素组成。图13为实施例1中制得的TiO2中空全介孔纳米纤维相应的选取电子衍射(SAED)图，从图可得，该纳米纤维为锐钛矿或金红石型TiO2组成的复合晶体相，且具有良好的晶体结构。Figure 12 is the energy spectrum (EDS) of the TiO2 hollow fully mesoporous nanofibers prepared in Example 1. It can be seen from the figure that the nanofibers are mainly composed of Ti and O elements. Figure 13 is the selected electron diffraction (SAED) figure corresponding to theTiO2 hollow fully mesoporous nanofibers prepared in Example 1. It can be seen from the figure that the nanofibers are anatase or rutileTiO2 Composite crystal phase , and has a good crystal structure.
将对比例1中制得的TiO2纳米纤维在不同放大倍数下进行电镜(SEM)扫描，得到的典型扫描电镜(SEM)如图14和图15所示，表明所制备的材料为实心结构的全介孔纳米纤维。TheTiO nanofibers prepared in Comparative Example 1 were scanned by electron microscope (SEM) at different magnifications, and the typical scanning electron microscope (SEM) obtained is shown in Figure 14 and Figure 15, indicating that the prepared material is a solid structure. Fully mesoporous nanofibers.
比较实施例1和对比例1，比较图4-7和图14-15，可得：在初始原料中石蜡油的量较少时，最后通过煅烧所制备的材料为非中空结构，说明石蜡油的含量对制备具有中空结构的复合纤维材料至关重要。Comparing Example 1 and Comparative Example 1, comparing Figures 4-7 and Figures 14-15, it can be obtained that: when the amount of paraffin oil in the initial raw material is small, the material prepared by calcination finally has a non-hollow structure, indicating that paraffin oil The content of is very important for the preparation of composite fiber materials with hollow structure.
将对比例2中制得的TiO2纳米纤维在不同放大倍数下进行电镜(SEM)扫描，得到的典型扫描电镜(SEM)如图16和图17所示，表明所制备的材料为多级空心结构的全介孔纳米纤维。TheTiO nanofibers prepared in Comparative Example 2 were scanned by electron microscope (SEM) at different magnifications, and the typical scanning electron microscope (SEM) obtained is shown in Figure 16 and Figure 17, indicating that the prepared material is a multi-level hollow Structured fully mesoporous nanofibers.
比较实施例1、对比例1、对比例2，比较图4-7、图14-15、图16-17，可得：在初始原料中石蜡油的量较多时，最后通过煅烧所制备的材料为多级中空结构，说明石蜡油的含量对制备具有中空结构的复合纤维材料至关重要，通过改变石蜡油在初始纺丝液中的含量，能够有效实现纤维内部结构的调控。Comparing Example 1, Comparative Example 1, and Comparative Example 2, comparing Figures 4-7, Figures 14-15, and Figures 16-17, it can be obtained: when the amount of paraffin oil in the initial raw material is large, the material prepared by calcination It is a multi-level hollow structure, indicating that the content of paraffin oil is very important for the preparation of composite fiber materials with a hollow structure. By changing the content of paraffin oil in the initial spinning solution, the internal structure of the fiber can be effectively regulated.
应用实施例1Application Example 1
称取实施例1中制得的0.05gTiO2中空全介孔纳米纤维分散在40ml的蒸馏水中，超声分散15min后，再加入10ml的甲醇作为牺牲剂，采用300W氙灯作为模拟光源，产生的氢气通过在线的气相色谱仪检测，每隔15min检测一次，5个小时后结束测试。Weigh 0.05g of theTiO2 hollow fully mesoporous nanofibers prepared in Example 1 and disperse them in 40ml of distilled water. After ultrasonic dispersion for 15 minutes, add 10ml of methanol as a sacrificial agent, and use a 300W xenon lamp as a simulated light source. The online gas chromatograph detects once every 15 minutes, and ends the test after 5 hours.
对比应用实施例1Comparative application example 1
现有技术中商业的P25纳米粉体光催化剂在300W氙灯作为模拟光源下产生氢气，产生的氢气通过在线的气相色谱仪检测，每隔15min检测一次，5个小时后结束测试。The commercial P25 nano-powder photocatalyst in the prior art generates hydrogen gas under a 300W xenon lamp as a simulated light source, and the generated hydrogen gas is detected by an online gas chromatograph every 15 minutes, and the test ends after 5 hours.
图18为本发明TiO2中空全介孔纳米纤维作为光催化剂与P25的光催化产氢活性对比图，说明本发明制备的TiO2中空全介孔纳米纤维作光催化剂相比P25具有显著提高的光催化性能。在一次催化结束后，将催化剂滤出，洗涤干净后多次循环使用。Fig. 18 is the photocatalytic hydrogen production activity comparison chart ofTiO2 hollow fully mesoporous nanofiber of the present invention as photocatalyst and P25, illustrate that theTiO2 hollow fully mesoporous nanofiber prepared by the present invention has significantly improved compared with P25 as photocatalyst Photocatalytic performance. After one catalysis is finished, the catalyst is filtered out, washed and recycled for multiple times.
图19为本发明TiO2中空全介孔纳米纤维作为光催化剂与P25的光催化剂循环3次后产氢结果对比图，P25在经过三次循环使用后其光催化产氢活性明显降低，而TiO2中空全介孔纳米纤维光催化剂的产氢量基本维持在一个比较恒定的值，说明本发明制备的TiO2中空全介孔纳米纤维光催化剂具有更加稳定的光催化性能。Figure 19 is a comparison chart of hydrogen production results after three cycles of photocatalyst withTiO2 hollow fully mesoporous nanofibers of the present invention and P25 photocatalyst. The hydrogen production of the hollow fully mesoporous nanofiber photocatalyst basically maintains a relatively constant value, indicating that the TiO2 hollow fully mesoporous nanofiber photocatalyst prepared by the present invention has more stable photocatalytic performance.
本发明的TiO2中空全介孔纳米纤维可有效稳定地应用在光催化剂中，TiO2中空全介孔纳米纤维的制备方法简单易行，可通过改变石蜡油在初始纺丝液中的含量，有效实现纤维内部结构的调控。The TiO2 hollow fully mesoporous nanofibers of the present invention can be effectively and stably applied in photocatalysts, and the preparation method of TiO2 hollow fully mesoporous nanofibers is simple and easy. By changing the content of paraffin oil in the initial spinning solution, Effectively realize the control of the internal structure of the fiber.
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the definition of the appended claims range.
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| CN201510393523.1ACN105013462A (en) | 2015-07-01 | 2015-07-01 | Application of TiO2 Hollow Mesoporous Nanofibers in Photocatalysts |
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| CN201510393523.1ACN105013462A (en) | 2015-07-01 | 2015-07-01 | Application of TiO2 Hollow Mesoporous Nanofibers in Photocatalysts |
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