CN102976401A - Ultrasonic chemical preparation method for nitrogen-doped nano-titanium dioxide crystal - Google Patents
Ultrasonic chemical preparation method for nitrogen-doped nano-titanium dioxide crystal Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 33
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000005285 chemical preparation method Methods 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
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- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
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Abstract
本发明涉及二氧化钛纳米晶的制备工艺，特别公开了一种氮掺杂二氧化钛晶体的超声化学制备方法。该超声化学制备方法，其特征在于：以四价钛盐为钛源，以氨水或铵盐为氮源，加入分散剂，混合制成反应液，控制反应液温度为60~90℃，在常压下超声处理3~4小时，得到白色沉淀；将所得沉淀离心分离、洗涤、真空干燥，最后得到产品。本发明操作步骤简单，设计合理，反应温度低，工艺简洁，生产的纳米二氧化钛具有产品粒径小、粒径分布范围窄的优点，适于广泛推广应用。
The invention relates to a preparation process of titanium dioxide nanocrystals, and particularly discloses a sonochemical preparation method of nitrogen-doped titanium dioxide crystals. The sonochemical preparation method is characterized in that: tetravalent titanium salt is used as the titanium source, ammonia water or ammonium salt is used as the nitrogen source, a dispersant is added, and the reaction solution is mixed, and the temperature of the reaction solution is controlled at 60-90°C. Ultrasonic treatment under pressure for 3 to 4 hours to obtain a white precipitate; the resulting precipitate was centrifuged, washed, and vacuum-dried to finally obtain the product. The invention has simple operation steps, reasonable design, low reaction temperature and simple process, and the produced nano-titanium dioxide has the advantages of small product particle size and narrow particle size distribution range, and is suitable for wide popularization and application.
Description
（一） 技术领域 (one) technical field
本发明涉及二氧化钛纳米晶的制备工艺，特别涉及一种氮掺杂二氧化钛晶体的超声化学制备方法。 The invention relates to a preparation process of titanium dioxide nanocrystals, in particular to a sonochemical preparation method of nitrogen-doped titanium dioxide crystals.
（二） 背景技术 (two) Background technique
纳米TiO2作为一种性能优良的光催化剂可降解水和空气中的各种有机污染物，同时也具有杀菌消毒作用，且由于自身无毒无污染，使其在环境净化方面具有良好的应用前景。但是TiO2只能在波长小于387nm的紫外线作用下才能产生电子−空穴对，再转化为羟基自由基等活性物种而对污染物起降解作用；而太阳光中紫外波段部分的能量仅占全部太阳能的5%左右，绝大部分可见光的能量(45%左右)尚未得到充分利用。为了高效利用太阳光，必须开发具有可见光催化活性的新型光催化剂。Asahi等的理论和实践证明，非金属元素N掺杂是TiO2可见光敏化的一种有效途径，从而引导了世界范围内基于N掺杂TiO2光催化剂的研究和开发热潮。N掺杂TiO2光催化剂的制备方法较多，主要有焙烧法、溶胶凝胶法、液相反应法、水热法等。如Asahi等以商品TiO2做钛源,在NH3/Ar的混合气氛中600 ℃高温焙烧得到TiO2-xNx 粉末；杨鸿辉等以TiCl4为原料，氨水为中和剂控制水解制备出胶体，然后在400℃下焙烧4h 得到锐钛矿型TiO2-xNx光催化剂；T.Ihara等将Ti(SO4)2溶液与氨水的水解制得的凝胶在400℃下焙烧制得N掺杂TiO2；包南等以钛酸四丁酯和氨水为原料, 通过水热法制得层状钛酸铵前驱体, 再在400℃下进行热分解, 制得了N掺杂的锐钛矿TiO2纳米晶。上述方法操作条件各异，但是都需要多步操作，都离不开高温处理，因而高耗时、高耗能。 As a photocatalyst with excellent performance, nano-TiO 2 can degrade various organic pollutants in water and air, and also has sterilizing and disinfecting effects, and because it is non-toxic and pollution-free, it has a good application prospect in environmental purification . However, TiO 2 can only generate electron-hole pairs under the action of ultraviolet rays with a wavelength less than 387nm, and then convert them into active species such as hydroxyl radicals to degrade pollutants; while the energy in the ultraviolet band of sunlight only accounts for all About 5% of solar energy, most of the energy of visible light (about 45%) has not been fully utilized. In order to efficiently utilize sunlight, novel photocatalysts with visible light catalytic activity must be developed. The theory and practice of Asahi et al. proved that N-doping of non-metallic elements is an effective way to sensitize TiO 2 to visible light, thus leading the research and development upsurge of N-doped TiO 2 photocatalysts worldwide. There are many preparation methods for N-doped TiO2 photocatalysts, mainly including roasting method, sol-gel method, liquid phase reaction method, hydrothermal method and so on. For example, Asahi et al. used commercial TiO 2 as the titanium source, and roasted it at a high temperature of 600 ℃ in a mixed atmosphere of NH3/Ar to obtain TiO 2-x N x powder; , and then calcined at 400°C for 4h to obtain anatase-type TiO 2-x N x photocatalyst; T.Ihara et al. calcined the gel prepared by the hydrolysis of Ti(SO 4 ) 2 solution and ammonia water at 400°C to obtain N-doped TiO 2 ; Bao Nan et al. used tetrabutyl titanate and ammonia water as raw materials to prepare a layered ammonium titanate precursor by hydrothermal method, and then thermally decomposed it at 400°C to prepare N-doped anatase. Ore TiO 2 nanocrystals. The operating conditions of the above methods are different, but they all require multi-step operations, and all of them are inseparable from high-temperature treatment, so they are time-consuming and energy-consuming.
近年来超声化学已被证明是一种制备特异性能纳米材料的十分有效的技术手段。液体在超声波作用下可产生声空化, 即液体中微气泡的形成、生长和快速崩溃，由于塌陷气泡中气相的绝热压缩或冲击, 会产生局部“热点”, 其瞬态温度高达5000K, 压强可达5×107Pa 以上, 同时这种局部高温、高压存在的时间非常短, 仅有几微秒, 所以温度变化率高达109K·s-1, 从而引发一系列物理、化学变化。超声空化作用可以极大地提高非均相反应的速率，实现非均相反应物间的介观均匀混合，加速反应物和产物的扩散过程，促进固体新相的生成，控制颗粒的尺寸和分布。超声波在强化非均相界面之间的传质方面和传统的方法相比具有明显的优势和独到之处，有利于材料特殊结构和性能的形成。 In recent years, sonochemistry has been proved to be a very effective technique for preparing nanomaterials with specific properties. Under the action of ultrasonic waves, liquid can produce acoustic cavitation, that is, the formation, growth and rapid collapse of micro-bubbles in the liquid. Due to the adiabatic compression or impact of the gas phase in the collapsed bubbles, local "hot spots" will be generated. The transient temperature is as high as 5000K, and the pressure At the same time, the local high temperature and high pressure exist for a very short time, only a few microseconds, so the temperature change rate is as high as 10 9 K·s -1 , thus triggering a series of physical and chemical changes. Ultrasonic cavitation can greatly increase the rate of heterogeneous reactions, realize mesoscopic uniform mixing between heterogeneous reactants, accelerate the diffusion process of reactants and products, promote the formation of new solid phases, and control the size and distribution of particles . Compared with traditional methods, ultrasonic has obvious advantages and unique features in strengthening the mass transfer between heterogeneous interfaces, which is beneficial to the formation of special structures and properties of materials.
（三） 发明内容 (three) Contents of the invention
本发明为了弥补现有技术的不足，提供了一种操作简单、反应温度低的氮掺杂纳米二氧化钛晶体的超声化学制备方法。 In order to make up for the deficiencies of the prior art, the invention provides a sonochemical preparation method of nitrogen-doped nano-titanium dioxide crystals with simple operation and low reaction temperature.
本发明是通过如下技术方案实现的： The present invention is achieved through the following technical solutions:
一种氮掺杂纳米二氧化钛晶体的超声化学制备方法，其特征在于：以四价钛盐为钛源，以氨水或铵盐为氮源，加入分散剂，混合制成反应液，控制反应液温度为60~90℃，在常压下超声处理3~4小时，得到白色沉淀；将所得沉淀离心分离、洗涤、真空干燥，最后得到产品。 A method for sonochemically preparing nitrogen-doped nano-titanium dioxide crystals, characterized in that: tetravalent titanium salt is used as the titanium source, ammonia water or ammonium salt is used as the nitrogen source, a dispersant is added, mixed to form a reaction solution, and the temperature of the reaction solution is controlled At 60-90°C, ultrasonic treatment under normal pressure for 3-4 hours, a white precipitate was obtained; the obtained precipitate was centrifuged, washed, and vacuum-dried to obtain the product.
本发明的更优方案为： A better solution of the present invention is:
超声处理时，超声波频率为大于20KHz，强度为大于20W/cm2。 During ultrasonic treatment, the ultrasonic frequency is greater than 20KHz, and the intensity is greater than 20W/cm 2 .
所述分散剂为聚乙二醇、聚乙烯醇和聚吡咯烷酮中的一种或多种。 The dispersant is one or more of polyethylene glycol, polyvinyl alcohol and polypyrrolidone.
所述四价钛盐为浓度为0.1~2.0mol/L的TiCl4或Ti(SO4)2的水溶液。 The tetravalent titanium salt is an aqueous solution of TiCl 4 or Ti(SO 4 ) 2 with a concentration of 0.1-2.0 mol/L.
所述氮源为氨水、氯化铵或硫酸铵。 The nitrogen source is ammonia water, ammonium chloride or ammonium sulfate.
本发明对在超声波作用下不同钛源和氮源合成纳米N-TiO2的粒子进行了研究。实验发现：以硫酸钛为钛源，NH3·H2O、或(NH4)2SO4为氮源，可以直接得到分散性良好N-TiO2的粒子，粒径大小为8-15nm，且分布范围较窄；通过控制溶液酸度，可以分别得到锐钛矿型和金红石型N-TiO2晶体。在强酸性介质中（pH＜1)，产物为金红石晶体。随着反应介质pH 值的升高, 产物中金红石晶粒逐渐减少, 锐钛矿晶粒开始出现。当反应介质pH 值为1~3时, 产物中同时生成金红石型和锐钛矿型晶粒。将反应介质pH＞3, 产物主要是锐钛矿晶粒,将反应介质pH值调至5~7，反应产物为纯锐钛矿型晶粒。以四氯化钛为钛源，NH4Cl或NH3·H2O为氮源，可一步直接合成出金红石相的-TiO2的粒子，其结构为连生聚集成羽状枝蔓晶，柱状粒子大小为7×16nm(W/L)。 The invention studies the synthesis of nanometer N- TiO2 particles under the action of ultrasonic waves with different titanium sources and nitrogen sources. Experiments have found that with titanium sulfate as the titanium source and NH 3 ·H 2 O or (NH 4 ) 2 SO 4 as the nitrogen source, N-TiO 2 particles with good dispersion can be directly obtained, with a particle size of 8-15nm. And the distribution range is narrow; by controlling the acidity of the solution, anatase and rutile N-TiO 2 crystals can be obtained respectively. In strongly acidic medium (pH<1), the product is rutile crystals. As the pH value of the reaction medium increases, the rutile grains in the product gradually decrease, and the anatase grains begin to appear. When the pH value of the reaction medium is 1~3, rutile and anatase crystal grains are simultaneously formed in the product. If the pH of the reaction medium is greater than 3, the product is mainly anatase crystal grains; if the pH value of the reaction medium is adjusted to 5-7, the reaction product is pure anatase crystal grains. Using titanium tetrachloride as the titanium source, NH 4 Cl or NH 3 ·H 2 O as the nitrogen source, the rutile-TiO 2 particles can be directly synthesized in one step. The size is 7×16nm (W/L).
本发明操作步骤简单，设计合理，反应温度低，工艺简洁，生产的纳米二氧化钛具有产品粒径小、粒径分布范围窄的优点，适于广泛推广应用。 The invention has simple operation steps, reasonable design, low reaction temperature and simple process, and the produced nano-titanium dioxide has the advantages of small product particle size and narrow particle size distribution range, and is suitable for wide popularization and application.
（四） 附图说明 (Four) Description of drawings
下面结合附图对本发明作进一步的说明。 The present invention will be further described below in conjunction with the accompanying drawings.
图1为以Ti(SO4)2为钛源，(NH4)2SO4为为氮源，在pH值6.0、反应温度80℃条件下，不同反应阶段产物的X-衍射图谱；
Figure 1 is the X-diffraction patterns of products in different reaction stages under the conditions of pH 6.0 and
图2为样品A晶体表面X-射线光电子能谱图； Fig. 2 is sample A crystal surface X-ray photoelectron energy spectrogram;
图3为样品B的X-衍射图谱和透射电镜照片； Fig. 3 is the X-diffraction spectrum and transmission electron microscope picture of sample B;
图4为样品B晶体表面X-射线光电子能谱图； Fig. 4 is sample B crystal surface X-ray photoelectron energy spectrogram;
图5为不同晶型TiO2晶核形成示意图； Figure 5 is a schematic diagram of the formation of different crystal forms of TiO2 crystal nuclei;
图6为氮掺杂TiO2样品A和样品B的紫外-可见吸收光谱； Fig. 6 is the ultraviolet-visible absorption spectrum of sample A and sample B of nitrogen- doped TiO;
图7为可见光照射下甲基紫在不同TiO2上的降解曲线。 Figure 7 shows the degradation curves of methyl violet on different TiO2 under visible light irradiation.
（五） 具体实施方式 (five) Detailed ways
由附图1可以看出，超声反应1h，所得产物无明显X-衍射峰，说明此时产物为无定形态；超声反应2h，开始出现明显的X-衍射峰，但是峰型较宽，说明形成的产物颗粒细小；超声反应3h，产物产生7个X-衍射峰，且与JCPDS卡片21—1272一致，说明产物为锐钛矿型纳米TiO2颗粒。图1中***的电镜照片为超声反应3h所得锐钛矿型N-TiO2（样品A）的TEM的照片，可以看到制得的N-TiO2为柱状粒子，粒径分布范围较窄，其大小为10×20nm(W/L)。 As can be seen from accompanying drawing 1, ultrasonic reaction 1h, the obtained product has no obvious X-diffraction peak, illustrates that the product is amorphous at this moment; Ultrasonic reaction 2h, begins to appear obvious X-diffraction peak, but peak type is wider, illustrates The formed product particles are fine; after ultrasonic reaction for 3 hours, the product produces 7 X-diffraction peaks, which are consistent with JCPDS card 21-1272, indicating that the product is anatase nano-TiO 2 particles. The electron microscope photo inserted in Figure 1 is the TEM photo of anatase N-TiO 2 (sample A) obtained by ultrasonic reaction for 3 hours. It can be seen that the prepared N-TiO 2 is columnar particles with a narrow particle size distribution range. Its size is 10×20 nm (W/L).
附图2中除O元素的O1s 特征峰、Ti元素的Ti2s和Ti2p特征峰外，在399.8eV处还有明显的N1s特征峰，说明N元素进入了TiO2晶格，形成了N-Ti键，产生了氮掺杂纳米TiO2晶体。 In Figure 2, in addition to the O1s characteristic peak of the O element and the Ti2s and Ti2p characteristic peaks of the Ti element, there is also an obvious N1s characteristic peak at 399.8eV, indicating that the N element has entered the TiO 2 lattice and formed an N-Ti bond , resulting in nitrogen-doped nano-TiO2 crystals.
附图3为本发明以TiCl4为钛源、NH4Cl为氮源，在pH值0.5、反应温度70℃条件下，超声反应3h，所得产物(样品B)的X-衍射图谱和透射电镜照片。与JCPDS卡片21—1276相对照，TiO2为金红石型，图中出现的六个强度较强衍射峰分别与金红石型TiO2的（110）面、（101）面、（111）面、（211）面、（002）面和（301）相对应，说明生成的TiO2晶粒晶型良好。根据X—射线衍射宽化分析法计算出晶粒的平均粒径D（ 111 ）=7.6nm。由电镜照片可以看出，以TiCl4为原料制备的N-TiO2，粒度为7×16 nm，呈长柱状，晶粒间相互取向连生，聚集形成枝蔓晶，聚集体为羽状，其延伸方向与柱状晶粒的长度方向一致。平行于晶轴C。 Accompanying drawing 3 is the X-diffraction pattern and transmission electron microscope of the product (sample B) obtained by ultrasonic reaction for 3 hours with TiCl 4 as the titanium source and NH 4 Cl as the nitrogen source at a pH value of 0.5 and a reaction temperature of 70° C. photo. Compared with JCPDS card 21-1276, TiO 2 is rutile type, and the six diffraction peaks with stronger intensity appearing in the figure are respectively related to the (110) plane, (101) plane, (111) plane, (211) plane of rutile TiO 2 ) plane, (002) plane and (301) correspond to each other, indicating that the crystal shape of the TiO2 grains generated is good. The average grain size D ( 111 ) = 7.6nm is calculated according to the X-ray diffraction broadening analysis method. It can be seen from the electron microscope photos that N-TiO 2 prepared from TiCl 4 has a particle size of 7×16 nm and is long columnar. The extension direction is consistent with the length direction of the columnar crystal grains. parallel to the crystal axis C.
附图4中399.5eV处的N1s特征峰，说明N元素进入了TiO2晶格，形成了N-Ti键，产生了氮掺杂纳米TiO2晶体。 The N1s characteristic peak at 399.5eV in Figure 4 indicates that N element has entered the TiO 2 lattice, forming N-Ti bonds, and producing nitrogen-doped nano TiO 2 crystals.
如附图5所示，溶液酸碱度对TiO2晶体的相变具有决定性影响，金红石产生于强酸环境, 此时Ti4+主要以[TiO(H2O)5]2+单聚体存在,单聚体通过"羟基"作用，脱去2个水分子，以赤平面内的棱相连,形成直链的多聚体，并由此形成金红石的晶核。弱酸和中性条件下, Ti4 +主要以[Ti(OH)2•(H2O)4]2+单聚体存在，他们可以通过“羟基”作用，脱去2个水分子, 以不在赤平面的斜棱相连，形成锐钛矿的晶核，进而形成锐钛矿型晶体。 As shown in Figure 5, the pH of the solution has a decisive influence on the phase transition of TiO 2 crystals. Rutile is produced in a strong acid environment. At this time, Ti 4+ mainly exists as [TiO(H 2 O) 5 ] 2+ monomers. The polymer removes two water molecules through the action of "hydroxyl", and connects with the edges in the red plane to form a straight-chain polymer, and thus form the crystal nucleus of rutile. Under weak acid and neutral conditions, Ti 4 + mainly exists as [Ti(OH) 2 •(H 2 O) 4 ] 2+ monomers, and they can remove 2 water molecules through the action of "hydroxyl", so that they are not in the The oblique edges of the red plane are connected to form the crystal nucleus of anatase, and then form anatase crystal.
由附图6可知，Degussa P-25(未掺杂纳米TiO2)吸收边在400nm以下，光响应范围仅限于紫外区域。而本发明制备的氮掺杂TiO2样品A和样品B吸收光谱发生明显红移，在可见光区有较强的吸收，光吸收范围一直拓展到近500nm。这种吸收光谱的红移来自进入TiO2品格中的氮元素。在超声反应过程中，氮元素取代TiO2晶格中的氧元素进入TiO2晶胞，使TiO2的价带和导带之间产生中间能级，光生电子和空穴可以经过这些中间能级发生跃迁，因此所需的激发能量降低至可见光范围，从而使氮掺杂TiO2吸收光谱发生明显的红移。这种光吸收性能的改变使其具有良好的可见光催化活性。 It can be seen from Figure 6 that the absorption edge of Degussa P-25 (undoped nano-TiO 2 ) is below 400 nm, and the photoresponse range is limited to the ultraviolet region. However, the nitrogen-doped TiO 2 sample A and sample B prepared by the present invention have obvious red-shifted absorption spectra, strong absorption in the visible light region, and the light absorption range has been extended to nearly 500nm. This red shift of the absorption spectrum comes from the nitrogen element entering the TiO2 lattice. During the ultrasonic reaction, the nitrogen element replaces the oxygen element in the TiO2 lattice to enter the TiO2 unit cell, so that an intermediate energy level is generated between the valence band and the conduction band of TiO2 , and photogenerated electrons and holes can pass through these intermediate energy levels transition occurs, and thus the required excitation energy is reduced to the visible range, resulting in an obvious red-shift in the absorption spectrum of nitrogen-doped TiO2 . This light absorption property change makes it have good visible light catalytic activity.
由附图7可以看出，N掺杂后TiO2 的可见光催化活性显著提高, 在1000W氙灯照射下，一样品A、样品B位光催化剂，甲基紫染料60min 内的降解率分别为81%和99%，而未掺杂N 的P-25对甲基紫的降解率只有42%。样品A的催化效果之所以明显优于样品B，是由于锐钛矿型晶体催化性能优于金红石型晶体之故。 It can be seen from Figure 7 that the visible light catalytic activity of TiO2 after N doping is significantly improved. Under the irradiation of a 1000W xenon lamp, the degradation rates of the photocatalyst and methyl violet dye of sample A and sample B within 60 minutes are respectively 81% and 99%, while the degradation rate of methyl violet for P-25 without N doping was only 42%. The reason why the catalytic effect of sample A is obviously better than that of sample B is that the catalytic performance of anatase crystal is better than that of rutile crystal.
实施例1： Example 1:
将5.0gTi(SO4)2和0.2g(NH4)2SO4溶于50ml去离子水中，以氨水调节pH值至6.0，然后将超声波发生器的钛合金探头浸入其中进行超声处理，超声波频率为20KHz，强度为25 W/cm2，控制反应温度80℃，反应时间为3h，然后加入0.2g聚吡咯烷酮分散剂，磁力搅拌1h后，离心分离，所得沉淀分别用去离子水洗涤二次，无水乙醇洗涤一次，最后真空干燥，得到N-TiO2，大小为7×16nm，晶型为锐钛矿型。 Dissolve 5.0gTi(SO 4 ) 2 and 0.2g(NH 4 ) 2 SO 4 in 50ml deionized water, adjust the pH value to 6.0 with ammonia water, then immerse the titanium alloy probe of the ultrasonic generator in it for ultrasonic treatment, the ultrasonic frequency The temperature is 20KHz, the intensity is 25 W/cm 2 , the reaction temperature is controlled at 80°C, the reaction time is 3h, then 0.2g polypyrrolidone dispersant is added, after magnetic stirring for 1h, centrifuged, the obtained precipitates are washed twice with deionized water respectively, Washed once with absolute ethanol, and finally vacuum-dried to obtain N-TiO 2 with a size of 7×16 nm and anatase crystal form.
实施例2： Example 2:
将6.0gTi(SO4)2溶于40ml去离子水中，将20ml2%NH3·H2O滴入Ti(SO4)2溶液中，然后将超声波发生器的钛合金探头浸入其中进行超声处理，超声波频率为380KHz，强度为40W/cm2，控制反应液温度70℃，反应时间为3h，然后加入0.1g聚乙烯醇分散剂，磁力搅拌1h后，离心分离，所得沉淀分别用去离子水洗涤二次，无水乙醇洗涤一次，最后真空干燥。所得产品为柱状，大小为6×15nm(W/L)，晶型为锐钛矿型。 Dissolve 6.0g Ti(SO 4 ) 2 in 40ml deionized water, drop 20ml 2%NH 3 ·H 2 O into the Ti(SO 4 ) 2 solution, then immerse the titanium alloy probe of the ultrasonic generator in it for ultrasonic treatment, The ultrasonic frequency is 380KHz, the intensity is 40W/cm 2 , the temperature of the reaction solution is controlled at 70°C, and the reaction time is 3h, then 0.1g of polyvinyl alcohol dispersant is added, after magnetic stirring for 1h, centrifuged, and the obtained precipitates are washed with deionized water respectively twice, washed once with absolute ethanol, and finally dried under vacuum. The obtained product is columnar, the size is 6×15nm (W/L), and the crystal form is anatase.
实施例3： Example 3:
将5.0 g硫酸钛和0.2gNH4Cl溶于50ml1M盐酸水溶液中，然后将超声波发生器的钛合金探头浸入其中进行超声处理，超声波频率为100KHz，强度为35W/cm2，控制反应温度60℃，反应时间为4h，然后加入0.1g聚乙二醇（PEG）和0.1g聚吡咯烷酮的混合分散剂，磁力搅拌1h后，离心分离，所得沉淀分别用去离子水洗涤二次，无水乙醇洗涤一次，最后真空干燥，所得产品为长柱状，大小为5×20nm(W/L)，晶型为金红石型。 Dissolve 5.0 g of titanium sulfate and 0.2 g of NH 4 Cl in 50 ml of 1M hydrochloric acid aqueous solution, and then immerse the titanium alloy probe of the ultrasonic generator in it for ultrasonic treatment. The ultrasonic frequency is 100KHz, the intensity is 35W/cm 2 , and the reaction temperature is controlled at 60°C. The reaction time is 4 hours, then add a mixed dispersant of 0.1g polyethylene glycol (PEG) and 0.1g polypyrrolidone, magnetically stir for 1 hour, then centrifuge, and the obtained precipitates are washed twice with deionized water and once with absolute ethanol , and finally vacuum-dried, the obtained product is long columnar, the size is 5×20nm (W/L), and the crystal form is rutile.
实施例4： Example 4:
在冰水浴中，将4mlTiCl4逐滴加入到50ml含有0.2gNH3的去离子水中，然后将超声波发生器的钛合金探头浸入其中进行超声处理，超声波频率为25KHz，强度为80W/cm2，控制反应液温度90℃，反应时间为3h，然后加入0.1g聚乙二醇（PEG）分散剂，磁力搅拌1h后，离心分离，所得沉淀分别用去离子水洗涤二次，无水乙醇洗涤一次，最后真空干燥。所得为金红石型，呈羽状聚集体，为粒度为7×16nm。 In an ice-water bath, add 4ml of TiCl4 dropwise to 50ml of deionized water containing 0.2gNH3 , and then immerse the titanium alloy probe of the ultrasonic generator in it for ultrasonic treatment. The ultrasonic frequency is 25KHz and the intensity is 80W/ cm2 . The temperature of the reaction solution was 90°C, and the reaction time was 3 hours. Then, 0.1 g of polyethylene glycol (PEG) dispersant was added, stirred by magnetic force for 1 hour, and then centrifuged. The obtained precipitates were washed twice with deionized water and once with absolute ethanol. Finally vacuum dry. The resultant was rutile type, in the form of plume aggregates, with a particle size of 7×16 nm.
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