CN101880067B

CN101880067B - A kind of preparation method of rod-shaped NiTiO3 nanocrystal

Info

Publication number: CN101880067B
Application number: CN2010102277951A
Authority: CN
Inventors: 黄剑锋; 郝品; 曹丽云; 吴建鹏
Original assignee: Shaanxi University of Science and Technology
Current assignee: Shaanxi University of Science and Technology
Priority date: 2010-07-15
Filing date: 2010-07-15
Publication date: 2011-12-28
Anticipated expiration: 2030-07-15
Also published as: CN101880067A

Abstract

一种棒状NiTiO₃纳米晶的制备方法，将六水硝酸镍加入乙醇中所得溶液记为A；向A溶液中加入钛酸四丁酯、草酸和水所得溶液记为B；将溶液B放在紫外光一微波仪中照射一定时间后，溶液有沉淀产生。将过滤出的沉淀经丙酮清洗后放入干燥箱中干燥，即得到最终产物一不含任何杂质的棒状NiTiO₃纳米晶。本发明制得的NiTiO₃纳米晶晶粒尺寸较小，分散良好，粒子分布均匀，团聚现象较少，并且不含任何杂质；制备NiTiO₃纳米晶反应周期短，重复性好，制备简单，操作方便，原料易得，制备成本较低。A kind of preparation method of rod-shaped NiTiO ₃ nanocrystals, nickel nitrate hexahydrate is added in the gained solution in ethanol and marked as A; Add tetrabutyl titanate, oxalic acid and water gained solution to A solution and be marked as B; Solution B is placed in After a certain period of time in the ultraviolet light-microwave instrument, the solution has precipitation. The filtered precipitate was washed with acetone and then dried in a drying oven to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without any impurities. The NiTiO ₃ nanocrystals prepared by the present invention have small grain size, good dispersion, uniform particle distribution, less agglomeration, and no impurities; the preparation of NiTiO ₃ nanocrystals has a short reaction cycle, good repeatability, simple preparation, and easy operation. The method is convenient, the raw materials are easy to obtain, and the preparation cost is low.

Description

一种棒状NiTiO<sub>3</sub>纳米晶的制备方法A preparation method of rod-like NiTiO<sub>3</sub> nanocrystals

技术领域 technical field

本发明涉及一种NiTiO₃纳米晶的制备方法，具体涉及一种棒状NiTiO₃纳米晶的紫外光-微波相结合的制备方法。The invention relates to a method for preparing _NiTiO3 nanocrystals, in particular to a method for preparing rod-shaped _NiTiO3 nanocrystals combined with ultraviolet light and microwave.

背景技术 Background technique

NiTiO₃属于钛铁矿结构的三角晶系。在半导体整流，烃类脱氢加硫催化等工业中有着广泛的应用。另外，NiTiO₃还可以在没有液体润滑剂的条件下用作高温降低摩擦和损耗的包覆材料。由于纳米材料具有尺寸小，比表面大，以及表面效应和量子尺寸效应等特性，预期纳米NiTiO₃的性能会明显地优于常规NiTiO₃材料，因而引起人们极大的研究兴趣。NiTiO ₃ belongs to the trigonal crystal system of the ilmenite structure. It is widely used in industries such as semiconductor rectification and hydrocarbon dehydrogenation and sulfuration catalysis. In addition, NiTiO ₃ can also be used as a cladding material to reduce friction and loss at high temperatures without liquid lubricants. Due to the characteristics of small size, large specific surface, surface effect and quantum size effect of nanomaterials, it is expected that the performance of nano-NiTiO ₃ will be significantly better than that of conventional NiTiO ₃ materials, which has aroused great research interest.

目前制备NiTiO₃纳米粉体的报道较少，主要的制备方法有固相烧结法(F.Tietz，F.J.Dias，B.Dubiel，et al.Materials Science and Engineering.1999，68：35-41)、化学沉淀法(A.Vadivel Murugan，Violet Samuel，S.C.Navale，et al.Materials Letters，2006，60：1791-1792)(彭子飞，汪国忠，张立德.合成化学，1996，(2)：99-101)(周岚，刘晓峻，张淑仪，等.南京大学学报，1997，33(1)：32-36)等，其中固相烧结法通常需要在至少1000℃的高温下才能制得结晶完全的NiTiO₃粉体，而采用其他方法低温下制备的粉体一般都含有杂质，在相对较低的温度下制备出纯净的NiTiO₃粉体的报道较少。因此，如何采用合理的工艺路线，制备出高纯度纳米级粒度的产品，已成为研究领域里的重要课题。At present, there are few reports on the preparation of NiTiO ₃ nanopowders. The main preparation methods are solid-phase sintering (F.Tietz, FJDias, B.Dubiel, et al.Materials Science and Engineering.1999, 68:35-41), chemical Precipitation method (A. Vadivel Murugan, Violet Samuel, SCNavale, et al. Materials Letters, 2006, 60: 1791-1792) (Peng Zifei, Wang Guozhong, Zhang Lide. Synthetic Chemistry, 1996, (2): 99-101) (Zhou Lan, Liu Xiaojun, Zhang Shuyi, etc. Journal of Nanjing University, 1997, 33(1): 32-36), etc., wherein the solid-state sintering method usually needs to be at least 1000°C at a high temperature to obtain a fully crystallized NiTiO ₃ powder, However, powders prepared by other methods at low temperatures generally contain impurities, and there are few reports on the preparation of pure NiTiO ₃ powders at relatively low temperatures. Therefore, how to adopt a reasonable process route to prepare high-purity nano-sized products has become an important topic in the research field.

发明内容Contents of the invention

本发明的目的在于克服上述现有技术的缺点，提供了一种不仅制备成本低，操作简单、反应周期短，而且能够在较低温度下制备出不含杂质的棒状NiTiO₃纳米晶的制备方法。The purpose of the present invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of not only preparation cost is low, simple operation, short reaction cycle, and can prepare the preparation method of impurity-free rod-shaped NiTiO ₃ nanocrystal at lower temperature .

为达到上述目的，本发明采用技术方案是：In order to achieve the above object, the technical scheme adopted by the present invention is:

步骤一：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为0.5mol/L～1mol/L的透明溶液记为A；Step 1: Add analytically pure nickel nitrate hexahydrate into absolute ethanol, and keep stirring to prepare a transparent solution with a Ni2 ⁺ concentration of 0.5mol/L to 1mol/L, which is designated as A;

步骤二：向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为(0.5～2)∶1，最后再加入无水乙醇体积4～8的水，搅拌均匀后静置形成溶液记为B；Step 2: Add analytically pure tetrabutyl titanate to solution A so that the molar ratio of Ni ²⁺ to Ti ⁴⁺ is 1:1, and keep stirring to obtain a mixed solution, and then add oxalic acid to the mixed solution to make The molar ratio of oxalic acid to all cations is (0.5-2): 1, and finally add water with a volume of 4-8 in absolute ethanol, stir evenly and let stand to form a solution, which is recorded as B;

步骤三：将上述溶液B放在紫外光-微波仪中照射12h～72h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在80℃～120℃下干燥8h～12h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Step 3: Put the above solution B in a UV-microwave instrument for 12h to 72h, and the solution has precipitates, filter the precipitates and wash them with acetone, put them in a drying oven, and dry them at 80°C to 120°C for 8h to 12h. That is, the final product-rod-shaped NiTiO ₃ nanocrystals without impurities is obtained.

本发明制得的棒状NiTiO₃纳米晶晶粒尺寸较小，分散良好，粒子分布均匀，团聚现象较少，并且不含任何杂质；制备NiTiO₃纳米晶反应周期短，温度低，重复性好，制备简单，操作方便，原料易得，制备成本较低。The rod-shaped _NiTiO3 nanocrystals prepared by the present invention have small grain size, good dispersion, uniform particle distribution, less agglomeration, and no impurities; the reaction period for preparing _NiTiO3 nanocrystals is short, the temperature is low, and the repeatability is good. The preparation is simple, the operation is convenient, the raw materials are easily obtained, and the preparation cost is low.

附图说明 Description of drawings

图1为本发明制备的NiTiO₃纳米晶的X-射线衍射(XRD)图谱；Fig. 1 is the _NiTiO prepared by the present invention The X-ray diffraction (XRD) collection of nanocrystals;

图2为本发明制备的棒状NiTiO₃纳米晶的扫描电镜(SEM)照片。Fig. 2 is a scanning electron microscope (SEM) photo of rod-shaped NiTiO ₃ nanocrystals prepared in the present invention.

具体实施方式 Detailed ways

下面结合附图对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings.

实施例1：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为0.5mol/L的透明溶液记为A；向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为0.5∶1，最后再加入无水乙醇体积4倍的水，搅拌均匀后静置形成溶液记为B；将上述溶液B放在紫外光-微波仪中照射25h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在80℃下干燥12h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Embodiment 1: Add analytically pure nickel nitrate hexahydrate in dehydrated alcohol, and keep stirring, and the transparent solution that is mixed with Ni ²⁺ concentration and is 0.5mol/L is denoted as A; Add analytically pure titanic acid in A solution Tetrabutyl ester, make the molar ratio of Ni ²⁺ and Ti ⁴⁺ be 1: 1, and constantly stir to obtain the mixed solution, then add oxalic acid in the mixed solution, make the molar ratio of oxalic acid and all cations be 0.5: 1, finally Then add water with 4 times the volume of absolute ethanol, stir evenly and let it stand to form a solution, which is recorded as B; after the above solution B is irradiated in a UV-microwave instrument for 25 hours, the solution has precipitation, filter the precipitation and wash it with acetone into a drying oven and dried at 80° C. for 12 hours to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without impurities.

将所得的NiTiO₃纳米晶用日本理学D/max2000PC X-射线衍射仪分析样品，发现产物为JCPDS编号为33-0960的NiTiO₃(图1)。将该样品用日本JEOL公司生产的JSM-6390A型扫描电子显微镜(图2)进行观察，从照片可以看出所制备的NiTiO₃纳米晶为棒状颗粒。The obtained NiTiO ₃ nanocrystal sample was analyzed by a Japanese Rigaku D/max2000PC X-ray diffractometer, and it was found that the product was NiTiO ₃ with JCPDS number 33-0960 ( FIG. 1 ). The sample was observed with a JSM-6390A scanning electron microscope (FIG. 2) produced by JEOL Corporation of Japan. It can be seen from the photo that the prepared NiTiO ₃ nanocrystals are rod-shaped particles.

实施例2：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为0.6mol/L的透明溶液记为A；向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为1∶1，最后再加入无水乙醇体积4倍的水，搅拌均匀后静置形成溶液记为B；将上述溶液B放在紫外光-微波仪中照射12h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在100℃下干燥10h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Embodiment 2: Add analytically pure nickel nitrate hexahydrate in dehydrated alcohol, and keep stirring, be mixed with the transparent solution that Ni ²⁺ concentration is 0.6mol/L and be denoted as A; Add analytically pure titanic acid in A solution Tetrabutyl ester, make the molar ratio of Ni ²⁺ and Ti ⁴⁺ be 1: 1, and constantly stir to obtain the mixed solution, then add oxalic acid in the mixed solution, make the molar ratio of oxalic acid and all cations be 1: 1, finally Then add water 4 times the volume of absolute ethanol, stir evenly and let it stand to form a solution, which is recorded as B; after the above solution B is irradiated in a UV-microwave instrument for 12 hours, the solution has precipitation, filter the precipitation and wash it with acetone into a drying oven and dried at 100° C. for 10 h to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without impurities.

实施例3：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为0.8mol/L的透明溶液记为A；向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为1.5∶1，最后再加入无水乙醇体积6倍的水，搅拌均匀后静置形成溶液记为B；将上述溶液B放在紫外光-微波仪中照射36h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在90℃下干燥11h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Embodiment 3: Add analytically pure nickel nitrate hexahydrate in dehydrated alcohol, and constantly stir, be mixed with the transparent solution that Ni ²⁺ concentration is 0.8mol/L and be denoted as A; Add analytically pure titanic acid in A solution Tetrabutyl ester, make the molar ratio of Ni ²⁺ and Ti ⁴⁺ be 1: 1, and constantly stir to obtain the mixed solution, then add oxalic acid in the mixed solution, make the molar ratio of oxalic acid and all cations be 1.5: 1, finally Then add water with 6 times the volume of absolute ethanol, stir evenly and let it stand to form a solution, which is recorded as B; after the above solution B is irradiated in a UV-microwave instrument for 36 hours, the solution has precipitation, filter the precipitation and wash it with acetone into a drying oven and dried at 90° C. for 11 hours to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without impurities.

实施例4：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为1mol/L的透明溶液记为A；向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为0.9∶1，最后再加入无水乙醇体积5倍的水，搅拌均匀后静置形成溶液记为B；将上述溶液B放在紫外光-微波仪中照射72h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在120℃下干燥8h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Embodiment 4: Add analytically pure nickel nitrate hexahydrate in dehydrated alcohol, and constantly stir, be mixed with the transparent solution that Ni ²⁺ concentration is 1mol/L and be marked as A; Add analytically pure tetratitanate in A solution Butyl ester, so that the molar ratio of Ni ²⁺ to Ti ⁴⁺ is 1:1, and keep stirring to obtain a mixed solution, then add oxalic acid to the mixed solution, so that the molar ratio of oxalic acid to all cations is 0.9:1, and finally Add water 5 times the volume of absolute ethanol, stir evenly and let it stand to form a solution, which is recorded as B; after irradiating the above solution B in a UV-microwave instrument for 72 hours, there is precipitation in the solution, filter the precipitate and wash it with acetone, then put it into In a drying oven, dry at 120° C. for 8 hours to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without impurities.

实施例5：将分析纯的六水合硝酸镍加入无水乙醇中，并不断搅拌，配制成Ni²⁺浓度为0.7mol/L的透明溶液记为A；向A溶液中加入分析纯的钛酸四丁酯，使得Ni²⁺与Ti⁴⁺的摩尔比为1∶1，并不断搅拌得混合溶液，然后再向混合溶液中加入草酸，使草酸与所有阳离子的摩尔比为2∶1，最后再加入无水乙醇体积8倍的水，搅拌均匀后静置形成溶液记为B；将上述溶液B放在紫外光-微波仪中照射60h后，溶液有沉淀产生，过滤沉淀并用丙酮清洗后放入干燥箱中，在110℃下干燥9h，即得到最终产物-不含杂质的棒状NiTiO₃纳米晶。Example 5: Add analytically pure nickel nitrate hexahydrate in absolute ethanol, and keep stirring, and prepare a transparent solution with a Ni2 ⁺ concentration of 0.7mol/L, which is denoted as A; add analytically pure titanic acid to the A solution Tetrabutyl ester, make the molar ratio of Ni ²⁺ and Ti ⁴⁺ be 1: 1, and constantly stir to obtain the mixed solution, then add oxalic acid in the mixed solution, make the molar ratio of oxalic acid and all cations be 2: 1, finally Then add water with 8 times the volume of absolute ethanol, stir evenly and let it stand to form a solution, which is recorded as B; after the above solution B is irradiated in a UV-microwave instrument for 60 hours, the solution has precipitation, filter the precipitation and wash it with acetone into a drying oven and dried at 110° C. for 9 hours to obtain the final product—rod-shaped NiTiO ₃ nanocrystals without impurities.

Claims

1. bar-shaped NiTiO ₃Preparation of nano crystal is characterized in that:

Step 1: analytically pure Nickelous nitrate hexahydrate is added in the dehydrated alcohol, and constantly stir, be mixed with Ni ²⁺Concentration is that the clear solution of 0.5mol/L～1mol/L is designated as A;

Step 2: in A solution, add analytically pure tetrabutyl titanate, make Ni ²⁺With Ti ⁴⁺Mol ratio be 1: 1, and constantly stir mixing solutions, and then in mixing solutions, add oxalic acid, make oxalic acid and all cationic mol ratios be (0.5～2): 1, the last water that adds 4～8 times of dehydrated alcohol volumes again leaves standstill formation solution and is designated as B after stirring;

Step 3: with above-mentioned solution B be placed on shine 12h～72h in UV-light-microwave instrument after, solution has precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 80 ℃～120 ℃ dry 8h～12h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.