CN101880067B - Preparation method of bar-shaped NiTiO3 nano-crystalline - Google Patents

Abstract

The invention relates to a preparation method of bar-shaped NiTiO3 nano-crystalline, which comprises the following steps that: nickel nitrate hexahydrate is added into ethanol to obtain solution A; tetrabutyl titanate, oxalic acid and water are added into solution A to obtain solution B; after the solution B is arranged into a ultraviolet microwave instrument to be radiated for a given period of time, sediment is produced in the solution. The filtered sediment is arranged inside a drying box to be dried after being washed by acetone to obtain the final product - bar-shaped NiTiO3 nano-crystalline without any foreign matters. The prepared NiTiO3 nano-crystalline particles have small size, good dispersion, uniform distribution of particles, less agglomeration phenomenon and is free from containing any foreign matters; the prepared NiTiO3 nano-crystalline has short reaction period, good repeatability, simple preparation, convenient operation, easy obtaining of raw material and low preparation cost.

Description

A kind of bar-shaped NiTiO＜sub〉3＜/sub〉preparation of nano crystal

Technical field

The present invention relates to a kind of NiTiO ₃Preparation of nano crystal is specifically related to a kind of bar-shaped NiTiO ₃The preparation method that nanocrystalline UV-light-microwave combines.

Background technology

NiTiO ₃The trigonal system that belongs to ilmenite structure.At semiconductor rectifier, dehydrogenation of hydrocarbons adds in the industry such as sulfur catalysis and has a wide range of applications.In addition, NiTiO ₃Can also be at the coating material that does not have to reduce as high temperature under the condition of liquid lubricant friction and loss.Because it is little that nano material has size, specific surface is big, and characteristics such as surface effects and quantum size effect, expection nanometer NiTiO ₃Performance can be better than conventional NiTiO significantly ₃Material, thereby cause that people study interest greatly.

Prepare NiTiO at present ₃The report of nano-powder is less, main preparation method has solid sintering technology (F.Tietz, F.J.Dias, B.Dubiel, et al.Materials Science and Engineering.1999,68:35-41), chemical precipitation method (A.Vadivel Murugan, Violet Samuel, S.C.Navale, 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. Nanjing University's journal, 1997,33 (1): 32-36) etc., wherein solid sintering technology need just can make crystallization NiTiO completely usually under at least 1000 ℃ high temperature ₃Powder, and the powder that adopts additive method low temperature to prepare down generally all contains impurity, prepares purified NiTiO under relatively low temperature ₃The report of powder is less.Therefore, how to adopt rational operational path, prepare the product of high-purity nano level granularity, become the important topic in the research field.

Summary of the invention

The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide that a kind of not only preparation cost is low, simple to operate, reaction time is short, and can prepare bar-shaped NiTiO free from foreign meter at a lower temperature ₃Preparation of nano crystal.

For achieving the above object, the present invention adopts technical scheme to be:

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 dehydrated alcohol volume 4～8 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.

The bar-shaped NiTiO that the present invention makes ₃Nanocrystalline grain-size is less, good dispersion, and particle distribution is even, and agglomeration is less, and does not contain any impurity; Preparation NiTiO ₃Nanocrystalline reaction time is short, and temperature is low, good reproducibility, and preparation is simple, and easy to operate, raw material is easy to get, and preparation cost is lower.

Description of drawings

Fig. 1 is the NiTiO of the present invention's preparation ₃Nanocrystalline X-ray diffraction (XRD) collection of illustrative plates;

Fig. 2 is the bar-shaped NiTiO of the present invention's preparation ₃Nanocrystalline scanning electron microscope (SEM) photo.

Embodiment

Below in conjunction with accompanying drawing the present invention is described in further detail.

Embodiment 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 is designated as A; 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, making oxalic acid and all cationic mol ratios is 0.5: 1, adds the water of 4 times of dehydrated alcohol volumes at last again, leaves standstill after stirring to form solution and be designated as B; After above-mentioned solution B was placed in UV-light-microwave instrument irradiation 25h, solution had precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 80 ℃ of dry 12h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.

NiTiO with gained ₃The Japanese D/max2000PC x-ray diffractometer analytic sample of science of nanocrystalline usefulness finds that product is the NiTiO that JCPDS is numbered 33-0960 ₃(Fig. 1).This sample is observed with the JSM-6390A type scanning electronic microscope (Fig. 2) that Japanese JEOL company produces, from the prepared as can be seen NiTiO of photo ₃Nanocrystalline is rod-shpaed particle.

Embodiment 2: 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 0.6mol/L is designated as A; 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, making oxalic acid and all cationic mol ratios is 1: 1, adds the water of 4 times of dehydrated alcohol volumes at last again, leaves standstill after stirring to form solution and be designated as B; After above-mentioned solution B was placed in UV-light-microwave instrument irradiation 12h, solution had precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 100 ℃ of dry 10h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.

Embodiment 3: 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 0.8mol/L is designated as A; 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, making oxalic acid and all cationic mol ratios is 1.5: 1, adds the water of 6 times of dehydrated alcohol volumes at last again, leaves standstill after stirring to form solution and be designated as B; After above-mentioned solution B was placed in UV-light-microwave instrument irradiation 36h, solution had precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 90 ℃ of dry 11h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.

Embodiment 4: 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 1mol/L is designated as A; 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, making oxalic acid and all cationic mol ratios is 0.9: 1, adds the water of 5 times of dehydrated alcohol volumes at last again, leaves standstill after stirring to form solution and be designated as B; After above-mentioned solution B was placed in UV-light-microwave instrument irradiation 72h, solution had precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 120 ℃ of dry 8h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.

Embodiment 5: 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 0.7mol/L is designated as A; 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, making oxalic acid and all cationic mol ratios is 2: 1, adds the water of 8 times of dehydrated alcohol volumes at last again, leaves standstill after stirring to form solution and be designated as B; After above-mentioned solution B was placed in UV-light-microwave instrument irradiation 60h, solution had precipitation to produce, filtering-depositing and clean with acetone after put into loft drier, at 110 ℃ of dry 9h down, promptly obtain final product-bar-shaped NiTiO free from foreign meter ₃Nanocrystalline.

Claims (1)

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.

Images