CN102502887B - Method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry - Google Patents

Method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry Download PDF

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CN102502887B
CN102502887B CN201110375676.5A CN201110375676A CN102502887B CN 102502887 B CN102502887 B CN 102502887B CN 201110375676 A CN201110375676 A CN 201110375676A CN 102502887 B CN102502887 B CN 102502887B
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ultrasonic
deionized water
reaction
cobalt sulfide
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CN102502887A (en
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曹丽云
李碧
李意峰
黄剑锋
吴建鹏
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QIDONG SHENGHAN MEDICAL TECHNOLOGY Co.,Ltd.
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Shaanxi University of Science and Technology
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Abstract

The invention provides a method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry. The method comprises the steps of: adding cobalt nitrate hexahydrate to deionized water to obtain a solution A; adding EDTA (Ethylene Diamine Tetraacetic Acid) to the solution A and stirring to obtain a solution B; adding an H2S solution to the solution B to obtain a solution C; adding (NH4)2S to deionized water to obtain a solution D; oscillating the solution C in an ultrasonic cleaner, and simultaneously dropwise adding the solution D; adding the solution obtained after an ultrasonic reaction to a hydrothermal kettle for sealed reacting; after the reaction is finished, taking out the hydrothermal kettle, cooling to room temperature, separating the product, washing with deionized water and absolute ethanol respectively and drying to obtain black cobalt sulfide nanocrystals. According to the invention, prepared cobalt sulfide nanocrystals are controllable in appearance and are of a nanorod structure with a diameter about 10 nm; and the preparing process is simple, the operation is convenient, the temperature is low, the energy consumption is low and the preparing cost is lower.

Description

A kind of method of preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry
Technical field
The invention belongs to sulfide nano-material technical field, be specifically related to a kind of method of preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry.
Background technology
Transient metal sulfide nano material as a kind of nontoxic, environmental protection, cobaltous sulfide, except having special 3d valence electron shell structure, also has the due non-linear nature of nano material, fluorescent characteristic, quantum size effect and other important physical chemical property.Due to such characteristic, make nano Co S material have more superior physics, chemistry, optics, pigment performance and purposes more widely.Find after deliberation, the energy gap of cobalt sulfide nano particle is approximately 3.91eV[S.P.Tandon, J.P.Gupta.Measurement of Forbidden Energy Gap of Semiconductors by Diffuse Reflectance Technique.Physica Status Solidi (b), 1970, 381 (1): 363-367], cobaltous sulfide nano material will be in high energy density cells, these aspects such as solar energy electric material [M.S.Sadjadi that is widely used, A.Pourahmad, Sh.Sohrabnezhad, K.Zare.Formation of NiS and CoS semiconductor nanoparticles inside mordenite-type zeolite.Materials Letters, 2007, 61 (14-15): 2923-2926].
Sonochemical method is to utilize acoustic cavitation can accelerate or control chemical reaction, improves reaction yield and causes new chemical reaction, and be a kind of novel method of preparing nano material occurring in recent years.Utilize sonochemical method to prepare cobalt sulfide nanocrystalline, mainly due to hyperacoustic cavatition, by be about micron-sized region at yardstick, produce the high temperature and high pressure [M.Behboudnia of moment, M.H.Majlesara, B.Khanbabaee.Preparation of ZnS nanorods by ultrasonic waves[J] .Materials Science and Engineering B, 2005, 122 (2): 160-163], in addition, ul-trasonic irradiation is when solution, mechanics effect can pass through stirring action, promote interionic to interact, thereby promote that chemical reaction fully carries out, the strong shockwave that acoustic cavitation effect produces has suppressed the formation of large micelle, calorifics effect can promote CoS cohesion, chemical effect can accelerating oxidation reduction reaction, thus to CoS nanocrystalline be formed with good promoter action.
Hydrothermal method be also development in recent years than faster more a kind of method, research system is generally in imperfect nonequilibrium situations, the high-temperature high-pressure state in thermal and hydric environment is accelerated important interionic reaction, has so greatly saved reaction and has carried out the needed time
Summary of the invention
The object of the invention is to propose a kind of method of preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry.This method is simple to operate, the cobalt sulfide nanocrystalline well-crystallized of gained, and particle size dispersion is better.
For achieving the above object, the technical solution used in the present invention is:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 1.16g-5.80g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 0.58g-2.90g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 0.5-4.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.14mL-0.68mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 10-60min, ultrasonic power 200-500W, ultrasonic temperature 20-80 ℃;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 50%-80%, and sealing afterwards, at 170-210 ℃ of reaction 6-24h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
Due to the High Temperature High Pressure of sonochemistry power generation in reaction process, strong shockwave and jet at a high speed, having hindered particle becomes large micelle, and the criticality of thermal and hydric environment impels the crystallinity of crystal grain better, makes the product crystallinity of gained fine.Cobalt sulfide nanocrystalline pattern prepared by this method is controlled, is nano bar-shape structure, and diameter is in 10nm left and right; And preparation technology is simple, easy to operate, temperature is low, and energy consumption is little, and preparation cost is lower.
Accompanying drawing explanation
Fig. 1 is the transmission electron micrograph of the cobalt sulfide nanocrystalline of the embodiment of the present invention 1 preparation.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 2.32g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 1.16g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 2.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.28mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 30min, ultrasonic power 300W, 80 ℃ of ultrasonic temperature;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 8%, and sealing afterwards, at 190 ℃ of reaction 24h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
The cobalt sulfide nanocrystalline of gained is observed with transmission electron microscope, can be found out that prepared sample is nano bar-shape structure, diameter is in 10nm left and right (Fig. 1).
Embodiment 2:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 1.16g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 0.58g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 0.5mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.14mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 60min, ultrasonic power 500W, ultrasonic temperature 50 C;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 80%, and sealing afterwards, at 180 ℃ of reaction 18h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
Embodiment 3:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 5.80g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 2.90g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 4.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.68mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 15min, ultrasonic power 200W, 40 ℃ of ultrasonic temperature;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 50%, and sealing afterwards, at 170 ℃ of reaction 20h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
Embodiment 4:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 3.25g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 2.30g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 1.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.55mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 20min, ultrasonic power 400W, 20 ℃ of ultrasonic temperature;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 60%, and sealing afterwards, at 200 ℃ of reaction 6h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
Embodiment 5:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 4.60g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 1.65g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 3.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.32mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 40min, ultrasonic power 500W, ultrasonic temperature 60 C;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 70%, and sealing afterwards, at 210 ℃ of reaction 6h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
Embodiment 6:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 5.00g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 0.80g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 0.8mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.22mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 50min, ultrasonic power 300W, ultrasonic temperature 70 C;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 60%, and sealing afterwards, at 200 ℃ of reaction 10h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.

Claims (1)

1. a method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry, is characterized in that:
1) get the analytical pure cobalt nitrate hexahydrate (Co (NO of 1.16g-5.80g 3) 26H 2o) be placed in Erlenmeyer flask, in Erlenmeyer flask, add deionized water, stir, be configured to the red clear solution A of 40mL;
2) getting 0.58g-2.90g ethylenediamine tetraacetic acid (EDTA) (EDTA) adds and in solution A, stirs to obtain solution B;
3) H that is 2% to the mass concentration that adds 0.5-4.0mL in solution B 2s solution, solution C stirs to obtain;
4) get (NH of 0.14mL-0.68mL 4) 2s is placed in small beaker, and adds deionized water to be configured to the solution D of 40mL;
5) solution C is put into ultrasonic cleaner and shake, dropwise add solution D simultaneously, set ultrasonic time 10-60min, ultrasonic power 200-500W, ultrasonic temperature 20-80 ℃;
6) solution after ultrasonic reaction is added in water heating kettle, controlling its packing ratio is 50%-80%, and sealing afterwards, at 170-210 ℃ of reaction 6-24h;
7) after reaction finishes, water heating kettle is taken out and is cooled to room temperature, product is carried out after separation, the product after separation cleans with deionized water and dehydrated alcohol respectively, and the baking oven of putting into 80 ℃ is dried, and obtains the cobalt sulfide nanocrystalline of black.
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Citations (2)

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CN101746837A (en) * 2009-12-24 2010-06-23 东北师范大学 Preparation method of cobalt sulfide micro tube with hiberarchy structure
CN101786671A (en) * 2009-10-30 2010-07-28 陕西科技大学 Method for preparing bar-shaped cobalt sulfide nanocrystalline

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101786671A (en) * 2009-10-30 2010-07-28 陕西科技大学 Method for preparing bar-shaped cobalt sulfide nanocrystalline
CN101746837A (en) * 2009-12-24 2010-06-23 东北师范大学 Preparation method of cobalt sulfide micro tube with hiberarchy structure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
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Wenjun Dong et al..Hydrothermal synthesis and structure evolution of hierarchical cobalt sulfide nanostructures.《Dalton Trans》.2010,第40卷243-248.

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