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.
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.