CN109837534B - Method for preparing nano cobalt film on gas-liquid interface - Google Patents
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Abstract
The invention discloses a method for preparing a nano cobalt film on a gas-liquid interface, which is characterized in that hydrazine hydrate is taken as a gas phase precursor, cobalt acetate is taken as a raw material, ethylene diamine tetraacetic acid is taken as a complexing agent, sodium citrate is taken as an initiator, cobalt ions in a liquid phase are reduced to form nano crystal nuclei on the interface where gas enters a liquid phase, the cobalt ions on the gas-liquid interface are further reduced by volatilized hydrazine hydrate, the cobalt ions grow directionally on the crystal nuclei, a layer of nano cobalt film is formed on the gas-liquid interface by slow expansion, and the nano cobalt film is lowered to the bottom of a reaction solution under the action of gravity, and finally the nano cobalt film consisting of nano cobalt particles is obtained. The method has the advantages of simple operation, low requirement on equipment, good crystal form of the obtained nano cobalt film, high purity, uniform size of nano cobalt particles and high controllability.
Description
Technical Field
The invention belongs to the technical field of preparation of nano materials, and particularly relates to a method for preparing a nano cobalt film on a gas-liquid interface.
Background
Cobalt exists as an octahedrally coordinated divalent cobalt ion with 4 lateral and 2 axial coordination, each occupied by a water molecule. When other complexing agents are added, the water molecules migrate out of the octahedral position, first from the equatorial position and then from the axial position, confining the Co2+By the delivery of the solution to the surface. After the nano material is prepared, the nano cobalt has two structures of hexagonal close packing and face-centered cubic close packing, and the critical transition temperature is 417 ℃. After the nano material is generated, the nano cobalt has more excellent catalytic performance, shows a plurality of unique performances in the fields of ceramic catalysis, magnetic materials, hydrogen storage alloy electrodes, special coatings and the like, and has wide application prospects in the aspects of anticancer drug transportation, ultrahigh density information storage and the like. The nano cobalt can reduce the porosity of the hard alloy, and the cluster can be effectively inhibited. After the nano material is formed, the structure of the nano cobalt substance is changed, the specific surface area is increased, and the number of surface atoms and ions is increased.
The current preparation methods of the nano cobalt comprise the following steps: one is mechanical comminution, which is the milling of large masses into nanoscale materials. The nano material is prepared by the method at the earliest time, the prepared material has poor uniformity, and the appearance is damaged in the preparation process. The second is a reduction method, from bottom to top, which is an indirect reduction method that cobalt ions are reduced by a reducing agent to form nanoscale cobalt, such as cobalt oxide and cobalt oxalate, and cobalt oxalate is mainly used as a raw material, and is reduced by hydrogen in one step or calcined into an oxide and then reduced by hydrogen; the third is decomposition method, from top to bottom, that is, under closed condition, cobalt source is directly cracked into metal cobalt powder, for example, cobalt oxalate is directly heated and decomposed, and its uniformity can be effectively improved. Fourthly, gamma ray irradiation preparation method: adding a certain amount of free radical cleaning agent namely isopropyl ketone and dispersant namely polyvinyl alcohol into a cobalt solution with a certain concentration, then adjusting the pH value by using acetic acid and sodium hydroxide, then carrying out ultrasonic degassing on the prepared solution, introducing nitrogen to reduce the oxygen content in the solution, and then carrying out gamma-ray irradiation. Fifthly, an electrolytic method, namely a method for preparing the nano cobalt by discharging and depositing cobalt ions at a cathode by introducing direct current into an aqueous solution containing the cobalt ions. In addition, there are some preparation methods which are not commonly used, such as a high-pressure water spraying method, which is a method of preparing metallic cobalt powder mainly by using a high-pressure water flow and then crushing a molten metallic flow.
The biggest problem of the existing preparation method is that the prepared nano cobalt has poor uniformity and low controllability.
Disclosure of Invention
The invention aims to provide a method for preparing a nano cobalt film with good crystal form and high purity on a gas-liquid two-phase interface.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1: 1-1: 3, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 60-80 ℃, and adjusting the pH value of the mixed solution to 9-12 by using a sodium hydroxide aqueous solution to obtain a precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.001-0.01 mol/L, and the mass concentration of the sodium citrate is 0.01-0.05%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 40-80% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 12-24 hours to form a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
In the step 1, preferably, the cobalt acetate and disodium salt of ethylene diamine tetraacetic acid are added into deionized water according to the molar ratio of 1:1, and a sodium citrate aqueous solution is added, stirred and mixed uniformly at 80 ℃, and the pH value of the mixed solution is adjusted to 11-12 by a sodium hydroxide aqueous solution, so as to obtain a precursor solution.
In the step 1, the molar concentration of cobalt acetate in the precursor solution is preferably 0.005-0.01 mol/L, and the mass concentration of sodium citrate is preferably 0.03-0.04%.
In the step 2, the mass concentration of the hydrazine hydrate aqueous solution is preferably 60 to 80%.
The invention has the following beneficial effects:
the invention adopts a gas-liquid contact method, takes hydrazine hydrate as a reducing agent as a gas phase, and takes a complex aqueous solution formed by cobalt acetate, sodium citrate and EDTA as a liquid phase to prepare the nano cobalt film. The method is characterized in that sodium citrate is used as an initiator at an interface of a gas phase and a liquid phase, so that cobalt ions in the liquid phase are reduced to form a nano crystal nucleus, the cobalt ions on the interface of the gas phase and the liquid phase are further reduced by volatile hydrazine hydrate to grow directionally on the crystal nucleus, a layer of nano cobalt film is formed at the interface of the gas phase and the liquid phase by slow expansion, the nano cobalt film is settled to the bottom of a reaction solution under the action of gravity, and finally the cobalt film consisting of nano cobalt particles is obtained. The method has the advantages of simple operation, low requirement on equipment, good crystal form of the obtained nano cobalt film, high purity, uniform size of nano cobalt particles and high controllability.
Drawings
Fig. 1 is an X-ray diffraction pattern of the nano cobalt film prepared in example 1.
Fig. 2 is a graph of the ultraviolet absorption spectrum of the nano cobalt film prepared in example 1.
Fig. 3 is a scanning electron microscope image of the nano cobalt film prepared in example 1.
Fig. 4 is a back scattered electron diagram of the nano cobalt film prepared in example 1.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:1, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 80 ℃, and adjusting the pH value of the mixed solution to 11 by using a sodium hydroxide aqueous solution to obtain 100mL of precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.01mol/L, and the mass concentration of the sodium citrate is 0.04%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 80% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 16 hours, forming a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
The structure of the obtained product is characterized by adopting a D2 Phaser X-ray diffractometer, an ultraviolet absorption spectrometer and a JSM-6390 scanning electron microscope, and the result is shown in a figure 1-4. As can be seen from fig. 1, compared with the standard map, three characteristic diffraction peaks of the cobalt nanoparticles are respectively shown at positions 2 θ ═ 17 °, 30 ° and 42 °, and correspond to hcp crystal faces, the peak profile is sharp, and the peak profile is good, which indicates that the prepared cobalt nanoparticle film has a complete and high crystal structure. As can be seen from fig. 2, the nano cobalt exhibits an ultraviolet absorption curve at 280nm, and compared with the nano cobalt prepared by liquid phase reduction, the absorption peak is red-shifted, which indicates that the nano cobalt is assembled to form a nano film because of the increase of the size of the nano particles. As can be seen from fig. 3, the nanocobalt formed on the gas-liquid interface is nanospheres with diameters of about 50nm and is uniformly dispersed, and the whole nanospheres are distributed in a film shape; as shown in FIG. 4, the thickness of the film is uniform, and the nano cobalt dispersed on the surface is uniform and dense.
Comparative example 1
A precursor solution was prepared according to the method of step 1 of example 1, and then an aqueous solution of hydrazine hydrate with a mass concentration of 80% was directly introduced to the surface of the precursor solution without heating, and reacted in a fume hood for 16 hours. The test results show that no product is generated in the system. This is because hydrazine hydrate has a small gas amount when unheated and is difficult to diffuse into the liquid phase to cause a coherent reduction reaction, while hydrazine hydrate can form a gas flow smoothly and smoothly when slightly boiling, and a reduction reaction occurs when entering the liquid phase to obtain a product at the phase interface.
Example 2
1. Adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:1, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 80 ℃, and adjusting the pH value of the mixed solution to 11 by using a sodium hydroxide aqueous solution to obtain 100mL of precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.005mol/L, and the mass concentration of the sodium citrate is 0.03%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 80% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 12 hours, forming a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
Example 3
1. Adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:1, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 80 ℃, and adjusting the pH value of the mixed solution to 12 by using a sodium hydroxide aqueous solution to obtain 100mL of precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.001mol/L, and the mass concentration of the sodium citrate is 0.01%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 60% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 24 hours to form a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
Example 4
1. Adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:2, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 70 ℃, and adjusting the pH value of the mixed solution to 9 by using a sodium hydroxide aqueous solution to obtain 100mL of precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.01mol/L, and the mass concentration of the sodium citrate is 0.05%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 60% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 15 hours, forming a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
Example 5
1. Adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:3, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 90 ℃, and adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide aqueous solution to obtain 100mL of precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.01mol/L, and the mass concentration of the sodium citrate is 0.01%.
2. And (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 40% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 24 hours to form a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
Claims (5)
1. A method for preparing a nano cobalt film on a gas-liquid interface is characterized by comprising the following steps:
(1) adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1: 1-1: 3, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 60-80 ℃, and adjusting the pH value of the mixed solution to 9-12 by using a sodium hydroxide aqueous solution to obtain a precursor solution; the molar concentration of the cobalt acetate in the precursor solution is 0.001-0.01 mol/L, and the mass concentration of the sodium citrate is 0.01-0.05%;
(2) and (2) heating a hydrazine hydrate aqueous solution with the mass concentration of 40-80% to a slightly boiling state, introducing the hydrazine hydrate aqueous solution to the surface of the precursor solution in the step (1), reacting in a fume hood for 12-24 hours to form a nano cobalt film on a gas-liquid interface, and settling to the bottom of the reaction solution.
2. The method for preparing a nano cobalt film at a gas-liquid interface according to claim 1, wherein: in the step (1), adding cobalt acetate and disodium salt of ethylene diamine tetraacetic acid into deionized water according to a molar ratio of 1:1, adding a sodium citrate aqueous solution, stirring and mixing uniformly at 80 ℃, and adjusting the pH value of the mixed solution to 11-12 by using a sodium hydroxide aqueous solution to obtain a precursor solution.
3. The method for preparing a nano cobalt film at a gas-liquid interface according to claim 1 or 2, wherein: in the step (1), the molar concentration of the cobalt acetate in the precursor solution is 0.005-0.01 mol/L.
4. The method for preparing a nano cobalt film at a gas-liquid interface according to claim 1 or 2, wherein: in the step (1), the mass concentration of the sodium citrate in the precursor solution is 0.03-0.04%.
5. The method for preparing a nano cobalt film at a gas-liquid interface according to claim 1, wherein: in the step (2), the mass concentration of the hydrazine hydrate aqueous solution is 60-80%.
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| JP2004267878A (en) * | 2003-03-06 | 2004-09-30 | Japan Science & Technology Agency | Heat-resistant catalyst prepared by using quasi-crystal aluminum alloy as precursor and its manufacturing method |
| CN102921960A (en) * | 2012-11-19 | 2013-02-13 | 扬州大学 | Preparation method of magnetic cobalt nanometer material |
| CN104261489A (en) * | 2014-09-25 | 2015-01-07 | 安徽师范大学 | Hexagonal beta-cobalt hydroxide nanosheet and preparation method thereof as well as super capacitor and electrode thereof |
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