CN1263677C - Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly - Google Patents

Abstract

The invention is a method for preparing a composite material in which metals or metal oxides are evenly distributed on the surface of carbon nanotubes. The method is based on the precursor, that is, the organometallic compound and the carbon nanotubes treated with concentrated nitric acid, through long-term ultrasound or/and stirring and standing, so that the organometallic compound and the carboxyl group and/or carbonyl group and/or hydroxyl group on the surface of the carbon nanotube Coordination reaction, under the action of alcohol solvent, nucleates on the wall of carbon nanotubes, and crystallizes and grows into quantum dots with a size of several nanometers or crystals of tens of nanometers along the limited preferential crystal plane growth direction, and finally forms a distributed Uniform nano metal/carbon nanotube and nano metal oxide/carbon nanotube composites. The composite material has application prospects in sensors, nanoelectronic devices, ultra-high magnetic recording multimedia, lithium batteries and solar cells based on nanomaterials, and new catalysts.

Description

Preparation of composite materials with nanometer metals or metal oxides uniformly distributed on the surface of carbon nanotubes

technical field

The invention belongs to a method for preparing a composite material in which nanometer metal or metal oxide is evenly distributed on the surface of carbon nanotubes.

Background technique

Due to the unique structure, special mechanical and electrical properties of carbon nanotubes, they have attracted widespread attention since they were discovered in 1991. At present, carbon nanotubes can form various composite materials with other materials, such as polymer composites, ceramic composites, layered composites, nitrogen-doped composites and carbon/carbon nanotube composites, etc. (Ann.Rev.Mater.Res.2003, 33, 419), these composite materials have potential application prospects in reinforcing fibers, new catalysts and electronic nanodevices. There are two ways to prepare composite materials using carbon nanotubes as templates, one is to obtain chemical bonding by functionalizing the surface of carbon nanotubes (Acc.Chem.Res.2002, 35, 1096), and the other is to coat on A layer of film is formed on the surface of carbon nanotubes (Langmuir. 2003, 19, 7026). These two methods finally use high-temperature heating (calcination) to obtain the combination of inorganic compounds and carbon nanotubes. Although inorganic compound/carbon nanotube composites have been synthesized, there is still little skill in controlling the distribution of inorganic compounds on the surface of carbon nanotubes and the degree of formation of nanoparticles or even quantum dots.

Using alcohols as solvents to synthesize various metal or metal oxide nanomaterials is a widely used method (Angew.Chem.Int.Ed.2001, 40, 359), using this method TiO ₂ , CoO, ZnO, Cu ₂ O, Fe ₂ O ₃ , Nb ₂ O ₃ , Ta ₂ O ₃ , Al ₂ O ₃ and many other inorganic nanomaterials can be prepared. In this method, the solvent alcohol can not only play the role of hydrolysis, some solvents can also reduce the compound in an unstable valence state, and even reduce it to the metal element. The main advantage of this method is that the shape, size and uniformity of the precipitated particles can be controlled by changing the experimental conditions (J. Mater. Chem. 1996, 6, 1047; Science, 2000, 287, 1989).

Metal oxides and carbon nanotubes and metal and carbon nanotube composites. It has application prospects in sensors, nanoelectronic devices, ultra-high magnetic recording multimedia, lithium batteries and solar cells based on nanomaterials, and new catalysts.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a composite material in which nanometer metal or metal oxide is uniformly distributed on the surface of carbon nanotubes.

The method of the present invention utilizes the formation of coordination bonds between the organometallic compound and the functionalized carbon nanotubes, and then hydrolyzes and/or reduces them under the action of an alcohol solvent to obtain uniform distribution of nanoparticles or even quantum dots on the carbon nanotubes. Metal oxide and carbon nanotubes or metal and carbon nanotube composite materials on the surface of the tube.

Principle of the present invention is:

The surface functionalized carbon nanotubes can be combined with metals in organometallic compounds by coordination bonds through pretreatment, and the expression is as follows:

In the formula, n and m represent any number, 1=2 or 3 or 4, CNTs represents carbon nanotubes, Me represents a metal element, R is a hydrocarbon group or a hydrocarbon group with a carbonyl group; the expression is represented by a carboxyl group, a carbonyl group or a hydroxyl group The expressions involved in the reaction are similar.

When the valence state of the metal is +2, adjacent carboxyl groups and/or carbonyl groups and/or hydroxyl groups on one carbon nanotube, or carboxyl groups and/or carbonyl groups and/or hydroxyl groups on different carbon nanotubes will interact with the organometallic Coordination of the compound occurs; when the valence state of the metal is +3 or +4, the carboxyl and/or carbonyl and/or hydroxyl on different carbon nanotubes will coordinate with the organometallic compound. In this way, the precursors are chemically bonded to the carbon nanotubes.

Under the action of alcohol solvent, the organometallic compound combined with carbon nanotubes undergoes a hydrolysis reaction, and its expression is as follows:

  (R’＝H or Hydrocarbyl)

After the reaction lasts for a long time, the metal hydroxide on the surface of the carbon nanotubes will undergo a decomposition reaction to form a composite material of metal oxide and carbon nanotubes. When the solvent itself has a certain reducing ability, the composite material of metal and carbon nanotubes will be finally obtained.

Generally, only carbon nanotubes that have undergone surface treatment and have carboxyl groups and/or carbonyl groups and/or hydroxyl groups on the surface can bond with organometallic compounds by coordination bonds under certain conditions. The carbon nanotubes are fully dispersed by ultrasonication and/or stirring for a long time, and the organometallic compound has the opportunity to contact with as many carbon nanotubes as possible, and reach its surface, ready to combine with the functional groups on it; stand for a long time It is to enable the organic metal compound to fully combine with the groups on the carbon nanotubes to form a coordination bond, and to lay the foundation for the crystallization nucleation of metal oxides or metal crystals on the surface of carbon nanotubes. By selecting a suitable solvent, controlling the concentration, time, and temperature of the reaction, it is possible to control the nucleation of different metal oxides or metals on the carbon nanotubes where they can form coordination bonds, and along the carbon nanotube-confined crystals The growth direction grows into quantum dots with only a few nanometers or particles with tens of nanometers.

The scheme that realizes the object of the present invention is: the preparation method that nanometer metal or metal oxide is evenly distributed on carbon nanotube surface composite material, it is characterized in that prepare by following two steps with alcohol solvent method:

The first step of preprocessing:

(1) dissolving metal oxides or metal precursor organometallic compounds in alcohols or lower ethers, sulfones, tetrahydrofuran, halogenated hydrocarbon organic solvents,

(2) Carbon nanotubes (commercially available, produced by Shenzhen Nanometer Port) are refluxed for 1 to 2 hours with concentrated nitric acid at a temperature of 150 to 240° C., so that the surface has carboxyl and/or carbonyl and/or hydroxyl polar groups , that is, surface functionalization,

(3) Put the carbon nanotubes whose surface has been functionalized into the solution obtained in step (1), fully ultrasonic and/or stir, and then fully stand, so that the metal oxide or metal organic compound and the surface of the carbon nanotubes are extremely Sexual groups form coordination bonds;

The second step of preparation: the coordination bond obtained in the first step of pretreatment is reacted with alcohols and their aqueous solutions as solvents, and the control conditions are: the concentration of the reaction conjugate is 1×10 ^-7 -500g/L solvent, The reaction temperature is 50-300° C., and the reaction time is 0.5-108 hours, and a composite material in which nanometer metals or metal oxides are evenly distributed on the surface of carbon nanotubes can be prepared.

The nano-metal or metal oxide composite materials uniformly distributed on the surface of carbon nanotubes include: CuO and carbon nanotubes, _Cu2O and carbon nanotubes, Cu and carbon nanotubes, ZnO and carbon nanotubes, CdO and carbon nanotubes , NiO and carbon nanotubes, Ni and carbon nanotubes, CoO and carbon nanotubes, Co and carbon nanotubes, TiO ₂ and carbon nanotubes, Al ₂ O ₃ and carbon nanotubes, SiO ₂ and carbon nanotubes, Fe ₂ O ₃ and carbon nanotubes, Fe and carbon nanotubes, Nb ₂ O ₅ and carbon nanotubes, WO ₃ and carbon nanotubes, V ₂ O ₅ and carbon nanotubes, Sb ₂ O ₅ and carbon nanotubes, Sb ₂ O ₃ with carbon nanotubes, SnO ₂ with carbon nanotubes, SnO with carbon nanotubes, Sn with carbon nanotubes, MoO ₃ with carbon nanotubes, MoO with carbon nanotubes, Mo with carbon nanotubes, Ta ₂ O ₅ with carbon Nanotubes, Bi ₂ O ₃ and carbon nanotubes, La ₂ O ₃ and carbon nanotubes, Y ₂ O ₃ and carbon nanotubes, ZrO ₂ and carbon nanotubes, Ag and carbon nanotubes, Pt and carbon nanotubes, Pa Composite with carbon nanotubes.

The above-mentioned solvents for dissolving precursor organometallic compounds are alcohols (such as methanol, ethanol, isopropanol, butanol), lower ethers (such as ether), sulfones (such as dimethyl sulfoxide), tetrahydrofuran, halogenated hydrocarbons (such as chloroform, carbon tetrachloride) organic solvents.

In the above pretreatment process of forming coordination bonds between the carbon nanotubes and the organometallic compound, the concentration of the organometallic compound in the organic solvent is 1×10 ^-5 -30M.

In the above pretreatment process of forming coordination bonds between carbon nanotubes and organometallic compounds, the amount of carbon nanotubes added is 1×10 ⁻⁶ -100 g/L solution.

During the above-mentioned pretreatment process of forming coordination bonds between carbon nanotubes and organometallic compounds, the time required for ultrasonication and/or stirring is 0.4-10 h.

In the above pretreatment process of forming coordination bonds between carbon nanotubes and organometallic compounds, the standing time after ultrasonic and/or stirring treatment is 0.5-72h.

Above-mentioned in the second step preparation stage of composite material, selected alcohols and its aqueous solution are ethanol or propanol, isopropanol, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, diglycerol, decano Hexanediol, polyvinyl alcohol.

In the preparation stage of the above-mentioned composite material, the temperature of the reaction hydrolysis is 50-300°C.

Detailed ways

The surface functionalized carbon nanotubes used in the following examples are commercially available carbon nanotubes (produced by Shenzhen Nanometer Port) with concentrated nitric acid at a temperature of 150 to 240° C., and after reflux for 1 to 2 hours, the surface has carboxyl groups and and/or carbonyl and/or hydroxyl polar groups of carbon nanotubes.

Example 1: Add 20 mg of surface-functionalized carbon nanotubes and 1 g of aluminum isopropoxide to 200 mL of isopropanol, heat and ultrasonically disperse for 4 hours, let stand for 12 hours, and then centrifuge the suspension to retain a black solid Substances, put the complexed mixture in an oven to dry. Take 20 mg of the above mixture and put it into 200 mL of diethylene glycol aqueous solution (volume ratio 3:1), react at 95 °C for 2 h, then raise the temperature to 250 °C, and continue the reaction for 8 h to obtain a black product.

Observing the Al ₂ O ₃ and carbon nanotube composite material with a high-resolution transmission electron microscope, it can be seen that there are irregular crystals of about 10nm on the surface of the carbon nanotubes, and the interval between the crystals is 500nm, and the distribution is relatively uniform. X-ray _diffraction reveals properties of _Al2O3 crystals.

Example 2: 10 mg of surface-functionalized carbon nanotubes and 300 mg of copper acetate were ultrasonically dispersed in ethanol for 3 h, left to stand for 24 h, and then the suspension was centrifuged, and the precipitate was put into an oven to remove the solvent. The obtained mixture of copper acetate deposited on the surface of carbon nanotubes was put into a closed reactor together with 200 mL of glycerol solvent, and nitrogen gas was introduced. The temperature was raised to 200°C under vigorous stirring, and the reaction was stopped after 3 hours. The resulting suspension was centrifuged, and the precipitate was washed 3 times with distilled water, and dried in a vacuum oven to obtain Cu ₂ O and carbon nanotube composite material.

The preparation method of metal Cu and carbon nanotube composite material is similar to that of Cu ₂ O and carbon nanotube composite material, that is, the reaction time is extended to more than 5 hours, and the temperature is increased to 250° C. at the same time.

The preparation method of CuO and carbon nanotube composites is the same as that of Cu ₂ O/carbon nanotube composites in the pretreatment stage of the precursor and carbon nanotubes to form coordination bonds. The hydrolysis reaction stage is as follows: the copper acetate has been deposited on the carbon Mix the mixture on the surface of the nanotubes with 200mL of water, react at 95°C for 5h, then increase the temperature to 250°C, and continue the reaction for 10h to obtain a black composite material of CuO and carbon nanotubes.

Under the high-resolution transmission electron microscope, the above three metal oxides and metals can be uniformly _distributed on the surface of carbon nanotubes, and the crystal particle size is 6-50nm. The quantum dots are arranged side by side. XRD analysis confirmed the presence of three crystals.

Example 3: 300 mg of surface-functionalized carbon nanotubes and 2 g of zinc acetate were ultrasonically dispersed in ethanol for 4 hours, left to stand for 24 hours, and the suspension was directly dried in an oven to remove the solvent. Mix 1 g of the obtained mixture of zinc acetate deposited on the surface of carbon nanotubes with 300 mL of diethylene glycol solvent, heat up to 300° C. under vigorous stirring, and continue the hydrolysis reaction for 3 hours. After centrifugation, washing, and repeating 3 times, put it into an oven to dry to obtain a dark gray ZnO and carbon nanotube composite material. The high-resolution transmission electron microscope observation found that in addition to the uniform distribution of ZnO of about 15-40nm on the surface of the carbon nanotubes, there are also some nano-ZnO crystals appearing alone in the background. XRD detection proves that the crystal is ZnO.

The preparation process of CdO and carbon nanotube composite material is basically the same as above, except that the solvent is hexadecane glycol.

Example 4: 2 g of tetrabutyl titanate and 500 mg of surface-functionalized carbon nanotubes were ultrasonically dispersed in 500 mL of ether solvent for 1 hour, then magnetically stirred for 12 hours, left to stand for 12 hours, and then dried to remove the solvent. Disperse 500 mg of the above mixture in 400 mL of 2% polyvinyl alcohol solution by vigorous stirring, and react for 10 hours at a temperature of 100 ° C. After stopping the reaction, centrifuge and wash, repeat 3 times, and dry the product. A gray-black composite material of TiO ₂ and carbon nanotubes was obtained. Electron microscope observation found that titanium dioxide crystals also grew on the surface of carbon nanotubes, and the dispersion was relatively uniform, but some titanium dioxide crystals gathered in the background. XRD analysis proves that the titanium dioxide crystals in the composite are mainly sharp, but there is also a small amount of rutile.

The preparation process of SiO ₂ , SnO ₂ , ZrO ₂ and carbon nanotube composite materials is similar, except that the hydrolysis solvents used are diethylene glycol, triethylene glycol and glycerin, respectively.

Example 5: ultrasonically disperse 1 g of niobium ethoxide and 10 mg of surface-functionalized carbon nanotubes in 300 mL of chloroform for 0.5 h, stir magnetically for 2 hours, and centrifuge the suspension after standing for 48 h, and remove the precipitate Place in an oven to remove solvent. Put the obtained mixture of niobium ethoxide deposited on the surface of carbon nanotubes together with 500mL of diethylene glycol solvent into the reactor, raise the temperature to 300°C under vigorous stirring, stop the reaction after 1h, and centrifuge the resulting suspension Separate, wash the precipitate with distilled water for 3 times, and put it into a vacuum oven to dry to obtain the composite material of Nb ₂ O ₅ and carbon nanotubes. Electron microscope analysis shows that Nb ₂ O ₅ crystals are evenly distributed on the surface of carbon nanotubes, and the particle size is 6-10nm, which should have a good quantum effect. XRD analysis shows that the granular quantum dots exist in the form of crystals.

The preparation method of the composite material of V ₂ O ₅ , Sb ₂ O ₅ , Ta ₂ O ₅ and carbon nanotubes is similar to the above process.

Example 6: 0.5 g of platinum acetate and 20 mg of surface-functionalized carbon nanotubes were ultrasonically dispersed in 200 mL of dimethyl sulfone solvent for 8 h, and after standing for 10 h, the suspension was directly dried to remove the solvent. Put the mixture of platinum acetate and carbon nanotubes into the reactor together with 300mL of 1,2-hexadecane diol solvent, stir vigorously, add the initiator oleic acid and raise the temperature to 200°C, stop the reaction after 10h, and suspend the obtained The liquid was separated by centrifugation, and the precipitate was washed three times with distilled water, and dried in an oven to obtain the Pt/carbon nanotube composite material. Electron microscope analysis showed that Pt crystals were evenly distributed on the surface of carbon nanotubes, and the particle size was 20nm. XRD analysis proves that the nanoparticles are Pt metal.

The preparation process of Ag and carbon nanotubes and Pa/carbon nanotube composites is basically the same as that of Pt and carbon nanotubes composites.

Example 7: 2g of nickel acetate and 50mg of surface-functionalized carbon nanotubes were ultrasonically dispersed in 500mL of tetrahydrofuran solvent for 3 hours, magnetically stirred for 10 hours, and after standing for 3 hours, the suspension was directly dried to remove the solvent. Put the mixture of nickel acetate and carbon nanotubes into the reactor together with 300mL of diethylene glycol solvent, stir vigorously, raise the temperature to 180°C, stop the reaction after 3h, centrifuge the resulting suspension, and wash the precipitate with distilled water 3 After drying, the composite material of NiO and carbon nanotubes was obtained. Electron microscopy analysis shows that NiO crystals are more uniformly distributed on the surface of carbon nanotubes, and the particle size is 2-3nm, which has a good quantum effect. XRD analysis proved that the nanoparticles were nickel oxide.

The preparation methods of Fe ₂ O ₃ and carbon nanotubes, CoO and carbon nanotubes, and MoO and carbon nanotubes and NiO and carbon nanotubes composite materials are similar. The preparation method of the nano-metal composite material corresponding to these four metal oxides is also basically the same as the above-mentioned process, except that the hydrolysis solvent needs to use glycerol or triethylene glycol with three hydroxyl groups and strong reducibility, and the reaction time is also shorter. It needs to be extended to more than 6 hours.

Example 8: 3 g of tin(II) oxalate and 300 mg of surface-functionalized carbon nanotubes were ultrasonically dispersed in 500 mL of isopropanol solvent for 3 h, and after standing for 8 hours, the suspension was directly dried to remove the solvent. Put the mixture of tin(II) oxalate and carbon nanotubes into the reactor together with 300mL ethylene glycol solvent, stir vigorously, raise the temperature to 150°C, stop the reaction after 6h, centrifuge the obtained suspension, and wash with distilled water The precipitate was dried three times, and the composite material of SnO and carbon nanotubes was obtained after drying. Electron microscope analysis showed that SnO crystals were evenly distributed on the surface of carbon nanotubes, and the particle size was 15-20nm. XRD analysis proved the nanoparticles to be stannous oxide.

During the reaction process, the hydrolysis solvent was replaced with triethylene glycol or glycerol, and the reaction time was extended to 10 h, finally obtaining the Sn/carbon nanotube composite material.

Example 9: 1 g of tungsten hexacarbonyl and 20 mg of surface-functionalized carbon nanotubes were dispersed in 300 mL of carbon tetrachloride solvent, magnetically stirred for 15 h, and left to stand for 8 hours before being centrifuged to remove the solvent. Put the mixture of tungsten hexacarbonyl and carbon nanotubes into the reactor together with 300mL of ethanol solvent, stir vigorously, raise the temperature to 120°C, and stop the reaction after reflux for 8h, centrifuge the obtained suspension, and wash the precipitate with distilled water 3 times, after drying, the composite material of WO ₃ and carbon nanotubes is obtained. Electron microscope analysis showed that WO ₃ crystals were evenly distributed on the surface of carbon nanotubes, and the particle diameter was below 50nm. XRD analysis proved the nanoparticles to be tungsten trioxide.

The preparation process of MoO ₃ and carbon nanotube composites is similar to that of WO ₃ and carbon nanotube composites.

Example 10: 0.3 g of bismuth salicylate and 10 mg of surface-functionalized carbon nanotubes were ultrasonically dispersed in butanol for 0.5 h, and after magnetic stirring for 12 h, the suspension was directly dried to remove the solvent. Put the mixture of bismuth salicylate and carbon nanotubes into the reactor together with 200mL of propanol solvent, stir vigorously, and reflux for 10 hours at a temperature of 150°C, centrifuge the suspension, and dry to obtain Bi ₂ O ₃ and carbon nanotube composites. TEM showed that Bi ₂ O ₃ nanoparticles were uniformly distributed on the surface of carbon nanotubes. XRD analysis showed that the crystal was Bi ₂ O ₃ .

The preparation process of La ₂ O ₃ , Y ₂ O and Sb ₂ O ₃ composites with carbon nanotubes is similar to that of Bi ₂ O ₃ and carbon nanotubes composites.

Claims (8)

1, a kind of preparation method of carbon nanotube surface evenly distributed nanometer metal or metal oxide composite material, it is characterized in that prepare by following two steps with alcohol solvent method: The first step of preprocessing: (1) dissolving metal oxides or metal precursor organometallic compounds in alcohols or lower ethers, sulfones, tetrahydrofuran, halogenated hydrocarbon organic solvents, (2) Carbon nanotubes are refluxed for 1 to 2 hours with concentrated nitric acid at a temperature of 150 to 240 ° C, so that the surface has carboxyl and/or carbonyl and/or hydroxyl polar groups, that is, the surface is functionalized, (3) Put the carbon nanotubes whose surface has been functionalized into the solution obtained in step (1), fully ultrasonic and/or stir, and then fully stand, so that the metal oxide or metal organic compound and the surface of the carbon nanotubes are extremely Sexual groups form coordination bonds; The second step of preparation: The coordination bond combination obtained in the first step of pretreatment is reacted with alcohols and their aqueous solutions as solvents, and the control conditions are: the concentration of the reaction combination is 1×10 ^-7 -500g/L solvent, and the reaction temperature is 50-300 ℃, the reaction time is 0.5-108h, and the composite material in which the nanometer metal or metal oxide is evenly distributed on the surface of the carbon nanotube can be prepared. 2. The preparation method according to claim 1, characterized in that the nano-metal or metal oxide composite materials uniformly distributed on the surface of the carbon nanotubes include: CuO and carbon nanotubes, Cu ₂ O and carbon nanotubes, Cu and Carbon nanotubes, ZnO and carbon nanotubes, CdO and carbon nanotubes, NiO and carbon nanotubes, Ni and carbon nanotubes, CoO and carbon nanotubes, Co and carbon nanotubes, TiO ₂ and carbon nanotubes, Al ₂ O ₃ and carbon nanotubes, SiO ₂ and carbon nanotubes, Fe ₂ O ₃ and carbon nanotubes, Fe and carbon nanotubes, Nb ₂ O ₅ and carbon nanotubes, WO ₃ and carbon nanotubes, V ₂ O ₅ and carbon nanotubes Nanotubes, Sb ₂ O ₅ and carbon nanotubes, Sb ₂ O ₃ and carbon nanotubes, SnO ₂ and carbon nanotubes, SnO and carbon nanotubes, Sn and carbon nanotubes, MoO ₃ and carbon nanotubes, MoO and carbon Nanotubes, Mo and carbon nanotubes, Ta ₂ O ₅ and carbon nanotubes, Bi ₂ O ₃ and carbon nanotubes, La ₂ O ₃ and carbon nanotubes, Y ₂ O ₃ and carbon nanotubes, ZrO ₂ and carbon nanotubes Tube, Ag and carbon nanotube, Pt and carbon nanotube, Pa and carbon nanotube composite material. 3. The preparation method according to claim 1, characterized in that the solvent for dissolving the precursor organometallic compound is methanol, ethanol, isopropanol, butanol, ether, dimethyl sulfoxide, tetrahydrofuran, chloroform, carbon tetrachloride . 4. The preparation method according to claim 1, characterized in that in the pretreatment process of carbon nanotubes and organometallic compounds forming coordination bonds, the concentration of organometallic compounds in organic solvents is 1×10 ^-5 -30M . 5. The preparation method according to claim 1, characterized in that in the pretreatment process of carbon nanotubes and organometallic compounds forming coordination bonds, the amount of carbon nanotubes added is 1×10 ^-6 -100g/L solution . 6. The preparation method according to claim 1, characterized in that in the pretreatment process of carbon nanotubes and organometallic compounds forming coordination bonds, the time of ultrasonication and/or stirring is 0.4-72h. 7. The preparation method according to claim 1, characterized in that in the pretreatment process of forming coordination bonds between carbon nanotubes and organometallic compounds, the standing time is 0.5-72h. 8. The preparation method according to claim 1, characterized in that in the second preparation stage, the selected alcohols and their aqueous solutions are ethanol or propanol, isopropanol, ethylene glycol, glycerol, diethylene glycol Alcohol, Triethylene Glycol, Diglycerin, Cetyl Glycol, Polyvinyl Alcohol.