CN101306357A - Binary nano composite photo-catalyst preparation method - Google Patents
Binary nano composite photo-catalyst preparation method Download PDFInfo
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- CN101306357A CN101306357A CNA2007100992914A CN200710099291A CN101306357A CN 101306357 A CN101306357 A CN 101306357A CN A2007100992914 A CNA2007100992914 A CN A2007100992914A CN 200710099291 A CN200710099291 A CN 200710099291A CN 101306357 A CN101306357 A CN 101306357A
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Abstract
The invention relates to a method used for preparing a binary-nano composite photo-catalyst which takes titanium dioxide as the main body, and the prepared catalyst is applied to the organic wastewater treatment. The preparation method is characterized in that the supercritical fluid drying technology or the common chemical drying technology is combined with four preparation methods of the coprecipitation method, the successive precipitation method, the surface coating method and the mechanical mixing method to prepare the nano composite photo-catalyst which takes the titanium dioxide as the main body, thereby enlarging the range of the spectral response, enabling the absorption wavelength of the catalyst to be shifted toward the visual light wavelength, and improving the quantum effect.
Description
Technical field
What the present invention relates to is the binary nano composite photo-catalysts of four kinds of different preparation method's preparations based on titanium dioxide.Emphasis is by adopting supercritical fluid drying technology or ordinary chemical method dry technology in conjunction with coprecipitation, successively the precipitation method, surperficial coating method or four kinds of different preparation methods of mechanical mixing prepare the binary nano composite photo-catalyst based on titanium dioxide respectively.The catalyst of four kinds of method preparations adopts ultraviolet light and visible light as light source respectively, and effectively degradable organic pollutant has not only improved photocatalytic activity, has also reduced the compound degree in light induced electron and hole, and has realized TiO
2Light absorption is shifted to visible light, a kind of ideal environment pollution control catalyst of can yet be regarded as.
Technical background
In recent years, the conductor photocatalysis oxidizing process is paid close attention to by people as a kind of deep oxidation technology of degradation of organic substances, this pollutes treatment technology and has that energy consumption is low, easy and simple to handle, reaction condition gentle (carrying out under the normal temperature and pressure), in the short time organic pollution is degraded fully to CO
2, H
2O and inorganic matter reduce secondary pollution.Many difficult degradations or the general all available the method for the material that is difficult to remove with additive method advantage such as are effectively removed and are expected to become a kind of emerging wastewater processing technology.But still have two vital factors restricting the industrialization of conductor photocatalysis material, the one, how to prepare high catalytic activity catalyst, the 2nd, how effectively to utilize visible light.Wherein studying maximum is semiconductor material with wide forbidden band TiO
2Yet, TiO
2Only can be as photochemical catalyst by ultraviolet excitation; In addition in order to increase specific area, improve catalytic efficiency and the nano effect pursued, make the optical absorption edge band of catalyst tend to because of the further blue shift of quantum size effect; And the actual face of land solar radiation concentration of energy that arrives is in the 460-500nm wave-length coverage, the visible light composition accounts for 50%, and ultraviolet composition (300-400nm) less than 5%, therefore how efficiently to utilize sunshine, especially wherein visible light, exploitation can be become the target that researcher is pursued day by day by the photochemical catalyst of excited by visible light.Semiconductor is compound as a kind of effective method of modifying, and it is the modification of a kind of particle to another kind of particle in essence.The photoactive raising of composite semiconductor owing to different can level semiconductors between the transporting and separate of photo-generated carrier, improve the separation of charge effect of system, thereby the scope of spread spectrum response improves quantum effect.The application develops the nano composite photo-catalyst that has high-efficiency catalytic activity under ultraviolet light and visible light source by the investigation to different preparation methods.
Summary of the invention
The present invention adopts two kinds of different dry technologies of supercritical fluid drying technology and ordinary chemical method dry technology to prepare nano composite photo-catalyst in conjunction with coprecipitation, the priority precipitation method, four kinds of different preparation methods of surperficial coating method and mechanical mixing respectively.Its objective is that particle diameter is little, decentralization is high, specific area is big in order to obtain, Heat stability is good, the nano composite photo-catalyst that can under ultraviolet light and visible light source condition, have highlight catalytic active respectively that catalytic activity is high.Advantage of the present invention mainly is:
1, the present invention relates to coprecipitation, successively the precipitation method, four kinds of different preparation methods of surperficial coating method and mechanical mixing prepare binary nano composite photo-catalyst.Wherein, in the nano-complex particle of coprecipitation preparation, Ti
4+And Cd
2+Precipitate more even, Cd
2+Replace Ti
4+, cause the oxygen room, thereby form nano-complex particle than small particle diameter.
2, adopt common seasoning preparation in dry run, have to equipment require low, easy to operate simple advantage.And the aeroge that adopts supercritical fluid drying to prepare, its dry run is carried out under the ethanol super critical condition, and liquid will expand rapidly and make particle refinement once more in the hole.Release fluids can make the gel pore structure not be destroyed under no surface tension supercriticality, and the specific surface area of catalyst of avoiding particle aggregation to grow up obtaining is big, and pore capacities is big, and density is little, and complicated microcellular structure is arranged, thereby has very high catalytic activity.
3, narrow gap semiconductor metal oxide or sulfide and titanium dioxide are compound, prepare novel nano composite photo-catalyst, and it can make light induced electron at different transition between the energy levels, thereby electronics is separated with the hole, reduce compoundly, improve photocatalytic activity.
4, narrow gap semiconductor metal oxide or sulfide and titanium dioxide are compound, under the radiation of visible light, because energy level is interlaced, can increase the photoresponse scope of catalyst, and its absorption to light is moved to visible light by ultraviolet region.Solved the shortcoming that titanium dioxide can only absorb ultraviolet light, be able to make full use of the solar energy of green non-pollution, also improved utilizing the purpose of optical absorption intensity.
5, the present invention prepares four kinds of preparation methods that catalyst adopts and has simple to operately, to the less demanding characteristics of equipment, can satisfy industrial requirement.
6, four kinds of preparation methods adopting of prepared catalyst of the present invention organic industrial sewage of can effectively degrading under the solar light irradiation condition has utilized solar energy fully, can solve industrial energy demand.
The present invention mainly by the following technical solutions
1, with quantitative solvent with titanium-containing compound or contain cadmium salt soln and fully mix, stirring condition adds certain amount of surfactant down makes it to become emulsion, after fully stirring certain hour, regulate above-mentioned pH of mixed value to alkalescence with certain density alkaline solution and obtain hydrogel.Ageing through 20 hours, with above-mentioned hydrogel centrifuge washing to there not being chlorion.Make it to become alcogel with the water in the absolute ethyl alcohol replacing water gel at last, dry or put into autoclave under 50～150 ℃ temperature, do to extract solvent with absolute ethyl alcohol, at 262 ℃, ethanol reaches dry under the supercriticality under the 8.5MPa condition.The above-mentioned catalyst precursor that obtains is calcined in Muffle furnace, and temperature is at 500 ℃, and calcination time is 1 hour, makes good dispersion, particle diameter is little, catalytic activity is high nano titanium oxide or cadmium oxide or cadmium sulfide photochemical catalyst at last.
2, coprecipitation: quantitative solvent is fully mixed with titanium-containing compound, stirring condition drips a kind of metal salt solution of a certain amount of concentration down, and the adding certain amount of surfactant makes it to become emulsion, after fully stirring certain hour, regulate above-mentioned pH of mixed value to alkalescence with certain density alkaline solution and obtain hydrogel.Ageing through 20 hours, with above-mentioned hydrogel centrifuge washing to there not being chlorion.Make it to become alcogel with the water in the absolute ethyl alcohol replacing water gel at last, dry or put into autoclave under 50～150 ℃ temperature, do to extract solvent with absolute ethyl alcohol, at 262 ℃, ethanol reaches dry under the supercriticality under the 8.5MPa condition.The above-mentioned catalyst precursor that obtains is calcined in Muffle furnace, and temperature is at 500 ℃, and calcination time is 1 hour, makes good dispersion, particle diameter is little, catalytic activity is high nanometer binary composite photo-catalyst at last.
3, step-by-step precipitation method: quantitative solvent is fully mixed with titanium-containing compound, stirring condition descends and adds certain amount of surfactant to make it to become emulsion, after fully stirring certain hour, regulate above-mentioned pH of mixed value to alkalescence with certain density alkaline solution and obtain hydrogel.Drip a kind of metal salt solution of a certain amount of concentration again, regulate above-mentioned pH of mixed value to alkalescence with certain density alkaline solution and obtain hydrogel.Ageing through 20 hours, with above-mentioned hydrogel centrifuge washing to there not being chlorion.Make it to become alcogel with the water in the absolute ethyl alcohol replacing water gel at last, dry or put into autoclave under 50～150 ℃ temperature, do to extract solvent with absolute ethyl alcohol, at 262 ℃, ethanol reaches dry under the supercriticality under the 8.5MPa condition.The above-mentioned catalyst precursor that obtains is calcined in Muffle furnace, and temperature is at 500 ℃, and calcination time is 1 hour, makes good dispersion, particle diameter is little, catalytic activity is high nanometer binary composite photo-catalyst at last.
4, surperficial coating method: nano titanium dioxide photocatalyst powder in 1 is added a certain amount of deionized water, drip a kind of metal salt solution of a certain amount of concentration, and the adding certain amount of surfactant makes it to become emulsion, after fully stirring certain hour, regulate above-mentioned pH of mixed value to alkalescence with certain density alkaline solution and obtain hydrogel.Ageing through 20 hours, with above-mentioned hydrogel centrifuge washing to there not being chlorion.Make it to become alcogel with the water in the absolute ethyl alcohol replacing water gel at last, dry or put into autoclave under 50～150 ℃ temperature, do to extract solvent with absolute ethyl alcohol, at 262 ℃, ethanol reaches dry under the supercriticality under the 8.5MPa condition.The above-mentioned catalyst precursor that obtains is calcined in Muffle furnace, and temperature is at 500 ℃, and calcination time is 1 hour, makes good dispersion, particle diameter is little, catalytic activity is high binary nano composite photo-catalyst at last.
5, mechanical mixing: nano titanium oxide in 1 and cadmium oxide are mixed with the ratio of certain molar content, promptly get nanometer binary composite photo-catalyst.
6, with the light-catalyzed reaction system of design processing voluntarily photocatalysis performance is tested.There are uviol lamp or fluorescent lamp in the center, adds reactant liquor and oxidant, and catalyst consumption is 0.3Kg/m
3, at reactant liquor bottom bubbling air, its flow is 1～12m
3/ h, 25 ± 1 ℃ of temperature are dispersed in the reactant liquor catalyst, pipette an amount of reactant liquor at regular intervals, after the centrifugation, measure the COD value with potassium dichromate method.
Titanium compound can be the mixture of a kind of, two or more inorganic salts in titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, isopropyl titanate, titanium propanolate, tetrabutyl titanate, iso-butyl titanate, the tetraethyl titanate in the above-mentioned said sol-gal process.
The solvent of above-mentioned said dissolving titanium compound and transition metal has a kind of, two or more mixtures in the following monohydric alcohol dihydroxylic alcohols of dilute hydrochloric acid solution, deionized water, diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol and four carbon atom and isomer thereof, glycerine, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, toluene, dimethylbenzene, cyclohexane, alkane, the fragrant alkane.
The above-mentioned slaine that mixes is a kind of, two or more mixtures in cadmium nitrate, cadmium sulfate, cadmium acetate, caddy, cadmium 2-ethylhexoate, cadmium laurate, cadmium oleate, substituted benzoic acid cadmium, aphthenic acids cadmium, the neodecanoic acid cadmium.
Above-mentioned said surfactant or dispersant are a kind of, two or more mixtures in diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol, tween, polyvinylpyrrolidone, polyvinyl alcohol, neopelex, odium stearate, lauryl sodium sulfate, acetate, AEO, the oleic acid.
Above-mentioned said precipitating reagent comprises a kind of, two or more mixtures in NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, vulcanized sodium, potassium hydroxide, potash, saleratus, ammoniacal liquor, the urea.
Above-mentioned said degradation solution is that organic industrial sewage can contain phenol, acrylic acid, acrylate, acetate, formic acid, acetaldehyde, benzene, toluene, nitrobenzene, methyl orange, methyl blue, rhodamine-6G, rhodamine B, hydroxyazobenzene, salicylic acid, disperse scarlet, contain sulfonic polarity azo dyes; Surfactant is as a kind of, two or more mixtures in chloro thing trichloro-ethylene, trichloro-benzene, chloroform, carbon tetrachloride, 4-chlorophenol, tetrachloro biphenyl, fluorine Lyons, Pentafluorophenol, fluoroolefin, fluorinated aromatic hydrocarbon and the floating oils of the water surface such as ten disulfobenzene sodium sulfonates, chlorination Bian Ji ten disulfo dimethyl amines, nonyl polyoxyethylene benzene, ethyoxyl alkyl phenol.
The concrete mode of implementing
Embodiment 1: accurately measure the volumetric flask that the 248.4mL concentrated hydrochloric acid is put into 500mL, add deionized water and be diluted to graduation mark and shake up and be made into the 6mol/L hydrochloric acid solution.Accurately measure 236.4mL TiCl
4Concentrated solution slowly joins in ventilating kitchen in the 2000mL beaker that is placed in the ice-water bath, slowly adds the hydrochloric acid solution that 263.60mL has prepared simultaneously, and constantly stirs until TiCl fast
4All dissolve, get the TiCl of 4mol/L
4Solution.Accurately measure the TiCl of the 4mol/L of 9.37mL
4Solution is put into the 500mL beaker and is added deionized water 124.9mL again, adds 0.5mL AEO-3, adds the Cd (NO of 0.3mol/L
3)
2Solution 6.25mL.Slowly drip 3moL/lNH
3To pH value to 8～9.Ageing 20 hours is washed to and does not contain Cl
-Get alcogel with the ethanol exchanged water, at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 97.4%.
Embodiment 2: the TiCl of accurately measuring 9.37mL 4mol/L
4Put into the 500mL beaker and add deionized water 124.9mL again, add 0.5mLAEO-3, slowly drip 3moL/lNH
3Get hydrogel to pH value to 8～9.Continue to drip the Cd (NO of 0.3mol/L
3)
2Solution 6.25mL slowly drips 3moL/lNH
3Get hydrogel to pH value to 8～9.Ageing 20 hours is washed to and does not contain Cl
-Get alcogel with the ethanol exchanged water, at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 94.9%.
Embodiment 3: the TiCl of accurately measuring 9.37mL 4mol/L
4Solution is put into the 500mL beaker and is added deionized water 124.9mL again, adds 0.5mLAEO-9, slowly adds 3moL/lNH then
3To the pH value is 8～9 to end, and ageing 20 hours is washed to no Cl
-The back gets alcogel with the ethanol exchanged water, and at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly get nano titanium dioxide photocatalyst.Put into the 500mL beaker with this nano titanic oxide catalyst 3g and add the 10mL deionized water, add 0.5mLAEO-9, drip the Cd (NO of 0.3mol/L
3)
2Solution 6.25mL slowly adds 3moL/lNH then
3To the pH value is 8～9 to end, and ageing 20 hours is washed to no Cl
-The back gets alcogel with the ethanol exchanged water, and at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 95.1%.
Embodiment 4: the TiCl of accurately measuring 9.37mL 4mol/L
4Put into the 500mL beaker and add deionized water 124.9mL again, add 0.5mLAEO-9, slowly add 3moL/lNH then
3To the pH value is 8～9 to end, and ageing 20 hours is washed to no Cl
-The back gets alcogel with the ethanol exchanged water, and at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly get nano titanium dioxide photocatalyst.Accurately measure the Cd (NO of 100mL 0.3mol/L
3)
2Solution is put into the 500mL beaker, adds 0.5mLAEO-9, slowly adds 3moL/lNH then
3To the pH value is 8～9 to end, and ageing 20 hours is washed to no Cl
-The back gets alcogel with the ethanol exchanged water, and at 262 ℃, ethanol reaches under the supercriticality after the drying under the 8.5MPa condition, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly get nano oxidized cadmium photochemical catalyst.The nano titanium oxide and the cadmium oxide photochemical catalyst that make are mixed with mol ratio at 1: 20, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 91.4%.
Embodiment 5: the TiCl of accurately measuring 9.37mL 4mol/L
4Put into the 500mL beaker and add deionized water 124.9mL again, add 0.5mLAEO-3, the Cd (NO of 0.3mol/L
3)
2Solution 6.25mL.Slowly add 1.0mol/L Na then
2S to pH is worth 8～9.Ageing 20 hours is washed to and does not contain Cl
-After the 50-150 ℃ of air dry, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 97.9%.
Embodiment 6: the TiCl of accurately measuring 9.37mL 4mol/L
4Put into the 500mL beaker and add deionized water 124.9mL again, add 0.5mLAEO-3, the Cd (NO of 0.3mol/L
3)
2Solution 6.25mL.Slowly add 1.0mol/LNa then
2S to pH is worth 8～9.Ageing 20 hours is washed to and does not contain Cl
-After the 50-150 ℃ of air dry, with the catalyst that obtains in Muffle furnace in 500 ℃ of calcination 1h, promptly obtain nano composite photo-catalyst.The catalyst that obtains is got 0.3g degrades to the 300mL acrylic acid wastewater.Under visible light radiation, add 1ml H
2O
2, through the acrylic acid wastewater degraded to the about 3000mg/L of concentration in 6 hours, the COD degradation rate was 91.7%.
Claims (10)
1, adopt supercritical fluid drying technology or two kinds of different dry technologies of ordinary chemical method dry technology to prepare binary nano composite photo-catalyst in conjunction with coprecipitation, the priority precipitation method, four kinds of different preparation methods of surperficial coating method and mechanical mixing, adopt that the catalyst of this four kinds of preparation methods preparation has all that particle diameter is little, good dispersion, characteristics that photocatalytic activity is high, and composition is by following several compositions: TiO
2Molar content is 90.0%～100.0%, and other metallic compound molar content is 0.00%～10.0%.
2, preparing binary nano composite photo-catalyst according to claim a kind of described employing supercritical fluid drying technology or two kinds of different dry technologies of ordinary chemical method dry technology in conjunction with coprecipitation is characterized in that: it is evenly mixed to get titanium-containing compound and metal salt solution, add surfactant, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, again through ageing, ordinary chemical method drying or Supercritical Ethanol fluid drying, 500 ℃ of calcining 1h make binary nano composite photo-catalyst.
3, preparing binary nano composite photo-catalyst according to claim a kind of described employing supercritical fluid drying technology or two kinds of different dry technologies of ordinary chemical method dry technology in conjunction with step-by-step precipitation method is characterized in that: get titanium-containing compound and add surfactant, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, in hydrogel, add metal salt solution again, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, again through ageing, ordinary chemical method drying or Supercritical Ethanol fluid drying, 500 ℃ of calcining 1h make binary nano composite photo-catalyst.
4, coating legal systems according to two kinds of different dry technology mating surfaces of claim a kind of described employing supercritical fluid drying technology or ordinary chemical method dry technology is equipped with binary nano composite photo-catalyst and it is characterized in that: get titanium-containing compound and add surfactant, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, again through ageing, ordinary chemical method drying or Supercritical Ethanol fluid drying, calcine 1h down for 500 ℃, make nano titanium dioxide photocatalyst, it is evenly mixed to get this catalyst and metal salt solution, adds surfactant, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, again through ageing, ordinary chemical method drying or Supercritical Ethanol fluid drying, calcine 1h down, make binary nano composite photo-catalyst for 500 ℃.
5, preparing binary nano composite photo-catalyst according to claim a kind of described employing supercritical fluid drying technology or two kinds of different dry technologies of ordinary chemical method dry technology in conjunction with mechanical mixing is characterized in that: get titanium-containing compound or contain cadmium salt soln and add surfactant, dripping alkali liquid, regulate the pH value between 8～9, get hydrogel, again through ageing, ordinary chemical method drying or Supercritical Ethanol fluid drying, calcine 1h down for 500 ℃, make nano titanium dioxide photocatalyst or nano oxidized cadmium or cadmium sulfide photochemical catalyst, the nano metal photochemical catalyst is mixed obtaining binary nano composite photo-catalyst with nano titanium dioxide photocatalyst with certain mol proportion.
6,, it is characterized in that titanium-containing compound is selected from a kind of, two or more mixtures in titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, isopropyl titanate, titanium propanolate, tetrabutyl titanate, iso-butyl titanate, the tetraethyl titanate according to claim 2,3,4 and 5 described preparation methods.
7,, it is characterized in that metal salt solution is selected from a kind of, two or more mixtures in cadmium nitrate, cadmium sulfate, cadmium acetate, caddy, cadmium 2-ethylhexoate, cadmium laurate, cadmium oleate, substituted benzoic acid cadmium, aphthenic acids cadmium, the neodecanoic acid cadmium according to claim 2,3,4 and 5 described preparation methods.
8,, it is characterized in that surfactant is selected from a kind of, two or more mixtures in diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol, tween, polyvinylpyrrolidone, polyvinyl alcohol, neopelex, odium stearate, lauryl sodium sulfate, acetate, AEO, the oleic acid according to claim 2,3,4 and 5 described preparation methods; Used alkali lye is a kind of, two or more mixtures in NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, potassium hydroxide, potash, saleratus, ammoniacal liquor, the urea.
9,, it is characterized in that used precipitating reagent comprises a kind of, two or more mixtures in NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, potassium hydroxide, potash, saleratus, ammoniacal liquor, the urea according to claim 2,3,4 and 5 described preparation methods.
10, according to claim 2,3,4 and 5 described preparation methods, it is characterized in that the ordinary chemical method drying is that the control temperature is carried out at 50～150 ℃ in baking oven, supercritical fluid drying is to put into autoclave, make to extract solvent with absolute ethyl alcohol, at 262 ℃, carry out drying when ethanol reaches supercriticality under the 8.5MPa condition.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773098A (en) * | 2012-08-27 | 2012-11-14 | 河北麦森钛白粉有限公司 | Preparation process of nanometer titanium-dioxide denitration catalyst |
| CN101792116B (en) * | 2009-05-25 | 2014-05-07 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
| CN104353444A (en) * | 2014-11-19 | 2015-02-18 | 黑龙江大学 | Method of synthesizing metatitanic acid/TiO2 nano composite material for hydrogen production from water by photodecomposition via one-step solvothermal method |
| CN106040262A (en) * | 2016-05-23 | 2016-10-26 | 南昌航空大学 | Preparation method and application for semiconductor composite nanometer material photocatalyst |
| CN109420485A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | CdO-TiO for hydrogenation of carbon dioxide methanol2Catalyst and preparation and application |
| CN109420484A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of metal oxide solid solution catalyst and preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792116B (en) * | 2009-05-25 | 2014-05-07 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
| CN102773098A (en) * | 2012-08-27 | 2012-11-14 | 河北麦森钛白粉有限公司 | Preparation process of nanometer titanium-dioxide denitration catalyst |
| CN102773098B (en) * | 2012-08-27 | 2014-04-02 | 河北麦森钛白粉有限公司 | Preparation process of nanometer titanium-dioxide denitration catalyst |
| CN104353444A (en) * | 2014-11-19 | 2015-02-18 | 黑龙江大学 | Method of synthesizing metatitanic acid/TiO2 nano composite material for hydrogen production from water by photodecomposition via one-step solvothermal method |
| CN106040262A (en) * | 2016-05-23 | 2016-10-26 | 南昌航空大学 | Preparation method and application for semiconductor composite nanometer material photocatalyst |
| CN109420484A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of metal oxide solid solution catalyst and preparation and application |
| CN109420484B (en) * | 2017-08-21 | 2021-12-17 | 中国科学院大连化学物理研究所 | Metal oxide solid solution catalyst, preparation and application thereof |
| CN109420485A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | CdO-TiO for hydrogenation of carbon dioxide methanol2Catalyst and preparation and application |
| CN111545136A (en) * | 2020-04-05 | 2020-08-18 | 北京化工大学 | Preparation method and application of self-suspended polymer aerogel with efficient photothermal conversion |
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