CN1911786A - Preparation method of mesopore metal oxide - Google Patents
Preparation method of mesopore metal oxide Download PDFInfo
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- CN1911786A CN1911786A CN200610088467.1A CN200610088467A CN1911786A CN 1911786 A CN1911786 A CN 1911786A CN 200610088467 A CN200610088467 A CN 200610088467A CN 1911786 A CN1911786 A CN 1911786A
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- -1 Xiao Suangu Chemical compound 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000000463 material Substances 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229960001296 zinc oxide Drugs 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
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- Inorganic Compounds Of Heavy Metals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The preparation process of mesoporous metal oxide includes dissolving metal salt in acrylic acid, with the molar ratio between metal salt and acrylic acid being 1 to 0.1-10; stirring for 0.2-2 hr, sucking filtering, washing the product with distilled water and alcohol for 1-3 times each; drying to obtain powder; spreading the powder in crucible and roasting in muffle at 200-350 deg.c for 3-8 hr in the temperature raise rate of 2-8 deg.c/min. The preparation process of the process has short reaction time and short preparation period.
Description
One, technical field
The present invention relates to a kind of mesopore metal oxide (comprising CeO2, Nb
2O
5, Ta
2O
5, CuO, V
2O
5, NiO, ZnO, Fe
2O
3, Al
2O
3, TiO
2, ZrO
2, SnO
2And SiO
2) the novel preparation method of powder body material.
Two, background technology
The material of nano-scale has become the problem that numerous Science and Technologies are studied in recent years, because these materials are in the potential application of different field, in these researchs, because their electricity and magnetic property, the potential application of metal oxide is subjected to more concern.
As Co
3O
4Ultrafine powder also is widely used in aspects such as pigment, tinted shade, magneticsubstance, pottery, in electronic industry, requires its purity height, fine size, particle size distribution range is narrow, sintering activity good; In the environment protection chemical engineering, it is CO reduction SO
2, ammonia oxidation, methane reduction NO effective catalyst; In ceramic functional materials, be widely used in and make temperature-sensitive and pressure-sensitive electrode, gas sensor, magneticsubstance and lithium ion anode material.During all these are used, Co
3O
4Microtexture, be influence and determine the key parameter nano Co of its performance as grain size, distribution range, crystal morphology
3O
4Be powder russet, water insoluble, have magnetic.
Fe
2O
3Be one of main raw material of making soft magnetic ferrite, it is having purposes very widely aspect the electronic products such as colour TV, video recorder, computer, communication equipment; α-Fe
3O
4Also can be used for coating industry, market demand is very big.Can be used as catalyzer and produce the cleaning transport fuel, also can be used to make charged lithium cells, important use also be arranged in the magnetic detection field.
ZnO is a kind of wide bandgap semiconductor materials with hexagonal structure, energy gap under the room temperature is 3.34eV, exciton binding energy is up to 60meV, it is the excellent material of preparation ultraviolet photoelectron device, it is important semiconductor material, also be that a few is easy to one of oxide semiconductor of realizing quantum size effect, be widely used as photocell, pottery, pressure-sensitive, transmitter, catalyzer, luminescent material etc.At present, along with the discovery of zinc-oxide nano Development of Preparation Technology and low-voltage high-efficiency fluorescence property, the application of material further expands to fields such as optical filtering, cosmetic, flat pannel display again.These application are all closely related with size of particles and character thereof.
Al
2O
3, TiO
2, ZrO
2, SnO
2And SiO
2At aspects such as catalysis and transmitter manufacturings wide purposes is arranged all Deng material, and large specific surface and have the mesoporous material that uniform pore size distributes and have a wide range of applications.
The meso-hole structure (20-150 ) of preparation metal oxide can bring these oxide material special nature.This cavernous structure has significantly increased the surface-area of metal oxide.And the place that takes place of catalyzed reaction often, the surface of these metal oxides, thereby between Kong Yukong significant electricity, magnetics and the optical property that changes material.The silicon of meso-hole structure, pure aluminium silicate, aluminum phosphate and associated materials are well made.Yet the meso-hole structure of synthesis of metal oxide is wanted the many of difficulty.Because for oxide material,, make progress slow relatively because of the hydrolysis chemistry that is subject to the metal ion complexity and numerous thing phases of corresponding oxide.The work of some establishments has obtained some successes, as Nb
2O
5, TiO
2, ZrO
2, WO
3, and MnOx, used surfactant, comprise the auxiliary surfactant of coordination.1992, utilize the order mesoporous SiO of the synthetic M41S series of template
2The research work of material is in the news out, after this multiple material (TiO
2, Nb
2O
5, Tb
2O
5, ZrO
2, V
2O
5Deng) meso-hole structure all be synthesized out in succession.Mesoporous material has bigger specific surface area, and the duct of aperture and rule distributes uniformly, makes it have the incomparable advantage of common material on catalytic applications.Make catalytic material on using, more be tending towards reality.Yet traditional mesoporous synthetic method is comparatively loaded down with trivial details, and synthesis cycle is also longer, and tradition use tensio-active agent etc. are also comparatively expensive.
Yang Ru; Liu Jianhong; The Chinese patent " preparation method of mesoporous rare-earth oxide " (patent No. 02158777.9) of Li Min application relates to a kind of preparation method of mesoporous rare-earth oxide, comprises preparing gel, solvent exchange and roasting process.The rare earth strong acid salt that will have crystal water is dissolved in the deionized water wiring solution-forming, add water-soluble polymer or water-soluble organic pure and mild organic amine more respectively as mixed templates, under the high-speed stirring condition, with the molten formation chelating of rare earth strong acid salt body, with ammoniacal liquor, urea and urea derivative is precipitation agent, the precipitation from homogeneous solution reaction generates the mesoporous intermediate phase of rare earth element hydroxide, after reacting completely, product is through ageing, deionized water wash, dehydrated alcohol displacement, dry, roasting get the mesoporous rare-earth oxide powder.Do not use vinylformic acid in its method, the present invention is also noncontradictory with it.
Zhang Jinlong; Yuan Shuai; Sheng Qiaorong; Chen Feng; Tian Baozhu; The Chinese patent application of Sun Jian " a kind of method for preparing titanium dioxide mesoporous material " (patent No. 200410025753.4) employing segmented copolymer is a template, adopt the Prepared by Sol Gel Method titanium dioxide mesoporous material, its invention must be used segmented copolymer, and the present invention is not conflict with it.
Sun Yinyong; Former sharp Na; The Chinese patent of Xiao Fengshou " has high specific surface area and mesoporous super acids material and preparation method ", and (patent No. 02132454.9) has high specific surface area and mesoporous super acids material and the preparation method belongs to inorganic chemistry and physical chemistry field.These super acids materials are made up of sulfurized metal oxide MXOY/SO42-, M=Zr4+, and Fe3+, Ti4+, Sn4+ etc., their specific surface area is at 150～200m2/g, and mesoporous variation range is 20nm～200nm.Its preparation method is earlier the soluble salt of metal oxide to be added water in the presence of tensio-active agent to stir, placed 0.5～500 hour at 30～80 ℃, to make the pH value of solution value be 7～10 in the dropping ammonia hydrolysis then, obtains presoma, makes the super acids material through aging, sulfuration, calcining again.The present invention does not need sol-gel process, calcines not conflict with it but will add the precipitation that vinylformic acid moment forms.
Three, summary of the invention
The present invention seeks to: develop the method that a kind of series prepares the mesopore metal oxide powder body material, this method is convenient, and fast, cost is low, highly versatile.Resulting mesoporous material duct size 3nm～10nm, pore size distribution is narrow, is the unordered pore passage structure of vermiform.
The object of the invention also is: at the shortcoming of prior synthesizing method, improve on synthetic work and grope, propose a kind of simple, efficient, quick, cheap synthetic method.
Technical solution of the present invention is: mesoporous metal oxide preparation method: concrete experimental procedure comprises that promptly specific embodiment is:
1 (comprises nitrate with metal-salt, metal-salt such as muriate and vitriol) be dissolved in the aqueous solution of vinylformic acid, butenoic acid and other olefin(e) acid, the mol ratio (stoichiometric ratio) of metal-salt and vinylformic acid or other olefin(e) acid is 1: 0.1～10 to stir in beaker.
2 stir 0.2-2h respectively with beaker.
3 distinguish suction filtrations, and respectively wash drying 1-3 time with distilled water, alcohol.
4 are tiled in dried powder in the crucible, and respectively at certain 200-350 ℃ of temperature roasting 3-8h, temperature rise rate all is 2-8 ℃/min in retort furnace.
5 the present invention are placed on when dry that baking entered roasting in the retort furnace in 2-5 hour again in 50-80 ℃ the baking oven.
Can heat or reconcile the pH value of solution in 6 preparation process of the present invention.
The present invention also comprises, beaker is put into ultrasonic cleaning machine supersound process 3-15min wash suction filtration again.
Described metal-salt comprises vitriol or the nitrate of titanium tetrachloride, Xiao Suangu, zinc sulfate, Tai-Ace S 150, Zn, Sn, Si, Nb, Ti, Zr, W, Mn, V, Ni, Al, promptly comprises vitriol or the nitrate of transition metal, Nb, Ti, Zr, W or V.
The inventive method is not with expensive metal alkoxide, but cheap nitrate, vitriol or the muriate of use cost is as presoma.
Secondly, the inventive method does not use the tensio-active agent of traditional costliness as complexing agent, and is to use comparatively cheap industrial raw material vinylformic acid.
The 3rd, preparation time tapers to several hrs by tens hours to several days of traditional method, has accelerated the production cycle greatly.
The 4th, present method use range is wider, for traditional synthetic method, and synthetic CeO
2, Nb
2O
5, Ta
2O
5, CuO, V
2O
5, NiO, ZnO, Fe
2O
3, Al
2O
3, TiO
2, ZrO
2, SnO
2And SiO
2) must select different tensio-active agents (as cats product and anion surfactant or the like), and the inventive method can only be used one type tensio-active agent.
The 5th, the present invention does not need sol-gel process, calcines but will add the precipitation that vinylformic acid and other organic acids form, and this is and other method essence difference.
Characteristics of the present invention are:
1, reaction times weak point, preparation cycle is short.The mixing process of the raw material of present method and the time of reaction process are all shorter, and the reaction times generally is no more than 5 hours.
2, with low cost.Cost of material of the present invention is comparatively cheap, and production unit requires very simple, does not relate to the higher equipment of cost such as autoclave, and the cost of scale operation is comparatively cheap.
3, of reduced contamination to environment, present method does not relate to the use of other organic solvent except that vinylformic acid, and vinylformic acid is participated in reaction substantially fully, can not produce waste water and waste residue.
4, can synthesize multiple mesopore metal oxide, have good versatility.Present method can be synthesized Nb
2O
5, Ta
2O
5, CuO, V
2O
5, NiO, ZnO, Fe
2O
3, Al
2O
3, TiO
2, ZrO
2, SnO
2And SiO
2Etc. multiple mesopore metal oxide.
Four, description of drawings
Fig. 1 is the XRD figure of the product of embodiment 1,
Fig. 2 is the pore size distribution curve of the product of embodiment 1;
Five. embodiment
Embodiment 1: stoichiometric ratio is that 1: 1 Xiao Suangu mixed in beaker ten minutes with vinylformic acid, gained sedimentation and filtration, washing, the clay crucible of packing into, be positioned in the retort furnace, take out through 300 degrees centigrade of calcinings of five hours, the suitable grinding of the product that obtains can obtain mesoporous Co
4O
3Increase acrylic acid consumption, make stoichiometric ratio be 1: 3 with had identical result at 1: 5 o'clock.
Embodiment 2: stoichiometric ratio is that 1: 2 aluminum chloride mixed in beaker ten minutes with vinylformic acid, gained sedimentation and filtration, washing, the clay crucible of packing into, be positioned in the retort furnace, take out through 300 degrees centigrade of calcinings of five hours, the suitable grinding of the product that obtains can obtain mesoporous Al
2O
3, temperature rise rate 5 or 8 ℃/min do not have remarkable difference.Tai-Ace S 150, zinc sulfate or ferrous sulfate obtain mesoporous Al with above-mentioned technology is corresponding
2O
3,, meso-porous ZnO, mesoporous Fe
2O
3
Embodiment 3: stoichiometric ratio is that 1: 9 titanium tetrachloride mixed in beaker ten minutes with vinylformic acid, the gained sedimentation and filtration, washing, the clay crucible of packing into, be positioned in the retort furnace through the calcining of 300 or 350 degrees centigrade five or three hours and take out, the suitable grinding of the product that obtains can obtain mesoporous TiO
2,, temperature rise rate 3-8 ℃/min does not have remarkable difference.The amount of substance of butenoic acid also can obtain mesoporous TiO with acrylic acid amount as above-mentioned condition
2
Xiao Suangu, zinc sulfate or Tai-Ace S 150 are that raw material obtains mesoporous cobalt oxide, zinc oxide or aluminium sesquioxide.But the calcination temperature difference in the retort furnace is respectively through 300,320 or 350 degrees centigrade of calcination in four hours.When being raw material with the single nickel salt with the condition of zinc sulfate.
According to The above results, this preparation mesopore metal oxide synthetic method range of application of the present invention is wider.By the control reaction conditions, just can obtain sulfide through simple calcining from corresponding oxide compound, reaction conditions is simple, with low cost, speed of response is fast, does not need complicated conversion unit, invest lessly, very big application prospect is arranged, very big advantage is arranged with respect to traditional synthetic method.
Suitably add stopper 0.5-2% during reaction, commonly used as toluhydroquinone or Resorcinol.
The embodiment of other metal: as above-mentioned condition, the embodiment of strontium nitrate or Strontium Sulphate, manganous sulfate, zirconium sulfate, Sn, V, Nb, W is with the result of embodiment 3.
Fig. 1 is the XRD figure of the product of embodiment 1, by with Co
3O
4The standard diagram of (PDF file number 76-1802) is compared, and can find prepared Co
3O
4Become phase, there is no other impurity.
Fig. 2 is the pore size distribution curve of the product of embodiment 1, and therefrom the pore size distribution range of resultant product is narrower as can be seen, between 7-12nm.
Claims (6)
1, mesoporous metal oxide preparation method: it is characterized in that metal-salt is dissolved in the vinylformic acid, metal-salt and acrylic acid mol ratio are 1: 0.1～10 stirring 0.2-2h, difference suction filtration, and respectively wash 1-3 all over also dry with distilled water, alcohol; Dried powder is tiled in the crucible, and respectively at 200-350 ℃ of temperature roasting 3-8h, temperature rise rate all is 2-8 ℃/min in retort furnace.
2, by the described mesoporous metal oxide preparation method of claim 1: it is characterized in that putting into ultrasonic cleaning machine supersound process 3-15min and wash suction filtration again.
3, by the described mesoporous metal oxide preparation method of claim 1: it is characterized in that metal-salt is comprised transition metal, Nb, Ti, Zr, W, Al, or V, metal-salt comprises muriate, nitric acid or vitriol.
4, by the described mesoporous metal oxide preparation method of claim 1: in 50-80 ℃ baking oven, dried by the fire when it is characterized in that drying 2-5 hour.
5, by the described mesoporous metal oxide preparation method of claim 1: the pH value that it is characterized in that in reaction process, heating or reconciling solution.
6, by the described mesoporous metal oxide preparation method of claim 1: it is characterized in that described metal-salt comprises titanium tetrachloride, Xiao Suangu, zinc sulfate, Tai-Ace S 150.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101434384A (en) * | 2007-11-13 | 2009-05-20 | 科学与工业研究委员会 | Process for preparing of nanowires of metal oxides with dopants in lower valence state |
| CN102169987A (en) * | 2011-01-14 | 2011-08-31 | 南京大学 | Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1198759C (en) * | 2002-06-16 | 2005-04-27 | 吉林大学 | Oxide material with high specific surface area and mesoporous structure and its preparing process |
| CN1239393C (en) * | 2002-12-27 | 2006-02-01 | 北京化工大学 | Method for preparing mesoporous rare-earth oxide |
| DE102004020767A1 (en) * | 2004-04-27 | 2005-11-24 | Basf Ag | Surface-modified metal oxides, process for their preparation and their use in cosmetic preparations |
| CN1296284C (en) * | 2004-08-09 | 2007-01-24 | 武汉大学 | Process for preparing nano metal oxide material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434384A (en) * | 2007-11-13 | 2009-05-20 | 科学与工业研究委员会 | Process for preparing of nanowires of metal oxides with dopants in lower valence state |
| CN102169987A (en) * | 2011-01-14 | 2011-08-31 | 南京大学 | Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material |
| CN102169987B (en) * | 2011-01-14 | 2014-12-24 | 南京大学 | Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material |
| CN109266341A (en) * | 2018-09-28 | 2019-01-25 | 东北大学 | A kind of method of electrochemical modification embedded photoluminescent material |
| CN109266341B (en) * | 2018-09-28 | 2020-03-31 | 东北大学 | Method for electrochemically modifying photoluminescence material |
| CN115745015A (en) * | 2023-01-07 | 2023-03-07 | 山东泰和科技股份有限公司 | Magnetic nanoscale Co 3 O 4 Material, preparation method and application thereof |
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