CN106732498A - The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material - Google Patents
The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material Download PDFInfo
- Publication number
- CN106732498A CN106732498A CN201611138625.XA CN201611138625A CN106732498A CN 106732498 A CN106732498 A CN 106732498A CN 201611138625 A CN201611138625 A CN 201611138625A CN 106732498 A CN106732498 A CN 106732498A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- composite material
- halloysite nanotubes
- dioxide composite
- nanometer titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 82
- 239000002071 nanotube Substances 0.000 title claims abstract description 81
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 96
- 239000002253 acid Substances 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 150000001298 alcohols Chemical class 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 21
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 20
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 18
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Its technical scheme is:The alcohols dispersant of the galapectite after the galapectite of 15 ~ 60 parts of quality or heat treatment, the deionized water of 100 parts of quality, the surfactant of 0 ~ 2 part of quality and 0 ~ 20 part of quality is uniform, acid is added to 3≤pH value < 7 or adds alkali to 7 < pH value≤10, slurry is obtained.According to the mass ratio of Er Yangization Tai ︰ galapectites for (1 ~ 5) ︰ 10, to titaniferous material is added in slurry, are uniformly dispersed, then the mixed material after dispersion is loaded into reactor, and 6 ~ 24h is reacted under the conditions of 100 ~ 220 DEG C;Washing, dries, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.The present invention has the characteristics of process is simple, relatively low, environment-friendly production cost and easy large-scale production, and the halloysite nanotubes/nanometer titanium dioxide composite material specific surface area prepared with the method is big, absorption property is good, photocatalysis efficiency is high.
Description
Technical field
The invention belongs to galapectite nano composite material technical field.Specifically related to a kind of halloysite nanotubes/nanometer two
The preparation method of titanium oxide composite material.
Background technology
Galapectite is a kind of natural nano clay mineral with nano tubular structure, perfect crystalline and Large ratio surface, with
Kaolinite belongs to polymorphic form, aboundresources, low production cost and cleanliness without any pollution.Due to its special nano tubular structure, compared with
Big specific surface area so that halloysite nanotubes have adsorptivity higher, the organic pollution that can be used in adsorptive liquid(Such as
Dyestuff, agricultural chemicals etc.), microorganism, heavy metal ion etc., it can also be used to composite activeness and quietness, surface be modified and efficient catalytic
Carrier of agent etc..
Titanium dioxide has ultraviolet catalytic activity higher, is widely used in organic pollution(Such as decis, organophosphor
Agricultural chemicals, phenol, methyl alcohol etc.)And the catalytic oxidation-reduction degraded of some inorganic matters, so as to play a part of to purify sewage.By
Doping vario-property, can be expanded to visible light wave range by excitation source wavelength, greatly improve catalytic efficiency.
Halloysite nanotubes/nanometer titanium dioxide composite material, the both excellent absorption property with halloysite nanotubes
And dispersive property, water pollutant can be adsorbed, while there is the photocatalysis performance of nano titanium oxide, the pollution that will can be adsorbed
Thing is degraded, therefore, halloysite nanotubes/nanometer titanium dioxide composite material is at a kind of ideal water pollutant purification
Reason material.
At present, preparing the method for halloysite nanotubes/titanium dioxide has sol-gel process, solvent-thermal method etc..Colloidal sol-solidifying
Glue method is that butyl titanate is obtained into precursor sol in galapectite suspension reclaimed water solution, by centrifugation, dry, roasting, grinding, system
Obtain the nano titanium oxide of halloysite nanotubes load(Elegant cloud is passed, the spring heat treatment of Lu elder generation is sub- to titanium dioxide/galapectite degraded
The influence of methyl blue characteristic, Chinese powder industry, 2008, (4):31-34.), the product that butyl titanate is hydrolyzed to form at room temperature
It is amorphous state, by being changed into anatase after the heat treatment under the conditions of uniform temperature, calcining heat is improved, and can promote anatase
Generation and crystal grain growth, but the structure of galapectite can be destroyed.Solvent-thermal method is that butyl titanate is dissolved in into isopropanol to be obtained two
Titania precursor liquid solution, adds galapectite, watery hydrochloric acid regulation pH value, and it is anti-in 160 DEG C to carry out solvent heat in autoclave
24h is answered, washing, the dry content of titanium dioxide that obtains are the titanium dioxide/halloysite nanotubes catalyst of 31.8wt%(Wang essences
The research of titanium dioxide and BiOBr modified composite photocatalysis degradation organic contaminants, Institutes Of Technology Of Zhejiang, 2013.).The party
Titanium dioxide obtained in method is Detitanium-ore-type, particle diameter about 5 ~ 15nm, because the method uses organic matter as solvent, cost compared with
There is certain security risk under height, high temperature and high pressure environment, waste reaction solution has to environment and necessarily pollutes, it is necessary to process.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide a kind of process is simple, low production cost, environment-friendly
With the preparation method of the halloysite nanotubes/nanometer titanium dioxide composite material of easy large-scale production, with the method prepare angstrom
The specific surface area of Lip river stone nanotube/nanometer titanium dioxide composite material is big, adsorption efficiency is high and photocatalysis efficiency is high.
To achieve the above object, the technical solution adopted by the present invention is:
By the galapectite after the galapectite of 15 ~ 60 parts of quality or heat treatment, the deionized water of 100 parts of quality, 0 ~ 2 part of quality table
Face activating agent and 0 ~ 20 part of alcohols dispersant of quality, are uniformly dispersed, and add acid to 3≤pH value < 7 or add alkali to 7
< pH value≤10, are obtained slurry.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (1 ~ 5) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixed material;The mixed material is loaded into reactor again, 6 ~ 24h is reacted under the conditions of 100 ~ 220 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after the heat treatment refers to:Galapectite is heat-treated 0.5 ~ 5h under the conditions of 200 ~ 800 DEG C, heat is obtained final product
Galapectite after treatment.
The surfactant is cetyl trimethylammonium bromide, polyacrylamide, polyethylene glycol, dodecyl sulphate
One kind in sodium and neopelex.
The alcohols dispersant is in ethanol, normal propyl alcohol, diglycol, n-butanol, isobutanol and ethylene glycol
Kind.
The titaniferous material is in butyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid
More than kind.
The acid is the one kind in hydrochloric acid, nitric acid, sulfuric acid and acetic acid.
The alkali is the one kind in ammoniacal liquor, NaOH and KOH.
There is following positive role compared with prior art due to using above-mentioned technical proposal, the present invention:
1st, the raw material that the present invention is used is easy to get, cheap, with low production cost.
2nd, the present invention, can be by hydro-thermal reaction in galapectite nanometer by surfactant, the selection of alcohols dispersant
The nano titanium oxide crystal grain of various grain sizes and pattern is grown on pipe.
3rd, the present invention prepares halloysite nanotubes/nanometer titanium dioxide composite material using hydro-thermal method, with reaction temperature
Low, energy consumption is low, and epigranular is controllable, reunion degree is small, and course of reaction environmental pollution it is small the characteristics of.
4th, manufacturing parameter of the present invention is easy to control, easily realizes automated production, technological process is simple, the production cycle is shorter,
Efficiency high, is easy to industrialized production.
Therefore, the present invention has the characteristics of relatively easy technique, low production cost, environment-friendly and easy large-scale production,
Prepared halloysite nanotubes/nanometer titanium dioxide composite material specific surface area is big, adsorption efficiency is high and photocatalysis efficiency is high.
Brief description of the drawings
Fig. 1 is a kind of XRD spectrum of halloysite nanotubes/nanometer titanium dioxide composite material prepared by the present invention;
Fig. 2 is the TEM photos of the halloysite nanotubes/nanometer titanium dioxide composite material shown in Fig. 1;
Fig. 3 is the TEM photos of another halloysite nanotubes/nanometer titanium dioxide composite material prepared by the present invention;
Fig. 4 is the TEM photos of another halloysite nanotubes/nanometer titanium dioxide composite material prepared by the present invention.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
Embodiment 1
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
By the galapectite after 15 ~ 25 parts of heat treatments of quality, the deionized water of 100 parts of quality and 1 ~ 6 part of alcohols dispersion of quality
Agent mixes, and is uniformly dispersed, and adds acid to 3≤pH value < 7, and slurry is obtained.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (1 ~ 2) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixture grain;The mixed material is loaded into reactor again, 6 ~ 10h is reacted under the conditions of 100 ~ 150 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after described heat treatment refers to:Galapectite is heat-treated 0.5 ~ 2.5h under the conditions of 200 ~ 400 DEG C, i.e.,
Galapectite after must being heat-treated.
The surfactant is cetyl trimethylammonium bromide.
The alcohols dispersant is ethanol.
The titaniferous material is butyl titanate.
The acid is sulfuric acid.
Embodiment 2
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 1:
The titaniferous material is the mixture of butyl titanate and tetraisopropyl titanate.
Embodiment 3
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 1:
The titaniferous material is the mixture of butyl titanate and titanium tetrachloride.
The acid is nitric acid.
Embodiment 4
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 1:
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate and titanium tetrachloride.
The acid is nitric acid.
Embodiment 5
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 1:
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate and titanium trichloride.
The acid is hydrochloric acid.
Embodiment 6
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 1:
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate, titanium tetrachloride and titanium trichloride.
The acid is acetic acid.
Embodiment 7
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
The surface of the galapectite after 25 ~ 35 parts of heat treatments of quality, the deionized water of 100 parts of quality, 0.1 ~ 0.8 part of quality is lived
Property agent and 5 ~ 11 parts of alcohols dispersants of quality, be uniformly dispersed, add alkali to 7 < pH value≤10, slurry is obtained.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (2 ~ 3) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixture grain;The mixed material is loaded into reactor again, 10 ~ 15h is reacted under the conditions of 120 ~ 170 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after described heat treatment refers to:Galapectite is heat-treated 2.5 ~ 3.5h under the conditions of 350 ~ 550 DEG C, i.e.,
Galapectite after must being heat-treated.
The surfactant is polyacrylamide.
The alcohols dispersant is normal propyl alcohol.
The titaniferous material is the mixing of butyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid
Thing.
The alkali is ammoniacal liquor.
Embodiment 8
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 7:
The titaniferous material is tetraisopropyl titanate.
Embodiment 9
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 7:
The titaniferous material is the mixture of butyl titanate and titanium trichloride.
The alkali is NaOH.
Embodiment 10
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 7:
The titaniferous material is the mixture of butyl titanate and metatitanic acid.
The alkali is NaOH.
Embodiment 11
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 7:
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate and metatitanic acid.
The alkali is KOH.
Embodiment 12
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 7:
The titaniferous material is the mixture of butyl titanate, titanium tetrachloride and titanium trichloride.
The alkali is KOH.
Embodiment 13
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
The surface of the galapectite after 35 ~ 45 parts of heat treatments of quality, the deionized water of 100 parts of quality, 0.6 ~ 1.4 part of quality is lived
Property agent and 10 ~ 16 parts of alcohols dispersants of quality, be uniformly dispersed, add acid to 3≤pH value < 7, slurry is obtained.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (3 ~ 4) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixed material;The mixed material is loaded into reactor again, 12 ~ 17h is reacted under the conditions of 140 ~ 190 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after the heat treatment refers to:Galapectite is heat-treated 3 ~ 4h under the conditions of 500 ~ 700 DEG C, hot place is obtained final product
Galapectite after reason.
The surfactant is polyethylene glycol.
The alcohols dispersant is diglycol.
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate, titanium tetrachloride and metatitanic acid.
The acid is hydrochloric acid.
Embodiment 14
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 13:
The titaniferous material is titanium tetrachloride.
Embodiment 15
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 13:
The titaniferous material is the mixture of tetraisopropyl titanate and titanium tetrachloride.
The acid is acetic acid.
Embodiment 16
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 13:
The titaniferous material is the mixture of tetraisopropyl titanate and titanium trichloride.
The acid is acetic acid.
Embodiment 17
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 13:
The titaniferous material is the mixture of butyl titanate, titanium tetrachloride and metatitanic acid.
The acid is sulfuric acid.
Embodiment 18
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 13:
The titaniferous material is the mixture of butyl titanate, titanium trichloride and metatitanic acid.
The acid is nitric acid.
Embodiment 19
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
The surface of the galapectite after 45 ~ 55 parts of heat treatments of quality, the deionized water of 100 parts of quality, 1.2 ~ 1.8 parts of quality is lived
Property agent and 15 ~ 20 parts of alcohols dispersants of quality, be uniformly dispersed, add alkali to 7 < pH value≤10, slurry is obtained.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (4 ~ 5) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixed material;The mixed material is loaded into reactor again, 17 ~ 20h is reacted under the conditions of 160 ~ 200 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after the heat treatment refers to:Galapectite is heat-treated 4 ~ 5h under the conditions of 600 ~ 800 DEG C, hot place is obtained final product
Galapectite after reason.
The surfactant is lauryl sodium sulfate.
The alcohols dispersant is n-butanol.
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate, titanium trichloride and metatitanic acid.
The alkali is ammoniacal liquor.
Embodiment 20
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 19:
The titaniferous material is titanium trichloride.
Embodiment 21
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 19:
The titaniferous material is the mixture of tetraisopropyl titanate and metatitanic acid.
The alkali is NaOH.
Embodiment 22
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 19:
The titaniferous material is the mixture of titanium tetrachloride and titanium trichloride.
The alkali is NaOH.
Embodiment 23
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 19:
The titaniferous material is the mixture of tetrabutyl titanate, titanium tetrachloride and titanium trichloride.
The alkali is KOH.
Embodiment 24
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 19:
The titaniferous material is the mixture of tetrabutyl titanate, titanium tetrachloride and metatitanic acid.
The alkali is KOH.
Embodiment 25
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
50 ~ 60 parts of galapectites of quality, the deionized water of 100 parts of quality and 1.6 ~ 2 parts of surfactants of quality are mixed, point
Dissipate uniform, add acid to 3≤pH value < 7, slurry is obtained.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (2.5 ~ 3.5) ︰ 10, to titaniferous material is added in the slurry, divide
Dissipate uniform, obtain mixed material;The mixed material is loaded into reactor again, 20 ~ 24h is reacted under the conditions of 180 ~ 220 DEG C;So
After be washed with deionized, dry, be obtained halloysite nanotubes/nanometer titanium dioxide composite material.
The surfactant is neopelex.
The alcohols dispersant is isobutanol.
The titaniferous material is the mixture of butyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid.
The acid is acetic acid.
Embodiment 26
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 25:
The titaniferous material is metatitanic acid.
Embodiment 27
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 25:
The titaniferous material is the mixture of titanium tetrachloride and metatitanic acid.
The acid is sulfuric acid.
Embodiment 28
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 25:
The titaniferous material is the mixture of titanium trichloride and metatitanic acid.
The acid is sulfuric acid.
Embodiment 29
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 25:
The titaniferous material is the mixture of tetrabutyl titanate, titanium trichloride and metatitanic acid.
The acid is nitric acid.
Embodiment 30
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 25:
The titaniferous material is the mixture of titanium tetrachloride, titanium trichloride and metatitanic acid.
The acid is acetic acid.
Embodiment 31
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
The galapectite of 40 ~ 50 parts of quality and 100 parts of deionized waters of quality are mixed, is uniformly dispersed, add acid to 3≤pH value
< 7, is obtained slurry.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (2 ~ 3) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixed material;The mixed material is loaded into reactor again, 8 ~ 10h is reacted under the conditions of 140 ~ 160 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
The surfactant is polyethylene glycol.
The alcohols dispersant is ethylene glycol.
The titaniferous material is the mixture of tetraisopropyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid.
The acid is sulfuric acid.
Embodiment 32
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 31:
The titaniferous material is titanium tetrachloride.
The acid is hydrochloric acid.
Embodiment 33
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 31:
The titaniferous material is the mixture of tetraisopropyl titanate and titanium trichloride.
The acid is acetic acid.
Embodiment 34
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.Preparation method is described in the present embodiment:
Galapectite after 30 ~ 50 parts of heat treatments of quality and 100 parts of deionized waters of quality are mixed, is uniformly dispersed, added
Alkali is obtained slurry to 7 < pH value≤10.
According to the mass ratio of Er Yangization Tai ︰ galapectites for (3 ~ 4) ︰ 10, to titaniferous material is added in the slurry, dispersion is equal
It is even, obtain mixed material;The mixed material is loaded into reactor again, 12 ~ 16h is reacted under the conditions of 180 ~ 200 DEG C;Then use
Deionized water is washed, and is dried, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
Galapectite after the heat treatment refers to:Galapectite is heat-treated 2 ~ 3h under the conditions of 400 ~ 600 DEG C, hot place is obtained final product
Galapectite after reason.
The surfactant is cetyl trimethylammonium bromide.
The alcohols dispersant is ethylene glycol.
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate, titanium trichloride and metatitanic acid.
The alkali is ammoniacal liquor.
Embodiment 35
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 35:
The titaniferous material is the mixture of tetrabutyl titanate, titanium tetrachloride and metatitanic acid.
The alkali is NaOH.
Embodiment 36
A kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material.The present embodiment in addition to following materials, remaining
With embodiment 35:
The titaniferous material is the mixture of butyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid.
The alkali is KOH.
This specific embodiment has following good effect compared with prior art:
1st, the raw material that this specific embodiment is used is easy to get, cheap, with compared with production cost.
2nd, this specific embodiment is by surfactant, the selection of alcohols dispersant, can by hydro-thermal reaction angstrom
The nano titanium oxide crystal grain of various grain sizes as shown in drawings and pattern is grown on the stone nanotube of Lip river.Fig. 1 is implementation
The XRD spectrum of a kind of halloysite nanotubes/nanometer titanium dioxide composite material prepared by example 3, it will be seen from figure 1 that titanium dioxide
The crystal formation of titanium is, with preferable photocatalytic activity Detitanium-ore-type, the grain size of nano titanium oxide to be calculated using Scherrer formula
About 10nm.Fig. 2 is the TEM photos of the halloysite nanotubes/nanometer titanium dioxide composite material shown in Fig. 1, can from Fig. 2
Go out, nano titanium oxide is more evenly distributed on the outer wall of halloysite nanotubes, grain size is about 10nm, with XRD points
Analysis result is consistent.Fig. 3 is that the TEM of another halloysite nanotubes/nanometer titanium dioxide composite material prepared by embodiment 6 shines
Piece, from figure 3, it can be seen that the load capacity of nano titanium oxide is larger, the crystallite dimension of nano titanium oxide is about 10nm.Fig. 4
It is the TEM photos of another halloysite nanotubes/nanometer titanium dioxide composite material prepared by embodiment 28, can from Fig. 4
Go out, the galapectite after heat treatment still maintains the average crystal grain of nano tubular structure, nano titanium oxide to be about 10nm.
3rd, this specific embodiment prepares halloysite nanotubes/nanometer titanium dioxide composite material using hydro-thermal method, has
Reaction temperature is low, energy consumption is low, and epigranular is controllable, reunion degree is small, and course of reaction environmental pollution it is small the characteristics of.
4th, this specific embodiment manufacturing parameter is easy to control, easily realizes automated production, and technological process is simple, production week
Phase is shorter, efficiency high, is easy to industrialized production.
Therefore, this specific embodiment also has that technique is relatively easy, production cost is relatively low, environment-friendly and easy scale metaplasia
The characteristics of product, the halloysite nanotubes/nanometer titanium dioxide composite material specific surface area of preparation is big, adsorption efficiency is high and photocatalysis
Efficiency high.
The present invention has the characteristics of controllable product property and easy large-scale production, the galapectite nanometer prepared with the method
Pipe/nanometer titanium dioxide composite material, has the advantages that specific surface area is big, adsorption efficiency is high, photocatalysis efficiency is high.
Claims (7)
1. a kind of preparation method of halloysite nanotubes/nanometer titanium dioxide composite material, it is characterised in that by 15 ~ 60 parts of quality
Galapectite or heat treatment after galapectite, the deionized water of 100 parts of quality, the surfactant of 0 ~ 2 part of quality and 0 ~ 20 part
The alcohols dispersant of quality, is uniformly dispersed, and adds acid to 3≤pH value < 7 or adds alkali to 7 < pH value≤10, is obtained
Slurry;
According to Er Yangization Tai ︰ galapectites mass ratio for (1 ~ 5) ︰ 10, to titaniferous material is added in the slurry, are uniformly dispersed,
Obtain mixed material;The mixed material is loaded into reactor again, 6 ~ 24h is reacted under the conditions of 100 ~ 220 DEG C;Then spend from
Sub- water washing, dries, and halloysite nanotubes/nanometer titanium dioxide composite material is obtained.
2. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
Refer in the galapectite after the heat treatment:Galapectite is heat-treated 0.5 ~ 5h under the conditions of 200 ~ 800 DEG C, after obtaining final product heat treatment
Galapectite.
3. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
In the surfactant be cetyl trimethylammonium bromide, polyacrylamide, polyethylene glycol, lauryl sodium sulfate and ten
One kind in dialkyl benzene sulfonic acids sodium.
4. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
One kind in the alcohols dispersant is ethanol, normal propyl alcohol, diglycol, n-butanol, isobutanol and ethylene glycol.
5. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
In the titaniferous material is butyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium trichloride and metatitanic acid it is a kind of with
On.
6. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
One kind in the acid is for hydrochloric acid, nitric acid, sulfuric acid and acetic acid.
7. the preparation method of halloysite nanotubes/nanometer titanium dioxide composite material according to claim 1, its feature exists
One kind in the alkali is ammoniacal liquor, NaOH and KOH.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611138625.XA CN106732498A (en) | 2016-12-12 | 2016-12-12 | The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611138625.XA CN106732498A (en) | 2016-12-12 | 2016-12-12 | The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106732498A true CN106732498A (en) | 2017-05-31 |
Family
ID=58879960
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611138625.XA Pending CN106732498A (en) | 2016-12-12 | 2016-12-12 | The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106732498A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107349924A (en) * | 2017-08-07 | 2017-11-17 | 浙江工业大学 | BiVO4/ galapectite composite nano catalysis material and preparation method thereof |
CN107837802A (en) * | 2017-11-03 | 2018-03-27 | 盛槿滺 | A kind of composite photo-catalyst and preparation method thereof |
CN108479780A (en) * | 2018-05-08 | 2018-09-04 | 宁波工程学院 | A kind of preparation method of optomagnetic response halloysite nanotubes hollow microsphere |
CN113842875A (en) * | 2021-10-15 | 2021-12-28 | 内蒙古工业大学 | Preparation method of halloysite-loaded zirconium oxide nanocomposite |
CN115135602A (en) * | 2020-02-28 | 2022-09-30 | 杰富意矿物股份有限公司 | Halloysite powder |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105195119A (en) * | 2015-10-28 | 2015-12-30 | 内蒙古科技大学 | Preparation method and application of basalt fiber-TiO2 composite material |
CN105597798A (en) * | 2016-03-03 | 2016-05-25 | 电子科技大学 | Three-phase composite photocatalyst and preparation method thereof |
-
2016
- 2016-12-12 CN CN201611138625.XA patent/CN106732498A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105195119A (en) * | 2015-10-28 | 2015-12-30 | 内蒙古科技大学 | Preparation method and application of basalt fiber-TiO2 composite material |
CN105597798A (en) * | 2016-03-03 | 2016-05-25 | 电子科技大学 | Three-phase composite photocatalyst and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
DIMITRIOS PAPOULIS ET AL.: "Halloysite–TiO2 nanocomposites: Synthesis, characterization and photocatalytic activity", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
程志林,孙伟: "埃洛石纳米硅铝管(HNTs)的结构和物理性能", 《石油学报(石油加工)》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107349924A (en) * | 2017-08-07 | 2017-11-17 | 浙江工业大学 | BiVO4/ galapectite composite nano catalysis material and preparation method thereof |
CN107837802A (en) * | 2017-11-03 | 2018-03-27 | 盛槿滺 | A kind of composite photo-catalyst and preparation method thereof |
CN108479780A (en) * | 2018-05-08 | 2018-09-04 | 宁波工程学院 | A kind of preparation method of optomagnetic response halloysite nanotubes hollow microsphere |
CN115135602A (en) * | 2020-02-28 | 2022-09-30 | 杰富意矿物股份有限公司 | Halloysite powder |
CN113842875A (en) * | 2021-10-15 | 2021-12-28 | 内蒙古工业大学 | Preparation method of halloysite-loaded zirconium oxide nanocomposite |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106732498A (en) | The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material | |
CN102489284B (en) | Graphene composite titanium dioxide photocatalyst capable of magnetic separation and recovery, and preparation method thereof | |
Gao et al. | Preparation and properties of silica nanoparticles from oil shale ash | |
Zhao et al. | Unique bar-like sulfur-doped C3N4/TiO2 nanocomposite: excellent visible light driven photocatalytic activity and mechanism study | |
CN101062475B (en) | Metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof | |
CN1915835A (en) | Method for preparing Nano line of titania, and application of the prepared Nano line of titania | |
CN102319564B (en) | Preparation method of urchin-like titanium dioxide magnetic microspheres having double-layer cavity structures | |
Li et al. | Effective photocatalytic decolorization of methylene blue utilizing ZnO/rectorite nanocomposite under simulated solar irradiation | |
CN101670280B (en) | Titanium dioxide microspheroidal photocatalyst with high active surface and preparation method thereof | |
CN104759273B (en) | A kind of preparation method of carbon doping hollow titanium dioxide visible light catalyst in situ | |
CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
CN103752330B (en) | A kind of preparation method of ZnO/ZnS composite photocatalyst thin-film | |
CN103657623A (en) | Microballoon-type titanium dioxide photocatalyst and preparation method thereof | |
Ren et al. | In situ synthesis of gC 3 N 4/TiO 2 heterojunction nanocomposites as a highly active photocatalyst for the degradation of Orange II under visible light irradiation | |
CN101485981B (en) | Method for preparing inorganic antimicrobial composite material | |
CN101371981A (en) | Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method | |
CN102180515A (en) | Preparation method for nano titanium dioxide with high visible light catalytic activity and water dispersion thereof | |
CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
CN104923230A (en) | Titanium dioxide/ferroferric oxide nanocomposite and preparation method therefor | |
CN1686823A (en) | Method for preparing anatase type nano-titanium dioxide in high phase-transition temperature and high specific area | |
CN102872846A (en) | Coal ash microsphere loaded one-dimensional nanometer titanium dioxide (TiO2) composite photocatalyst and preparation method thereof | |
Ehsan et al. | ZnO nanocomposites supported by acid-activated kaolinite as photocatalysts for the enhanced photodegradation of an organic dye | |
CN106238088B (en) | A kind of polymolecularity g-C3N4/TiO2Photocatalyst inorganic aqueous sol preparation method | |
CN104785304A (en) | Preparation and application of novel nano-heterostructure solar photocatalyst | |
CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |