CN106955683A - A kind of visible light-responded TiO2The preparation method of presoma and obtained TiO2Presoma and catalyst - Google Patents
A kind of visible light-responded TiO2The preparation method of presoma and obtained TiO2Presoma and catalyst Download PDFInfo
- Publication number
- CN106955683A CN106955683A CN201610017971.6A CN201610017971A CN106955683A CN 106955683 A CN106955683 A CN 106955683A CN 201610017971 A CN201610017971 A CN 201610017971A CN 106955683 A CN106955683 A CN 106955683A
- Authority
- CN
- China
- Prior art keywords
- presoma
- tio
- preparation
- visible light
- catalyst
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002738 chelating agent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 12
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000005286 illumination Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 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 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910011210 Ti—O—N Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 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 description 1
- 150000003839 salts Chemical class 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of visible light-responded TiO2The preparation method of presoma and obtained TiO2Presoma and catalyst, wherein preparation method comprise the following steps:1) titanate esters are placed in reaction vessel, add nitrogen-containing compound, be heated to reflux;2) at room temperature~100 DEG C, chelating agent is added, is heated to reflux;3) at room temperature~80 DEG C, the mixed liquor of water and alcohol is instilled, drips off and is depressurized after backflow, cooling except solvent obtains described TiO2Presoma.Visible light-responded TiO provided by the present invention2Forerunner's physical efficiency is dissolved in usual vehicle, so that can be loaded by simply impregnating on fiber, sheet material, porous material (such as molecular sieve) matrix, then the matrix high temperature sintering under air of presoma will be loaded, presoma is transformed into visible light-responded TiO2Photocatalyst solved the problems, such as the recovery of catalyst on matrix, both, and general T iO is solved again2Catalyst to visible ray without response the problem of.
Description
Technical field
The invention belongs to material science, specifically, it is related to a kind of visible light-responded TiO2The preparation method of presoma
And obtained TiO2Presoma and catalyst.
Background technology
Since twentieth century, with the continuous development of scientific technology with progress, global industry has obtained unprecedented development.
However, industrial expansion is while promoting economic development with being offered convenience for human lives, but also people is destroyed in merciless
The influence that the environment that class is depended on for existence, the air pollution brought by industrial development and water pollution problems are lived to people has become to get over
Come more obvious.Photocatalysis oxidation technique based on semiconductor catalyst is increasingly subject to domestic and international as a kind of high-level oxidation technology
The concern of person.Almost all of organic matter under photocatalysis can complete oxidation be CO2And H2The simple inorganic matter such as O,
In addition, photochemical catalyst can also reduce the heavy metal ion in water.In conventional semiconductor light-catalyst, TiO2With work
Property high, good stability, can not produce secondary pollution without the various organic pollutions of selectively mineralising, harmless, valency
Many advantages, such as lattice are cheap, the photochemical catalyst as most being paid attention to and with broad prospect of application.
TiO2The photocatalysis characteristic of semiconductor confirms by many research institutes, but to move towards practical and also need to solve two keys
Problem:1. traditional photocatalysis research is general is carried out in suspended state light-catalyzed reaction system, there is TiO2Powder is easily reunited,
It is difficult to the problems such as continuous separation, recovery and regeneration of catalyst;②TiO2Many the having in ultraviolet light of photochemical catalytic oxidation
It could be carried out in the long scope of notch, it is low using the ratio of sunshine, limit to the popularization and application of photocatalysis technology.Therefore, will
Being fixed of catalyst, and how by changing TiO2Property, makes it be reacted under visible light, for photocatalysis
Application of the oxidation technology in air cleaning and water process has a great deal of practical meanings.
CN102515271A discloses a kind of TiO with visible light catalysis activity2Powder and preparation method thereof.Described
TiO2Each crystal content scope of powder is:Anatase (TiO2) 90-100wt%, rutile (TiO2) 0-10wt%, it is made
Standby process main points are that precursor liquid A is prepared by raw material of tetra-n-butyl titanate, absolute ethyl alcohol and glacial acetic acid, by redistilled water
With absolute ethyl alcohol wiring solution-forming, salt acid for adjusting pH value 1-5 is added, dropping liquid B is prepared, dropping liquid B is added drop-wise to precursor liquid
In A, constant temperature water bath stirring stands a period of time drying, grinding and calcining again, that is, obtaining has high light catalytic activity
TiO2Powder, the TiO of the invention2Powder has stronger in the range of wide spectrum under the irradiation of ultraviolet light and visible ray
Light absorbs and photoresponse, are a kind of TiO with visible light catalysis activity2Powder, its preparation technology is simple, equipment is cheap,
Course of reaction is easily controlled, but two kinds of solution are used in the invention, and what is obtained after two kinds of solution mixing is still powder, powder
Catalyst is obtained by drying and calcining, but resulting catalyst exists in powder form, is unfavorable for the recycling of catalyst,
Even if reclaim there is also after recovery it is secondary use when easily reunite, so as to reduce photocatalysis performance so that the dioxy of unit mass
Change the problem of titanium utilization rate is low.
" visible light activity TiO2Preparation and sign "【Zhao Dan, E Lei, wait visible light activities TiO2Preparation and sign [J],
Urban Construction Institutes Of Tianjin's journal, in March, 2010, the 1st phase of volume 16:33-36】With TiOSO4It is logical for raw material with ammoniacal liquor
Cross chemical precipitation method and be prepared for the nanometer Ti-O-N photochemical catalysts with visible light activity, and using SEM, BET, XRD,
The detection methods such as UV-vis, ESR and XPS are characterized to its performance, and have studied light by methyl orange solution degradation experiment urges
The catalytic activity of agent under visible light, discusses the factors such as specific surface area, visible absorption intensity, crystalline structure to its light
The influence of catalytic activity, obtained nanometer Ti-O-N photochemical catalysts after heat treatment can stronger absorbing wavelength scope be
400-600nm visible ray, and visible absorption intensity and the heat treatment temperature of powder are closely related.Photocatalysis test shows:
Absorption of the photochemical catalyst through 400 DEG C of heat treatment to visible ray is most strong, and with relatively large specific surface area and develops more complete
Whole crystalline structure, therefore best photocatalytic activity is shown under visible light.But resulting catalyst is in powder form
In the presence of, be unfavorable for the recycling of catalyst, even if reclaim there is also after recovery it is secondary use when easily reunite, so as to reduce
Photocatalysis performance so that the problem of titanium dioxide utilization rate of unit mass is low.
To sum up, the TiO that prepared by prior art2Photochemical catalyst typically exists in powder form, and light-catalyzed reaction is typically in suspended state
Carried out in light-catalyzed reaction system, there is that sedimentation is difficult, recovery difficult is big, TiO2Powder is easily reunited, it is difficult to realize catalyst
Continuous separation, recovery and regeneration the problems such as;Also there is the correlative study for being loaded powder, but generally existing is loaded
It is uneven, the problem of easy dry linting;Furthermore, general T iO2Catalyst only has response to ultraviolet light, and the ultraviolet light in sunshine
Part only account for less than 5%, and these problems seriously limit TiO2The application of photochemical catalyst in practice.Polymer precursor
Adjustable with structure, component is adjustable, and doping is convenient, good film-forming property, it is easier to the advantages of soft template is combined, and is preparing load
There is certain advantage in terms of type photochemical catalyst, visible light-responded photochemical catalyst and coating.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to overcome drawbacks described above, there is provided a kind of visible light-responded TiO2The preparation method of presoma.Adopt
Be a kind of macromolecular organic compound with presoma made from preparation method provided by the present invention, with organic macromolecule plus
Work characteristic, can be loaded by simply impregnating on fiber, sheet material or porous material (such as molecular sieve) matrix,
Then the matrix high temperature sintering under air of presoma will be loaded, presoma occurs inorganization, is transformed into visible light-responded TiO2
Photocatalyst is on matrix, and this had both solved the problems, such as the recovery of catalyst, and general T iO is solved again2Catalyst is to visible
The problem of light is without response.
To achieve the above object, the present invention is adopted the following technical scheme that:
A kind of visible light-responded TiO2The preparation method of presoma, wherein, described preparation method comprises the following steps:
1) titanate esters are placed in reaction vessel, add nitrogen-containing compound, be heated to reflux;
2) at room temperature~100 DEG C, chelating agent is added, is heated to reflux;
3) at room temperature~80 DEG C, instill the mixed liquor of water and alcohol, drip off depressurized after backflow, cooling except solvent obtain described in can
See the TiO of photoresponse2Presoma.
In the prior art, TiO2Photochemical catalyst typically exists in powder form, and light-catalyzed reaction is typically in suspended state light-catalyzed reaction
Carried out in system, there is that sedimentation is difficult, recovery difficult is big, TiO2Powder is easily reunited, it is difficult to realize catalyst continuous separation,
The problems such as recovery and regeneration;Also there is the correlative study for being loaded powder, but generally existing loads uneven, easy dry linting
The problem of;Furthermore, general T iO2Catalyst only has response to ultraviolet light, and the ultraviolet portion in sunshine only account for less than 5%,
These problems seriously limit TiO2The application of photochemical catalyst in practice.
In the present invention, titanate esters are placed in reaction vessel first, nitrogen-containing compound is then added, are heated to reflux after a period of time,
Chelating agent is added at room temperature~100 DEG C, is heated to reflux after a period of time again at room temperature~80 DEG C, the mixed liquor of water and alcohol is instilled,
Drip off removal of solvent under reduced pressure after backflow, cooling and obtain a kind of visible light-responded TiO2Photochemical catalyst presoma, this presoma is one
Macromolecular organic compound is planted, with organic macromolecule processing characteristics, can be dissolved in usual vehicle, therefore can be by simple
Dipping can be loaded on fiber, sheet material or porous material (such as molecular sieve) matrix, then will load presoma
Matrix high temperature sintering under air, presoma occurs inorganization, is transformed into visible light-responded TiO2Photocatalyst is in base
On body, this had both solved the problems, such as the recovery of catalyst, and general T iO is solved again2Catalyst to visible ray without response the problem of.
In above-mentioned preparation method, wherein, titanate esters, nitrogen-containing compound, the mol ratio of chelating agent and water are 1:(0.1~3):
(0.3~1):(0.8~1.3).
Titanate esters, nitrogen-containing compound, chelating agent and water mol ratio selection it is improper will be unable to obtain solvable presoma, reacted
Precipitation occurs in journey.The present invention passes through substantial amounts of experiment, and the mol ratio for determining titanate esters, nitrogen-containing compound, chelating agent and water is
1:(0.1~3):(0.3~1):(0.8~1.3).In the molar ratio range, you can obtain solvable presoma.
Described water and the mixed liquor reclaimed water of alcohol and the mol ratio of alcohol are 1:(3~20).
Step 1) described in time for being heated to reflux be 0.5~5h;Step 2) described in time for being heated to reflux be 0.5~5h;
Step 3) described in time for flowing back be 1~8h.
Step 1) in, described titanate esters are tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, butyl titanate or
One or more of mixtures in tetrabutyl titanate.
Step 1) in, described nitrogen-containing compound is monoethanolamine, acetamide, DMA, glycine or the third ammonia
One or more of mixtures in acid, preferred alcohol amine, acetamide or DMA.
Step 2) described in chelating agent be one or two kinds of mixtures in acetylacetone,2,4-pentanedione or ethyl acetoacetate.
Step 3) described in water and alcohol mixed liquor in, alcohol be ethanol, normal propyl alcohol, isopropanol, n-butanol or isobutanol in
One or more of mixtures.
The present invention also aims to provide a kind of visible light-responded TiO2Presoma.
Described visible light-responded TiO2Presoma is prepared using above-mentioned preparation method of the invention.
Described visible light-responded TiO2Presoma is dissolved in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol
In the mixed solvent of any of single ether, toluene or dimethylbenzene solvent or several solvents.
The present inventor is by described visible light-responded TiO2Presoma is dissolved in normal propyl alcohol, and the Ti contents for controlling solution are 2%,
The mass ratio for adding PEG-600, wherein PEG-600 and Ti is 1:2, the precursor solution of configuration is carried out on Si pieces
It is coated with, 500 DEG C of sintering 30min can obtain Si pieces load TiO2Catalyst coat, the electricity for the coating clapped from different perspectives
Mirror photo is as shown in Fig. 1-1 and Fig. 1-2.Show, visible ray TiO of the invention2Presoma has good film forming, and
The porous of film can be regulated and controled by adding pore-foaming agent PEG, the TiO after cracking2Catalyst can be carried on Si pieces well.
In the present invention, described visible light-responded TiO2Presoma is dissolved in usual vehicle, expands its application, can
Preparation for the various products such as coating, fiber.
The present invention also provides a kind of visible light-responded TiO2Catalyst.
Specifically, described TiO2Catalyst is the visible light-responded TiO for preparing preparation method of the present invention2Before
Drive body and crack what is obtained for 350~500 DEG C under air.
Compared with prior art, the invention has the advantages that:
In the prior art, TiO2Photochemical catalyst typically exists in powder form, and light-catalyzed reaction is typically anti-in suspended state photocatalysis
Answer in system and carry out, there is TiO2Powder is easily reunited, it is difficult to realize that continuous separation, recovery and regeneration of catalyst etc. are asked
Topic;Also there is a correlative study for being loaded powder, but generally existing load is uneven, the problem of easy dry linting;Furthermore, it is general
Logical TiO2Catalyst only has response to ultraviolet light, and the ultraviolet portion in sunshine only account for less than 5%, and these problems are tight
TiO is limited again2The application of photochemical catalyst in practice.The present invention is prepared for a kind of visible light-responded TiO2Before photochemical catalyst
Body is driven, this presoma is a kind of macromolecular organic compound, with organic macromolecule processing characteristics, therefore can pass through letter
Single dipping can be loaded on fiber, sheet material or porous material (such as molecular sieve) matrix, before then loading
Drive the matrix high temperature sintering under air of body, presoma occurs inorganization, is transformed into visible light-responded TiO2Photochemical catalyst is born
It is loaded on matrix, this had both solved the problems, such as the recovery of catalyst, general T iO is solved again2Catalyst is to visible ray without response
Problem.Specifically, the beneficial effects of the invention are as follows be prepared for TiO nitrogenous in a kind of molecular structure2Presoma, the forerunner
Except there is good photo-catalysis capability under ultraviolet light, (under 500W Hg lamp irradiations, 25min can make first to products obtained therefrom after body cracking
Base orange is degradable), also having good photo-catalysis capability under visible light, (under the irradiation of 500W xenon lamps, 3h is to trichlorophenol, 2,4,6,-T
Degradation rate is 56%, and 52.1%) degradation rate to methyl orange is.
Brief description of the drawings
Fig. 1-1 is that Si pieces load TiO2The electromicroscopic photograph of catalyst coat;
Fig. 1-2 is that Si pieces load TiO2The electromicroscopic photograph of catalyst coat;
Fig. 2 be presoma under air 450 DEG C processing 3h XRD curves.
Embodiment
It is below the embodiment of the present invention, described embodiment is rather than the limitation in order to further describe the present invention
The present invention.
Embodiment 1
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol metatitanic acid orthocarbonates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add monoethanolamine 0.1
Mol, is heated to reflux 0.5h;
(2) room temperature is adjusted the temperature to, 1mol acetylacetone,2,4-pentanediones is added, is heated to reflux 0.5h;
(3) 80 DEG C are adjusted the temperature to, the mixed liquor of 0.8mol water and 2.5mol normal propyl alcohols is instilled, backflow 1h, drop is dripped off
Depressurized after temperature except solvent obtains the presoma.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 8h under 350 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 15mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 4h, degradation rate is 19.2%.
Embodiment 2
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol tetraisopropyl titanates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add monoethanolamine
0.3mol, is heated to reflux 1h;
(2) 100 DEG C are adjusted the temperature to, 0.8mol ethyl acetoacetates is added, is heated to reflux 1h;
(3) room temperature is adjusted the temperature to, the mixed liquor of 1.2mol water and 6mol isopropanols is instilled, backflow 3h, cooling is dripped off
After depressurize except solvent obtains the presoma.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 30min under 500 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 15mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 4h, degradation rate is 25.7%.
The presoma is dissolved in normal propyl alcohol, the Ti contents for controlling solution are 2%, add pore-foaming agent PEG-600, wherein
PEG-600 and Ti mass ratio is 1:2, the precursor solution of configuration is coated with Si pieces, 500 DEG C of sintering 30min,
It can obtain the supported porous TiO of Si pieces2Catalyst coat, electromicroscopic photograph such as Fig. 1-1 and Fig. 1-2 of the coating clapped from different perspectives
It is shown, found out by figure, gained coating has loose structure.Show, the presoma has good film forming, and by adding
The porous of film can be regulated and controled by entering pore-foaming agent PEG, the TiO after cracking2Catalyst can be carried on Si pieces well.
Embodiment 3
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol butyl titanates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add acetamide 3
Mol, is heated to reflux 5h;
(2) room temperature is adjusted the temperature to, 0.3mol ethyl acetoacetates is added, is heated to reflux 5h;
(3) 80 DEG C are adjusted the temperature to, the mixed liquor of 0.8mol water and 2.5mol n-butanols is instilled, backflow 8h, drop is dripped off
Depressurized after temperature except solvent obtains the presoma.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 3h under 450 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml trichlorophenol, 2,4,6,-T solution (concentration 20mg/L), (filter of 500W xenon lamps
Wave plate wavelength-filtered<420nm light) illumination 5h, degradation rate is 56%.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 15mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 3h, degradation rate is that 52.1%, 500W high-pressure sodium lamps shine 25min, degradation rate
100%.
Catalyst obtained by taking 30mg is added into 30ml rhodamine B solution (concentration 15mg/L), (filter of 500W xenon lamps
Wave plate wavelength-filtered<420nm light) illumination 3h, degradation rate is 26%.500W high-pressure sodium lamps shine 60min, degradation rate
99.6%.
The presoma handles 3h XRD curves as shown in Fig. 2 as can be seen from Figure after presoma cracking for 450 DEG C under air
Obtained TiO2Catalyst is Detitanium-ore-type.
Embodiment 4
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol tetrabutyl titanates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add glycine
2mol, is heated to reflux 2h;
(2) 60 DEG C are adjusted the temperature to, 0.6mol acetylacetone,2,4-pentanediones is added, is heated to reflux 3h;
(3) 40 DEG C are adjusted the temperature to, the mixed liquor of 0.8mol water and 2.5mol normal propyl alcohols is instilled, backflow 5h, drop is dripped off
Depressurized after temperature except solvent obtains the presoma.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 1h under 350 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 20mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 4h, degradation rate is 20.1%.
Embodiment 5
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol tetraethyl titanates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add alanine 2
Mol, is heated to reflux 2h;
(2) 50 DEG C are adjusted the temperature to, 0.6mol acetylacetone,2,4-pentanediones is added, is heated to reflux 3h;
(3) 75 DEG C are adjusted the temperature to, the mixed liquor of 0.8mol water and 2.4mol isobutanols is instilled, backflow 5h, drop is dripped off
Depressurized after temperature except solvent obtains the presoma.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 1h under 350 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 20mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 4h, degradation rate is 15%.
Embodiment 6
Visible light-responded TiO in the present embodiment2Presoma is synthesized according to the following steps:
(1) 1mol tetraethyl titanates are placed in the dry reaction kettle for being equipped with condenser pipe and drying tube, add N, N- bis-
Methylacetamide 2mol, is heated to reflux 2h;
(2) 90 DEG C are adjusted the temperature to, 0.6mol acetylacetone,2,4-pentanediones is added, is heated to reflux 3h;
(3) 70 DEG C are adjusted the temperature to, the mixed liquor of 1.3mol water and 26mol ethanol is instilled, backflow 5h is dripped off, after cooling
Decompression obtains the presoma except solvent.
The presoma is in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene or dimethylbenzene
Any solvent or several solvents mixed solvent in have preferable dissolubility.
The presoma of gained is handled into 1h under 350 DEG C of air, TiO is obtained2Catalyst.
Catalyst obtained by taking 30mg is added into 30ml methyl orange solutions (concentration 20mg/L), 500W xenon lamp (filter plates
Wavelength-filtered<420nm light) illumination 4h, degradation rate is 52.7%.500W high-pressure sodium lamps shine 30min, degradation rate 100%.
Catalyst obtained by taking 30mg is added into 30ml rhodamine B solution (concentration 15mg/L), (filtering of 500W xenon lamps
Piece wavelength-filtered<420nm light) illumination 3h, degradation rate is 36.6%.
Claims (10)
1. a kind of visible light-responded TiO2The preparation method of presoma, it is characterised in that described preparation method includes as follows
Step:
1) titanate esters are placed in reaction vessel, add nitrogen-containing compound, be heated to reflux;
2) at room temperature~100 DEG C, chelating agent is added, is heated to reflux;
3) at room temperature~80 DEG C, instill the mixed liquor of water and alcohol, drip off depressurized after backflow, cooling except solvent obtain described in can
See the TiO of photoresponse2Presoma.
2. preparation method according to claim 1, it is characterised in that titanate esters, nitrogen-containing compound, chelating agent and water
Mol ratio is 1:(0.1~3):(0.3~1):(0.8~1.3).
3. preparation method according to claim 2, it is characterised in that described water and the mixed liquor reclaimed water of alcohol and rubbing for alcohol
You are than being 1:(3~20).
4. the preparation method according to claim 1-3 any one, it is characterised in that step 1) described in be heated to reflux
Time be 0.5~5h;Step 2) described in time for being heated to reflux be 0.5~5h;Step 3) described in time for flowing back
For 1~8h.
5. the preparation method according to claim 1-4 any one, it is characterised in that step 1) in, described metatitanic acid
Ester is the one or more in tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, butyl titanate or tetrabutyl titanate
Mixture.
6. preparation method according to claim 5, it is characterised in that step 1) in, described nitrogen-containing compound is second
One or more of mixtures in hydramine, acetamide, DMA, glycine or alanine, preferred alcohol amine,
Acetamide or DMAC N,N' dimethyl acetamide.
7. preparation method according to claim 6, it is characterised in that step 2) described in chelating agent be acetylacetone,2,4-pentanedione
Or one or two kinds of mixtures in ethyl acetoacetate.
8. the preparation method according to claim any one of 1-7, it is characterised in that step 3) described in water and alcohol
In mixed liquor, alcohol is one or more of mixtures in ethanol, normal propyl alcohol, isopropanol, n-butanol or isobutanol.
9. a kind of visible light-responded TiO2Presoma, it is characterised in that the preparation method described in claim any one of 1-8
The visible light-responded TiO prepared2Presoma be dissolved in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether,
In the mixed solvent of any of toluene or dimethylbenzene solvent or several solvents.
10. a kind of visible light-responded TiO2Catalyst, it is characterised in that by the preparation side described in claim any one of 1-8
Visible light-responded TiO prepared by method2Presoma 350~500 DEG C of cracking under air, produce described visible light-responded TiO2
Catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610017971.6A CN106955683B (en) | 2016-01-12 | 2016-01-12 | Visible light response TiO2Preparation method of precursor and obtained TiO2Precursor and catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610017971.6A CN106955683B (en) | 2016-01-12 | 2016-01-12 | Visible light response TiO2Preparation method of precursor and obtained TiO2Precursor and catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106955683A true CN106955683A (en) | 2017-07-18 |
CN106955683B CN106955683B (en) | 2020-01-21 |
Family
ID=59481433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610017971.6A Active CN106955683B (en) | 2016-01-12 | 2016-01-12 | Visible light response TiO2Preparation method of precursor and obtained TiO2Precursor and catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106955683B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111617792A (en) * | 2020-04-26 | 2020-09-04 | 中国科学院化学研究所 | B, N codoped SnO responding to visible light2/TiO2Precursor and preparation method and application thereof |
CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
CN115382529A (en) * | 2022-09-30 | 2022-11-25 | 张桂花 | Preparation method of aqueous-phase titanium oxide polymer and photocatalyst and sterilization module |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101157020A (en) * | 2007-10-26 | 2008-04-09 | 东华大学 | A preparation method of low temperature standard atmosphere plasma modified load type titania photocatalyst |
CN101352675A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing shell powder supported active nano titanic oxide |
CN102491484A (en) * | 2011-11-22 | 2012-06-13 | 河海大学 | Application of photocatalyst of TiO2 (titanium dioxide) loaded on glass fiber fabric to treating microcystin |
-
2016
- 2016-01-12 CN CN201610017971.6A patent/CN106955683B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101157020A (en) * | 2007-10-26 | 2008-04-09 | 东华大学 | A preparation method of low temperature standard atmosphere plasma modified load type titania photocatalyst |
CN101352675A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing shell powder supported active nano titanic oxide |
CN102491484A (en) * | 2011-11-22 | 2012-06-13 | 河海大学 | Application of photocatalyst of TiO2 (titanium dioxide) loaded on glass fiber fabric to treating microcystin |
Non-Patent Citations (2)
Title |
---|
M. KRUNKS 等: "Thermoanalytical study of acetylacetonate-modified titanium(IV) isopropoxide as a precursor for TiO2 films", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》 * |
雷鸣 等: "用双络合剂制备超亲水多孔TiO2薄膜", 《材料导报》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111617792A (en) * | 2020-04-26 | 2020-09-04 | 中国科学院化学研究所 | B, N codoped SnO responding to visible light2/TiO2Precursor and preparation method and application thereof |
CN111617792B (en) * | 2020-04-26 | 2021-08-03 | 中国科学院化学研究所 | B, N codoped SnO responding to visible light2/TiO2Precursor and preparation method and application thereof |
CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
CN115382529A (en) * | 2022-09-30 | 2022-11-25 | 张桂花 | Preparation method of aqueous-phase titanium oxide polymer and photocatalyst and sterilization module |
Also Published As
Publication number | Publication date |
---|---|
CN106955683B (en) | 2020-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109603880B (en) | Hollow tubular carbon nitride photocatalyst and preparation method and application thereof | |
Zhang et al. | Preparation and performances of mesoporous TiO2 film photocatalyst supported on stainless steel | |
CN103143380B (en) | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material | |
CN101391811B (en) | Method for preparing high specific surface area titanic oxide | |
CN107096556A (en) | A kind of visible light-responded TiO2The preparation method of presoma and obtained TiO2Presoma and catalyst | |
CN106955683A (en) | A kind of visible light-responded TiO2The preparation method of presoma and obtained TiO2Presoma and catalyst | |
CN105195198B (en) | A kind of mpg-C3N4/Bi0.9Nd0.1VO4Composite photo-catalyst and its preparation method and application | |
CN101497038A (en) | Nano titanic oxide photocatalyst responding to visible light and preparation method thereof | |
CN107051422A (en) | Amorphous bismuth composite photo-catalyst, preparation method and application method | |
CN101367035A (en) | Preparation method for nano-titanium dioxide film photocatalyst | |
CN101491757B (en) | Synthetic method of TiO2 composite photocatalyst with high selective degradation | |
CN102527423B (en) | Preparation method of molybdenum-nitrogen-codoped TiO2 granule and application thereof | |
CN103041866A (en) | Preparation method of titanium dioxide-mesoporous polymer nano porous composite visible light catalytic material | |
CN110354895A (en) | A kind of oxide porous photochemical catalyst of molecular screen base Ce-Mn and its preparation method and application | |
CN108993466A (en) | A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ | |
CN106423223A (en) | MoSe2@TiO2 photocatalyst in caky porous structure and preparation method of MoSe2@TiO2 photocatalyst in caky porous structure | |
CN101177299A (en) | Method for preparing porous TiO2 particle | |
CN105439198A (en) | Preparation method of nano-titanium dioxide powder with high ethanol and water dispersibility | |
CN110681405B (en) | N, B codoped In responding to visible light2O3/TiO2Precursor, preparation method and application thereof | |
CN108355634A (en) | A kind of mesoporous TiO2The preparation method of photochemical catalyst | |
CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire | |
Yuying et al. | Microemulsion synthesis of nanosized SiO2/TiO2 particles and their photocatalytic activity | |
CN104386742A (en) | Mesoporous titanium dioxide having high crystallinity and large specific surface area and preparation method thereof | |
CN111234295A (en) | Molecularly imprinted photocatalytic material and preparation method and application thereof | |
CN108479746A (en) | A kind of preparation method and application of bismuth titanates nanometer sheet |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |