CN107999097A - A kind of lanthanum iodine codope photocatalyst compound material and preparation method - Google Patents
A kind of lanthanum iodine codope photocatalyst compound material and preparation method Download PDFInfo
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- CN107999097A CN107999097A CN201711022797.5A CN201711022797A CN107999097A CN 107999097 A CN107999097 A CN 107999097A CN 201711022797 A CN201711022797 A CN 201711022797A CN 107999097 A CN107999097 A CN 107999097A
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- lanthanum
- iodine
- codope
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- XBPMMPWZSQVGAJ-UHFFFAOYSA-N [La].[I] Chemical compound [La].[I] XBPMMPWZSQVGAJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 25
- 229910052681 coesite Inorganic materials 0.000 claims description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims description 22
- 229910052682 stishovite Inorganic materials 0.000 claims description 22
- 229910052905 tridymite Inorganic materials 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005642 Oleic acid Substances 0.000 claims description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002114 nanocomposite Substances 0.000 claims description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 238000001802 infusion Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000003643 water by type Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 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 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000005408 paramagnetism Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of magnetic lanthanum iodine codope photocatalyst compound material and preparation method thereof, the composite material is prepared by the following method：Using ferriferrous oxide nano-particle as magnetic core, by silicon source of ethyl orthosilicate using sol-gal process its surface coat one layer of porous active silicon layer obtain porous magnetic carrier, be then titanium source using titanate esters, acid iodide be raw material, roasting obtain presoma；Again using precipitation infusion process, using lanthanum nitrate as raw material, the magnetic porous titanic oxide composite microsphere of the visible light catalytic of lanthanum iodine codope is made, i.e., described magnetic lanthanum iodine codope photocatalyst compound material.The lanthanum iodine codope photocatalyst compound material that the present invention is prepared using the method for fractional steps, can doped lanthanum iodine and anatase titanium dioxide at the same time, and invest in magnetic matrix, can not only improve the photoresponse ability of material but also the ability of the circulation and stress of gained catalyst can be strengthened.
Description
(1) technical field
The present invention relates to a kind of magnetic lanthanum iodine codope photocatalyst compound material and preparation method thereof.
(2) background technology
With global water pollution problem getting worse, it was recognized that water conservation, improvement water pollution are very urgent.
But the amount of pollutant that is discharged into water is big, complicated component and easily spreads, and does not allow degradable.Conventional method takes time and effort, and produces effects
It is little.And recent years, photochemical catalyst are attracted attention because of its efficient ability in terms of treated sewage.Wherein, half
Conductor photochemical catalyst TiO2As a kind of environmentally protective administering method having a extensive future, not only technique is simple, Er Qiezhi
Manage positive effect.Enjoy the favor of researchers.But usually single photochemical catalyst TiO2It is not easily recycled, light utilization efficiency is low
The compound TiO Deng shortcomings2Photochemical catalyst, can not only solve to be not easily recycled this problem, also substantially increase photocatalysis
Efficiency.
In recent years, semiconductor particle becomes the most commonly used photochemical catalyst of scientists study.This kind of material can be in light
According under the conditions of, the pollutant of those difficult degradations is resolved into the inorganic matters such as water and carbon dioxide.TiO2As a kind of most commonly seen
Semiconductor light-catalyst, although there is high catalytic efficiency, nonhazardous, difficult soda acid performance is good, a variety of advantages such as of low cost.But
It there is also it is many problem of, such as wider energy gap (3.2eV) causes the absorption rate to sunlight not high,
It is only capable of reaching 4%, and recycles more difficulty, seriously limits its practical application.Therefore, urgent the looking on the bright side of things of scientists is sent
A kind of new photochemical catalyst, can effectively improve disadvantages mentioned above.To TiO2In terms of modification during research, scientists hair
The doping of existing some transition metal, can effectively improve TiO2Photocatalytic activity.And if select magnetic matrix load photocatalysis
Agent can effectively improve its circulation and stress ability.
At present, because TiO2The preparation method of photochemical catalyst mainly has vapor phase method, sol-gal process, hydro-thermal method, microemulsion
Method, liquid phase method and template etc..Wherein most widely used is exactly liquid phase method.In addition, catalytic efficiency often determines one
One major criterion of kind catalyst quality.And influence factor can be divided into external cause and internal cause.External cause be broadly divided into environment temperature,
PH value of solution, the intensity of light source, substance classes for being degraded etc.；Internal cause mainly includes its internal structural form, band gap width, generation
The potential of conduction band and valence band in electronics and hole etc..TiO2The TiO of Detitanium-ore-type in three kinds of different crystalline state in nature2
Catalytic efficiency with higher.Its energy gap is width of the 3.2e V than rutile-type (3.0e V), and the energy gap of bigger
The redox ability possessed is stronger.In addition, anatase crystal grain has less size and larger specific surface area.Size is got over
Small, internal energy gap is bigger, so that the hole/electronics produced moves the electric charge with stronger redox ability and higher
Move speed.
The current application value maximum of magnetic matrix is exactly with paramagnetism ferroso-ferric oxide, and there is higher magnetic field to satisfy for it
And intensity, adjustable size and pattern, effective and feasible convenient and reliable preparation method.If one layer of cladding is active on its surface
The coated with silica layer of the biocompatibility of hydroxyl, it is numerous to can be applicable to biology, medicine, catalyst, magnetic response, magnetic imaging etc.
Field.Preparation method main at present has coprecipitation, sol-gal process, hydro-thermal method etc..
If in conclusion using the ferroso-ferric oxide of coated with silica as magnetic matrix, then it is aided with the two of lanthanum iodine codope
Titanium oxide, with reference to the paramagnetism of ferroso-ferric oxide, the biocompatibility and hydroxyl reactive group of silica, lanthanum iodine codope
The wide optical Response of titanium dioxide, is expected to prepare with good renewable ability, is easy to circulation and stress, wider light sound
Should be able to power, preferable photocatalytic activity novel magnetic photocatalytic activity agent, there is good prospects for commercial application.
(3) content of the invention
The object of the present invention is to provide a kind of novel magnetic lanthanum iodine codope photocatalyst compound material and preparation method thereof,
Lanthanum iodine codope effectively can be entered titanium dioxide matrix by the catalyst, while it is carried on four oxidations of coated with silica
On three-iron matrix so that while prepared catalyst has higher photoresponse ability, and can have magnetic responsiveness.
The technical solution adopted by the present invention is：
A kind of magnetism lanthanum iodine codope photocatalyst compound material, is prepared by the following method：Received with ferroso-ferric oxide
Rice corpuscles is magnetic core, is obtained by silicon source of ethyl orthosilicate using sol-gel process in its surface one layer of porous active silicon layer of cladding
To porous magnetic carrier, be then titanium source using titanate esters, acid iodide be raw material, roasting obtains presoma；Precipitation-impregnation is used again
Method, using lanthanum nitrate as raw material, is made the magnetic porous titanic oxide composite microsphere of the visible light catalytic of lanthanum iodine codope, i.e., described
Magnetic lanthanum iodine codope photocatalyst compound material.
The Fe3O4, ethyl orthosilicate, the ratio between titanate esters quality dosage be：5~300：1~5：50~200, Ti：I：La
Molar ratio is 1：10~50%：0.5%~2.5%..
The invention further relates to the method for preparing the composite material, the described method includes：
(1) with Fe2+Salt and Fe3+Salt is raw material, and spherical Fe is prepared using hydro-thermal reaction method3O4Nanometer magnetic core；
(2)Fe3O4Nanometer magnetic core adds absolute ethyl alcohol and deionized water, and 10~20min of sonic oscillation after mixing, is being stirred
Under NH is added dropwise3·H2O, after stirring 10~20min, adds ethyl orthosilicate under stirring, is reacted at 30~40 DEG C
5~6h, is made Fe3O4@nSiO2With absolute ethyl alcohol and deionized water, respectively cleaning three times, adds cetyl trimethylammonium bromide
And deionized water, it is uniformly mixed, adds absolute ethyl alcohol, NH under agitation3·H2O, reacts 20 at a temperature of 30~40 DEG C
After~30min, ethyl orthosilicate is added dropwise under stirring, 5~6h, obtained product nothing are reacted at 30~40 DEG C
Respectively cleaning three times, after vacuum drying, adds absolute ethyl alcohol and NH for water-ethanol and deionized water4NO3, stirred at 50~60 DEG C
React, separated after 10~20min with magnet and use cold washes of absolute alcohol three times, this wash products step is repeated twice, very
Sky is dry, and porous magnetic carrier Fe is made3O4@SiO2；
(3) acid iodide is dissolved in deionized water at room temperature, and tetra-n-butyl titanate is added dropwise in the case of quick stirring, added
Fe prepared by step (2)3O4@SiO2, after 20~30min of ultrasonic disperse, 8~10h in 70~80 DEG C of water-baths is positioned over, is obtained molten
Glue, and dried in 90~100 DEG C of baking ovens to constant weight, obtain powder I/TiO2Catalyst precursor, finally at 200~400 DEG C
It is lower by powder I/TiO2After catalyst precursor roasts 2~4h, room temperature is naturally cooled to, that is, obtains flaxen Fe3O4@SiO2@
I/TiO2Nano composite photo-catalyst, it is dry to constant weight, 200~400 DEG C of 1~2h of roasting, cooled to room temperature, up to described
Magnetic lanthanum iodine codope photocatalyst compound material.
The Fe2+Salt is FeCl2, Fe3+Salt is FeCl3。
Preferably, calcination temperature is 200 DEG C in step (4).
Step (1) method is as follows：Distilled water is added into three-neck flask, adds FeCl2·4H2O and FeCl3·
6H2O, stirs to being completely dissolved, is heated to 80 DEG C, the oxygen being passed through in high pure nitrogen removing reaction unit, rapid after reaction 30min
Add NH3·H2After O, the reaction was continued 30min, oleic acid is added dropwise into three-neck flask, temperature is risen into 85 DEG C of reactions
180min, products therefrom, which is washed with distilled water, removes unreacted oleic acid, then is dried through high temperature, grinds, obtains spherical Fe3O4Receive
Rice magnetic core.
Specifically, the method for the present invention can carry out as follows：
(1) 80mL~120mL distilled water is added into the three-neck flask of 250mL, by 7.8g~12.8g FeCl2·
4H2O, 20g~28g FeCl3·6H2It is placed in one in O, the solid stirred into three-neck flask is completely dissolved.When temperature heats
To after 80 DEG C, it is passed through high pure nitrogen and removes oxygen in reaction unit, the NH of 50~70mL is rapidly added after reacting 30min3·H2O
(25%), after the reaction was continued 30min, 0.5~3mL oleic acid is added dropwise into three-neck flask, temperature is risen into 85 DEG C of reactions
180min.Products therefrom is washed with distilled water removes unreacted oleic acid for several times.Dried by high temperature, grind, finally obtain
Fe3O4Nano-particle；
(2) Fe made from above-mentioned steps is weighed3O40.05~3.0g, add 30~80ml absolute ethyl alcohols and 5~30ml go from
Sub- water is placed in 250ml three-neck flasks, and Ultrasound Instrument sonic oscillation 20min is utilized after mixing, be added dropwise under agitation 0.5ml~
2mLNH3·H2O (28%), after stirring 10min, TEOS0.01g~0.04g is added under stirring, is reacted at 30 DEG C
6h, is made Fe3O4@nSiO2, obtained Fe3O4@nSiO2Respectively cleaned three times with absolute ethyl alcohol and deionized water, addition 0.01g~
0.04gCTAB and 40~80ml deionized waters, are uniformly mixed, add under agitation 20~80ml absolute ethyl alcohols, 0.5~
2.5gNH3·H2O (28%), after reacting 30min at a temperature of 30 DEG C, be added dropwise under stirring TEOS0.10~
0.5g, reacts 6h at 30 DEG C, and Fe is made3O4@nSiO2@mCTAB@mSiO2, obtained product absolute ethyl alcohol and deionized water
Each cleaning is three times, dry in vacuum drying chamber.
Weigh foregoing obtained Fe3O4@nSiO2@mCTAB@mSiO20.5~2.5g, adds 100~200ml of absolute ethyl alcohol
With 0.20g~0.5gNH4NO3, reaction is stirred at 60 DEG C, is separated after 15min with magnet and uses cold washes of absolute alcohol three
Secondary, this step is repeated twice, obtained Fe3O4@SiO2Dried with vacuum drying chamber.
(3) (0.66g~2.65g) acid iodide is dissolved in 50mL deionized waters at room temperature, and in the case of quick stirring
Suitable tetra-n-butyl titanate (Ti is gradually added dropwise：I=10:1~10:5) (0.05g~0.2g) above-mentioned preparation, is added
Fe3O4@SiO2, then in water bath sonicator instrument after ultrasonic disperse 30min, 10h in 80 DEG C of water-baths is placed, that is, is obtained molten
Glue, and dry 2h is to constant weight in 100 DEG C of baking ovens, so as to obtain I/TiO2Catalyst precursor.Finally will at 200~400 DEG C
Powder I/TiO2After catalyst precursor roasting 2h, room temperature is naturally cooled to, that is, obtains flaxen Fe3O4@SiO2@I/TiO2
Nano composite photo-catalyst.
The beneficial effects are mainly as follows：The magnetic coupling for the lanthanum iodine codope that the present invention is prepared using the method for fractional steps
Material, can doped lanthanum iodine and anatase titanium dioxide at the same time, and invest in magnetic matrix, can both improve the photoresponse energy of material
Power can strengthen the ability of the circulation and stress of gained catalyst again.
(4) illustrate
Fig. 1 is that the lanthanum iodine codope magnetic catalyst prepared under different sintering temperatures and La/Ti proportionings is water-soluble to rhodamine B
The treatment effect of liquid.A figures are that the lanthanum iodine codope magnetic catalyst prepared under different sintering temperatures takes off rhodamine B aqueous solution
The treatment effect of color rate；B figures are the different lower lanthanum iodine codope magnetic catalysts prepared of La/Ti proportionings to rhodamine B aqueous solution
Percent of decolourization treatment effect.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
90mL distilled water is added into the three-neck flask of 250mL, by 8.8g FeCl2·4H2O、 22g FeCl3·
6H2It is placed in one in O, the solid stirred into three-neck flask is completely dissolved.After temperature is heated to 80 DEG C, high pure nitrogen is passed through
The oxygen in reaction unit is removed, the NH of 55mL is rapidly added after reaction 30min3·H2After O (25%), the reaction was continued 30min, to
0.9mL oleic acid is added dropwise in three-neck flask, temperature is risen into 85 DEG C of reaction 180min.Products therefrom is washed with distilled water for several times
Remove unreacted oleic acid.Dried by high temperature, grind, finally obtain Fe3O4Nano-particle.
Weigh Fe made from above-mentioned steps3O40.05g, adds 40mL absolute ethyl alcohols and 10mL deionized waters are placed in 250mL tri-
In neck flask, Ultrasound Instrument sonic oscillation 20min is utilized after mixing, 0.5mLNH is added dropwise under agitation3·H2O (28%), is stirred
After mixing 10min, TEOS0.02g is added under stirring, reacts 6h at 30 DEG C, Fe is made3O4@nSiO2, obtained Fe3O4@
nSiO2With absolute ethyl alcohol and deionized water, respectively cleaning three times, adds 0.02gCTAB and 60mL deionized waters, is uniformly mixed,
40mL absolute ethyl alcohols, 0.5gNH are added under agitation3·H2O (28%), after reaction 30min at a temperature of 30 DEG C, in stirring shape
TEOS0.20g is added dropwise under state, reacts 6h at 30 DEG C, Fe is made3O4@nSiO2@mCTAB@mSiO2, obtained product use
Respectively cleaning is three times, dry in vacuum drying chamber for absolute ethyl alcohol and deionized water.
Weigh Fe made from above-mentioned steps3O4@nSiO2@mCTAB@mSiO21.0g, add absolute ethyl alcohol 150mL and
0.30gNH4NO3, reaction is stirred at 60 DEG C, is separated after 15min with magnet and uses cold washes of absolute alcohol three times, this step
It is repeated twice, obtained Fe3O4@SiO2Dried with vacuum drying chamber.
0.66g acid iodide is dissolved in 50mL deionized waters at room temperature, and is gradually added dropwise in right amount in the case of quick stirring
Tetra-n-butyl titanate (Ti：I=10:1), then in water bath sonicator instrument after ultrasonic disperse 30min, it is above-mentioned to add (0.05g)
The Fe of preparation3O4@SiO2Placed 10h in 80 DEG C of water-baths, that is, obtain colloidal sol, and in 100 DEG C of baking ovens dry 2h to constant weight,
So as to obtain I/TiO2Catalyst precursor.Finally by powder I/TiO at a certain temperature2After catalyst precursor roasting 2h,
Room temperature is naturally cooled to, that is, obtains flaxen Fe3O4@SiO2@I/TiO2Nano composite photo-catalyst.
By the above-mentioned Fe prepared3O4@SiO2@I/TiO2Nano composite photo-catalyst takes 0.05g to be placed into beaker
Stir in the middle and constantly, suitable La (NO are then slowly added dropwise3)3·6H2O solution, and according to La/Ti (0.5%,
1.0%th, 1.5%, 2.0%, 2.5%) a mole metering ratio weighs.Then by its ultrasonic disperse 30min, and it is placed on 80 DEG C of water-baths
In the moisture in product is evaporated.Finally product is dried to constant weight, and at different temperatures (200 DEG C, 250 DEG C,
300 DEG C, 350 DEG C, 400 DEG C) roasting 2h, then natural cooling, that is, obtain the La doped TiO at a temperature of different heat treatment2Nanometer
Catalyst (La/TiO2) so as to obtained magnetic lanthanum iodine codope photochemical catalyst.
Embodiment 2：
100mL distilled water is added into the three-neck flask of 250mL, by 9.8g FeCl2·4H2O、24g FeCl3·
6H2It is placed in one in O, the solid stirred into three-neck flask is completely dissolved.After temperature is heated to 80 DEG C, high pure nitrogen is passed through
The oxygen in reaction unit is removed, the NH of 50mL is rapidly added after reaction 30min3·H2After O (25%), the reaction was continued 30min, to
1mL oleic acid is added dropwise in three-neck flask, temperature is risen into 85 DEG C of reaction 180min.Products therefrom is washed with distilled water to be gone for several times
Except unreacted oleic acid.Dried by high temperature, grind, finally obtain Fe3O4Nano-particle.
Weigh Fe made from above-mentioned steps3O40.1g, adds 80mL absolute ethyl alcohols and 20mL deionized waters are placed in 250mL tri-
In neck flask, Ultrasound Instrument sonic oscillation 20min is utilized after mixing, 1.0mLNH is added dropwise under agitation3·H2O (28%), is stirred
After mixing 10min, TEOS0.03g is added under stirring, reacts 6h at 30 DEG C, Fe is made3O4@nSiO2, obtained Fe3O4@
nSiO2With absolute ethyl alcohol and deionized water, respectively cleaning three times, adds 0.03gCTAB and 80mL deionized waters, is uniformly mixed,
60mL absolute ethyl alcohols, 1.0gNH are added under agitation3·H2O (28%), after reaction 30min at a temperature of 30 DEG C, in stirring shape
TEOS0.40g is added dropwise under state, reacts 6h at 30 DEG C, Fe is made3O4@nSiO2@mCTAB@mSiO2, obtained product use
Respectively cleaning is three times, dry in vacuum drying chamber for absolute ethyl alcohol and deionized water.
Weigh Fe made from above-mentioned steps3O4@nSiO2@mCTAB@mSiO20.5g, add absolute ethyl alcohol 75mL and
0.15gNH4NO3, reaction is stirred at 60 DEG C, is separated after 15min with magnet and uses cold washes of absolute alcohol three times, this step
It is repeated twice, obtained Fe3O4@SiO2Dried with vacuum drying chamber.
1.32g acid iodide is dissolved in 50mL deionized waters at room temperature, and is gradually added dropwise in right amount in the case of quick stirring
Tetra-n-butyl titanate (Ti：I=10:3) Fe of (0.1g) above-mentioned preparation, is added3O4@SiO2Then surpass in water bath sonicator instrument
After sound disperses 30min, placed 10h in 80 DEG C of water-baths, that is, obtain colloidal sol, and in 100 DEG C of baking ovens dry 2h to constant weight, from
And obtain I/TiO2Catalyst precursor.Finally by powder I/TiO at a certain temperature2After catalyst precursor roasting 2h, from
Room temperature so is cooled to, that is, obtains flaxen Fe3O4@SiO2@I/TiO2Nano composite photo-catalyst.
By the above-mentioned Fe prepared3O4@SiO2@I/TiO2Nano composite photo-catalyst takes 0.1g to be placed into beaker ought
In and constantly stir, suitable La (NO are then slowly added dropwise3)3·6H2O solution, and according to La/Ti (0.5%,
1.0%th, 1.5%, 2.0%, 2.5%) a mole metering ratio weighs.Then by its ultrasonic disperse 30min, and it is placed on 80 DEG C of water-baths
In the moisture in product is evaporated.Finally product is dried to constant weight, and at different temperatures (200 DEG C, 250 DEG C,
300 DEG C, 350 DEG C, 400 DEG C) roasting 2h, then natural cooling, that is, obtain the La doped TiO at a temperature of different heat treatment2Nanometer
Catalyst (La/TiO2) so as to obtained magnetic lanthanum iodine codope photochemical catalyst.
Embodiment 3：
110mL distilled water is added into the three-neck flask of 250mL, by 10.8g FeCl2·4H2O、 27g FeCl3·
6H2It is placed in one in O, the solid stirred into three-neck flask is completely dissolved.After temperature is heated to 80 DEG C, high pure nitrogen is passed through
The oxygen in reaction unit is removed, the NH of 65mL is rapidly added after reaction 30min3·H2After O (25%), the reaction was continued 30min, to
1.1mL oleic acid is added dropwise in three-neck flask, temperature is risen into 85 DEG C of reaction 180min.Products therefrom is washed with distilled water for several times
Remove unreacted oleic acid.Dried by high temperature, grind, finally obtain Fe3O4Nano-particle.
Weigh Fe made from above-mentioned steps3O40.2g, adds 160mL absolute ethyl alcohols and 40mL deionized waters are placed in 500mL tri-
In neck flask, Ultrasound Instrument sonic oscillation 20min is utilized after mixing, 2.0mLNH is added dropwise under agitation3·H2O (28%), is stirred
After mixing 10min, TEOS0.06g is added under stirring, reacts 6h at 30 DEG C, Fe is made3O4@nSiO2, obtained Fe3O4@
nSiO2With absolute ethyl alcohol and deionized water, respectively cleaning three times, adds 0.06gCTAB and 160mL deionized waters, is stirred
It is even, 120mL absolute ethyl alcohols, 2.0gNH are added under agitation3·H2O (28%), after reaction 30min at a temperature of 30 DEG C, is being stirred
Mix and TEOS0.80g is added dropwise under state, react 6h at 30 DEG C, Fe is made3O4@nSiO2@mCTAB@mSiO2, obtained production
Respectively cleaning is three times, dry in vacuum drying chamber for thing absolute ethyl alcohol and deionized water.
Weigh Fe made from above-mentioned steps3O4@nSiO2@mCTAB@mSiO22.0g, add absolute ethyl alcohol 300mL and
0.60gNH4NO3, reaction is stirred at 60 DEG C, is separated after 15min with magnet and uses cold washes of absolute alcohol three times, this step
It is repeated twice, obtained Fe3O4@SiO2Dried with vacuum drying chamber.
2.65g acid iodide is dissolved in 50mL deionized waters at room temperature, and is gradually added dropwise in right amount in the case of quick stirring
Tetra-n-butyl titanate (Ti：I=10:5) Fe of (0.2g) above-mentioned preparation, is added3O4@SiO2Then surpass in water bath sonicator instrument
After sound disperses 30min, placed 10h in 80 DEG C of water-baths, that is, obtain colloidal sol, and in 100 DEG C of baking ovens dry 2h to constant weight, from
And obtain I/TiO2Catalyst precursor.Finally by powder I/TiO at a certain temperature2It is natural after catalyst precursor roasting 2h
Room temperature is cooled to, that is, obtains flaxen Fe3O4@SiO2@I/TiO2Nano composite photo-catalyst.
By the above-mentioned Fe prepared3O4@SiO2@I/TiO2Nano composite photo-catalyst takes 2.5g to be placed into beaker ought
In and constantly stir, suitable La (NO are then slowly added dropwise3)3·6H2O solution, and according to La/Ti (0.5%,
1.0%th, 1.5%, 2.0%, 2.5%) a mole metering ratio weighs.Then by its ultrasonic disperse 30min, and it is placed on 80 DEG C of water-baths
In the moisture in product is evaporated.Finally product is dried to constant weight, and at different temperatures (200 DEG C, 250 DEG C,
300 DEG C, 350 DEG C, 400 DEG C) roasting 2h, then natural cooling, that is, obtain the La doped TiO at a temperature of different heat treatment2Nanometer
Catalyst (La/TiO2) so as to obtained magnetic lanthanum iodine codope photochemical catalyst.
Detect the place of the lanthanum iodine codope magnetic catalyst that is prepared under different sintering temperatures to rhodamine B (RhB) aqueous solution
Effect is managed, specific processing step is as follows：It is formulated as 1.5 × 10-5The RhB of mol/L concentration, takes above-mentioned 60ml RhB solution, adds
Fe made from 50mg embodiments 13O4@SiO2@La-I/TiO2, stirred with magneton, and be placed on 20 watts of filtration ultraviolet wavelength
Under daylight light irradiation, the liquid of about 10ml, Magneto separate are taken out (depending on the specific time is by reaction color change) at regular intervals
Solid is removed, using the absorbance of spectrophotometric determination liquid, then with formula D=(A0-At)/A0× 100% calculates Luo Dan
The percent of decolourization of bright B.Wherein D is percent of decolourization, A0For the absorbance before illumination, AtFor the absorbance after illumination.
The lanthanum iodine codope magnetic catalyst prepared under different calcination temperatures (figure A) and different La/Ti mol ratios (figure B)
To the treatment effect of rhodamine B aqueous solution referring to Fig. 1.As seen from the figure, decolorizing effect declines with the rise of calcination temperature, most
Good calcination temperature is 200 DEG C, and percent of decolourization is up to 80% at this time；In addition, La/Ti mol ratios can also significantly affect decolorizing effect,
It is optimal when La/Ti mol ratios are 0.5.
Claims (6)
1. a kind of magnetism lanthanum iodine codope photocatalyst compound material, is prepared by the following method：With ferriferrous oxide nano
Particle is magnetic core, is obtained by silicon source of ethyl orthosilicate using sol-gel process in its surface one layer of porous active silicon layer of cladding
Then porous magnetic carrier is titanium source using titanate esters, acid iodide is raw material, and roasting obtains presoma；Precipitation-impregnation is used again
Method, using lanthanum nitrate as raw material, is made the magnetic porous titanic oxide composite microsphere of the visible light catalytic of lanthanum iodine codope, i.e., described
Magnetic lanthanum iodine codope photocatalyst compound material.
2. composite material as claimed in claim 1, it is characterised in that Fe3O4, ethyl orthosilicate, the ratio between titanate esters quality dosage
For：5~300：1~5：50~200, Ti：I：La molar ratios are 1：10~50%：0.5%~2.5%.
3. the method for composite material described in claim 1 is prepared, the described method includes：
(1) with Fe2+Salt and Fe3+Salt is raw material, and spherical Fe is prepared using hydro-thermal reaction method3O4Nanometer magnetic core；
(2)Fe3O4Nanometer magnetic core adds absolute ethyl alcohol and deionized water, 10~20min of sonic oscillation after mixing, under agitation by
It is added dropwise to NH3·H2O, stir 10~20min after, add ethyl orthosilicate under stirring, at 30~40 DEG C react 5~
6h, is made Fe3O4@nSiO2With absolute ethyl alcohol and deionized water, respectively cleaning three times, adds cetyl trimethylammonium bromide and goes
Ionized water, is uniformly mixed, and adds absolute ethyl alcohol, NH under agitation3·H2O, at a temperature of 30~40 DEG C react 20~
After 30min, ethyl orthosilicate is added dropwise under stirring, 5~6h is reacted at 30~40 DEG C, obtained product is with anhydrous
Respectively cleaning three times, after vacuum drying, adds absolute ethyl alcohol and NH for ethanol and deionized water4NO3, stirred at 50~60 DEG C anti-
Should, separated after 10~20min with magnet and use cold washes of absolute alcohol three times, this wash products step is repeated twice, vacuum
It is dry, porous magnetic carrier Fe is made3O4@SiO2；
(3) acid iodide is dissolved in deionized water at room temperature, and tetra-n-butyl titanate is added dropwise in the case of quick stirring, add step
(2) Fe prepared3O4@SiO2, after 20~30min of ultrasonic disperse, 8~10h in 70~80 DEG C of water-baths is positioned over, obtains colloidal sol, and
Dried in 90~100 DEG C of baking ovens to constant weight, obtain powder I/TiO2Catalyst precursor, finally by powder at 200~400 DEG C
Last I/TiO2After catalyst precursor roasts 2~4h, room temperature is naturally cooled to, that is, obtains flaxen Fe3O4@SiO2@I/TiO2
Nano composite photo-catalyst, it is dry to constant weight, 200~400 DEG C of 1~2h of roasting, cooled to room temperature, up to the magnetic lanthanum
Iodine codope photocatalyst compound material.
4. method as claimed in claim 3, it is characterised in that the Fe2+Salt is FeCl2, Fe3+Salt is FeCl3。
5. method as claimed in claim 3, it is characterised in that calcination temperature is 200 DEG C in step (4).
6. method as claimed in claim 3, it is characterised in that step (1) method is as follows：Distilled water is added to three-neck flask
In, add FeCl2·4H2O and FeCl3·6H2O, stirs to being completely dissolved, is heated to 80 DEG C, is passed through high pure nitrogen and removes dereaction
Oxygen in device, NH is rapidly added after reacting 30min3·H2After O, the reaction was continued 30min, oil is added dropwise into three-neck flask
Acid, rises to 85 DEG C of reaction 180min, products therefrom, which is washed with distilled water, removes unreacted oleic acid, then is dried through high temperature by temperature
Dry, grinding, obtains spherical Fe3O4Nanometer magnetic core.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201655A (en) * | 2019-05-07 | 2019-09-06 | 浙江理工大学 | A kind of one-step method prepares hollow TiO2The method and application of nanosphere |
| CN114054062A (en) * | 2020-08-06 | 2022-02-18 | 重庆工商大学 | g-C3N4Preparation and application method of base composite photocatalytic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562464A (en) * | 2004-03-31 | 2005-01-12 | 深圳清华大学研究院 | Magnetic nano T102 composite photocatalysis and preparation method |
| CN101474556A (en) * | 2009-01-13 | 2009-07-08 | 东华大学 | Preparation method of fluorine and lanthanum co-doped nano titanic oxide visible light photocatalyst |
| WO2011080304A2 (en) * | 2009-12-30 | 2011-07-07 | Foundation For Research And Technology - Hellas / Forth | Method of production of photocatalytic powder comprising titanium dioxide and manganese dioxide active under ultraviolet and visible light |
| CN103638934B (en) * | 2013-12-03 | 2016-02-24 | 江西理工大学 | A kind of preparation method of La doped titanium dioxide magnetic nano-photocatalyst |
-
2017
- 2017-10-27 CN CN201711022797.5A patent/CN107999097A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562464A (en) * | 2004-03-31 | 2005-01-12 | 深圳清华大学研究院 | Magnetic nano T102 composite photocatalysis and preparation method |
| CN101474556A (en) * | 2009-01-13 | 2009-07-08 | 东华大学 | Preparation method of fluorine and lanthanum co-doped nano titanic oxide visible light photocatalyst |
| WO2011080304A2 (en) * | 2009-12-30 | 2011-07-07 | Foundation For Research And Technology - Hellas / Forth | Method of production of photocatalytic powder comprising titanium dioxide and manganese dioxide active under ultraviolet and visible light |
| CN103638934B (en) * | 2013-12-03 | 2016-02-24 | 江西理工大学 | A kind of preparation method of La doped titanium dioxide magnetic nano-photocatalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201655A (en) * | 2019-05-07 | 2019-09-06 | 浙江理工大学 | A kind of one-step method prepares hollow TiO2The method and application of nanosphere |
| CN110201655B (en) * | 2019-05-07 | 2021-11-30 | 浙江理工大学 | One-step method for preparing hollow TiO2Method and application of nano-microspheres |
| CN114054062A (en) * | 2020-08-06 | 2022-02-18 | 重庆工商大学 | g-C3N4Preparation and application method of base composite photocatalytic material |
| CN114054062B (en) * | 2020-08-06 | 2023-05-23 | 重庆工商大学 | g-C 3 N 4 Preparation and application methods of base composite photocatalytic material |
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