CN107117649A - Mesoporous P25 titanium dioxide microballoon spheres and preparation method thereof - Google Patents
Mesoporous P25 titanium dioxide microballoon spheres and preparation method thereof Download PDFInfo
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- CN107117649A CN107117649A CN201710283621.9A CN201710283621A CN107117649A CN 107117649 A CN107117649 A CN 107117649A CN 201710283621 A CN201710283621 A CN 201710283621A CN 107117649 A CN107117649 A CN 107117649A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229920000428 triblock copolymer Polymers 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229940074355 nitric acid Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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—
-
- B01J35/51—
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
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- B01J35/647—
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C01—INORGANIC CHEMISTRY
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- C01P2006/40—Electric properties
Abstract
The invention belongs to advanced porous material technical field, and in particular to mesoporous P25 titanium dioxide microballoon spheres and preparation method thereof.The method that the present invention utilizes solvent evaporation induced self-assembly, using commercialized amphipathic three block copolymer PEO PPO PEO as template, organic titanium is titanium source, inorganic acid is titanium dioxide skeleton crystal structure adjusting agent, during solvent volatilizees, mesoporous P25 titanium dioxide microballoon spheres are obtained after forming homogeneous spherical morphology, the mesopore orbit of diverging and the skeleton that coexists of rutile anatase, roasting removed template method.The microballoon has big specific surface area, big pore volume, rutile anatase is tightly packed in skeleton and ratio is adjustable, it is obviously improved the photogenerated charge of the material and the separative efficiency of photohole, so that photoelectric conversion and photocatalytic water splitting production hydrogen reaction efficiency are greatly improved.The inventive method is simple, prepared by wet method, and raw material is easy to get, and suitable for amplification production, is with a wide range of applications in various fields such as environment, the energy, catalysis.
Description
Technical field
The invention belongs to advanced porous material technical field, and in particular to mesoporous P25 titanium dioxide microballoon spheres and its preparation side
Method.
Background technology
Titanium dioxide (TiO2) it is a kind of important inorganic functional material, with abundance is high, chemical property is stable, anti-light corruption
The features such as erosion, inexpensive, nontoxic and excellent semiconducting behavior, it is used widely in the field such as opto-electronic conversion and photocatalysis, work
Industry, commercialization titanium dioxide product emerge in an endless stream.Titanium dioxide has anatase, rutile, three kinds of crystalline phases of brockite, by difference
Crystalline phase mixes the heterogeneous boundary of structure, can improve light induced electron and hole separative efficiency, it is considered to be a kind of effective
Improve a kind of method of photocatalysis and photoelectric conversion performance.It by average grain diameter is about 25 that commercialized P25 nano titanium oxides, which are,
Nm rutile and anatase particles accumulation is formed, and the ratio of wherein rutile and anatase is about 1:3.Due to containing abundant
Rutile and the heterogeneous boundary of anatase, commercialized P25 show good performance in photocatalysis and photoelectric conversion field,
It is used widely, produces huge economic benefit.But there are shortcomings by commercialized P25 prepared by vapor phase method：1st, gas
Phase combustion hydrolytic method is difficult to control, and granular size is irregular, and accumulation is chaotic, makes commercialization P25 specific surface areas low（< 50 m2/g）
It is small with aperture（< 5 nm）, it is unfavorable for the conveying of material and the absorption of light in light-catalyzed reaction.2nd, commercialized P25 crystallizations are endless
Whole, the amorphous titania particle containing part causes rutile and anatase linkage interface imperfect, it is impossible to form perfect
Heterogeneous interface accumulation, further resulted in the reduction of light induced electron and hole separative efficiency.How commercialization P25 nanometer is improved
Prepared by the synthetic method of titanium dioxide have mesoporous P25, puies forward the separative efficiency of high-ratio surface, aperture and photogenerated charge-hole
Have become the focus studied now.
The content of the invention
It is an object of the invention to provide it is a kind of it is simple to operate, easy to control, be easy to repeat, it is capable of being industrialized mesoporous
P25 titanium dioxide microballoon spheres and preparation method thereof.
The preparation method for the mesoporous P25 titanium dioxide microballoon spheres that the present invention is provided, with commercialized triblock copolymer PEO-
PPO-PEO is template, and organic titanium is titanium source, and inorganic acid is the skeleton crystal structure adjusting agent of titanium dioxide（Adjust rutile-rutile titania
The ratio of ore deposit）, during solvent volatilizees, the bone that the homogeneous spherical morphology of formation, diverging orifices and rutile-anatase coexist
Mesoporous P25 titanium dioxide microballoon spheres are obtained after frame, roasting removed template method.Comprise the following steps that：
（1）A certain amount of template Ampliphilic triblock copclymer PEO-PPO-PEO is dissolved into volatile organic solvent,
Form homogeneous solution（0.2-30wt %）, a certain amount of inorganic acid regulation skeleton crystal formation is added, is sufficiently stirred for, obtains colourless
In bright solution, the solution that a certain amount of organic titanium source is added to above-mentioned water white transparency, golden yellow solution is formed.Above-mentioned synthesis
During, it is 0.2-2.2 to keep the ratio between amount of template and titanium source presoma quantity of material；
（2）By above-mentioned steps（1）In obtained golden yellow mixed solution be transferred in the vial of opening, be placed in 20-50 DEG C of baking
Volatilize 8-48 h in case, and rise temperature obtains the powder of white to 60-150 DEG C of continuation volatilization 2-32 h；
（3）Above-mentioned powder sample is placed in tube furnace, under inert gas atmosphere, with 0.2-10 DEG C/min heating rate from
Room temperature is increased to 200-500 DEG C, and keeps 3-12h, obtains grey black TiO2/ C composite；Again by gained sample in atmosphere
300-800 DEG C of roasting 2-10h removes carbon therein, that is, obtains mesoporous P25 titanium dioxide microballoon spheres.
In the present invention, described plate agent is selected from F127 (EO106-PO70-EO106)、P65（EO20-PO30-EO20）、P85
（EO26-PO39-EO20）、P123（EO20-PO70-EO20）、F108（EO132-PO50-EO132）F68（EO132-PO30-EO132）、F98
（EO132-PO45-EO132）、F88（EO132-PO40-EO132）Or F87（EO106-PO40-EO106）In one or more.
In the present invention, the one kind or several of described titanium source in the fourth fat of metatitanic acid four, isopropyl titanate, tetraethyl titanate
Kind.
In the present invention, described acid in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, hydroiodic acid, hydrobromic acid or hydrofluoric acid one
Plant or several.
In the present invention, described solvent is selected from tetrahydrofuran, dioxane, hexamethylene, ethanol, acetone, dichloromethane, chlorine
One or more in imitative or hexane.
In the present invention, described mesoporous P25 titanium dioxide microballoon spheres size can between 50 nm ~ 50 μm modulation.
The mesoscopic structure that the mesopore orbit that there is mesoporous P25 titanium dioxide microballoon spheres prepared by the present invention center to dissipate is constituted.
Mesoporous P25 titanium dioxide microballoon spheres prepared by the present invention have bigger serface（70~220 m2/g）, large aperture (5 ~
40 nm) and big pore volume (0.15 ~ 0.40 cm3/g)。
Mesoporous P25 titanium dioxide microballoon spheres prepared by the present invention are by the tightly packed skeleton formed of rutile-anatase, golden red
Stone is 1 with anatase ratio:3, and can obtain rutile content by the regulation and control of the species and concentration of acid（0-100%）It is different
Mesoporous TiO 2 microballoon.
Mesoporous P25 titanium dioxide microballoon spheres prepared by the present invention have high electricity conversion and high Photocatalyzed Hydrogen Production effect
Rate.Photoelectric current is the 150% of commercialization P25, and Photocatalyzed Hydrogen Production amount is the 170% of commercialization P25.
Mesoporous P25 titanium dioxide microballoon spheres prepared by the present invention have homogeneous size, the mesopore orbit of diverging, big ratio table
Rutile-anatase is tightly packed in area, big pore volume, skeleton and ratio is adjustable（Rutile content is generally 25%, can be from
Adjusted between 0-100%）.Because Large ratio surface, big pore volume and the abundant heterogeneous boundary of rutile-anatase make the material
The separative efficiency of photogenerated charge and photohole is obviously improved, so that photoelectric conversion and photocatalytic water splitting production hydrogen reaction efficiency meeting
Greatly improve.Its photoelectric current is the 150% of commercialization P25, and Photocatalyzed Hydrogen Production amount is the 170% of commercialization P25.
The inventive method is a kind of novel wet preparation method, simple to operate, it is easy to repeated, easily-controlled reaction conditions,
It is easy to industrialization.
Brief description of the drawings
Fig. 1：Mesoporous P25 titanium dioxide microballoon spheres electromicroscopic photograph.Wherein, (a) is ESEM（SEM）Photo, (b) is height
Resolution Scan Electronic Speculum (HRSEM) photo；（c）The transmission electron microscope of ultra-thin section（TEM）Photo,（d）High-resolution-ration transmission electric-lens
（HRTEM）Photo.
Fig. 2：The XRD diffraction patterns of mesoporous P25 titanium dioxide microballoon spheres and commercialization P25 nano titanium oxides.
Fig. 3：The nitrogen adsorption desorption curve of mesoporous P25 titanium dioxide microballoon spheres and commercialization P25 nano titanium oxides, illustration is
Pore-size distribution.
Fig. 4：The mesoporous TiO 2 microballoon stereoscan photograph constituted with different crystalline phases.Wherein, (a) is pure anatase
The ESEM of the mesoporous TiO 2 microballoon of composition（SEM）Photo, the mesoporous TiO 2 microballoon of (b) pure rutile composition
ESEM（SEM）Photo.
Fig. 5：The photoelectric current performance comparision of mesoporous P25 titanium dioxide microballoon spheres and commercialization P25 nano titanium oxides.
Fig. 6：The Photocatalyzed Hydrogen Production performance comparision of mesoporous P25 titanium dioxide microballoon spheres and commercialization P25 nano titanium oxides.
Embodiment
Embodiment 1：The synthesis of mesoporous anatase titanium dioxide microballoon sphere
1.6g F127 are dissolved into 32g tetrahydrofurans or dioxane solution, stirring obtains homogeneous solution（5.0 wt %）,
The 1.0-3.0g concentrated sulfuric acids are added, 1.2-3.6g glacial acetic acid stirs to form colourless transparent solution, adds 2.2-4.8g titaniums
Sour four butyl esters stirring 0.5-6 h, solution is gradually changed into golden yellow from colourless.
In the vial that the solution is transferred to opening, volatilize 8-48h in the baking oven that vial is transferred to 20-50 DEG C,
Oven temperature is further increased to 60-150 DEG C, volatilize 2-32 h, obtains white powder.
Brand-new sample is placed in tube furnace, in a nitrogen atmosphere, 350 DEG C of roasting 2-6 h, heating rate is 0.2-10 DEG C
/ min, obtains grey black TiO2/ C composite.Gained sample is calcined 2-5 h for 400 DEG C in atmosphere again, removed therein
Carbon, obtains the mesoporous TiO 2 microballoon that the anatase that size is 600 nm is constituted.Its specific surface area is 175m2/ g, photoelectric current
For 0.42 mA/cm2。
Embodiment 2：The synthesis of mesoporous P25 titanium dioxide microballoon spheres
1.6g F127 are dissolved into 32g tetrahydrofurans or dioxane solution, stirring obtains homogeneous solution（5.0 wt %）,
1.0-3.0g concentrated hydrochloric acids are added, 1.2-3.6g glacial acetic acid stirs to form colourless transparent solution, adds 2.2-4.8g titaniums
Sour four butyl esters stirring 0.5-6 h, solution is gradually changed into golden yellow from colourless.
In the vial that the solution is transferred to opening, vial is transferred to volatilization 8-48 h in 20-50 DEG C of baking oven,
Oven temperature is further increased to 60-150 DEG C, volatilizees 2-32 hour, obtains white powder.
Brand-new sample is placed in tube furnace, in a nitrogen atmosphere, 350 DEG C of roasting 2-6 h, heating rate is 0.2-10 DEG C
/ min, obtains grey black TiO2/ C composite.Gained sample is calcined 2-5 h for 400 DEG C in atmosphere again, removed therein
Carbon, it is 3 to obtain anatase that size is 1.2 μm and rutile ratio:1 mesoporous P25 titanium dioxide microballoon spheres.Its specific surface area
For 78m2/ g, photoelectric current is 0.70 mA/cm2。
Embodiment 3：The synthesis of mesoporous rutile titanium dioxide microballoon
1.6g F127 are dissolved into 32 g tetrahydrofurans or dioxane solution, stirring obtains homogeneous solution（5.0 wt %）,
3.0-6.0g concentrated hydrochloric acids are added, 3.0-6.0g glacial acetic acid stirs to form colourless transparent solution, adds 2.2-4.8g titaniums
Sour four butyl esters stirring 0.5-6 h, solution is gradually changed into golden yellow from colourless.
In the vial that the solution is transferred to opening, vial is transferred to volatilization 8-24 h in 20-50 DEG C of baking oven,
Oven temperature is further increased to 60-100 DEG C, volatilize 2-8 h, obtains white powder.
Brand-new sample is placed in tube furnace, in a nitrogen atmosphere, 350 DEG C of roasting 2-6 h, heating rate is 0.2-10
DEG C/min, obtain grey black TiO2/ C composite.Gained sample is calcined 2-5 h for 400 DEG C in atmosphere again, removed wherein
Carbon, it is 2.0 μm of mesoporous rutile titanium dioxide microballoon to obtain size.Its specific surface area is 73m2/ g, photoelectric current is 0.08
mA/cm2。
Claims (7)
1. a kind of preparation method of mesoporous P25 titanium dioxide microballoon spheres, it is characterised in that comprise the following steps that：
（1）Template Ampliphilic triblock copclymer PEO-PPO-PEO is dissolved into volatile organic solvent, forms uniform
Solution, its concentration is 0.2-30wt %；Inorganic acid regulation skeleton crystal formation is added, is sufficiently stirred for, obtains colourless transparent solution, will
Organic titanium source is added in the solution of above-mentioned water white transparency, forms golden yellow solution；Wherein, template is used with titanium source presoma
The ratio between amount of quantity of material is 0.2-2.2；
（2）By step（1）In obtained golden yellow mixed solution be transferred in the vial of opening, be placed in 20-50 DEG C of baking oven
Volatilize 8-48 h, and rise temperature obtains the powder of white to 60-150 DEG C of continuation volatilization 2-32 h；
（3）Above-mentioned powder sample is placed in tube furnace, under inert gas atmosphere, with 0.2-10 DEG C/min heating rate from
Room temperature is increased to 200-500 DEG C, and keeps 3-12h, obtains grey black TiO2/ C composite；Again by gained sample in atmosphere
300-800 DEG C of roasting 2-10h removes carbon therein, that is, obtains mesoporous P25 titanium dioxide microballoon spheres.
2. the preparation method of mesoporous P25 titanium dioxide microballoon spheres according to claim 1, it is characterised in that described plate agent
Selected from F127 (EO106-PO70-EO106)、P65（EO20-PO30-EO20）、P85（EO26-PO39-EO20）、P123（EO20-PO70-
EO20）、F108（EO132-PO50-EO132）F68（EO132-PO30-EO132）、F98（EO132-PO45-EO132）、F88（EO132-PO40-
EO132）Or F87（EO106-PO40-EO106）In one or more.
3. the preparation method of mesoporous P25 titanium dioxide microballoon spheres according to claim 1 or 2, it is characterised in that described titanium
One or more of the source in the fourth fat of metatitanic acid four, isopropyl titanate, tetraethyl titanate.
4. the preparation method of mesoporous P25 titanium dioxide microballoon spheres according to claim 3, it is characterised in that described acid choosing
One or more from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, hydroiodic acid, hydrobromic acid or hydrofluoric acid.
5. the preparation method of the mesoporous P25 titanium dioxide microballoon spheres according to claim 1,2 or 4, it is characterised in that described
One or more of the solvent in tetrahydrofuran, dioxane, hexamethylene, ethanol, acetone, dichloromethane, chloroform or hexane.
6. the preparation method of mesoporous P25 titanium dioxide microballoon spheres according to claim 5, it is characterised in that described is mesoporous
P25 titanium dioxide microballoon spheres size is 50 nm ~ 50 μm.
7. a kind of mesoporous P25 titanium dioxide microballoon spheres obtained by one of the claim 1-6 preparation methods, by rutile-sharp
The skeleton of the tightly packed formation of titanium ore, rutile is 1 with anatase ratio:3；Its particle diameter is 50 nm ~ 50 μm, specific surface area
For 70 ~ 220 m2/ g, aperture is 5 ~ 40 nm, and pore volume is 0.15 ~ 0.40 cm3/g。
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