CN105771950B - A kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material - Google Patents
A kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 70
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 45
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 45
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 45
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000001338 self-assembly Methods 0.000 claims abstract description 31
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000010842 industrial wastewater Substances 0.000 abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003001 depressive effect Effects 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- -1 specifically Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- B01J21/08—Silica
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, belong to catalysis material technical field, organic pollution content in industrial wastewater discharge can be reduced.The preparation method, including：Silica precursor and TiO 2 precursor are added into organic solvent, stirs, obtains precursor solution；The precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring juxtaposition and stands at room temperature, centrifugal treating is carried out after standing, obtains white precipitate；White precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dries, obtains one-dimensional TiO2/SiO2Nano-photocatalyst material.The present invention can be used for preparing one-dimensional TiO2/SiO2Nano-photocatalyst material.
Description
Technical field
The present invention relates to catalysis material technical field, more particularly to a kind of one-dimensional TiO2/SiO2Nano-photocatalyst material
Preparation method.
Background technology
Along with the fast development of economy, water pollution problems increasingly highlights, and the organic pollution of industrial wastewater discharge is right
The Jiankang of ecological safety and the mankind constitute threat.At present, the main method for removing Industry Waste organic pollutants includes gas
Float glass process, absorption method, chemical oxidization method and biologic treating technique etc., but these methods and people expect it is efficient, economical, green
The target of organic pollutant treatment technology also there is a big difference.
Titanium dioxide is a kind of absorbing semi-conducting material, when the light irradiation of a branch of suitable wavelength is on its surface,
Electronics in valence band, which is stimulated, transits to conduction band up, so as to produce moveable high activity light on conduction band and valence band respectively
Raw electronics (e-) and hole (h+).Conduction band electron is good reducing agent, and valence band hole is good oxidant, and most of light are urged
Oxidation is the oxidability for directly or indirectly utilizing hole.Utilize the photochemical catalytic oxidation of luminous energy and titanic oxide material
Organic pollution in ability degraded industrial wastewater, as a kind of green, the pollution treatment means of energy-saving and environmental protection, leads in environmental improvement
Domain has bright future.
The catalytic capability of titanium dioxide it is relevant with its pattern, size and surface nature (referring to Ma, Y. etc.,《The energy and ring
Border science》, 2012,5：6345；And Sun, Z. etc.,《JACS》, 2011,133：19314.), when the chi of titanium dioxide
It is very little when being reduced to nanoscale, due to quantum confined effect, the electrons transporting of nano-titania particle can be caused
Matter, electronic band structure etc. change, and specifically, specific surface area increase increases with reaction site can effectively improve semiconductor table
Face redox reaction speed and to the sorption enhanced efficiency of light (referring to Yang, H. G. etc.,《It is natural》, 2008,453：638).
But inventor has found that, when titanium dioxide is reduced in size to nanoscale, its agglomeration can directly result in actual applications
The reduction of effective ratio area, also, in removal process, it is difficult bigger for the particle of nanoscale, so as to cause
Application cost increase.
Therefore, it is possible to research and develop efficient, economic wastewater processing technology, can reduce organic in industrial wastewater discharge
Pollutant load, especially cation organic pollution content, turn into urgent and very important subject under discussion during current environment is administered
One of.
The content of the invention
It is an object of the invention to provide a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, it can reduce
Organic pollution content in industrial wastewater discharge.
The invention provides a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, including：
Silica precursor and TiO 2 precursor are added into organic solvent, stirs, it is molten to obtain presoma
Liquid；
The precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring juxtaposition and stands at room temperature, treat
Centrifugal treating is carried out after standing, obtains white precipitate；
White precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dries, obtains
To one-dimensional TiO2/SiO2Nano-photocatalyst material.
Preferably, the mol ratio of the silica precursor and TiO 2 precursor is 1:1-1:15.
Optionally, the manner of formulation of the one-dimensional self-assembly solution includes：
Amphipathic organic molecule is dispersed in water, ultrasonic disperse, is placed in room temperature placement, it is molten to obtain one-dimensional self-assembly
Liquid.
Optionally, one end of the amphipathic organic molecule be containing the hydrophobic units that can form hydrogen bond, the other end be containing
Have the hydrophilic unit of basic group, wherein, the basic group in primary amine groups, tertiary amine groups, guanidine radicals and imidazole radicals at least
It is a kind of.
Preferably, the rotating speed of the centrifugal treating is 3000-10000rpm, and the time is 5-40 minutes.
Preferably, white precipitate is heated into 0.5-6 hours in 30 DEG C -80 DEG C of acid solution, it is one-dimensional from group to remove
Fill body.
Optionally, the carrying out washing treatment, which specifically includes, is used alternatingly pure water, washes of absolute alcohol white precipitate.
Optionally, the TiO 2 precursor is selected from tetrabutyl titanate, isopropyl titanate, two (2 hydroxy propanoic acid) dihydros
Aoxidize two ammoniums and close at least one of titanium；The silica precursor be selected from tetraethyl orthosilicate, methyl silicate, positive silicic acid,
At least one of sodium metasilicate.
A kind of one-dimensional TiO as any one of above-mentioned technical scheme2/SiO2The preparation method of nano-photocatalyst material
Preparation-obtained one-dimensional TiO2/SiO2Nano-photocatalyst material.
A kind of one-dimensional TiO as described in above-mentioned technical scheme2/SiO2Nano-photocatalyst material has in selective catalysis degraded
Application in organic pollutants.
The invention provides a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, compared to prior art
Speech, to TiO2Nanocrystal is handled, and makes it by the SiO of several nano thickness2Cladding forms core shell structure, and passes through two
The bonding of silica and support are anchored on one-dimensional organic self-assembly.Protection and fixation due to surface silica dioxide,
So that fusion and the agglomeration of titanium dioxide nano-crystal not only can be effectively avoided, the higher specific surface area of holding and photocatalysis
Efficiency, can also show strong suction-operated to organic pollution especially cation organic pollution, further obtain compared with
High photocatalytic degradation effect.It is strong that the preparation method avoids high temperature in titanium dioxide prior synthesizing method, high pressure and strong acid
The harsh synthesis condition such as alkali, there is the characteristics of simple, energy-conservation, environment-friendly.
Brief description of the drawings
The TiO using amphipathic organic molecular assembly body as templated synthesis that Fig. 1 is provided by the embodiment of the present invention2/SiO2's
High-resolution transmission microscopy photo (a) and its local enlargement display (b, c)；
The TiO using amphipathic organic molecular assembly body as templated synthesis that Fig. 2 is provided by the embodiment of the present invention2/SiO2's
Energy spectrum analysis figure；
The one-dimensional TiO that Fig. 3 is provided by the embodiment of the present invention under light protected environment2/SiO2Nano-photocatalyst material is to rhodamine
6G (model compound) adsorption curve (a) and the degradation curve (b) of photocatalysis rhodamine 6G.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The embodiments of the invention provide a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, including：
S1：Silica precursor and TiO 2 precursor are added into organic solvent, stirs, obtains presoma
Solution.
In this step, occur to overcome single titanium dioxide in the prior art after size reduction to nanoscale
Agglomeration, silica is introduced in this step, to form the core shell structure of coated with silica titanium dioxide, so as to avoid
Above-mentioned agglomeration.In this step, the precursor solution containing the two is prepared first.Specifically, the presoma by said two devices
It is dissolved in organic solvent, specifically, organic solvent may be selected from least one of methanol, ethanol, the tert-butyl alcohol and acetone, this area
Technical staff can voluntarily select according to service condition.
S2：The precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring juxtaposition and stands at room temperature,
Centrifugal treating is carried out after standing, obtains white precipitate.
In this step, in order to effectively reduce the agglomeration of nano-particle, will easily can be received also for the later stage
Rice corpuscles separates and recovers from solution, is easy to be used repeatedly, specifically, being added drop-wise to precursor solution in this step one-dimensional
To by TiO in self-assembly solution2/SiO2Nano-particle is fixed in one-dimensional self-assembly template.Then by centrifugation at
Reason, obtains white precipitate.
S3：White precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dried,
Obtain one-dimensional TiO2/SiO2Nano-photocatalyst material.
In this step, white precipitate is heated, wash after can obtain one-dimensional TiO2/SiO2Nano-photocatalyst material.
Wherein, heating be in order to remove one-dimensional self-assembly template, washing be in order to remove the organic molecule of de-assembly, finally give it is pure
Net one-dimensional TiO2/SiO2Nano-photocatalyst material.
The embodiments of the invention provide a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, compared to existing
For technology, to TiO2Nanocrystal is handled, and makes it by the SiO of several nano thickness2Cladding forms core shell structure, and
It is anchored on by the bonding and support of silica on one-dimensional organic self-assembly.Due to the protection and fixation of surface silica dioxide
Effect, not only can effectively avoid fusion and the agglomeration of titanium dioxide nano-crystal, make its keep higher specific surface area and
Photocatalysis efficiency, can also strong suction-operated be shown to organic pollution especially cation organic pollution, further
Obtain higher photocatalytic degradation effect.This method is simple to operate, and universality is high.
In one embodiment of this invention, the mol ratio of the silica precursor and TiO 2 precursor is 1:1-
1:15.In the present embodiment, in order to form the core shell structure of stable coated with silica titanium dioxide, forerunner is being prepared
The each component added during liquid solution in the range of aforementioned proportion, it will be appreciated by persons skilled in the art that institute within the above range
The precursor solution of preparation can meet the needs of the follow-up monodimension nanometer material for preparing and meeting demand, therefore can exist as needed
It is adjusted in above range, for example, the mol ratio of silica precursor and TiO 2 precursor is 1:2、1:3、1:4、
1:5、1:6、1:7、 1:8、1:9、1:10、1:11、1:12、1:13、1:14 etc..
In one embodiment of this invention, the manner of formulation of the one-dimensional self-assembly solution includes：Will be amphipathic organic
Molecule is dispersed in water, ultrasonic disperse, is placed in room temperature placement, is obtained one-dimensional self-assembly solution.In the present embodiment, selection will
The mode that amphipathic organic molecule is dispersed in water is come to obtain one-dimensional self-assembly be in order to which resulting one-dimensional self-assembly is molten
Liquid is then able to preferably mix with precursor solution, to form uniform white precipitate.
In one embodiment of this invention, one end of the amphipathic organic molecule is to contain the hydrophobic list that can form hydrogen bond
Member, the other end are the hydrophilic unit containing basic group, wherein, the basic group is selected from primary amine groups, tertiary amine groups, guanidine radicals and miaow
At least one of oxazolyl.In the present embodiment, by hydrophobe effect and intermolecular hydrogen bonding act on etc. structure periphery covered with
The one-dimensional organic formwork of basic group, it can so be regulated and controled by adjusting hydrophilic, hydrophobic part composition, structure or assembling condition
Size, pattern and surface nature of organic formwork etc..
In one embodiment of this invention, the rotating speed of the centrifugal treating is 3000-10000rpm, and the time is 5-40 points
Clock.In the present embodiment, for isolated one-dimensional TiO2/SiO2Nano-photocatalyst material, by it by the way of centrifugal treating
Separation.It it is understood that when the rotating speed of centrifugal treating and time limit within the above range, can imitate the separation of nano material
Fruit is preferable, and those skilled in the art can be adjusted within the above range according to actual conditions.Specifically, the rotating speed of centrifugal treating
Can be 4000,5000,6000,7000,8000,9000rpm, the time can also be 10,15,20,25,30,35 minutes etc.,
In addition, as long as the arbitrary value of the rotating speed of centrifugal treating and time within the above range.
In one embodiment of this invention, white precipitate is heated into 0.5-6 hours in 30 DEG C -80 DEG C of acid solution,
To remove one-dimensional self-assembly.In the present embodiment, because one-dimensional self-assembly has larger solubility in an acidic solution,
Therefore selection is heated white precipitate in an acidic solution, so that one-dimensional self-assembly disaggregation., in addition, selection is 30
It is to keep one-dimensional TiO while organic formwork is removed to carry out heating at a temperature of DEG C -80 DEG C2/SiO2Nanostructured
Integrality, it is to be understood that for the heat time, in the application and be not specifically limited, as long as can be by one-dimensional self assembly
Body is removed completely, and whether removal effect can be disappeared judgement by C-H stretching vibration peaks in infrared spectrum.
In one embodiment of this invention, the carrying out washing treatment specifically includes that pure water, washes of absolute alcohol is used alternatingly is white
Color precipitates, to remove unreacted TiO 2 precursor and silica precursor.
In one embodiment of this invention, the TiO 2 precursor is selected from tetrabutyl titanate, isopropyl titanate, two
The ammonium of (2 hydroxy propanoic acid) two hydroxide two closes at least one of titanium；The silica precursor is selected from tetraethyl orthosilicate, just
At least one of methyl silicate, positive silicic acid, sodium metasilicate.In the present embodiment, before due to TiO 2 precursor, silica
Driving body has different hydrolysis condensation reaction speed, therefore, from different TiO 2 precursors, silica precursor,
The reaction rate of titanium dioxide, silica can be adjusted, the control of association reaction technique, can obtain that there are different titanium dioxides
The one-dimensional TiO of nanocrystalline Ti size and coated with silica thickness degree2/SiO2Nano-photocatalyst material.
A kind of one-dimensional TiO as any one of above-mentioned embodiment2/SiO2The preparation method institute of nano-photocatalyst material
The one-dimensional TiO being prepared2/SiO2Nano-photocatalyst material.It is prepared the embodiments of the invention provide one kind by the above method
One-dimensional TiO2/SiO2Nano-photocatalyst material, the material have SiO2Coat TiO2The core shell structure of formation, and pass through dioxy
SiClx bonding and support are anchored on one-dimensional organic self-assembly.Protection and fixation due to surface silica dioxide, not only
Fusion and the agglomeration of titanium dioxide nano-crystal can be effectively avoided, it is kept higher specific surface area and photocatalysis effect
Rate, can also strong suction-operated be shown to organic pollution especially cation organic pollution, further obtain higher
Photocatalytic degradation effect.
A kind of one-dimensional TiO as described in above-mentioned embodiment2/SiO2Nano-photocatalyst material is degraded organic in selective catalysis
Application in pollutant.In the present embodiment, due to one-dimensional TiO2/SiO2Nano-photocatalyst material has SiO2Coat TiO2Shape
Into core shell structure so that can have by the protection of surface silica dioxide and fixation to organic pollution especially cation
Organic pollutants show strong suction-operated, obtain higher photocatalytic degradation effect.
In order to become apparent from introducing the one-dimensional TiO that the embodiment of the present invention is provided in detail2/SiO2Nano-photocatalyst material
Preparation method, illustrated below with reference to specific embodiment.
Embodiment 1
One-dimensional TiO2/SiO2The preparation of nano-photocatalyst material
(1) preparation of one-dimensional self-assembly solution
The amphipathic organic molecule of certain mass is dispersed in water, ultrasonic disperse, is placed in room temperature and places 1-14 days, obtain
To one-dimensional self-assembly solution；
(2) one-dimensional TiO2/SiO2The synthesis of nano material
A it is 1 that mol ratio) is added into organic solvent:1-1:15 silica precursor and TiO 2 precursor, is stirred
Mix uniformly, obtain precursor solution；
B) in whipping process, precursor solution is added drop-wise in one-dimensional self-assembly solution (1), continued after being added dropwise
10-120 minutes are stirred, are stored at room temperature 1-5 days, centrifugal treating (rotating speed 3000-10000rpm, time 5-40 are carried out after standing
Minute), obtain white precipitate；
C) resulting white precipitate heats to 0.5-6 hours in 30-80 DEG C of acid solution removes one-dimensional self assembly
Body, and alternately using water, ethanol cleaning white precipitate；
D) by C) gained white precipitate be dried, obtain one-dimensional TiO2/SiO2Nano-photocatalyst material.
Embodiment 2
One-dimensional TiO2/SiO2The pattern and structural characterization of nano-photocatalyst material
High resolution transmission electron microscopy, model：JEM-2100UHR, instrument manufacturer facility man：JEOL (JEOL), adds
Fast voltage：200kV；
Energy depressive spectroscopy (EDS), model：EDAX XM2-30T, instrument manufacturer facility man：JEOL (JEOL), it is transmission
The subsidiary accessory of electron microscope.
The present embodiment combination high-resolution transmission microscopy and energy depressive spectroscopy observe one-dimensional TiO2/SiO2Nano-photo catalytic
The pattern and structure of material, specifically, by sample dispersion in ethanol, dropping in and being coated with the copper mesh of carbon film, using special after drying
Specimen holder is put into sample room, vacuumizes, and adjusts suitable resolution ratio and focal length, selects suitable time for exposure, shooting figure
Picture, and utilize energy depressive spectroscopy analysis sample composition.
As a result find, gained sample has one-dimensional nano structure, its a diameter of tens nanometers, length be hundreds of nanometers even
Several microns, this point can be found out from Fig. 1 (a).From EDAX results (Fig. 2), the sample is by silica and two
Titanium oxide forms, and it was found from the transmission electron microscope collection of illustrative plates (Fig. 1 (b) (c)) of amplification, the one-dimentional structure is by nanocrystal and surrounding
Amorphous materials forms, and judges the crystal by interplanar distance for titanium dioxide nanocrystalline, and the amorphous materials of nanocrystalline surrounding
For silica.Nanocrystalline size and the thickness of surrounding silicon dioxide clad can be by contrasting to obtain with scale.
Embodiment 3
Absorption, photocatalytic degradation efficiency test
Rhodamine 6G has characteristic absorption in ultraviolet spectra, and in the range of finite concentration, its absorbance is directly proportional to concentration,
Therefore the concentration of rhodamine 6G in solution can be judged by the change of absorbance.By the one-dimensional TiO of preparation2/SiO2Nanometer light is urged
Change material to be added in the solution containing rhodamine 6G, be kept in dark place, sample at regular intervals, centrifuging and taking supernatant carries out purple
External spectrum determines, to judge the concentration of rhodamine 6G not to be adsorbed.
The one-dimensional TiO provided is provided2/SiO2Nano-photocatalyst material is sent out the adsorption curve (Fig. 3 a) of rhodamine 6G
Existing, it can reach adsorption equilibrium in a short period of time, show the one-dimensional TiO provided2/SiO2Nano-photocatalyst material is to sieve
Red bright 6G has very strong suction-operated.By the exposure of the mixture of adsorption saturation under ultraviolet light, the concentration of rhodamine 6G continue with
Speed quickly reduces, and shows one-dimensional TiO2/SiO2Nano-photocatalyst material has good photocatalytic degradation effect to rhodamine 6G
Fruit, and can reuse, the photocatalysis efficiency of five recyclings is positively retained at more than 85%.
Claims (8)
- A kind of 1. one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, it is characterised in that including：Silica precursor and TiO 2 precursor are added into organic solvent, stirs, obtains precursor solution；The precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring juxtaposition and stands at room temperature, wait to stand After carry out centrifugal treating, obtain white precipitate；The white precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dries, obtains To one-dimensional TiO2/SiO2Nano-photocatalyst material；Wherein：The manner of formulation of the one-dimensional self-assembly solution includes：Amphipathic organic molecule is dispersed in water, ultrasonic disperse, put Placed in room temperature, obtain the one-dimensional self-assembly solution；Wherein, one end of the amphipathic organic molecule is containing can be formed The hydrophobic units of hydrogen bond, the other end are the hydrophilic unit containing basic group, the basic group be selected from primary amine groups, tertiary amine groups, At least one of guanidine radicals and imidazole radicals.
- 2. preparation method according to claim 1, it is characterised in that silica precursor and the titanium dioxide forerunner The mol ratio of body is 1:1-1:15.
- 3. preparation method according to claim 1, it is characterised in that the rotating speed of the centrifugal treating is 3000- 10000rpm, time are 5-40 minutes.
- 4. preparation method according to claim 1, it is characterised in that by acidity of the white precipitate at 30 DEG C -80 DEG C 0.5-6 hours are heated in solution, to remove one-dimensional self-assembly.
- 5. preparation method according to claim 1, it is characterised in that the carrying out washing treatment specifically include be used alternatingly it is pure White precipitate described in water, washes of absolute alcohol.
- 6. preparation method according to claim 1, it is characterised in that the TiO 2 precursor is selected from the positive fourth of metatitanic acid Ester, isopropyl titanate, the ammonium of two (2 hydroxy propanoic acid) two hydroxide two close at least one of titanium；The silica precursor choosing From at least one of tetraethyl orthosilicate, methyl silicate, positive silicic acid, sodium metasilicate.
- A kind of 7. one-dimensional TiO as any one of claim 1-62/SiO2The preparation method of nano-photocatalyst material is made Standby obtained one-dimensional TiO2/SiO2Nano-photocatalyst material.
- A kind of 8. one-dimensional TiO as claimed in claim 72/SiO2Nano-photocatalyst material is in selective catalysis degraded organic contamination Application in thing.
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