CN105771950A - Preparation method of one-dimensional TiO2/SiO2 nano photocatalytic material - Google Patents
Preparation method of one-dimensional TiO2/SiO2 nano photocatalytic material Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 47
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 46
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 46
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 46
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 39
- 238000001338 self-assembly Methods 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 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
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 239000011941 photocatalyst Substances 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 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
- 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
- WUPZNKGVDMHMBS-UHFFFAOYSA-N azane;dihydrate Chemical compound [NH4+].[NH4+].[OH-].[OH-] WUPZNKGVDMHMBS-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 239000010936 titanium Substances 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 16
- 239000010842 industrial wastewater Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 9
- 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 8
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 239000002159 nanocrystal Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005253 cladding Methods 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003001 depressive effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000007667 floating Methods 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
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- 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
- 238000000870 ultraviolet spectroscopy 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a preparation method of a one-dimensional TiO2/SiO2 nano photocatalytic material, belongs to the technical field of photocatalytic materials, and aims to reduce the content of organic pollutants during discharging of industrial wastewater. The preparation method comprises the following steps: adding a silicon dioxide precursor and a titanium dioxide precursor into an organic solvent, and uniformly stirring to obtain a precursor solution; dropping the precursor solution into a one-dimensional self-assembly solution, continuously stirring, placing the solution under room temperature, and stewing and centrifugating the solution to obtain white precipitates; heating the white precipitates in an acidic solution, removing a one-dimensional self-assembly, and washing and drying to obtain the one-dimensional TiO2/SiO2 nano photocatalytic material. The preparation method can be used for preparing the one-dimensional TiO2/SiO2 nano photocatalytic material.
Description
Technical field
The present invention relates to catalysis material technical field, particularly relate to a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material.
Background technology
Along with economic fast development, water pollution problems highlights day by day, and the Jiankang of ecological safety and the mankind is constituted threat by the organic pollution of industrial wastewater discharge.At present, the main method removing Industry Waste organic pollutants includes By Bubble-floating Method, absorption method, chemical oxidization method and biologic treating technique etc., but the target of efficient, economic, green organic pollutant treatment technology expected of these methods and people also there is a big difference.
Titanium dioxide is an absorbing semi-conducting material of class, when the light of a branch of suitable wavelength is radiated at its surface, is in the electronics of valence band and is stimulated and transits to conduction band up, thus producing moveable high activity light induced electron (e respectively on conduction band and valence band-) and hole (h+).Conduction band electron is good reducing agent, and valence band hole is good oxidant, and most of photocatalysis oxidation reactions are the oxidabilities directly or indirectly utilizing hole.Utilize the organic pollution in the photochemical catalytic oxidation ability degraded industrial wastewater of luminous energy and titanic oxide material, as the pollution treatment means of a kind of green, energy-saving and environmental protection, in field of environmental improvement, there is bright future.
The catalytic capability of titanium dioxide relevant with its pattern, size and surface nature (referring to Ma, Y. etc., " energy and environment science ", 2012,5:6345；And Sun, Z. etc., " JACS ", 2011,133:19314.), when when being reduced in size to nanoscale of titanium dioxide, due to quantum confined effect, the electrons transport property of nano-titania particle, electronic band structure etc. can be made to change, and specifically, specific surface area increases and reaction site increases and can be effectively improved semiconductor surface redox reaction speed and to the sorption enhanced efficiency of light (referring to Yang, H.G. etc., " nature ", 2008,453:638).But inventor have found that in actual applications, when titanium dioxide is reduced in size to nanoscale, its agglomeration can directly result in the minimizing of effective ratio area, and, in removal process, for the particle of nanoscale, difficulty is bigger, thus causing that application cost increases.
Therefore, it is possible to research and develop efficient, economic wastewater processing technology, it is possible to reduce organic pollution content, especially cation organic pollution content in industrial wastewater discharge, become one of urgent during current environment is administered and very important subject under discussion.
Summary 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 is possible to 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:
In organic solvent, add silica precursor and TiO 2 precursor, stir, obtain precursor solution；
Described precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring and be placed in left at room temperature, after standing, carry out centrifugal treating, obtain white precipitate；
White precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dry, obtain one-dimensional TiO2/SiO2Nano-photocatalyst material.
Preferably, the mol ratio of described silica precursor and TiO 2 precursor is 1:1-1:15.
Optionally, the manner of formulation of described one-dimensional self-assembly solution includes:
Amphipathic organic molecule is dispersed in water, ultrasonic disperse, is placed in room temperature and places, obtain one-dimensional self-assembly solution.
Optionally, one end of described amphipathic organic molecule is containing the hydrophobic units that can form hydrogen bond, and the other end is the hydrophilic unit containing basic group, wherein, and described basic group at least one in primary amine groups, tertiary amine groups, guanidine radicals and imidazole radicals.
Preferably, the rotating speed of described centrifugal treating is 3000-10000rpm, and the time is 5-40 minute.
Preferably, white precipitate is heated 0.5-6 hour in the acid solution of 30 DEG C-80 DEG C, to remove one-dimensional self-assembly.
Optionally, described carrying out washing treatment specifically includes and pure water, washes of absolute alcohol white precipitate is used alternatingly.
Optionally, described TiO 2 precursor closes at least one in titanium selected from tetrabutyl titanate, isopropyl titanate, two (2 hydroxy propanoic acid) two hydroxide diammonium；Described silica precursor at least one in tetraethyl orthosilicate, methyl silicate, positive silicic acid, sodium silicate.
A kind of one-dimensional TiO as according to any one of technique scheme2/SiO2The preparation-obtained one-dimensional TiO of preparation method of nano-photocatalyst material2/SiO2Nano-photocatalyst material.
A kind of one-dimensional TiO as described in technique scheme2/SiO2Nano-photocatalyst material application in selective catalysis degradable organic pollutant.
The invention provides a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, compared to prior art, to TiO2Nanocrystal has processed so that it is by the SiO of several nano thickness2Cladding forms nucleocapsid structure, and the bonding and support by silicon dioxide is anchored on one-dimensional organic self-assembly.Protection and fixation due to surface silica dioxide; make not only can be prevented effectively from fusion and the agglomeration of titanium dioxide nano-crystal; keep higher specific surface area and photocatalysis efficiency; also organic pollution especially cation organic pollution can be shown strong adsorption, obtain higher photocatalytic degradation effect further.This preparation method avoids the synthesis condition that the high temperature in titanium dioxide prior synthesizing method, high pressure and strong acid and strong base etc. are harsh, has feature simple, energy-conservation, eco-friendly.
Accompanying drawing explanation
The TiO being templated synthesis with amphipathic organic molecular assembly body that Fig. 1 provides for the embodiment of the present invention2/SiO2High-resolution transmission microscopy photo (a) and local enlargement display (b, c)；
The TiO being templated synthesis with amphipathic organic molecular assembly body that Fig. 2 provides for the embodiment of the present invention2/SiO2Energy spectrum analysis figure；
The one-dimensional TiO that Fig. 3 provides for the embodiment of the present invention under light protected environment2/SiO2The degradation curve (b) of the nano-photocatalyst material adsorption curve (a) to rhodamine 6G (model compound) and photocatalysis rhodamine 6G.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiments provide a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, including:
S1: add silica precursor and TiO 2 precursor in organic solvent, stir, obtain precursor solution.
In this step, for the agglomeration overcoming titanium dioxide independent in prior art to occur after size reduction to nanoscale, this step introduces silicon dioxide, to forming the nucleocapsid structure of coated with silica titanium dioxide, thus avoiding above-mentioned agglomeration.In this step, first preparation is containing the precursor solution of the two.Concrete, the presoma of said two devices is dissolved in organic solvent, concrete, organic solvent is selected from least one in methanol, ethanol, the tert-butyl alcohol and acetone, and those skilled in the art can select voluntarily according to service condition.
S2: be added drop-wise to by described precursor solution in one-dimensional self-assembly solution, continues stirring and is placed in left at room temperature, carry out centrifugal treating, obtain white precipitate after standing.
In this step, in order to effectively reduce the agglomeration of nanoparticle, can easily nanoparticle be separated and recovered from solution also for the later stage, it is simple to repeatedly reuse, concrete, precursor solution is added drop-wise in one-dimensional self-assembly solution to by TiO by this step2/SiO2Nanoparticle is fixed in one-dimensional self-assembly template.Subsequently by centrifugal treating, obtain white precipitate.
S3: white precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dry, 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 is to remove one-dimensional self-assembly template, and washing is to remove the organic molecule of de-assembly, finally giving pure one-dimensional TiO2/SiO2Nano-photocatalyst material.
Embodiments provide a kind of one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, compared to prior art, to TiO2Nanocrystal has processed so that it is by the SiO of several nano thickness2Cladding forms nucleocapsid structure, and the bonding and support by silicon dioxide is anchored on one-dimensional organic self-assembly.Protection and fixation due to surface silica dioxide; not only can be prevented effectively from fusion and the agglomeration of titanium dioxide nano-crystal; it is made to keep higher specific surface area and photocatalysis efficiency; also organic pollution especially cation organic pollution can be shown strong adsorption, obtain higher photocatalytic degradation effect further.The method is simple to operate, and universality is high.
In one embodiment of this invention, the mol ratio of described silica precursor and TiO 2 precursor is 1:1-1:15.In the present embodiment, in order to form the nucleocapsid structure of stable coated with silica titanium dioxide, the each component within the scope of aforementioned proportion is added when preparing precursor solution, it will be understood by those skilled in the art that, the precursor solution prepared in above-mentioned scope all can meet the needs that follow-up preparation meets the monodimension nanometer material of demand, therefore can be adjusted as needed in above-mentioned scope, such as, 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 described one-dimensional self-assembly solution includes: be dispersed in water by amphipathic organic molecule, ultrasonic disperse, is placed in room temperature and places, obtains one-dimensional self-assembly solution.In the present embodiment, selecting the mode being dispersed in water by amphipathic organic molecule is in order to obtained one-dimensional self-assembly solution is then able to mix with precursor solution better to obtain one-dimensional self-assembly, to form uniform white precipitate.
In one embodiment of this invention, one end of described amphipathic organic molecule is containing the hydrophobic units that can form hydrogen bond, the other end is the hydrophilic unit containing basic group, wherein, and described basic group at least one in primary amine groups, tertiary amine groups, guanidine radicals and imidazole radicals.In the present embodiment, build periphery by hydrophobe effect and intermolecular hydrogen bonding effect etc. and be coated with the one-dimensional organic formwork of basic group, so can regulate and control the size of organic formwork, pattern and surface nature etc. by regulating hydrophilic, the composition of hydrophobic part, structure or assembling condition.
In one embodiment of this invention, the rotating speed of described centrifugal treating is 3000-10000rpm, and the time is 5-40 minute.In the present embodiment, one-dimensional TiO is obtained in order to separate2/SiO2Nano-photocatalyst material, adopts the mode of centrifugal treating to be isolated.It is understood that when the rotating speed of centrifugal treating and time are limited in above-mentioned scope, the separating effect that can make nano material is better, and those skilled in the art can be adjusted in above-mentioned scope according to practical situation.Concrete, the rotating speed of centrifugal treating can be 4000,5000,6000,7000,8000,9000rpm, time can also be 10,15,20,25,30,35 minutes etc., in addition, as long as the rotating speed of centrifugal treating and time are in the arbitrary value in above-mentioned scope.
In one embodiment of this invention, white precipitate is heated 0.5-6 hour in the acid solution of 30 DEG C-80 DEG C, to remove one-dimensional self-assembly.In the present embodiment, owing to one-dimensional self-assembly has bigger dissolubility in an acidic solution, therefore select to be heated white precipitate in an acidic solution, so that one-dimensional self-assembly disaggregation., additionally, selecting to be heated at the temperature of 30 DEG C-80 DEG C is to keep one-dimensional TiO removing organic formwork while2/SiO2The integrity of nanostructured, it is to be understood that for heat time heating time, in the application and be not specifically limited, as long as can be completely removed by one-dimensional self-assembly, whether removal effect can be passed through C-H stretching vibration peak in infrared spectrum and disappear judgement.
In one embodiment of this invention, described carrying out washing treatment specifically includes and pure water, washes of absolute alcohol white precipitate is used alternatingly, to remove unreacted TiO 2 precursor and silica precursor.
In one embodiment of this invention, described TiO 2 precursor closes at least one in titanium selected from tetrabutyl titanate, isopropyl titanate, two (2 hydroxy propanoic acid) two hydroxide diammonium；Described silica precursor at least one in tetraethyl orthosilicate, methyl silicate, positive silicic acid, sodium silicate.In the present embodiment, owing to TiO 2 precursor, silica precursor have different hydrolysis condensation reaction speed, therefore, select different TiO 2 precursor, silica precursor, the reaction rate of titanium dioxide, silicon dioxide can be regulated, the control of association reaction technique, it is possible to obtain the one-dimensional TiO with different titanium dioxide nanocrystalline size and coated with silica layer thickness2/SiO2Nano-photocatalyst material.
A kind of one-dimensional TiO as according to any one of above-described embodiment2/SiO2The preparation-obtained one-dimensional TiO of preparation method of nano-photocatalyst material2/SiO2Nano-photocatalyst material.Embodiments provide a kind of one-dimensional TiO prepared by said method2/SiO2Nano-photocatalyst material, this material has SiO2Cladding TiO2The nucleocapsid structure formed, and be anchored on one-dimensional organic self-assembly by silica-bonded and support.Protection and fixation due to surface silica dioxide; not only can be prevented effectively from fusion and the agglomeration of titanium dioxide nano-crystal; it is made to keep higher specific surface area and photocatalysis efficiency; also organic pollution especially cation organic pollution can be shown strong adsorption, obtain higher photocatalytic degradation effect further.
A kind of one-dimensional TiO as described in above-described embodiment2/SiO2Nano-photocatalyst material application in selective catalysis degradable organic pollutant.In the present embodiment, due to one-dimensional TiO2/SiO2Nano-photocatalyst material has SiO2Cladding TiO2The nucleocapsid structure formed so that organic pollution especially cation organic pollution can be shown strong adsorption by the protection of surface silica dioxide and fixation, it is thus achieved that higher photocatalytic degradation effect.
In order to become apparent from introducing the one-dimensional TiO that the embodiment of the present invention provides in detail2/SiO2The preparation method of nano-photocatalyst material, illustrates 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 one-dimensional self-assembly solution；
(2) one-dimensional TiO2/SiO2The synthesis of nano material
A) in organic solvent, add silica precursor and the TiO 2 precursor that mol ratio is 1:1-1:15, stir, obtain precursor solution；
B) in whipping process, precursor solution is added drop-wise in one-dimensional self-assembly solution (1), stirring 10-120 minute is continued after dropwising, room temperature stands 1-5 days, centrifugal treating (rotating speed 3000-10000rpm is carried out after standing, 5-40 minute time), obtain white precipitate；
C) obtained white precipitate is heated 0.5-6 hour in the acid solution of 30-80 DEG C remove one-dimensional self-assembly, and alternately adopt water, ethanol purge white precipitate；
D) by C) gained white precipitate is dried, and obtains one-dimensional TiO2/SiO2Nano-photocatalyst material.
Embodiment 2
One-dimensional TiO2/SiO2The pattern of nano-photocatalyst material and structural characterization
High resolution transmission electron microscopy, model: JEM-2100UHR, instrument manufacturer facility man: NEC (JEOL), accelerating potential: 200kV；
Energy depressive spectroscopy (EDS), model: EDAXXM2-30T, instrument manufacturer facility man: NEC (JEOL), is the subsidiary accessory of transmission electron microscope.
The present embodiment observes one-dimensional TiO in conjunction with high-resolution transmission microscopy and energy depressive spectroscopy2/SiO2The pattern of nano-photocatalyst material and structure, concrete, by sample dispersion in ethanol, drop on the copper mesh being coated with carbon film, utilize special specimen holder to put into sample room, evacuation after drying, regulate suitable resolution and focal length, select suitable time of exposure, shoot image, and utilize energy depressive spectroscopy to analyze sample composition.
It was found that gained sample has one-dimensional nano structure, its diameter is tens nanometers, and length is the even several micron of hundreds of nanometer, and this point can be found out from Fig. 1 (a).From EDAX results (Fig. 2), this sample is made up of silicon dioxide and titanium dioxide, from the transmission electron microscope collection of illustrative plates (Fig. 1 (b) (c)) amplified, this one-dimentional structure is made up of the amorphous materials of nanocrystal and surrounding, judged that this crystal is titanium dioxide nanocrystalline by interplanar distance, and nanocrystalline amorphous materials around is silicon dioxide.The thickness of nanocrystalline size and surrounding silicon dioxide clad can by obtaining with scale contrast.
Embodiment 3
Absorption, photocatalytic degradation efficiency test
Rhodamine 6G has characteristic absorption in ultraviolet spectra, and within the scope of finite concentration, its absorbance is directly proportional to concentration, and the change that therefore can pass through absorbance judges the concentration of rhodamine 6G in solution.One-dimensional TiO by preparation2/SiO2Nano-photocatalyst material joins in the solution containing rhodamine 6G, keeps in Dark Place, and samples at set intervals, and centrifuging and taking supernatant carries out ultraviolet spectroscopy, to judge the concentration of not adsorbed rhodamine 6G.
The one-dimensional TiO provided is provided2/SiO2The adsorption curve (Fig. 3 a) of rhodamine 6G is found by nano-photocatalyst material, and it can reach adsorption equilibrium in a short period of time, it was shown that the one-dimensional TiO provided2/SiO2Rhodamine 6G is had very strong adsorption by nano-photocatalyst material.Being exposed under ultraviolet light by mixture saturated for absorption, the concentration of rhodamine 6G continues to reduce with speed quickly, it was shown that one-dimensional TiO2/SiO2Rhodamine 6G is had good photocatalytic degradation effect by nano-photocatalyst material, and can reuse, and the photocatalysis efficiency of five recyclings is positively retained at more than 85%.
Claims (10)
1. an one-dimensional TiO2/SiO2The preparation method of nano-photocatalyst material, it is characterised in that including:
In organic solvent, add silica precursor and TiO 2 precursor, stir, obtain precursor solution；
Described precursor solution is added drop-wise in one-dimensional self-assembly solution, continues stirring and be placed in left at room temperature, after standing, carry out centrifugal treating, obtain white precipitate；
Described white precipitate is heated in an acidic solution, after one-dimensional self-assembly to be removed, carrying out washing treatment, dry, obtain one-dimensional TiO2/SiO2Nano-photocatalyst material.
2. preparation method according to claim 1, it is characterised in that the mol ratio of described silica precursor and TiO 2 precursor is 1:1-1:15.
3. preparation method according to claim 1, it is characterised in that the manner of formulation of described one-dimensional self-assembly solution includes:
Amphipathic organic molecule is dispersed in water, ultrasonic disperse, is placed in room temperature and places, obtain described one-dimensional self-assembly solution.
4. preparation method according to claim 3, it is characterized in that, one end of described amphipathic organic molecule is containing the hydrophobic units that can form hydrogen bond, the other end is the hydrophilic unit containing basic group, wherein, described basic group at least one in primary amine groups, tertiary amine groups, guanidine radicals and imidazole radicals.
5. preparation method according to claim 1, it is characterised in that the rotating speed of described centrifugal treating is 3000-10000rpm, the time is 5-40 minute.
6. preparation method according to claim 1, it is characterised in that described white precipitate is heated 0.5-6 hour in the acid solution of 30 DEG C-80 DEG C, to remove one-dimensional self-assembly.
7. preparation method according to claim 1, it is characterised in that described carrying out washing treatment specifically includes and pure water, washes of absolute alcohol described in white precipitate is used alternatingly.
8. preparation method according to claim 1, it is characterised in that described TiO 2 precursor closes at least one in titanium selected from tetrabutyl titanate, isopropyl titanate, two (2 hydroxy propanoic acid) two hydroxide diammonium；Described silica precursor at least one in tetraethyl orthosilicate, methyl silicate, positive silicic acid, sodium silicate.
9. the one-dimensional TiO as according to any one of claim 1-82/SiO2The preparation-obtained one-dimensional TiO of preparation method of nano-photocatalyst material2/SiO2Nano-photocatalyst material.
10. an one-dimensional TiO as claimed in claim 92/SiO2Nano-photocatalyst material application in selective catalysis degradable organic pollutant.
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