CN106693944A - Synthetic method of SiO2 modified TiO2 single crystal particle photocatalyst - Google Patents
Synthetic method of SiO2 modified TiO2 single crystal particle photocatalyst Download PDFInfo
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- CN106693944A CN106693944A CN201610986621.0A CN201610986621A CN106693944A CN 106693944 A CN106693944 A CN 106693944A CN 201610986621 A CN201610986621 A CN 201610986621A CN 106693944 A CN106693944 A CN 106693944A
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- synthetic method
- tetra
- butyl titanate
- tio
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 27
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 27
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 27
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 title claims abstract description 16
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 title abstract description 16
- 239000011941 photocatalyst Substances 0.000 title abstract description 11
- -1 SiO2 modified TiO2 Chemical class 0.000 title abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 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 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 21
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000000693 micelle Substances 0.000 description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- 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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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention belongs to the technical field of inorganic functional material preparation, in particular to a synthetic method of SiO2 modified TiO2 single crystal particle photocatalyst. The method comprises the following steps: mixing acetylacetone and tetra-n-butyl titanate to prepare the tetra-n-butyl titanate complex; adding cyclohexane, absolute ethyl alcohol, distilled water and ethyl orthosilicate into the complex, uniformly stirring, carrying out hydrothermal reaction, and naturally cooling to room temperature; subjecting the solid product to centrifugal separating, washing and drying to obtain the SiO2/TiO2 composite photocatalyst. In the composite photocatalyst, TiO2 is dispersed in a single crystal particle, so that the phenomenon of agglomeration between the TiO2 particles can be effectively avoided, and thus the photocatalytic efficiency of the catalyst is improved.
Description
Technical field
The invention belongs to inorganic functional material preparing technical field, more particularly to a kind of SiO2Modification TiO2Single crystal grain sub-light
The synthetic method of catalyst.
Background technology
Semiconductor TiO2There are good physical and chemical stability, stronger photocatalytic degradation capability, while have being prepared into
This it is low, nontoxic, environment-friendly the features such as and be widely used in the organic pollution in photocatalytic degradation water or air.Detitanium-ore-type
TiO2Energy gap be 3.2eV, its light-catalyzed reaction mechanism is：After the irradiation for receiving ultraviolet light, TiO2Electronics in valence band
The energy for obtaining photon is transitted in conduction band from valence band, while form a hole in valence band, transit to the electronics of conduction band with
The O of absorption2Form Superoxide anion free radical (O2 –), the OH that the hole in valence band is adsorbed with catalyst surface–Or H2O reacts shape
Into hydroxyl radical free radical (OH).Superoxide anion free radical, hole and hydroxyl radical free radical are respectively provided with oxidation activity.It is generally acknowledged that hydroxyl
Free radical has Strong oxdiative ability, is main oxidative species in light-catalyzed reaction, can be by the organic dirt in air or water
Dye thing molecular degradation is CO2And H2The small molecules such as O.
Nano-TiO2It is TiO2As a kind of principal mode of photochemical catalyst, but there are problems that in use
Such as difficult separation and recycling, it is easy to run off；Easily there is particle aggregation phenomenon in drying process and influence the normal performance of its activity；Treat
The organic pollution of degraded concentration in media as well is typically relatively low, and in the later stage of light-catalyzed reaction, treating in medium is degraded
Concentration of target molecules can also become very low, and in this case, the trend for reducing inevitably occurs in photocatalysis efficiency.
SiO2Because easily preparing high-specific surface area and being commonly used for TiO rich in the loose structure of hydroxyl2Modified grind
Study carefully, SiO2With TiO2Although the compound specific surface area that can greatly improve catalyst, absorption of the increase to organic pollutant molecule
Ability, but can not fundamentally solve TiO2The agglomeration traits of crystal grain.
Monocrystalline is undoubtedly the optimal dispersity of inorganic matter, uses it for as much as possible ensureing each in catalyst
Crystal grain all plays active function.And the preparation of monocrystalline is generally required and allows single grain growth to using special technique, equipment
Fixed size, relatively costly, technique is also complicated.
The content of the invention
The invention provides a kind of SiO2Modification TiO2The synthetic method of monocrystal particle photochemical catalyst：
(1) acetylacetone,2,4-pentanedione and tetra-n-butyl titanate are mixed with and obtain tetra-n-butyl titanate complex compound,
The volume ratio of acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 2：5；
(2) hexamethylene, absolute ethyl alcohol, distilled water and tetraethyl orthosilicate, stirring are added in the complex compound for obtaining to step (1)
Hydrothermal solution uniformly is obtained,
Wherein, hexamethylene, absolute ethyl alcohol, the volume ratio of distilled water are 1：20：20, the consumption and step of tetraethyl orthosilicate
(1) volume ratio of tetra-n-butyl titanate is 0.36~2.19 in：5,
Hexamethylene, absolute ethyl alcohol, distilled water are made into the present invention solvent of specific components, using the solvent and metatitanic acid four just
The interfacial tension of butyl ester complex compound makes titanium source presoma be dispersed into micelle；
(3) room temperature is naturally cooled to after the hydrothermal solution obtained in step (2) being carried out into sufficient hydro-thermal reaction,
Wherein, to react 10h at 150 DEG C, hydro-thermal reaction is to be placed directly within 150 DEG C by by whole reactor to hydro-thermal reaction
Completed in baking oven, allow it to heat up naturally,
During reaction temperature is elevated, the complex compound of the tetra-n-butyl titanate of partial hydrolysis is equally with the shape of micelle
Formula is disperseed in a solvent, and under the thermal and hydric environment, the TiO of the Detitanium-ore-type of dispersed is generated after these micelle mineralisings2
Single crystal grain；And the slower tetraethyl orthosilicate of hydrolysis rate is then by poly-condensation and hydrolysis grafting and modifying to the surface of titanium source, profit
Core shell structure is formed with two kinds of differences of presoma hydrolysing activity, kernel and decorative layer are by thoroughly hydrolysis-condensation reaction
It is converted into SiO2The TiO of parcel2Single crystal grain compound；
(4) solid product centrifugation, washing, the drying for obtaining hydro-thermal reaction in step (3), obtain TiO2/SiO2It is multiple
Closing light catalyst,
Wherein, after product centrifugation, first with distillation water washing, then washed with ethanol three times, in drying 2h at 100 DEG C.
In the composite photo-catalyst, TiO2Disperse in single crystal grain, can more effectively avoid TiO2Showing for reunion is formed between particle
As giving full play to TiO2Photocatalytic activity；SiO2After compound, the specific surface area of photochemical catalyst and total pore volume also have increase；
Make synthesized TiO2/SiO2Composite photo-catalyst has big specific surface area, can treat that degradable organic pollutant concentration is relatively low
In the case of by its adsorption and enrichment to TiO2Surface, make it very short with the life-span by (about 10 in time-9S) hydroxyl radical reaction,
The capture rate of hydroxyl radical free radical is improved, that is, improves the photocatalysis efficiency of catalyst.
Importantly, from preparation technology, in this patent firstly the need of by the control to each process procedure come
Form micelle；And generally if micelle surface is coated, although the particle that will can be also coated is kept apart,
The agglomeration of these particles is avoided, but micelle is not monocrystalline, and the particle for now being coated includes multiple crystal grain and coats
Be polycrystalline particle, so not thoroughly solve single crystal grain scattering problem；And this patent is during hydro-thermal is coated
But realize and the further dispersion of single micelle is disintegrated, finally ensure that in the clad to be formed with the monocrystalline of standard as core.
Brief description of the drawings
Fig. 1 is pure TiO2With the TiO prepared by embodiment 12/SiO2The FESEM photos of catalyst (TS20), it is upper right from figure
Than understanding：Pure TiO2Photo on particle surface it is smooth, size about 10nm；And the particle on TS20 photos is because being modified with size more
Small SiO2Particle and show rougher surface.
Fig. 2 is the TiO prepared by the embodiment 1 arrived with transmission electron microscope observation2/SiO2The photograph of catalyst (TS20)
Piece, it can be seen that the TiO being spread out from photo2Single crystal grain.
Fig. 3 is the pure TiO prepared by the comparative example 1 arrived with transmission electron microscope observation2Photo, from photo
It can be seen that TiO2The aggregating state of crystal grain.
Fig. 4 is embodiment 1 and the portioned product photo prepared by comparative example 2, the former product (TS20) be it is powdered,
The latter's product is in gel, it is seen that hexamethylene also plays the effect of key in the forming process of powder catalyst.
Fig. 5 is TiO prepared in embodiment 22/SiO2In the presence of catalyst, methylene blue solution absorbance curve is with purple
The change of outer light irradiation time.
Specific embodiment
Embodiment 1
(1) 2mL acetylacetone,2,4-pentanediones and 5mL tetra-n-butyl titanates are mixed, stirring reaction 0.5h obtains tetra-n-butyl titanate network
Compound；
(2) 2mL hexamethylenes and 40mL absolute ethyl alcohols, stirring 10min is added to be formed in the complex compound for obtaining to step (1)
Even solution, adds 40mL distilled water and stirs 30min, is subsequently adding 0.72mL tetraethyl orthosilicates, continues stirring 30min and obtains
To hydrothermal solution；
(3) it is naturally cold after 10h is reacted at 150 DEG C in the hydrothermal solution obtained in step (2) being gone into hydrothermal reaction kettle
But to room temperature (25 DEG C)；
(4) the solid product centrifugation for obtaining hydro-thermal reaction in step (3), with distillation water washing after washed with ethanol again
Wash three times, and 2h is dried in 100 DEG C of baking oven, obtain SiO2Molar fraction is 20% TiO2/SiO2Composite photo-catalyst
(TS20)。
It is heat-treated at different temperatures by TS20, then tests the XRD spectrum of each sample, it is public by Scherrer
Formula is simultaneously calculated by the sample crystal grain chi after 300,500,700 and 900 DEG C fully heat treatment according to (101) crystallographic plane diffraction peak
It is very little to be respectively 12.1,11.6,11.7 and 12.9nm, it is seen that heat treatment does not substantially change TiO2Crystallite dimension.This shows SiO2
To TiO2Crystal grain has carried out perfect cladding, prevents TiO2Growth of the crystal grain in heat treatment process.
Embodiment 2
(1) 2mL acetylacetone,2,4-pentanediones and 5mL tetra-n-butyl titanates are mixed, stirring reaction 0.5h obtains tetra-n-butyl titanate network
Compound；
(2) 2mL hexamethylenes and 40mL absolute ethyl alcohols, stirring 10min is added to be formed in the complex compound for obtaining to step (1)
Even solution, adds 40mL distilled water and stirs 30min, is subsequently adding 1.39mL tetraethyl orthosilicates, continues stirring 30min and obtains
To hydrothermal solution；
(3) it is naturally cold after 10h is reacted at 150 DEG C in the hydrothermal solution obtained in step (2) being gone into hydrothermal reaction kettle
But to room temperature (25 DEG C)；
(4) the solid product centrifugation for obtaining hydro-thermal reaction in step (3), with distillation water washing after washed with ethanol again
Wash three times, and 2h is dried in 100 DEG C of baking oven, obtain SiO2Molar fraction is 30% TiO2/SiO2Composite photo-catalyst
(TS30)。
The above-mentioned TS30 catalyst samples of 10mg are weighed, concentration is added to for 10mg/L, volume for the methylene blue of 40mL is molten
In liquid, the standing adsorption at dark；A small amount of supernatant liquor is taken by certain time interval to be centrifuged, its absorbance is surveyed, until methylene
The blue absorption on a catalyst of base reaches balance；Then beaker is moved under uviol lamp, liquid level is apart from uviol lamp distance in beaker
It is 10cm, supernatant liquor centrifugation is taken every 20min, the absorbance curve of solution, tool is determined using ultraviolet-uisible spectrophotometer
Body is as shown in Figure 2.
Embodiment 3
(1) 2mL acetylacetone,2,4-pentanediones and 5mL tetra-n-butyl titanates are mixed, stirring reaction 0.5h obtains tetra-n-butyl titanate network
Compound；
(2) 2mL hexamethylenes and 40mL absolute ethyl alcohols, stirring 10min is added to be formed in the complex compound for obtaining to step (1)
Even solution, adds 40mL distilled water and stirs 30min, is subsequently adding 2.19mL tetraethyl orthosilicates, continues stirring 30min and obtains
To hydrothermal solution；
(3) it is naturally cold after 10h is reacted at 150 DEG C in the hydrothermal solution obtained in step (2) being gone into hydrothermal reaction kettle
But to room temperature (25 DEG C)；
(4) the solid product centrifugation for obtaining hydro-thermal reaction in step (3), with distillation water washing after washed with ethanol again
Wash three times, and 2h is dried in 100 DEG C of baking oven, obtain SiO2Molar fraction is 50% TiO2/SiO2Composite photo-catalyst
(TS50)。
Table 1：TiO in pure titinium dioxide and the various embodiments described above2/SiO2The N of composite photo-catalyst2Isothermal adsorption tests number
According to
| Sample | SBET/m2·g–1 | Vp/cm3·g–1 | dp/nm |
| TS0 | 169.86 | 0.224 | 4.86 |
| TS20 | 164.53 | 0.391 | 7.39 |
| TS30 | 280.18 | 0.486 | 7.80 |
| TS50 | 338.11 | 0.477 | 7.32 |
Comparative example 1
Silicon source is not added in preparation process, remaining operation is with embodiment 1：
(1) 2mL acetylacetone,2,4-pentanediones and 5mL tetra-n-butyl titanates are mixed, stirring reaction 0.5h obtains tetra-n-butyl titanate network
Compound；
(2) 2mL hexamethylenes and 40mL absolute ethyl alcohols, stirring 10min is added to be formed in the complex compound for obtaining to step (1)
Even solution, adds 40mL distilled water and stirs 70min, obtains hydrothermal solution；
(3) it is naturally cold after 10h is reacted at 150 DEG C in the hydrothermal solution obtained in step (2) being gone into hydrothermal reaction kettle
But to room temperature (25 DEG C)；
(4) the solid product centrifugation for obtaining hydro-thermal reaction in step (3), with distillation water washing after washed with ethanol again
Wash three times, and 2h is dried in 100 DEG C of baking oven, obtain TiO2Photochemical catalyst.
Comparative example 2
Hexamethylene (being substituted with ethanol) is not added in hydrothermal solution, remaining operation is with embodiment 1：
(1) 2mL acetylacetone,2,4-pentanediones and 5mL tetra-n-butyl titanates are mixed, stirring reaction 0.5h obtains tetra-n-butyl titanate network
Compound；
(2) 42mL absolute ethyl alcohols, stirring 10min is added to form uniform solution in the complex compound for obtaining to step (1), then
Add 40mL distilled water and stir 30min, be subsequently adding 0.72mL tetraethyl orthosilicates, continue stirring 30min and obtain hydrothermal solution；
(3) it is naturally cold after 10h is reacted at 150 DEG C in the hydrothermal solution obtained in step (2) being gone into hydrothermal reaction kettle
But to room temperature (25 DEG C)；
(4) the solid product centrifugation for obtaining hydro-thermal reaction in step (3), with distillation water washing after washed with ethanol again
Wash three times, and 2h is dried in 100 DEG C of baking oven, obtain SiO2Molar fraction is 20% TiO2/SiO2Composite photo-catalyst.
Claims (7)
1. a kind of SiO2Modification TiO2The synthetic method of monocrystal particle photochemical catalyst, it is characterised in that：Described synthetic method is,
(1) acetylacetone,2,4-pentanedione and tetra-n-butyl titanate are mixed with and obtain tetra-n-butyl titanate complex compound；
(2) hexamethylene, absolute ethyl alcohol, distilled water and tetraethyl orthosilicate are added in the complex compound for obtaining to step (1), is stirred
Obtain hydrothermal solution；
(3) room temperature is naturally cooled to after the hydrothermal solution obtained in step (2) being carried out into sufficient hydro-thermal reaction；
(4) solid product centrifugation, washing, the drying for obtaining hydro-thermal reaction in step (3), obtain TiO2/SiO2Complex light
Catalyst.
2. synthetic method as claimed in claim 1, it is characterised in that：In step (1), acetylacetone,2,4-pentanedione and tetra-n-butyl titanate
Volume ratio is 2：5.
3. synthetic method as claimed in claim 1, it is characterised in that：In step (2), hexamethylene, absolute ethyl alcohol, distilled water
Volume ratio is 1：20：20.
4. synthetic method as claimed in claim 1, it is characterised in that：In step (2), the consumption and step of tetraethyl orthosilicate
(1) volume ratio of tetra-n-butyl titanate is 0.36~2.19 in：5.
5. synthetic method as claimed in claim 1, it is characterised in that：In step (3), hydro-thermal reaction is reaction at 150 DEG C
10h。
6. synthetic method as claimed in claim 1, it is characterised in that：In step (4), after product centrifugation, first with distillation
Water washing, then washed with ethanol three times.
7. synthetic method as claimed in claim 1, it is characterised in that：In step (4), dry specifically, being dried at 100 DEG C
2h。
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| CN102600881A (en) * | 2012-04-01 | 2012-07-25 | 河南理工大学 | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst |
| CN103127924A (en) * | 2013-01-28 | 2013-06-05 | 中北大学 | Preparation method of titanium oxide (TiO2) - silicon dioxide (SiO2) visible light compound light catalytic agent |
| CN103964502A (en) * | 2014-05-26 | 2014-08-06 | 国家纳米科学中心 | Nano TiO2 single crystal material as well as preparation method and application thereof |
| CN104549193A (en) * | 2015-01-08 | 2015-04-29 | 常州大学 | Low-density TiO2/SiO2 composite microsphere and preparation method thereof |
| CN105543961A (en) * | 2015-12-22 | 2016-05-04 | 国家纳米科学中心 | Nano TiO2 monocrystalline material, preparation method therefor and use of nano TiO2 monocrystalline material |
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| CN102600881A (en) * | 2012-04-01 | 2012-07-25 | 河南理工大学 | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst |
| CN103127924A (en) * | 2013-01-28 | 2013-06-05 | 中北大学 | Preparation method of titanium oxide (TiO2) - silicon dioxide (SiO2) visible light compound light catalytic agent |
| CN103964502A (en) * | 2014-05-26 | 2014-08-06 | 国家纳米科学中心 | Nano TiO2 single crystal material as well as preparation method and application thereof |
| CN104549193A (en) * | 2015-01-08 | 2015-04-29 | 常州大学 | Low-density TiO2/SiO2 composite microsphere and preparation method thereof |
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