CN105664919A - Sn-doped TiO2/CNTs/WO3 composite photocatalyst and preparation method thereof - Google Patents
Sn-doped TiO2/CNTs/WO3 composite photocatalyst and preparation method thereof 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 55
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 15
- 239000011240 wet gel Substances 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 238000003483 aging Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 8
- 238000005304 joining Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000547 structure data Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 titanium dioxide compound Chemical class 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Sn-doped TiO2/CNTs/WO3 composite photocatalyst and a preparation method thereof. The catalyst is mainly prepared through compounding Sn-doped carbon nanotubes, tungsten oxide and titanium dioxide. The method comprises the following steps: slowly adding a solution containing tin chloride and ammonium metatungstate and a single-walled carbon nanotube dispersion liquid to a butyl titanate-containing solution under a continuous stirring condition through adopting a sol-gel technology, stirring, ageing at normal temperature to obtain wet gel, washing the wet gel with distilled water and anhydrous ethanol, drying the washed wet gel in an oven to obtain xerogel, and heating and calcining the xerogel in an electric resistance furnace to prepare the Sn-doped TiO2/CNTs/WO3 composite photocatalyst. The Sn-doped TiO2/CNTs/WO3 composite photocatalyst has large specific surface area, and synergism among composition components of the Sn-doped TiO2/CNTs/WO3 composite photocatalyst promotes the charge transfer rate of nanometer titanium dioxide, so the photocatalysis efficiency is improved.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, especially relate to a kind of Sn doped Ti O in photocatalysis technology field2/CNTs/WO3Composite photo-catalyst and its preparation method.
Background technology
Nano titanium oxide is widely studied and application because of characteristics such as its Strong oxdiative ability under ultraviolet light, high chemical stability, low cost and environmental friendliness. But, the photocatalysis efficiency of titanium deoxide catalyst also not met current demand namely directly work under sunlight. The bigger broadband, taboo territory of titanium dioxide seriously governs its application, and the quick compound in the electronics-hole of titanium dioxide result also in its low quantum yield and more weak photocatalysis efficiency. In order to effectively utilize a large amount of green solar, in recent years, therefore, some method of modifying such as metal, nonmetal doping or are used to develop visible light-responded photocatalyst with other functional materials compounds gradually. The method strengthening optically catalytic TiO 2 efficiency can be classified as two classes: one is that titanium dioxide morphology is changed, and as made its complex shape by grafting, its crystalline state, aperture and size change; Two is chemical modification, by introducing other components in titanium dioxide structure, comprises load and doping.
Carbon nanotube (CNTs) has special specific surface area and gap structure, and the Atomic coordinate on its surface is incomplete, causes the activity site on surface to increase, for it provides primary condition as catalyzer. And Tungsten oxide 99.999 is as a kind of semiconductor material, its energy gap narrower (2.4-2.8eV), can act synergistically with its generation with titanium dioxide compound, is conducive to the transfer of light induced electron. For CNTs and TiO2The existing a large amount of report of the research of compound, it is many that study on mechanism is also carried out; WO3And TiO2Research also has a lot; But the rare people in existing field is TiO2、CNTs、WO3This three puts together compound research.
Summary of the invention
It is an object of the invention to for problems such as the photocatalysis efficiency of current carbon nanotube and titanium dioxide composite photocatalyst are not high, it is provided that a kind of Sn doped Ti O2/CNTs/WO3Composite photo-catalyst and its preparation method.
For achieving the above object, the present invention is by the following technical solutions:
One, a kind of Sn doped Ti O2/CNTs/WO3Composite photo-catalyst:
It is grouped into by the one-tenth of following weight part: the titanium dioxide of the carbon nanotube of 1-5 weight part, the Tungsten oxide 99.999 of 5-10 weight part and 85-95 weight part, wherein titania additive has the tin of its quality 5-10%.
Described composite photo-catalyst is microspheroidal, anatase octahedrite phase, particle size 5-15nm.
Two, a kind of Sn doped Ti O2/CNTs/WO3The preparation method of composite photo-catalyst, comprises the steps:
1) preparation contains tin chloride and the solution A of metatungstic acid, the solution B containing Single Walled Carbon Nanotube and the solution C containing butyl (tetra) titanate respectively;
2) continue solution A and solution B slowly to be added in solution C under stirring state, then stir after 30min ageing 24h under normal temperature, obtain wet gel, first with distilled water wash twice, then with absolute ethanol washing twice;
3) wet gel after washing is placed in baking oven drying and obtains xerogel;
4) xerogel obtained after drying is placed in resistance furnace within every minute, be warming up to 400 DEG C～500 DEG C from normal temperature with 2 DEG C after and holding temperature calcining 2h, obtain Sn doped Ti O2/CNTs/WO3Composite catalyst.
Step 2) plant major control make the weight ratio of water in mixing solutions, butyl (tetra) titanate and dehydrated alcohol be 1-2:2-4:8-16.
Described solution A is prepared in the following ways: first add in distilled water by 0.08-0.16 weight part tin chloride and 0.03-0.06 weight part ammonium metawolframate, maintains concentration respectively at 0.2-0.4mol L-1With 8-16mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 2.4-4.8 weight part, must solution A after fully dissolving.
Described solution B is prepared in the following ways: by 0.001-0.02 weight part single-walled carbon nanotube dispersion liquid magnetic stirrer 30min, obtaining solution B, in solution B, Single Walled Carbon Nanotube weight concentration is 0.1g L-1。
Described solution C is prepared in the following ways: dripped by the butyl (tetra) titanate of 2.4-4.8 weight part while stir in the dehydrated alcohol joining 7.2-14.4 weight part, then continues to stir 30min, obtains solution C.
Described single-walled carbon nanotube dispersion liquid is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Described step 3) in be placed in baking oven 105 DEG C of dry 12h.
Described step 4) in the xerogel obtained after drying is placed in resistance furnace within every minute, be warming up to 400 DEG C～500 DEG C from normal temperature with 2 DEG C after and holding temperature calcining 2h.
The useful effect of composite catalyst of the present invention is:
Compared with common binary composite catalyst, the matrix material of the present invention demonstrates bigger specific surface area, has synergistic effect between them, promotes the Charger transfer speed of nano titanium oxide, thus improves photocatalysis efficiency.
The invention process adopts sol-gel method to be prepared, and can be applicable to 10mg L-1Rhodamine B and 10mg L-1The photocatalytic degradation of tropeolin-D, has very high photocatalysis efficiency.
Attached caption
Fig. 1 is the degradation rate column diagram of the composite catalyst photocatalytic degradation 5mg L-1 rhodamine B aqueous solution, wherein P-25 uses on market to compare moral widely and admittedly match titanium dioxide, in figure, P-25 represents the degradation rate of the 60min rhodamine B aqueous solution under UV-light illumination, other Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3The degradation rate of composite catalyst 60min rhodamine B aqueous solution under UV-light illumination.
Fig. 2 is the degradation rate column diagram of composite catalyst photocatalytic degradation 5mg L-1 methyl orange aqueous solution, wherein P-25 uses on market to compare moral widely and admittedly match titanium dioxide, in figure, P-25 represents the degradation rate of 60min methyl orange aqueous solution under UV-light illumination, other Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3The degradation rate of composite catalyst 60min methyl orange aqueous solution under UV-light illumination.
Table 1 is the pore structure data of the different sample of composite catalyst, becomes with average aperture set primarily of specific surface area, specific pore volume, and in table, P-25 is that on market, use is compared moral widely and admittedly matched titanium dioxide, other Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
Table 2 is the XRD data of the different sample of composite catalyst, mainly lists 2 θ angle and the intensity that 2 θ angles maximum absorption band within the specific limits is corresponding, and in table, sample is the Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
Table 3 is the energy gap data of composite catalyst, calculates according to its uv drs data, and wherein P-25 uses on market to compare moral widely and admittedly match titanium dioxide, and in table, other samples are the Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
Below in conjunction with specific embodiment, set forth the present invention further. These embodiments are only not used in for illustration of the present invention and limit the scope of the invention. The experimental technique of unreceipted concrete condition in the following example, usually conveniently condition or according to manufacturer suggestion condition. Unless otherwise indicated, otherwise per-cent is all by weight, and raw materials used, reagent, solvent are commercially available prod.
Embodiments of the invention are as follows:
Embodiment 1:
First the tin chloride of 0.08 weight part and 0.03 weight part ammonium metawolframate are added in a certain amount of distilled water, maintain concentration respectively at 0.2mol L-1With 8mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 2.4 weight parts, must solution A after fully dissolving.
B) by the single-walled carbon nanotube dispersion liquid magnetic stirrer 30min of 0.001 weight part, obtaining solution B, wherein Single Walled Carbon Nanotube weight concentration is 10mg mL-1。
C) 2.4 weight part butyl (tetra) titanates are dripped while stir in the dehydrated alcohol joining 7.2 weight parts continue stir 30min, obtain solution C.
D) under continuing stirring state, solution A and solution B slowly being added in solution C, in major control mixing solutions, the weight ratio of water, butyl (tetra) titanate and dehydrated alcohol is 1:2:8, then stirs after 30min ageing 24h under normal temperature, obtain wet gel, respectively wash twice with distilled water and dehydrated alcohol.
E) it is put in baking oven by wet gel 105 DEG C of dry 12h, obtains xerogel.
F) powder obtained after drying is warming up to 450 DEG C of calcining 2h in resistance furnace for every minute with 2 DEG C, obtains Sn doped Ti O2/CNTs/WO3Composite catalyst.
Embodiment 2:
A) first the tin chloride of 0.16 weight part and 0.06 weight part ammonium metawolframate are added in distilled water, maintain concentration respectively at 0.4mol L-1 and 16mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 4.8 weight parts, must solution A after fully dissolving.
B) by the single-walled carbon nanotube dispersion liquid magnetic stirrer 30min of 0.02 weight part, obtaining solution B, wherein Single Walled Carbon Nanotube weight concentration is 10mg mL-1.
C) 4.8 weight part butyl (tetra) titanates are dripped while stir in the dehydrated alcohol joining 14.4 weight parts continue stir 30min, obtain solution C.
D) under continuing stirring state, solution A and solution B slowly being added in solution C, in major control mixing solutions, the weight ratio of water, butyl (tetra) titanate and dehydrated alcohol is 1:4:8, then stirs after 30min ageing 24h under normal temperature, obtain wet gel, respectively wash twice with distilled water and dehydrated alcohol.
E) it is put in baking oven by wet gel 105 DEG C of dry 12h, obtains xerogel.
F) powder obtained after drying is warming up to 450 DEG C of calcining 2h in resistance furnace for every minute with 2 DEG C, obtains Sn doped Ti O2/CNTs/WO3 composite catalyst.
Embodiment 3:
A) first the tin chloride of 0.12 weight part and 0.05 weight part ammonium metawolframate are added in distilled water, maintain concentration respectively at 0.3mol L-1 and 12mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 3.6 weight parts, must solution A after fully dissolving.
B) by the single-walled carbon nanotube dispersion liquid magnetic stirrer 30min of 0.01 weight part, obtaining solution B, wherein Single Walled Carbon Nanotube weight concentration is 10mg mL-1.
C) 3.6 weight part butyl (tetra) titanates are dripped while stir in the dehydrated alcohol joining 10.8 weight parts continue stir 30min, obtain solution C.
D) under continuing stirring state, solution A and solution B slowly being added in solution C, in major control mixing solutions, the weight ratio of water, butyl (tetra) titanate and dehydrated alcohol is 1:2:8, then stirs after 30min ageing 24h under normal temperature, obtain wet gel, respectively wash twice with distilled water and dehydrated alcohol.
E) it is put in baking oven by wet gel 105 DEG C of dry 12h, obtains xerogel.
F) powder obtained after drying is warming up to 500 DEG C of calcining 2h in resistance furnace for every minute with 2 DEG C, obtains Sn doped Ti O2/CNTs/WO3 composite catalyst.
Embodiment 4:
First the tin chloride of 0.1 weight part and 0.05 weight part ammonium metawolframate are added in a certain amount of distilled water, maintain concentration respectively at 0.3mol L-1 and 10mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 4.8 weight parts, must solution A after fully dissolving.
B) by the single-walled carbon nanotube dispersion liquid magnetic stirrer 30min of 0.005 weight part, obtaining solution B, wherein Single Walled Carbon Nanotube weight concentration is 10mg mL-1.
C) 4.8 weight part butyl (tetra) titanates are dripped while stir in the dehydrated alcohol joining 8.4 weight parts continue stir 30min, obtain solution C.
D) under continuing stirring state, solution A and solution B slowly being added in solution C, in major control mixing solutions, the weight ratio of water, butyl (tetra) titanate and dehydrated alcohol is 1:2:16, then stirs after 30min ageing 24h under normal temperature, obtain wet gel, respectively wash twice with distilled water and dehydrated alcohol.
E) it is put in baking oven by wet gel 105 DEG C of dry 12h, obtains xerogel.
F) powder obtained after drying is warming up to 400 DEG C of calcining 2h in resistance furnace for every minute with 2 DEG C, obtains Sn doped Ti O2/CNTs/WO3 composite catalyst.
The pore structure data of the different sample of the composite photo-catalyst that each embodiment of the present invention obtains are as shown in table 1 below, become with average aperture set primarily of specific surface area, specific pore volume, in table, P-25 uses on market to compare moral widely and admittedly match titanium dioxide as a comparison case, other Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
The pore structure data of the sample of table 1 different composite catalyzer
| Sample | Specific surface area (m2·g-1) | Specific pore volume (cm3g-1) | Mean pore size (nm) |
| P-25 | 50.28 | 0.182 | 13.55 |
| Embodiment 1 | 120.93 | 0.209 | 4.92 |
| Embodiment 2 | 102.32 | 0.195 | 5.37 |
| Embodiment 3 | 100.43 | 0.192 | 5.05 |
| Embodiment 4 | 105.92 | 0.197 | 5.82 |
The XRD data of the different sample of composite photo-catalyst that each embodiment of the present invention obtains are as shown in table 2 below, mainly contain 2 θ angle and the intensity that 2 θ angles maximum absorption band within the specific limits is corresponding, and in table, sample is the Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
The XRD data of table 2 different composite catalyst sample
The energy gap data of the composite photo-catalyst that each embodiment of the present invention obtains are as shown in table 3 below, calculate according to its uv drs data, wherein P-25 uses on market to compare moral widely and admittedly match titanium dioxide as a comparison case, and in table, other samples are the Sn doped Ti O prepared by embodiment 1-42/CNTs/WO3Composite catalyst.
The energy gap data of table 3 different composite catalyst sample
| Sample | P-25 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Energy gap/eV | 3.18 | 2.92 | 2.91 | 2.88 | 2.84 |
And adopt following verification experimental verification effect of the present invention:
The Sn doped Ti O obtained in this test2/CNTs/WO3The ultraviolet catalytic degraded of rhodamine B or methyl orange aqueous solution is carried out by compound catalyst series according to the following steps: be the tropeolin-D of 10mg L-1, rhodamine B solution as simulated wastewater taking concentration, it is placed in the photocatalytic degradation reaction unit designed voluntarily, carries out photocatalysis performance test. When magnetic agitation, taking the ultraviolet lamp of wavelength 254nm, power 20W as the light source light of photocatalytic degradation secretly adsorbs 30min according to front elder generation, get a certain amount of degradation solution every 10min afterwards after centrifugal, to get upper liquid survey its absorbance (maximum absorption wavelength is respectively 554nm and 463nm), with this, catalyzer being carried out photocatalysis performance evaluation, degradation effect figure is shown in attached Fig. 1 and 2.
It thus is seen that the present invention obtains matrix material and has bigger specific surface area, the Charger transfer speed of nano titanium oxide can be promoted, it is to increase photocatalysis efficiency.
Claims (9)
1. a Sn doped Ti O2/CNTs/WO3Composite photo-catalyst, it is characterised in that: it is grouped into by the one-tenth of following weight part: the titanium dioxide of the carbon nanotube of 1-5 weight part, the Tungsten oxide 99.999 of 5-10 weight part and 85-95 weight part, wherein titania additive has the tin of its quality 5-10%.
2. a kind of Sn doped Ti O according to claim 12/CNTs/WO3Composite photo-catalyst, it is characterised in that: described composite photo-catalyst is microspheroidal, anatase octahedrite phase, particle size 5-15nm.
3. a kind of Sn doped Ti O according to claim 1 and 22/CNTs/WO3The preparation method of composite photo-catalyst, it is characterised in that comprise the steps:
1) preparation contains tin chloride and the solution A of metatungstic acid, the solution B containing Single Walled Carbon Nanotube and the solution C containing butyl (tetra) titanate respectively;
2) continue solution A and solution B slowly to be added in solution C under stirring state, then stir after 30min ageing 24h under normal temperature, obtain wet gel, first with distilled water wash twice, then with absolute ethanol washing twice;
3) wet gel after washing is placed in baking oven drying and obtains xerogel;
4) xerogel obtained after drying is placed in resistance furnace within every minute, be warming up to 400 DEG C～500 DEG C from normal temperature with 2 DEG C after and holding temperature calcining 2h, obtain Sn doped Ti O2/CNTs/WO3Composite catalyst.
4. a kind of Sn doped Ti O according to claim 32/CNTs/WO3The preparation method of composite photo-catalyst, it is characterised in that: described solution A is prepared in the following ways: first add in distilled water by 0.08-0.16 weight part tin chloride and 0.03-0.06 weight part ammonium metawolframate, maintains concentration respectively at 0.2-0.4mol L-1With 8-16mmol L-1, stir 10min, by the absolute ethyl alcohol and stirring 30min of the solution that obtains with 2.4-4.8 weight part, must solution A after fully dissolving.
5. a kind of Sn doped Ti O according to claim 32/CNTs/WO3The preparation method of composite photo-catalyst, it is characterized in that: described solution B is prepared in the following ways: by 0.001-0.02 weight part single-walled carbon nanotube dispersion liquid magnetic stirrer 30min, obtaining solution B, in solution B, Single Walled Carbon Nanotube weight concentration is 0.1g L-1。
6. a kind of Sn doped Ti O according to claim 32/CNTs/WO3The preparation method of composite photo-catalyst, it is characterised in that: described solution C is prepared in the following ways: dripped by the butyl (tetra) titanate of 2.4-4.8 weight part while stir in the dehydrated alcohol joining 7.2-14.4 weight part, then continues to stir 30min, obtains solution C.
7. a kind of Sn doped Ti O according to claim 52/CNTs/WO3The preparation method of composite photo-catalyst, it is characterised in that: described single-walled carbon nanotube dispersion liquid is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
8. a kind of Sn doped Ti O according to claim 32/CNTs/WO3The preparation method of composite photo-catalyst, it is characterised in that: described step 3) in be placed in baking oven 105 DEG C of dry 12h.
9. the preparation method of a kind of Sn doped Ti O2/CNTs/WO3 composite photo-catalyst according to claim 3, it is characterised in that: described step 4) in the xerogel obtained after drying is placed in resistance furnace within every minute, be warming up to 400 DEG C～500 DEG C from normal temperature with 2 DEG C after and holding temperature calcining 2h.
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