CN110075891A - A kind of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst and its preparation method and application - Google Patents
A kind of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN110075891A CN110075891A CN201910313937.7A CN201910313937A CN110075891A CN 110075891 A CN110075891 A CN 110075891A CN 201910313937 A CN201910313937 A CN 201910313937A CN 110075891 A CN110075891 A CN 110075891A
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- titanium dioxide
- carbonate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 239000004744 fabric Substances 0.000 title claims abstract description 77
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001958 silver carbonate Inorganic materials 0.000 title claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 60
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007654 immersion Methods 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 12
- 230000004087 circulation Effects 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 239000000843 powder Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004064 recycling 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalysis material technical field, a kind of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst and its preparation method and application is disclosed.Carbon cloth carried titanium dioxide/silver carbonate the composite photo-catalyst is to be immersed in the carbon cloth of cleaning in nitric acid to carry out surface acid etching and drying；The mixed ethanol solution of butyl titanate and acetylacetone,2,4-pentanedione is added drop-wise in the ethanol solution of hydrochloric acid, solution A is obtained；Processed carbon cloth is added in solution A and is stirred, drying is taken out, product B is calcined to obtain at 400-600 DEG C；Product B is put into carbonate solution and is impregnated, is then put into silver nitrate solution and impregnates, places into carbonate solution and impregnates, the circulation immersion in silver nitrate solution and carbonate solution is made after freeze-drying.Method and process of the invention is simple, and titanium dioxide/silver carbonate composite photocatalyst material of gained carbon cloth load had both enhanced photocatalysis stability, while solving the problems, such as that photocatalytic powder is difficult to recycle.
Description
Technical field
The invention belongs to catalysis material technical fields, more particularly, to a kind of carbon cloth carried titanium dioxide/silver carbonate
(TiO2/Ag2CO3) composite photo-catalyst and its preparation method and application.
Background technique
In recent years, Dying Wastewater Treatment & causes the extensive worry of whole world scientist in the water got worse.Printing and dyeing are useless
Water not only makes water body color burn, and makes water quality deterioration, to seriously threaten diversity of organism in water body.Photocatalysis material
Material can be there is organic pollutants to be decomposed into the nontoxic substance such as water and carbon dioxide, to eliminate the pollution to environment.
In various catalysis materials, TiO2With good chemistry, biological stability, environmentally friendly, inexpensive, long service life
The advantages that.However, TiO2The disadvantages of difficult, can only be recycled by ultraviolet excitation, powder.
In recent years, a series of Ag based photocatalyst such as AgO and Ag3PO4When Deng degradable organic pollutant under visible light illumination
Show excellent photocatalytic activity.However, there is also be difficult to separate for powder after light-catalyzed reaction for these Ag based photocatalysts
The shortcomings that recycling and recycling.The fixed load technology of photochemical catalyst is one of the effective way to solve the above problems.Commercially
Carbon cloth is widely used as catalysis material because having good electron transport ability, higher mechanical strength and mechanical property
Carrier.Loaded on carbon cloth molybdenum disulfide and with silver carbonate is compound that its photocatalytic activity not only can be improved, but also be also easy to back
It receives and recycles.For example, application No. is the Chinese invention patent of CN201410105065.2 " photochemical catalyst nanometers capable of magnetic separating
Eu3+-CoFe2O4Raw powder's production technology ", preparation method is, by nCo (NO3)2·6H2O:nFe (NO3)3·9H2O:nEu
(NO3)3·6H2The ratio of O=1:2:0.05 is dissolved in a certain amount of propylene glycol, and stirring is evaporated to form brown at 80 DEG C
Vitreosol, and drying obtains xerogel for 24 hours at 110 DEG C, after xerogel taking-up is put into corundum crucible grinding, in groom's furnace
600 DEG C of baking 2h, by product it is finely ground after again in 800 DEG C of baking 2h, a nanometer Eu can be obtained in furnace cooling3+-CoFe2O4Powder
Photochemical catalyst.Although the method increase the recycling rate of waterused of catalysis material, preparation process is complex.For another example apply
Number for CN201810673527.9 Chinese invention patent it is " a kind of easily to recycle reusable nanocrystalline TiO2Coat hollow glass
Glass microballon photochemical catalyst and preparation method thereof ", preparation method is first to disperse hollow glass micropearl in deionized water,
It is dispersed with stirring；Then, solution is warming up to certain temperature, is slowly dropped into hollow glass micropearl using TiCl solution as presoma
In solution, the nanocrystalline TiO of photochemical catalyst is synthesized in hollow glass micropearl surface in situ2；Then, it is aged certain time；Finally, will
One kind is made after product filtering, washing, drying and easily recycles reusable nanocrystalline TiO2Coated hollow glass bead light is urged
Agent.Although above-mentioned preparation method is conducive to the recycling and reusing of catalysis material, still, TiO2It can only be under ultraviolet light
The organic matter that could be degraded in sewage has limitation.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art, primary and foremost purpose of the present invention is to provide a kind of carbon cloth negative
Carry TiO2/Ag2CO3Composite photo-catalyst.
Another object of the present invention is to provide above-mentioned carbon cloths to load TiO2/Ag2CO3The preparation method of composite photo-catalyst.
A further object of the present invention is to provide above-mentioned carbon cloths to load TiO2/Ag2CO3The application of composite photo-catalyst.
The purpose of the present invention is realized by following technical proposals:
A kind of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst, the carbon cloth carried titanium dioxide/silver carbonate are multiple
Light combination catalyst is to be immersed in the carbon cloth of cleaning in nitric acid to carry out surface acid etching and drying；By butyl titanate and acetylacetone,2,4-pentanedione
Ethanol solution be added drop-wise in the ethanol solution of hydrochloric acid, be made solution A；Processed carbon cloth is added in solution A and is stirred,
Drying is taken out, product B is calcined to obtain at 400-600 DEG C；Product B is put into carbonate solution and is impregnated, it is molten to be then put into silver nitrate
It is impregnated in liquid, places into carbonate solution and impregnate, the circulation immersion in silver nitrate solution and carbonate solution, after freeze-drying
It is made.
Preferably, the solvent of the cleaning is acetone, ethyl alcohol and deionized water, and the time of the cleaning is 10~20min；
The concentration of the nitric acid is 60~65%；The time of the surface acid etching be 10~for 24 hours；The time of the calcining is 1~2h.
Preferably, in the ethanol solution of the butyl titanate and acetylacetone,2,4-pentanedione butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol body
Product is than being (20~25): (1~3): (30~40)；The volume ratio of hydrochloric acid, water and ethyl alcohol is in the ethanol solution of the hydrochloric acid
(0.1~0.2): (5~8): (16~19).
Preferably, the number of the circulation immersion is 10~20 times.
Preferably, the carbonate solution is one or more of ammonium hydrogen carbonate, sodium bicarbonate, sodium carbonate or ammonium carbonate；
The concentration of the carbonate solution is 0.05~0.2mol/L；The concentration of the silver nitrate solution is 0.1~0.2mol/L.
Preferably, the condition of the freeze-drying are as follows: the temperature of freezing is -40~-46 DEG C, and vacuum degree is 35~45MPa.
Carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst preparation method, comprises the following specific steps that:
S1. carbon cloth is successively cleaned with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in nitric acid and carries out surface
Acid handles and drying；
S2. the mixed ethanol solution of butyl titanate and acetylacetone,2,4-pentanedione is added drop-wise in the ethanol solution of hydrochloric acid, obtains solution A；
S3. carbon cloth processed in step S1 is immersed in the solution A of step S2 and is stirred, take out drying, 400~
600 DEG C of calcinings, obtain product B；
S4. product B is impregnated in carbonate solution I, takes out and be put into silver nitrate solution and impregnates II；Again in carbonic acid
III is impregnated in salting liquid；
S5. step S4 is repeated to recycle 10~20 times, it is freeze-dried, carbon cloth is made and loads TiO2/Ag2CO3Composite photocatalyst
Material.
Preferably, the time of stirring described in step S3 is 1~2h, and the time of the calcining is 1~2h.
Preferably, described in step S5 immersion I time be 10~for 24 hours；The time of the immersion II is 10~20s, institute
The time for stating immersion III is 10~20s.
The carbon cloth carried titanium dioxide/application of the silver carbonate composite photo-catalyst in photocatalysis field.
Compared with prior art, the invention has the following advantages:
1. the TiO that carbon cloth of the invention loads2/Ag2CO3Composite photocatalyst material had both enhanced photocatalysis stability, in light
It can be transferred on silver carbonate conduction band according to the light induced electron of lower titanium dioxide, and carbon cloth is also beneficial to the transfer of light induced electron,
Light induced electron on silver carbonate conduction band can be further diverted on carbon cloth, and photohole stays in titanium dioxide and silver carbonate respectively
On, this process is conducive to the separation in light induced electron and hole, and then improves the degradation rate to rhodamine B.
2. preparation method simple process of the invention, required organic solvent is less, and carbon cloth loads catalysis material,
It has degraded under illumination after organic pollutants, carbon cloth need to only have been taken out, be conducive to the recycling and benefit again of catalysis material
With so as to avoid the secondary pollution of water body.
Detailed description of the invention
Fig. 1 is that the carbon cloth of embodiment 1 loads TiO2/Ag2CO3The scanning electron microscope (SEM) photograph of composite photocatalyst material.
Fig. 2 is that the carbon cloth of embodiment 1 loads TiO2/Ag2CO3Binary made from composite photocatalyst material and comparative example 1 is compound
The rate curve of catalysis material rhodamine B degradation under visible light.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. carbon cloth is successively cleaned 20min with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in 65% nitric acid
Middle progress surface acid etching is for 24 hours and dry.
It is sufficiently stirred 2. the acetylacetone,2,4-pentanedione of the butyl titanate of 22.6mL and 2mL is added in the ethyl alcohol of 36.8mL.
3. the hydrochloric acid solution of 0.1mL and 5mL water to be added in the ethyl alcohol of 18.4mL and be sufficiently stirred.
4. the solution that step 3 is stirred evenly is added dropwise in 2.
5. processed carbon cloth in step 1 is taken to be added in step 4,1h is stirred, 3mL deionized water is then added, is taken out
It is dry.
6. gained sample in step 5 is calcined, 500 DEG C of calcination temperature, time 1h.
7. taking in step 6 calcined sample to be put into the ammonium bicarbonate soln of 0.075mol/L to impregnate for 24 hours.
8. the carbon cloth impregnated in step 7 is taken out and is put into the silver nitrate solution of 0.15mol/L and impregnates 10s.
9. carbon cloth in step 8 is impregnated 10s in step 7 again.
10. repeating step 8,9 circulation 20 times, at -40 DEG C of condensation temperature, vacuum degree is to be freeze-dried under 35MPa, is made
It obtains carbon cloth and loads TiO2/Ag2CO3Composite photocatalyst material.
Fig. 1 is originally to apply carbon cloth made from example to load TiO2/Ag2CO3The scanning electron microscope (SEM) photograph of composite photocatalyst material.From Fig. 1
It is found that titanium dioxide and silver carbonate are supported on carbon cloth well；Illustrate that carbon cloth loads TiO2/Ag2CO3Composite photocatalyst material
Successfully prepare.Fig. 2 is that carbon cloth made from the present embodiment loads TiO2/Ag2CO3Composite photocatalyst material and comparison
The rate curve of the rhodamine B degradation under visible light of binary composite photocatalyst material made from example 1 and 2.Comparing from Fig. 2 can
Know, when the rhodamine B solution for same concentrations and the volume of degrading, carbon cloth loads TiO2/Ag2CO3Composite photocatalyst material degradation Luo Dan
The bright B used time is most short, illustrates that carbon cloth loads TiO2/Ag2CO3Composite photocatalyst material material is compared to pair prepared under the same terms
Carbon cloth loaded Ag in ratio 1 and 22CO3Catalysis material, carbon cloth load TiO2Material has higher photocatalytic activity and stabilization
Property.
Embodiment 2
1. carbon cloth is successively cleaned 20min with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in 65% nitric acid
Middle progress surface acid etching is for 24 hours and dry.
It is sufficiently stirred 2. the acetylacetone,2,4-pentanedione of the butyl titanate of 22.6mL and 2mL is added in the ethyl alcohol of 36.8mL.
3. the hydrochloric acid solution of 0.1mL and 5mL water to be added in the ethyl alcohol of 18.4mL and be sufficiently stirred.
4. the solution that step 3 is stirred evenly is added dropwise in step 2.
5. processed carbon cloth in step 1 is taken to be added in 4,1h is stirred, 3mL deionized water is then added, takes out drying.
6. gained sample in step 5 is calcined, 500 DEG C of calcination temperature, time 1h.
7. taking in step 6 calcined sample to be put into the sal volatile of 0.075mol/L to impregnate for 24 hours.
8. the carbon cloth impregnated in step 7 is taken out and is put into the silver nitrate solution of 0.15mol/L and impregnates 10s.
9. carbon cloth in step 8 is immersed in 10s in 7 again.
10. repeating step 8,9 circulation 20 times, at -40 DEG C of condensation temperature, vacuum degree is to be freeze-dried under 35MPa, is made
It obtains carbon cloth and loads TiO2/Ag2CO3Composite photocatalyst material.
Embodiment 3
Different from embodiment 1 is: the time of cleaning described in step 1 is 10min；The concentration of the nitric acid is
60%, the time of the surface acid etching is 10h；The acetylacetone,2,4-pentanedione of the butyl titanate of 25ml and 3ml is dissolved in step 2
In 40ml ethyl alcohol；It is that the hydrochloric acid solution of 0.2mL and 8mL water are added in the ethyl alcohol of 19mL and are sufficiently stirred in step 3；Step 6
Described in the temperature of calcining be 400 DEG C, time of calcining is 2h；The concentration of ammonium bicarbonate soln described in step 7 is 0.2mol/
L, the time of the immersion are 10h；The concentration of silver nitrate solution described in step 8 is 0.2mol/L, and the time of the immersion is
20s；The time of immersion described in step 9 is 20s；The number of circulation immersion described in step 10 is 10 times, described in condensation temperature
Degree is -46 DEG C, vacuum degree 45MPa.
Embodiment 4
Different from embodiment 2 is: the time of cleaning described in step 1 is 10min；The concentration of the nitric acid is
60%, the time of the surface acid etching is 10h；The acetylacetone,2,4-pentanedione of the butyl titanate of 20ml and 1ml is dissolved in step 2
In 30ml ethyl alcohol；It is that the hydrochloric acid solution of 0.15mL and 7mL water are added in the ethyl alcohol of 16mL and are sufficiently stirred in step 3；Step 6
Described in the temperature of calcining be 550 DEG C, time of calcining is 1.5h；The concentration of sal volatile described in step 7 is
0.05mol/L, the time of the immersion are 15h；The concentration of silver nitrate solution described in step 8 is 0.1mol/L, the immersion
Time be 15s；The time of immersion described in step 9 is 15s；The number of circulation immersion described in step 10 is 15 times, described
It is -46 DEG C in condensation temperature, vacuum degree 40MPa.
Embodiment 5
Different from embodiment 3 is: the time of cleaning described in step 1 is 15min；The concentration of the nitric acid is
62%, the time of the surface acid etching is 15h；The acetylacetone,2,4-pentanedione of the butyl titanate of 23ml and 2ml is dissolved in step 2
In 35ml ethyl alcohol；It is that the hydrochloric acid solution of 0.1mL and 6mL water are added in the ethyl alcohol of 16mL and are sufficiently stirred in step 3；Step 6
Described in the temperature of calcining be 600 DEG C, time of calcining is 1.5h；The concentration of sal volatile described in step 7 is
0.15mol/L, the time of the immersion are 20h；The concentration of silver nitrate solution described in step 8 is 0.15mol/L, the immersion
Time be 17s；The time of immersion described in step 9 is 17s；The number of circulation immersion described in step 10 is 18 times, described
It is -44 DEG C in condensation temperature, vacuum degree 37MPa.
Comparative example 1
1. carbon cloth is successively cleaned 20min with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in 65% nitric acid
Middle progress surface acid etching is for 24 hours and dry.
2. taking in 1 carbon cloth to be put into the ammonium bicarbonate soln of 0.075mol/L to impregnate for 24 hours.
3. the carbon cloth impregnated in 2 is taken out and is put into the silver nitrate solution of 0.15mol/L and impregnates 10s.
4. carbon cloth in step 3 is impregnated solution 10s in step 2 again.
5. repeating step 3 and 4 circulations 20 times, carbon cloth loaded Ag is made2CO3Catalysis material.
6. the carbon cloth Ag that step 5 is obtained2CO3It is freeze-dried, condensing condition are as follows: -40 DEG C of condensation temperature, vacuum degree
For 35MPa, carbon cloth loaded Ag is obtained2CO3Catalysis material.
Comparative example 2
1. carbon cloth is successively cleaned 20min with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in 65% nitric acid
Middle progress surface acid etching is for 24 hours and dry.
It is sufficiently stirred 2. the acetylacetone,2,4-pentanedione of the butyl titanate of 22.6mL and 2mL is added in the ethyl alcohol of 36.8mL.
3. the hydrochloric acid solution of 0.1mL and 5mL water to be added in the ethyl alcohol of 18.4mL and be sufficiently stirred.
4. the solution that step 3 is stirred evenly is added dropwise to solution in step 2.
5. processed carbon cloth in step 1 is taken to be added in step 4,1h is stirred, 3mL deionized water is then added, is taken out
It is dry.
6. gained sample in step 5 is calcined, 500 DEG C of calcination temperature, time 1h, carbon cloth load TiO is obtained2Material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst, which is characterized in that the carbon cloth loads titanium dioxide
Titanium/silver carbonate composite photo-catalyst is to be immersed in the carbon cloth of cleaning in nitric acid to carry out surface acid etching and drying；By metatitanic acid fourth
The ethanol solution of ester and acetylacetone,2,4-pentanedione is added drop-wise in the ethanol solution of hydrochloric acid, with obtained solution A；Processed carbon cloth is added to
It is stirred in solution A, takes out drying, product B is calcined to obtain at 400~600 DEG C；Product B is put into carbonate solution and is impregnated, then
It is put into silver nitrate solution and impregnates, place into carbonate solution and impregnate, leaching is recycled in silver nitrate solution and carbonate solution
Bubble is made after freeze-drying.
2. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1, which is characterized in that described
The solvent of cleaning is acetone, ethyl alcohol and deionized water, and the time of the cleaning is 10~20min；The concentration of the nitric acid is 60
~65%；The time of the surface acid etching be 10~for 24 hours；The time of the calcining is 1~2h.
3. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1, which is characterized in that described
The volume ratio of butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol is (20~25) in the ethanol solution of butyl titanate and acetylacetone,2,4-pentanedione: (1~
3): (30~40)；The volume ratio of hydrochloric acid, water and ethyl alcohol is (0.1~0.2): (5~8): (16 in the ethanol solution of the hydrochloric acid
~19).
4. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1, which is characterized in that described
The number of circulation immersion is 10~20 times.
5. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1, which is characterized in that described
Carbonate solution is one or more of ammonium hydrogen carbonate, sodium bicarbonate, sodium carbonate or ammonium carbonate；The concentration of the carbonate solution
For 0.05~0.2mol/L；The concentration of the silver nitrate solution is 0.1~0.2mol/L.
6. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1, which is characterized in that described
The condition of freeze-drying are as follows: the temperature of freezing is -40~-46 DEG C, and vacuum degree is 35~45MPa.
7. the preparation side of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 1-6
Method, which is characterized in that comprise the following specific steps that:
S1. carbon cloth is successively cleaned with acetone, ethyl alcohol and deionized water, then carbon cloth is immersed in nitric acid and is carried out at surface acid
It manages and dries；
S2. the mixed ethanol solution of butyl titanate and acetylacetone,2,4-pentanedione is added drop-wise in the ethanol solution of hydrochloric acid, obtains solution A；
S3. carbon cloth processed in step S1 is immersed in the solution A of step S2 and is stirred, drying is taken out, at 400~600 DEG C
Calcining, obtains product B；
S4. product B is impregnated in carbonate solution I, takes out and be put into silver nitrate solution and impregnates II；It is molten in carbonate again
III is impregnated in liquid；
S5. step S4 is repeated to recycle 10~20 times, it is freeze-dried, carbon cloth is made and loads TiO2/Ag2CO3Composite photocatalyst material
Material.
8. the preparation method of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 7, feature
It is, the time of stirring described in step S3 is 1~2h, and the time of the calcining is 1~2h.
9. the preparation method of carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst according to claim 7, feature
Be, described in step S5 immersion I time be 10~for 24 hours；The time of the immersion II is 10~20s, the immersion III
Time is 10~20s.
10. carbon cloth carried titanium dioxide/silver carbonate composite photo-catalyst described in any one of claims 1-6 is in photocatalysis field
In application.
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| CN112264069A (en) * | 2020-10-23 | 2021-01-26 | 南京信息工程大学 | Attapulgite photocatalyst and preparation method thereof |
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