CN108203142A - A kind of photocatalysis combination electrode and preparation method thereof and application in the treatment of waste water - Google Patents
A kind of photocatalysis combination electrode and preparation method thereof and application in the treatment of waste water Download PDFInfo
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- CN108203142A CN108203142A CN201711458448.8A CN201711458448A CN108203142A CN 108203142 A CN108203142 A CN 108203142A CN 201711458448 A CN201711458448 A CN 201711458448A CN 108203142 A CN108203142 A CN 108203142A
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- graphene oxide
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- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920000557 Nafion® Polymers 0.000 claims abstract description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001548 drop coating Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000004098 Tetracycline Substances 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 26
- 235000019364 tetracycline Nutrition 0.000 claims description 26
- 150000003522 tetracyclines Chemical class 0.000 claims description 26
- 229960002180 tetracycline Drugs 0.000 claims description 24
- 229930101283 tetracycline Natural products 0.000 claims description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229940072172 tetracycline antibiotic Drugs 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 description 18
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 16
- 229940063650 terramycin Drugs 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002689 soil Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 2
- 229960004475 chlortetracycline Drugs 0.000 description 2
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 2
- 235000019365 chlortetracycline Nutrition 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 150000007660 quinolones Chemical class 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- SVDOODSCHVSYEK-IFLJXUKPSA-N (4s,4ar,5s,5ar,6s,12ar)-4-(dimethylamino)-1,5,6,10,11,12a-hexahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydron;chloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O SVDOODSCHVSYEK-IFLJXUKPSA-N 0.000 description 1
- 239000004099 Chlortetracycline Substances 0.000 description 1
- 206010059410 Faecaluria Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000019802 Sexually transmitted disease Diseases 0.000 description 1
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 229940097572 chloromycetin Drugs 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002207 metabolite Chemical group 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses photocatalysis combination electrodes and preparation method thereof, and Bi is obtained by tetrabutyl titanate, bismuth nitrate and graphene oxide hydro-thermal reaction4Ti3O12/ graphene oxide, by Bi4Ti3O12/ graphene oxide is scattered in the mixed liquor of water and absolute ethyl alcohol, obtains suspension, and the suspension is uniformly coated on glassy carbon electrode surface, and Bi is obtained in electrode surface drop coating Nafion solution again after drying4Ti3O12/ graphene oxide/glassy carbon electrode；The present invention is also applied to using the photocatalysis combination electrode in wastewater treatment, difficult biological treatment tetracycline antibiotics wastewater treatment can effectively be solved, under ultraviolet light irradiation, tetracycline antibiotics in direct photoelectrocatalysis waste water, the method for the present invention is simple, easy to operate, processing cost is low, removal rate is high, energy conservation and environmental protection, and economic and social benefit is huge.
Description
Technical field
The invention belongs to environmental protection technical fields, and in particular to a kind of photocatalysis combination electrode and preparation method thereof and
Application in the treatment of waste water.
Background technology
Antibiotic is also known as bacterium medicine and antibacterial agent, has the function of to kill bacterium or inhibits bacteria growth.From nineteen twenty-nine
After British scientist finds antibiotic, it is widely applied in terms of medical and health, agricultural breeding.It is treating and preventing
Significant role has been played in terms of human bacterial's sexually transmitted disease, prevention animal epidemic and protection public health security.
It is reported that about 16.2 ten thousand tons of the usage amount of year of China's antibiotic, accounts for about the 50% of the total usage amount in the world, wherein 48% is
People's antibiotic, 52% is veterinary antibiotic.A large amount of antibiotic by people or can not move for human medical and livestock and poultry cultivation
Object is metabolized completely, most of to be discharged with active compound or metabolite form by fecaluria, eventually enters surface water environment.It is for example, northern
Detect Multiple Classes of Antibiotics class drug in the surface water body in capital, wherein concentration range 0 ~ 37.8 ng/L of sulfa antibiotics, four
The maximum concentration of ring element class antibiotic up to 444 ng/L and recall rate be 33.3%；Basin of Huaihe River has detected concentration level 116 ~ 481
The highest antibiotic of ng/L, wherein contribution of concentration are tetracycline antibiotics；Haihe basin also detected concentration range 178~
The antibiotic residue of 502ng/L；Guangzhou Section of Pearl River water body has detected the Multiple Classes of Antibiotics class drug of concentration level ng/L；Shanghai is yellow
It is residual that sulfamido, quinolones, Tetracyclines, lactams, chloromycetin and macrolide antibiotic have been measured in Pujiang basin
It stays；Detect quinolones, sulfamido and Tetracyclines three classes antibiotic in Nanchang City's surface water body, concentration range 0.21 ~
13.62 μg/L.It can be seen that exerted a pernicious influence to reduce antibiotic residue in surface water, while antibiotic usage amount is reduced,
It is discharged after need to carrying out efficient advanced treating to the waste water containing antibiotic.
At present, the means such as physical absorption, biodegradation and advanced oxidation degradation can be used in the removal of antibiotic in water.Physics
The effect of adsorption treatment antibiotic waste water is preferable, but is also easy to produce solid secondary pollution；Low energy consumption, cost for biodegradation processing
It is low, but biology has specificity, and a certain quasi-microorganism only has treatment effect to specific antibiotic；Advanced oxidation is antibiotic
The characteristics of wastewater treatment technology most with prospects, maximum is non-selectivity, can be almost used at the biology in distress of institute in water
Manage the degradation of organic pollution.
Therefore, the present invention removes the tetracycline in water removal using the photoelectrocatalysis in high-level oxidation technology, has certain theoretical
And practical significance.
Invention content
Based on the deficiencies of the prior art, the purpose of the present invention is to provide a kind of photocatalysis combination electrode and its preparation sides
Method.
The present invention also aims to provide the application of photocatalysis combination electrode in the treatment of waste water, urged using photoelectricity
Tetracycline antibiotics in water removal are gone in change, protect earth's surface water ecological environment.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of photocatalysis combination electrode, includes the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
It by tetrabutyl titanate and absolute ethyl alcohol, stirs evenly, obtains reactant A；Bismuth nitrate is dissolved in dust technology, obtains reactant B；It will
Reactant A is added in reactant B, obtains mixed liquor, then graphene oxide is scattered in mixed liquor, uniform stirring 5 ~ 6 hours,
Then under protection of argon gas, in 100 ~ 140 DEG C of hydro-thermal reactions 12 ~ 24 hours, room temperature is subsequently cooled to, separation of solid and liquid takes solid
Washing, drying, obtain Bi4Ti3O12/ graphene oxide；
Wherein, the mass ratio of tetrabutyl titanate, bismuth nitrate and graphene oxide is 1.36 ~ 5.44: 1.185 ~ 7.47: 2.0 ~ 4.6；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
By step（1）Gained Bi4Ti3O12/ graphene oxide is scattered in the mixed liquor of water and absolute ethyl alcohol, obtains suspension；
Then it uniformly coats the suspension 3 ~ 5 times on the glassy carbon electrode surface by polishing, cleaning, is dripped again in electrode surface after drying
It applies Nafion solution 3 ~ 5 times, dries, obtain Bi4Ti3O12/ graphene oxide/glassy carbon electrode, i.e. photocatalysis combination electrode；
Wherein, Bi in the suspension4Ti3O12The content of/graphene oxide is 5 ~ 7.5 g/L.
Preferably, step（1）Described in reactant A the content of tetrabutyl titanate be 0.13 ~ 0.68 g/mL.
Preferably, step（1）Described in reactant B the content of bismuth nitrate be 0.079 ~ 0.747 g/mL, dilute nitre
A concentration of 3 ~ 5 mol/L of acid.
Preferably, step（1）The washing is washed respectively using absolute ethyl alcohol and deionized water；The temperature of the drying is
60 ~ 90 DEG C, a length of 8 ~ 15 hours when dry.
Preferably, step（2）The glassy carbon electrode uses Al before coating2O3Powder is polished, and 5 are cleaned with deionized water
More than secondary.
Preferably, step（2）It is described to dry using infrared lamp.
Preferably, a concentration of the 5% of Nafion solution.
The photocatalysis combination electrode being prepared using the above method.
The application of above-mentioned photocatalysis combination electrode in the treatment of waste water：Waste water is placed in reaction vessel, adds sulfuric acid
For sodium as electrolyte, it is 5.52 ~ 6.68 to adjust pH with dilute hydrochloric acid, using photocatalysis combination electrode as working electrode, with platinum filament and is satisfied
With calomel electrode respectively as to electrode and reference electrode, 1.0 ~ 2.5V of applied voltage imposes the ultraviolet light that wavelength is 254 nm,
Concussion reaction.
Preferably, tetracycline is contained in the waste water.
The method of the present invention is that the degradation of antibiotic in water is realized using photoelectrocatalysis method, first using butyl titanate, nitric acid
Bismuth, graphene oxide and glass electrode prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode, and as working electrode, platinum
Silk and calomel electrode are used as to electrode and reference electrode, under applied voltage and ultraviolet lamp effect, in photoelectric catalysis degrading water
Occrycetin and aureomycin, by the variation of occrycetin and chlortetracycline concentration in liquid chromatogram measuring waste water, calculating has
The removal rate of machine phosphorus insecticide, method is simple, easy to operate, and treatment effeciency is high, energy conservation and environmental protection, and environmental and social benefits are huge.
Description of the drawings
Fig. 1 is the SEM figures of graphene oxide used in the present invention；
Fig. 2 is 1 gained Bi of embodiment4Ti3O12The SEM figures of/graphene oxide；
Fig. 3 is the reaction unit used in photoelectrocatalysis of the present invention.
Specific embodiment
In order to make the technical purpose of the present invention, technical solution and advantageous effect clearer, with reference to specific embodiment
Technical scheme of the present invention is further illustrated, but the embodiment is intended to explain the present invention, and it is not intended that right
The limitation of the present invention, in the examples where no specific technique or condition is specified, according to the described technology of document in the art or
Condition is carried out according to product description, and drug used is ordinary commercial products in following embodiments.
Embodiment 1
A kind of preparation method of photocatalysis combination electrode, includes the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
1.36 g tetrabutyl titanates are put into the beaker of 250 mL, the absolute ethyl alcohol of 8 mL is added in into beaker, is sufficiently stirred 5
Min obtains the reactant A of water white transparency；1.185 g bismuth nitrates are put into the beaker of 250 mL, add in 4 while stirring
10 mL of nitric acid of mol/L, obtains reactant B；Reactant A is poured slowly into reactant B, obtains mixed liquor, then to mixed liquor
2.0 g graphene oxides of middle addition under ultrasonic wave added effect, make graphene oxide be dispersed in mixed liquor, then uniformly
5 h are stirred, are subsequently poured into the constant pressure reaction kettle of built-in polytetrafluoroethyllining lining, degree of filling is about 80%, leads to argon gas protection, twists
Tight reaction kettle, reacts 12 h at 140 DEG C, is cooled to room temperature after reaction, and the precipitation in reaction kettle is packed into 10 mL centrifuge tubes
10 min of centrifugation are carried out, then is washed three times and is centrifuged respectively with 20 mL absolute ethyl alcohols, 20 mL distilled water, finally solid are taken to be put into
Dry 12 h, obtain Bi in 80 DEG C of drying box4Ti3O12/ graphene oxide；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
Weigh 10 mg steps（1）Gained Bi4Ti3O12/ graphene oxide is placed in the beaker of 10 mL, add 1.0 mL go from
Sub- water and 1.0 mL absolute ethyl alcohols, 30 min of ultrasonic disperse form finely dispersed suspension；A diameter of 3 mm, length is taken to be
The glassy carbon electrode of 15 cm, first uses Al2O3Powder polish 20 min, after cleaned 5 times or more with deionized water, then by suspension
On uniform coating glass carbon electrode（Divide 5 times and coat successively）, 2 μ L a concentration of 5% are added dropwise after being dried with infrared lamp on electrode again
Nafion solution（Divide 5 drop coatings successively）, after infrared lamp is dried, obtain Bi4Ti3O12/ graphene oxide/glassy carbon electrode,
That is photocatalysis combination electrode.
To common commercially available graphene oxide and step（1）Bi obtained4Ti3O12/ graphene oxide is characterized, SEM
Figure difference is as shown in Figure 1 and Figure 2.By the variation of microscopic appearance as it can be seen that graphene oxide is lamellar structure, after hydro-thermal reaction,
Bi4Ti3O12Firmly it is grown on surface of graphene oxide.
The reaction unit that above-mentioned photocatalysis combination electrode uses when applying in the treatment of waste water, as shown in figure 3, including magnetic force
Blender 1 and electrochemical workstation 10 are provided with disc 7 on magnetic stirring apparatus 1, quartz glass reactor are placed on disc 7
5, magnetic stir bar 6 is placed in quartz glass reactor 5；The side of quartz glass reactor 5 is provided with ultraviolet for providing
The ultraviolet lamp 8 of light, ultraviolet lamp 8 are covered with the ultraviolet lamp outer cover 9 of tubular；In quartz glass reactor 5 inserted with working electrode 4,
To electrode 2 and reference electrode 3, the working electrode 4 connect electrode 2 and reference electrode 3 with electrochemical workstation 10 respectively,
Electrochemical workstation 10 is connected with the computer 11 for showing and handling numerical control.
Tetracycline wastewater is derived from certain pharmaceutical factory, and main component is the occrycetin and terramycin in tetracycline, salt sour soil
The initial concentration of mycin is 82.5 mg/L, and the initial concentration of terramycin is 62.7 mg/L.
Waste water of 500 mL containing tetracycline is taken to be placed in quartz glass reactor 5, Bi4Ti3O12/ graphene oxide/glass
Carbon electrode as working electrode 4, platinum filament and saturated calomel electrode respectively as to electrode 2 and reference electrode 3, in tetracycline wastewater
Sodium sulphate is added in as electrolyte, and in tetracycline wastewater sodium sulphate a concentration of 500 ppm, applied voltage 1.0V, use is dilute
The pH that hydrochloric acid adjusts reaction solution is 6.68, and 8 dominant wavelength of ultraviolet lamp is 254 nm, and temperature sets 30 DEG C, after reacting 2 h, salt sour soil
The concentration of mycin and terramycin is respectively the removal rate difference of 6.48 mg/L, 6.24 mg/L, i.e. occrycetin and terramycin
For 92.14% and 90.05%.
Embodiment 2
A kind of preparation method of photocatalysis combination electrode, includes the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
2.72 g tetrabutyl titanates are put into the beaker of 250 mL, the absolute ethyl alcohol of 8.8 mL is added in into beaker, is fully stirred
5 min are mixed, obtain the reactant A of water white transparency；3.37 g bismuth nitrates are put into the beaker of 250 mL, add in 4 while stirring
12 mL of nitric acid of mol/L, obtains reactant B；Reactant A is poured slowly into reactant B, obtains mixed liquor, then to mixed liquor
3.0 g graphene oxides of middle addition under ultrasonic wave added effect, make graphene oxide be dispersed in mixed liquor, then uniformly
5.2 h are stirred, are subsequently poured into the constant pressure reaction kettle of built-in polytetrafluoroethyllining lining, degree of filling is about 80%, leads to argon gas protection,
Reaction kettle is tightened, 15 h is reacted at 140 DEG C, is cooled to room temperature after reaction, the precipitation in reaction kettle is packed into 10 mL centrifugations
Pipe carries out 10 min of centrifugation, then is washed three times and centrifuged respectively with 20 mL absolute ethyl alcohols, 20 mL distilled water, finally solid is taken to put
Enter dry 12 h in 80 DEG C of drying box, obtain Bi4Ti3O12/ graphene oxide；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
Weigh 12 mg steps（1）Gained Bi4Ti3O12/ graphene oxide is placed in the beaker of 10 mL, add 1.0 mL go from
Sub- water and 1.0 mL absolute ethyl alcohols, 33 min of ultrasonic disperse form finely dispersed suspension；A diameter of 3 mm, length is taken to be
The glassy carbon electrode of 15 cm, first uses Al2O3Powder polish 20 min, after cleaned 5 times or more with deionized water, then by suspension
On uniform coating glass carbon electrode（Divide 5 times and coat successively）, 3 μ L a concentration of 5% are added dropwise after being dried with infrared lamp on electrode again
Nafion solution（Divide 5 drop coatings successively）, after infrared lamp is dried, obtain Bi4Ti3O12/ graphene oxide/glassy carbon electrode,
That is photocatalysis combination electrode.
Tetracycline wastewater is derived from certain pharmaceutical factory, and main component is the occrycetin and terramycin in tetracycline, salt sour soil
The initial concentration of mycin is 100.25 mg/L, and the initial concentration of terramycin is 68.7 mg/L.
It takes in waste water of the 500mL containing tetracycline and is placed in quartz glass electrochemical reactor, Bi4Ti3O12/ graphite oxide
Alkene/glassy carbon electrode is as working electrode, platinum filament and saturated calomel electrode respectively as to electrode and reference electrode, reaction unit
As shown in figure 3, in tetracycline wastewater add in sodium sulphate as electrolyte, and in tetracycline wastewater sodium sulphate a concentration of 500
Ppm, 1.5 V of applied voltage use dilute hydrochloric acid to adjust the pH of reaction solution as 6.13, and ultraviolet lamp dominant wavelength is 254 nm, and temperature is set
30 DEG C fixed, after reacting 2h, the concentration of occrycetin and terramycin is respectively 8.16 mg/L, 4.77 mg/L, i.e. salt sour soil is mould
The removal rate of element and terramycin is respectively 91.86% and 93.05%.
Embodiment 3
A kind of preparation method of photocatalysis combination electrode, includes the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
4.08 g tetrabutyl titanates are put into the beaker of 250 mL, the absolute ethyl alcohol of 8 mL is added in into beaker, is sufficiently stirred 5
Min obtains the reactant A of water white transparency；3.56 g bismuth nitrates are put into the beaker of 250 mL, add in 4 mol/ while stirring
10 mL of nitric acid of L, obtains reactant B；Reactant A is poured slowly into reactant B, obtains mixed liquor, then add into mixed liquor
Enter 4.0 g graphene oxides, under ultrasonic wave added effect, graphene oxide is made to be dispersed in mixed liquor, then uniform stirring
5.6 h are subsequently poured into the constant pressure reaction kettle of built-in polytetrafluoroethyllining lining, and degree of filling is about 80%, are led to argon gas protection, are tightened
Reaction kettle, 140 DEG C react 20 h, be cooled to room temperature after reaction, by reaction kettle precipitation be packed into 10 mL centrifuge tubes into
Row 10 min of centrifugation, then washed three times and centrifuged respectively with 20 mL absolute ethyl alcohols, 20 mL distilled water, finally solid is taken to be put into 80
DEG C drying box in dry 12 h, obtain Bi4Ti3O12/ graphene oxide；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
Weigh 13.5 mg steps（1）Gained Bi4Ti3O12/ graphene oxide is placed in the beaker of 10 mL, is added 1.0 mL and is gone
Ionized water and 1.0 mL absolute ethyl alcohols, 36 min of ultrasonic disperse form finely dispersed suspension；Take a diameter of 3 mm, length
For the glassy carbon electrode of 15 cm, Al is first used2O3Powder is polished 20 min, after with deionized water clean 5 times or more, then will suspension
On the uniform coating glass carbon electrode of liquid（Divide 5 times and coat successively）, it is a concentration of that 4 μ L are added dropwise after being dried with infrared lamp on electrode again
5% Nafion solution（Divide 5 drop coatings successively）, after infrared lamp is dried, obtain Bi4Ti3O12/ graphene oxide/vitreous carbon electricity
Pole, i.e. photocatalysis combination electrode.
Tetracycline wastewater is derived from certain pharmaceutical factory, and main component is the occrycetin and terramycin in tetracycline, salt sour soil
The initial concentration of mycin is 120.36 mg/L, and the initial concentration of terramycin is 72.3 mg/L.
It takes in waste water of the 500mL containing tetracycline and is placed in quartz glass electrochemical reactor, Bi4Ti3O12/ graphite oxide
Alkene/glassy carbon electrode is as working electrode, platinum filament and saturated calomel electrode respectively as to electrode and reference electrode, reaction unit
As shown in figure 3, in tetracycline wastewater add in sodium sulphate as electrolyte, and in tetracycline wastewater sodium sulphate a concentration of 500
Ppm, 2.0 V of applied voltage use dilute hydrochloric acid to adjust the pH of reaction solution as 5.52 ~ 6.68, and ultraviolet lamp dominant wavelength is 254 nm, warm
30 DEG C of degree setting, after reacting 2 h, the concentration of occrycetin and terramycin is respectively 10.18 mg/L, 4.16 mg/L, i.e. salt
The removal rate of OXYTETRACYCLINE HCL and terramycin is respectively 91.54% and 94.24%.
Embodiment 4
A kind of preparation method of photocatalysis combination electrode, includes the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
5.44 g tetrabutyl titanates are put into the beaker of 250 mL, the absolute ethyl alcohol of 8 mL is added in into beaker, is sufficiently stirred 5
Min obtains the reactant A of water white transparency；7.47 g bismuth nitrates are put into the beaker of 250 mL, add in 4 mol/ while stirring
15 mL of nitric acid of L, obtains reactant B；Reactant A is poured slowly into reactant B, obtains mixed liquor, then add into mixed liquor
Enter 4.6 g graphene oxides, under ultrasonic wave added effect, graphene oxide is made to be dispersed in mixed liquor, then uniform stirring 6
H is subsequently poured into the constant pressure reaction kettle of built-in polytetrafluoroethyllining lining, and degree of filling is about 80%, is led to argon gas protection, is tightened reaction
Kettle, 140 DEG C react 24 h, be cooled to room temperature after reaction, by reaction kettle precipitation be packed into 10 mL centrifuge tubes carry out from
10 min of the heart, then washed three times and centrifuged respectively with 20 mL absolute ethyl alcohols, 20 mL distilled water, solid is finally taken to be put into 80 DEG C
Dry 12 h, obtain Bi in drying box4Ti3O12/ graphene oxide；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
Weigh 15 mg steps（1）Gained Bi4Ti3O12/ graphene oxide is placed in the beaker of 10 mL, add 1.0 mL go from
Sub- water and 1.0 mL absolute ethyl alcohols, 40 min of ultrasonic disperse form finely dispersed suspension；A diameter of 3 mm, length is taken to be
The glassy carbon electrode of 15 cm, first uses Al2O3Powder polish 20 min, after cleaned 5 times or more with deionized water, then by suspension
On uniform coating glass carbon electrode（Divide 5 times and coat successively）, 5 μ L a concentration of 5% are added dropwise after being dried with infrared lamp on electrode again
Nafion solution（Divide 5 drop coatings successively）, after infrared lamp is dried, obtain Bi4Ti3O12/ graphene oxide/glassy carbon electrode,
That is photocatalysis combination electrode.
Tetracycline wastewater is derived from certain pharmaceutical factory, and main component is the occrycetin and terramycin in tetracycline, salt sour soil
The initial concentration of mycin is 150.7 mg/L, and the initial concentration of terramycin is 79.1mg/L.
It takes in waste water of the 500mL containing tetracycline and is placed in quartz glass electrochemical reactor, Bi4Ti3O12/ graphite oxide
Alkene/glassy carbon electrode is as working electrode, platinum filament and saturated calomel electrode respectively as to electrode and reference electrode, reaction unit
As shown in figure 3, in tetracycline wastewater add in sodium sulphate as electrolyte, and in tetracycline wastewater sodium sulphate a concentration of 500
Ppm, applied voltage 2.5V use dilute hydrochloric acid to adjust the pH of reaction solution as 5.52, and ultraviolet lamp dominant wavelength is 254 nm, and temperature is set
30 DEG C, after reacting 2 h, the concentration of occrycetin and terramycin is respectively 14.51 mg/L, 3.92 mg/L, i.e. salt sour soil is mould
The removal rate of element and terramycin is respectively 90.37% and 95.05%.
In summary it is found that the method for the present invention uses Bi4Ti3O12/ graphene oxide/glassy carbon electrode photoelectric catalysis degrading
Tetracycline in waste water, this method can effective catalytic degradation various concentration practical tetracycline antibiotics waste water, removal rate is high,
Up to more than 90%, energy conservation and environmental protection, and it is easy to operate, simple for process, expense is low, there is very strong practicability, economic and society's effect
Benefit is huge.
Claims (10)
1. a kind of preparation method of photocatalysis combination electrode, which is characterized in that include the following steps：
（1）Prepare Bi4Ti3O12/ graphene oxide：
It by tetrabutyl titanate and absolute ethyl alcohol, stirs evenly, obtains reactant A；Bismuth nitrate is dissolved in dust technology, obtains reactant B；It will
Reactant A is added in reactant B, obtains mixed liquor, then graphene oxide is scattered in mixed liquor, uniform stirring 5 ~ 6 hours,
Then under protection of argon gas, in 100 ~ 140 DEG C of hydro-thermal reactions 12 ~ 24 hours, room temperature is subsequently cooled to, separation of solid and liquid takes solid
Washing, drying, obtain Bi4Ti3O12/ graphene oxide；
Wherein, the mass ratio of tetrabutyl titanate, bismuth nitrate and graphene oxide is 1.36 ~ 5.44: 1.185 ~ 7.47: 2.0 ~ 4.6；
（2）Prepare Bi4Ti3O12/ graphene oxide/glassy carbon electrode：
By step（1）Gained Bi4Ti3O12/ graphene oxide is scattered in the mixed liquor of water and absolute ethyl alcohol, obtains suspension；So
The suspension is uniformly coated on the glassy carbon electrode surface by polishing, cleaning afterwards, again in electrode surface drop coating after drying
Nafion solution is dried, and obtains Bi4Ti3O12/ graphene oxide/glassy carbon electrode, i.e. photocatalysis combination electrode；
Wherein, Bi in the suspension4Ti3O12The content of/graphene oxide is 5 ~ 7.5 g/L.
2. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Step（1）Described in react
The content of tetrabutyl titanate is 0.13 ~ 0.68 g/mL in object A.
3. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Step（1）Described in react
The content of bismuth nitrate is 0.079 ~ 0.747 g/mL, a concentration of 3 ~ 5 mol/L of the dust technology in object B.
4. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Step（1）The washing is adopted
It is washed respectively with absolute ethyl alcohol and deionized water；The temperature of the drying is 60 ~ 90 DEG C, a length of 8 ~ 15 hours when dry.
5. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Step（2）The vitreous carbon
Electrode uses Al before coating2O3Powder is polished, and is cleaned 5 times or more with deionized water.
6. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Step（2）Described dry is adopted
Use infrared lamp.
7. the preparation method of photocatalysis combination electrode according to claim 1, it is characterised in that：Nafion solution it is a concentration of
5%。
8. the photocatalysis combination electrode being prepared using any the method for claim 1 to 7.
9. the application of photocatalysis combination electrode in the treatment of waste water described in claim 9, it is characterised in that：Waste water is placed in reaction
In container, sodium sulphate is added as electrolyte, it is 5.52 ~ 6.68 to adjust pH with dilute hydrochloric acid, using photocatalysis combination electrode as work
Make electrode, using platinum filament and saturated calomel electrode as to electrode and reference electrode, 1.0 ~ 2.5V of applied voltage is imposed ultraviolet
Light, concussion reaction.
10. the application of photocatalysis combination electrode in the treatment of waste water according to claim 9, it is characterised in that：The waste water
In contain tetracycline.
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