CN106582518A - Graphene-TiO2 nanotube hydrogel, preparation method, and application thereof - Google Patents
Graphene-TiO2 nanotube hydrogel, preparation method, and application thereof Download PDFInfo
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- CN106582518A CN106582518A CN201611009191.3A CN201611009191A CN106582518A CN 106582518 A CN106582518 A CN 106582518A CN 201611009191 A CN201611009191 A CN 201611009191A CN 106582518 A CN106582518 A CN 106582518A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002071 nanotube Substances 0.000 title claims abstract description 68
- 239000000017 hydrogel Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000002351 wastewater Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 49
- 230000003115 biocidal effect Effects 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 17
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 4
- 229940088710 antibiotic agent Drugs 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 18
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229960003405 ciprofloxacin Drugs 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229930195503 Fortimicin Natural products 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009360 aquaculture Methods 0.000 description 1
- BIDUPMYXGFNAEJ-APGVDKLISA-N astromicin Chemical compound O[C@@H]1[C@H](N(C)C(=O)CN)[C@@H](OC)[C@@H](O)[C@H](N)[C@H]1O[C@@H]1[C@H](N)CC[C@@H]([C@H](C)N)O1 BIDUPMYXGFNAEJ-APGVDKLISA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
Abstract
The invention discloses a graphene-TiO2 nanotube hydrogel, a preparation method, and an application thereof. The preparation method includes the steps of: (1) adding water to graphene oxide to fully dissolve the graphene oxide to obtain a graphene oxide water solution; (2) adding the TiO2 nanotube to the graphene oxide water solution with full stirring to prepare a graphene-TiO2 nanotube solution; (3) preparing a FeSO4 water solution; (4) adding the FeSO4 water solution to the graphene-TiO2 nanotube solution with uniform mixing to obtain a mixed liquid; (5) performing self-assembly to the mixed liquid in the step (4) under a water bath environment to obtain the graphene-TiO2 nanotube hydrogel. The preparation method is simple and employs easy-to-obtain raw materials. During synthesis, the method abides by the principle of green chemistry and is free of catalysts and toxic solvents, so that the hydrogel is toxic-free. The hydrogel can be industrially produced and can effectively remove antibiotics from waste water.
Description
Technical field
The invention belongs to field of industrial waste water treatment, and in particular to a kind of graphene-titanium dioxide nanotube hydrogel and
Its preparation method and application.
Background technology
Our national antibiotic yields are high, because the not―rationality of medication, abuse of antibiotics is in China into normality so that
A large amount of antibiotic enter environment in the form of active compound or metabolite.General medicine is not readily dissolved in water, and with stronger suppression
System and the effect of killing bacterium, belong to recalcitrant substance.There are pharmacy factory production waste water, hospital wastewater, poultry in concrete source
And aquiculture waste water, at present in existing sewage disposal technology, there is certain drawback in biochemical treatment mode, at sewage
Reason factory is difficult that Ciprofloxacin is degradable.At present Ciprofloxacin is in underground water, surface water, hospital wastewater, sewage disposal
It is detected in factory's discharge water.And the absorption in physical method is utilized, the antibiotic waste water of high concentration and low concentration is had very
Good treatment effect, and it is simple to operate, and adsorption cycle is short.
Chinese invention patent, publication date is：2015.04.20, publication number：The A of CN 104525160, disclose one kind and pass through
Modified graphene oxide is wrapped on porous carbon microspheres, and while the monomer polymerization reactions for carrying out surface prepare polymeric adsorbent,
The composite of formation, for adsorbing water in terramycin, tetracycline, the simulated wastewater of fortimicin.But preparation method is loaded down with trivial details,
During high energy consumption, some gases, the solvent of employing etc. have certain pollution, and the waste water clearance to 200mg/L is less than 70%.
The content of the invention
It is an object of the present invention to be directed to energy consumption present in the antibiotic waste water processing procedure of existing Measurement for Biochemistry
A kind of technical problem of high, high cost and effect difference, there is provided preparation method of graphene-titanium dioxide nanotube hydrogel, it
Can realize that the efficient physical to antibiotic waste water adsorbs, the relatively low effect of cost is good, add and caused again after titania nanotube
Condensation material has regeneration and photocatalysis performance.Waste strength after process is less than national standard, and the water after process can be drained into
Water body, reduces the impact to aquatic plant and aquatic products.
Another object of the present invention is to said method prepare graphene-titanium dioxide nanotube hydrogel and its place
Reason is containing the application in antibiotic waste water.Input carries out the antibiotics in Adsorption water in the waste water containing antibiotic,
Wherein adsorption temp is normal temperature, is preferably 20～30 DEG C, and adsorption time is 4～5 days.After adsorption equilibrium, the adsorbance for reaching is
600～700mg/g, optimal adsorption pH is 7～8 (i.e. alkalescents).Experiment finds, after treatment, containing antibiotic solution
Its colourity of waste water and antibiotic content are all substantially reduced.
To solve the above problems, the technical scheme that the present invention is provided is：
A kind of preparation method of graphene-titanium dioxide nanotube hydrogel, comprises the following steps：
(1) graphene oxide is added water and fully graphene oxide water solution is made in dissolving；
(2) titania nanotube is added in the graphene oxide water solution of step (1) preparation and is sufficiently mixed and made
Graphene-titanium dioxide nanotube solution；
(3) FeSO is prepared4The aqueous solution；
(4) FeSO for adding step (3) to prepare in the graphene-titanium dioxide nanotube solution prepared to step (2)4Water
Solution simultaneously makes mixed liquor after being well mixed；
(5) self assembly is obtained graphene-titanium dioxide nanotube water-setting under the mixed liquor water bath for preparing step (4)
Glue.
The concentration of graphene oxide water solution described in step (1) is 1～5mg/mL；Preferably 2～3mg/mL；Further
Preferably 2.5mg/mL.
The concentration of titanium dioxide is 0.5～3mg/mL in graphene-titanium dioxide nanotube solution described in step (2)；
Preferably：1～2mg/mL；More preferably：1mg/mL.
FeSO described in step (3)4The concentration of the aqueous solution is 100～200g/L, preferably 140g/L；PH is 2～5, excellent
PH is selected to be 3.
Graphene-titanium dioxide nanotube solution and FeSO described in step (4)4The volume ratio of the aqueous solution is 10～25:
1；Preferably：16:1.
The temperature of water bath described in step (5) is 80～90 DEG C, and the heat time is 7～20h.
Fully the method for dissolving is ultrasonically treated 40～60 hours described in step (1)；Preferably 48 hours；Step (2)
Described in well-mixed method be ultrasonically treated 20～40 hours；Preferably 24 hours.
The graphene-titanium dioxide nanotube hydrogel obtained using above-mentioned preparation method.
Application of the above-mentioned graphene-titanium dioxide nanotube hydrogel in antibiotic waste water is processed.
Above-mentioned application is described graphene-titanium dioxide nanotube hydrogel to be put in antibiotic waste water, described anti-
The concentration of raw element waste water is 50～1000mg/L；Preferably 50～600mg/L.
Graphene-titanium dioxide nanotube hydrogel preparation method of the present invention is will by using hydrothermal synthesis method
Titania nanotube is fixed on graphene oxide.Under hydrothermal synthesizing condition, the hydrogel of formation has porous duct, height
Specific surface area and photocatalysis performance.
The detailed step of the preparation method optimal technical scheme is：
(1) add graphene oxide in distilled water, be configured to the graphene oxide water solution of 2～3mg/mL, by the water
Solution is put into ultrasonically treated 40～60 hours makes it fully dissolve；
(2) Gao Bibiao is prepared through stirring, centrifugation exchange, centrifugation, freeze-drying with titania powder (P25)
Area, the titania nanotube with absorption property, by titania nanotube the graphene oxide of abundant dissolving is added to
The aqueous solution, the concentration of titanium dioxide is 1～2mg/L；By the ultrasonically treated 20～40h of mixed liquor, it is sufficiently mixed and obtain completely graphite
Alkene-titania nanotube solution；
(3) FeSO of 100～200g/L is configured4, the HCl regulation pH for adding 1mol/L are 2～5；
(4) FeSO is added to graphene-titanium dioxide nanotube solution4Solution and ultrasound mixing, the Graphene-dioxy
Change titanium nanotube solution and FeSO4The volume ratio of the aqueous solution is 10～25：1；
(5) 7～20h is heated in the mixed liquor for preparing step (4) water bath with thermostatic control at 80～90 DEG C.
The FeSO that said method is used4Solution first with first using must prevent it to be oxidized；It is good in order to obtain during experiment
The hydrogel product of pattern, mixed liquor is added in the glass tube of 50mL, and in being put in similar to the small-sized water-bath of high honour HH-2 (but
This is not limited in specific operation process)；Water-bath must cover pot cover, and keeping temperature is 85 DEG C or so, uses wet towel lid
On water-bath, it is to avoid moisture evaporation is too fast；
The hydrogel that hydrothermal synthesis method is formed carefully carefully takes out from the aqueous solution isolated；Hydrogel is put into necessarily
In the antibiotic solution of concentration, solution is put in 125 revs/min of constant-temperature table, rotating speed is no more than 150 revs/min, in order to avoid hinder
The quick adsorption of antibiotic；Under the conditions of using lucifuge, incubated concussion case is covered with tinfoil, nature is avoided in adsorption process
The impact of light source；When hydrogel reaches adsorption saturation, be desorbed with ethanol, after with distilled water clean；Hydrogel Jing after desorption
Cross ultra violet lamp 45 minutes.
To be processed in the antibiotic waste water of hydrogel input variable concentrations obtained in said method, effluent quality index
Can reach《Integrated wastewater discharge standard》(GB8978-1996) primary standard in.The water outlet Jing after processing meets and is discharged into
Pyatyi water source, has saved water resource.
The present invention does not need electricity consumption, energy consumption low compared with biological treatment in processing procedure, reduce input cost, goes out
Residual is not had in water, water quality is not interfered with, while also reducing cost for wastewater treatment.
Hydrogel using present invention preparation significantly improves the adsorption capacity to larger molecular organics matter as adsorbent,
Using Static Adsorption mode.The polluted water that the present invention is used includes laboratory simulation waste water and pharmaceutical factory's waste discharge.
The present invention removes antibiotic such as Ciprofloxacin using efficient adsorbent, and effect is significant facilitates recovery constantly to weigh
It is multiple to utilize, compare environmentally friendly.This invention material prepare it is fairly simple, for process water in antibiotic there is good economic benefit
And environmental benefit.
The technical scheme provided using the present invention, compared with prior art, is had the advantages that：
(1) Graphene has a specific area, good hydrophilic property, and with loose structure；
(2) titanium dioxide has photocatalysis performance, and degradation of contaminant effect is good, but the pollution degradation after aqueous solution catalysis
It is not easily separate after thing and recycles.But by being supported on Graphene, it is easy to isolate solution, so improve absorption
The recycling property of agent.Adsorbent directly can be isolated after the completion of absorption from solution, it is not necessary to which complicated filtration, centrifugation etc. is separated
Operation；
(3) antibiotic for discharging is can be directly used for, for the antibiotic (100mg/L) of low concentration, removal effect rate is up to
99.5%, for the antibiotic (1000mg/L) of high concentration, removal effect is up to 27%；
(4) the hydrogel adsorbance of titanium dioxide is added to significantly improve.Titanium dioxide has good photocatalysis pollutant
Performance, recycle cost it is higher.By titanium dichloride load on Graphene, titanium dioxide can not only be securely fixed, and
And because titania nanotube has larger specific surface area, there is provided more adsorption sites.It can be seen that the present invention is for removal
Effects of antibiotics in water is good, with preferable economic use value.
Description of the drawings
Fig. 1：Graphene-titanium dioxide nanotube water-setting composes schematic diagram
Fig. 2：The graphene-titanium dioxide nanotube hydrogel of diameter 12mm, height 10mm
Fig. 3：XRD picture, anatase TiO2With the peak of ferro element
Fig. 4：SEM image, mutually overlaps between graphene layer and graphene layer
Fig. 5：TEM image, loaded titania nanotube on graphene layer
Fig. 6：XPS images, total peak (a) of C, Ti, O, Fe；C swarmings (b)；Fe swarmings (c)；Ti swarmings (d)
Fig. 7：Raman images, D peaks and G peaks
Fig. 8：Adsorption isotherm of the graphene-titanium dioxide nanotube hydrogel to Ciprofloxacin
Specific embodiment
To further appreciate that present disclosure, with reference to drawings and Examples, the present invention is described in detail.
Embodiment 1 prepares graphene-titanium dioxide nanotube hydrogel
(1) graphene oxide of nanometer powder shape is added in distilled water, is configured to the graphene oxide water of 2.5mg/mL
Solution；The aqueous solution is put into into ultrasonic drilling machine 48 hours through ultrasonically treated so as to which fully dissolving is completely dispersed；
(2) titania nanotube prepared by titania powder (P25), its specific surface area is 129.8m2/ g, hole
Footpath is 13.6nm；Titania nanotube specific surface area is high, with absorption property；Titania nanotube is added into fully dissolving
Graphene oxide water solution, the concentration of titanium dioxide is 1mg/L；By the ultrasonically treated 24h of mixed liquor, it is sufficiently mixed completely；
(3) FeSO of 140g/L is configured4Solution, the HCl for adding 1mol/L adjusts pH for 3；FeSO4Solution must now with existing
With in order to prevent its Quick Oxidation in atmosphere, the pH value for adjusting solution is 3；
(4) FeSO of 0.5mL is added in the graphene-titanium dioxide nanotube solution of 8mL4Solution, ultrasonic 5min systems
Into mixed liquor；
(5) mixed liquor is put in 50mL glass tubes the thermostat water bath heating 12h for being placed in 85 DEG C, notes keeping water-bath
The content of water in pot, the mixed liquor being sufficiently heated in glass tube and holding glass tube are vertically placed, obtained hydrogel shape
State is cylindric.
Prepared graphene-titanium dioxide nanotube hydrogel diameter 12mm, height 10mm.Through freeze-drying, survey
Its specific surface area is 40.44m2/ g, aperture is 0.126cm3/g。
Embodiment 2 prepares graphene-titanium dioxide nanotube hydrogel
(1) graphene oxide of nanometer powder shape is added in distilled water, the graphene oxide for being configured to 3mg/mL is water-soluble
Liquid；The aqueous solution is put into into ultrasonic drilling machine 50 hours through ultrasonically treated so as to which fully dissolving is completely dispersed；
(2) titania nanotube prepared by titania powder (P25), its specific surface area is 129.8m2/ g, hole
Footpath is 13.6nm；Titania nanotube specific surface area is high, with absorption property；Titania nanotube is added into fully dissolving
Graphene oxide water solution, the concentration of titanium dioxide is 2mg/L；By the ultrasonically treated 26h of mixed liquor, it is sufficiently mixed completely；
(3) FeSO of 150g/L is configured4Solution, the HCl for adding 1mol/L adjusts pH for 3；FeSO4Solution must now with existing
With in order to prevent its Quick Oxidation in atmosphere, the pH value for adjusting solution is 3；
(4) FeSO of 0.5mL is added in the graphene-titanium dioxide nanotube solution of 8mL4Solution, ultrasonic 5min systems
Into mixed liquor；
(5) mixed liquor is put in 50mL glass tubes the thermostat water bath heating 12h for being placed in 85 DEG C, notes keeping water-bath
The content of water in pot, the mixed liquor being sufficiently heated in glass tube and holding glass tube are vertically placed, obtained hydrogel shape
State is cylindric.
Embodiment 3 prepares graphene-titanium dioxide nanotube hydrogel
(1) graphene oxide of nanometer powder shape is added in distilled water, the graphene oxide for being configured to 2mg/mL is water-soluble
Liquid；The aqueous solution is put into into ultrasonic drilling machine 45 hours through ultrasonically treated so as to which fully dissolving is completely dispersed；
(2) titania nanotube prepared by titania powder (P25), its specific surface area is 129.8m2/ g, hole
Footpath is 13.6nm；Titania nanotube specific surface area is high, with absorption property；Titania nanotube is added into fully dissolving
Graphene oxide water solution, the concentration of titanium dioxide is 1.5mg/L；By the ultrasonically treated 25h of mixed liquor, it is sufficiently mixed completely；
(3) FeSO of 130g/L is configured4Solution, the HCl for adding 1mol/L adjusts pH for 3；FeSO4Solution must now with existing
With in order to prevent its Quick Oxidation in atmosphere, the pH value for adjusting solution is 3；
(4) FeSO of 0.5mL is added in the graphene-titanium dioxide nanotube solution of 8mL4Solution, ultrasonic 5min systems
Into mixed liquor；
(5) mixed liquor is put in 50mL glass tubes the thermostat water bath heating 12h for being placed in 85 DEG C, notes keeping water-bath
The content of water in pot, the mixed liquor being sufficiently heated in glass tube and holding glass tube are vertically placed, obtained hydrogel shape
State is cylindric.
Embodiment 4
Take 20mL initial concentrations be respectively 50,100,200,400,600,800, the ciprofloxacin solution of 1000mg/L adds
In 50mL glass tubes, graphene-titanium dioxide nanotube hydrogel prepared by 20mg embodiments 1 is put into respectively, finally solution
In being placed on the constant-temperature table that temperature is 303K.Supernatant is taken, 752 ultraviolet specrophotometers of concentration of the antibiotic in solution
Determine, and according to initial soln concentration and measure solution concentration, calculate adsorption capacity.
Under the conditions of this kind, the antibiotic absorption of low concentration is fast, adsorption equilibrium is reached within 2～3 days, for initial concentration is
The ciprofloxacin solution clearance of 100mg/L reaches 99.5% or so.For the antibiotic solution of high concentration, the ring of 600mg/L
The ciprofloxacin solution clearance that third husky star solution clearance reaches 39%, 1000mg/L reaches 27%, and its adsorbance is up to
600mg/g。
Embodiment 5
Graphene-titanium dioxide nanotube hydrogel prepared by embodiment 1 is put into in the original water outlet of Nanjing pharmaceutical factory；Water
Gel adsorber and wastewater quality ratio are 1:1, adsorption temp is room temperature, and waste water in pharmaceutical plants COD is 4500mg/L, and adsorption time is
3 days, the pH of solution was 6.6 after absorption, and the clearance of final COD, TOC is respectively 92% and 80%.
It can be seen that graphene-titanium dioxide nanotube hydrogel is regardless of the system complicated for single simulated wastewater or species
Pharmaceutical factory waste water has good absorption property.
As a result represent, graphene-titanium dioxide nanotube hydrogel intensity prepared by above-described embodiment is high, specific surface is big,
There are good absorption and photocatalysis performance.Using the strong suction-operated of hydrogel, polluter is firmly adsorbed, through de-
Be accompanied by and ultra violet lamp after, hydrogel can recover adsorption capacity, and the ultraviolet antibiotic to remaining on surface is carried out at degraded
Reason, high treating effect is simple to operate, and does not produce other polluters, is the side that a kind of clean and effective processes antibiotic waste water
Method, has broad application prospects.
Claims (10)
1. a kind of preparation method of graphene-titanium dioxide nanotube hydrogel, it is characterised in that comprise the following steps：
(1) graphene oxide is added water and fully graphene aqueous solution is made in dissolving；
(2) titania nanotube is added in the graphene aqueous solution of step (1) preparation and is sufficiently mixed and make Graphene-two
Titanium oxide nanotubes solution；
(3) FeSO is prepared4The aqueous solution；
(4) FeSO for adding step (3) to prepare in the graphene-titanium dioxide nanotube solution prepared to step (2)4The aqueous solution
And make mixed liquor after being well mixed；
(5) self assembly is obtained graphene-titanium dioxide nanotube hydrogel under the mixed liquor water bath for preparing step (4).
2. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(1) concentration of graphene aqueous solution described in is 1～5mg/mL；Preferably 2～3mg/mL；More preferably 2.5mg/mL.
3. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(2) concentration of titanium dioxide is 0.5～3mg/mL in graphene-titanium dioxide nanotube solution described in；Preferably：1～
2mg/mL；More preferably：1mg/mL.
4. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(3) FeSO described in4The concentration of the aqueous solution is 100～200g/L, preferably 140g/L；PH is 2～5, and preferred pH is 3.
5. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(4) graphene-titanium dioxide nanotube solution described in and FeSO4The volume ratio of the aqueous solution is 10～25:1；Preferably：16:
1。
6. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(5) temperature of water bath described in is 80～90 DEG C, and the heat time is 7～20h.
7. the preparation method of graphene-titanium dioxide nanotube hydrogel according to claim 1, it is characterised in that step
(1) fully the method for dissolving is ultrasonically treated 40～60 hours described in；Well-mixed method described in step (2) is ultrasound
Process 20～40 hours.
8. the graphene-titanium dioxide nanotube hydrogel for being obtained using arbitrary preparation method in claim 1～7.
9. application of the graphene-titanium dioxide nanotube hydrogel described in claim 8 in antibiotic waste water is processed.
10. application according to claim 9, it is characterised in that by described graphene-titanium dioxide nanotube hydrogel
In input antibiotic waste water, the concentration of the antibiotic waste water is 50～1000mg/L.
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