CN105749915A - Method for preparing magnetic graphene-based titanium dioxide composite - Google Patents
Method for preparing magnetic graphene-based titanium dioxide composite Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004005 microsphere Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000002360 preparation method Methods 0.000 claims description 26
- 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 claims description 16
- 229940043267 rhodamine b Drugs 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000011941 photocatalyst Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 claims description 3
- -1 RGOFe3O4C Chemical compound 0.000 claims description 3
- 238000002835 absorbance Methods 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 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 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000009102 absorption Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C02F1/30—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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
A method for preparing a magnetic graphene-based titanium dioxide composite includes: first, synthesizing a magnetic graphene composite modified with Fe3O4 nano microspheres of different sizes by means of a solvothermal method; second, mechanically stirring magnetic graphene and tetrabutyl titanate as raw materials to synthesize the magnetic graphene-based titanium dioxide composite.The invention has the advantages that the method is simple, and the process is reasonable and easy to implement; the prepared magnetic graphene-based titanium dioxide composite has good catalytic performance when applied to photo-catalytic dyes; the method integrates characteristics of magnetic graphene and characteristics of titanium dioxide nanoparticles, showing good performances such as adsorption, electron transfer, photocatalysis and separation easiness, and the method for preparing the magnetic graphene-based titanium dioxide composite is provided such that the applicable range of magnetic graphene materials in the field of photocatalysis is widened.
Description
[technical field]
The preparation method that the present invention relates to magnetic graphene based composites, adopt solvent-thermal method to prepare magnetic graphene that titanium dioxide nano-particle modifies and in the application of photocatalysis field.
[background technology]
Graphene, as mono-layer graphite, has huge specific surface area and is present in the pi-electron moved freely on surface in a large number, therefore becomes auxiliary conventional in photocatalyst and baseplate material.Therefore, by grapheme material and Fe3O4TiO2Catalyst combines, to improve the catalysis activity of photocatalyst further.
Magnetic graphene is a kind of novel graphite alkene composite, has extremely strong performance of the adsorbent, separates simple, energy consumption is little, compared to traditional separation method, for instance filtration, centrifugal, gravitational settling, as long as externally-applied magnetic field just can high efficiency separation magnetic graphene adsorbent.Magnetic Nano microsphere and Graphene are combined not only makes Graphene be easily isolated, and the magnetic Nano microsphere that load is thereon can be effectively prevented from and reduce graphene sheet layer and reunite and stacking, the steric effect of magnetic nano-particle and contiguous graphene sheet layer is also provided that available surface area as much as possible is to improve absorbability.
In numerous nano materials, titanium dioxide is as a kind of traditional semi-conducting material, and it has the superior functions such as low cost, catalytic efficiency anti-light corrosivity high, nontoxic, strong, stable chemical performance, becomes material most popular in current degradable organic pollutant.In light-catalysed application, the degraded titanium dioxide for dyestuff has shown relatively higher catalytic performance.But titanium dioxide is not readily separated recovery after a procedure as photocatalyst, under light illumination, the quick compound in light induced electron and hole and relatively low photon utilization ratio, limit its application in practice.
Therefore, using titanium dioxide nano-particle load in magnetic graphene as photocatalyst for degrading dyestuff, adsorptivity good for magnetic graphene, electron transfer capacity and the advantage that is easily recycled, the photo-catalysis capability remarkable with nano titanium oxide combines, shortcoming when overcoming nano titanium oxide separately as catalyst, improves photocatalysis performance.
[summary of the invention]
It is an object of the invention to be carried in magnetic graphene by titanium dioxide nano-particle, the magnetic graphene based composites that prepared titanium dioxide nano-particle is modified, integrate the characteristic of magnetic graphene and titanium dioxide nano-particle, show good absorption, electron transfer, photocatalysis, the ability such as be easily isolated, the preparation method providing a kind of magnetic graphene based titanium dioxide composite, and it is applied to photocatalysis field.
Technical scheme:
The preparation method of a kind of magnetic graphene based titanium dioxide composite, first passes through solvent structure different size Fe3O4The magnetic graphene composite that Nano microsphere is modified, then with magnetic graphene and butyl titanate for raw material, by mechanical agitation, synthesizing magnetic graphene-based titanium dioxide composite, comprises the steps:
1)RGOFe3O4The preparation of composite
Weigh FeCl3·6H2O, is dissolved in ethylene glycol, obtains yellow transparent solution by ultrasonic.It is subsequently adding graphite oxide (GO), ultrasonic 1h, is eventually adding anhydrous sodium acetate, after ultrasonic 30min, solution is proceeded in stainless steel cauldron, put into baking oven crystallization 12h at 200 DEG C.Taking out reactor after reaction and be cooled to room temperature, resulting materials ethanol is washed 6 times, vacuum drying 12h at 60 DEG C.
2)RGOFe3O4The preparation of C composite
First Fe is weighed3O4RGO, in the nitric acid of 2M ultrasonic 10 minutes, then uses deionized water wash.The Fe that will process3O4RGO microsphere is dispersed in dextrose hydrate solution, and adds cetyl trimethylammonium bromide, ultrasonic half an hour in glucose solution.After being stirred vigorously (stirring paddle) then through 10 minutes, suspension is transferred to autoclave, and reacts 4 hours at 180 DEG C.After reaction, by autoclave natural cooling in atmosphere, under the help of Magnet, suspension is separated, and wash three times respectively with deionized water and ethanol.RGOFe is obtained after dry about 4 hours at 80 DEG C in baking oven3O4C composite.
3)RGOFe3O4TiO2The preparation of composite photo-catalyst
Butyl titanate is dissolved in ethanol, to form the solution of clarification.Then within 5 minutes, RGOFe is made by ultrasonic Treatment3O4C composite is dispersed in the solution of just preparation.By water and the mixed liquor of ethanol be added dropwise to RGOFe3O4In the suspension of C composite, and with the strong agitation of about 15min.Hereafter, suspension is stirred for 2 hours, rear separation of ethanol and washing.With separation of ethanol/washing/redispersion, processing 5 times, the powder obtained dries in an oven, finally calcines 3 hours under 500 DEG C of nitrogen atmospheres.
Described FeCl3·6H2The amount ratio of O, ethylene glycol, graphene oxide, anhydrous sodium acetate and ethanol is 1-5g: 20-50ml: 50-200mg: 2-5g: 20-50mL.
Described Fe3O4RGO, nitric acid, deionized water, glucose solution, cetyl trimethylammonium bromide amount ratio be 10-100mg: 20-50ml: 50-200ml: 20-60ml: 10-100mg.
Described butyl titanate, ethanol, RGOFe3O4C, deionized water/ethanol amount ratio be 5-10mg: 20-50mol: 20-50mg: 1: 5.
A kind of photocatalytic applications of prepared magnetic graphene based titanium dioxide composite, concrete grammar is:
The rhodamine B solution of 6 parts of 20mL variable concentrations of preparation, concentration is 0.0005mM respectively, 0.001mM, 0.002mM, 0.005mM, 0.01mM, 0.02mM；RGOFe3O4TiO2The addition of photocatalyst is 0.25g/L.In the dark after absorption 30min, open high pressure xenon lamp (350W), be centrifuged separating every 5min or 10min sampling, test rhodamine B solution absorbance change.
Advantages of the present invention: the preparation method of magnetic graphene based titanium dioxide composite provided by the invention, rational technology, easy to implement；Good catalytic performance is shown when magnetic graphene based titanium dioxide composite prepared by this law is as photocatalyst for degrading dyestuff；This preparation method integrates the characteristic of magnetic graphene and nano-titania particle, show good adsorptivity, high electronics locomotivity and the advantage being easily recycled, with remarkable photo-catalysis capability, widened the magnetic graphene composite scope in photocatalytic applications field.
[accompanying drawing explanation]
Fig. 1 is Fe3O4The scanning electron microscope (SEM) photograph of Nano microsphere modified magnetic Graphene and transmission electron microscope picture.
Fig. 2 is Fe3O4The scanning electron microscope (SEM) photograph of magnetic graphene based titanium dioxide composite prepared by RGO and transmission electron microscope picture.
Fig. 3 is GO, Fe3O4RGO、RGOFe3O4C and RGOFe3O4TiO2The XRD figure of composite.
Fig. 4 is after magnetic graphene based titanium dioxide composite photocatalytic degradation variable concentrations rhodamine B prepared by magnetic graphene, the degraded trendgram of rhodamine B solution.
[detailed description of the invention]
Embodiment:
The preparation method of a kind of magnetic graphene based titanium dioxide composite, first passes through solvent structure different size Fe3O4The magnetic graphene composite that Nano microsphere is modified, then with magnetic graphene and butyl titanate for raw material, by mechanical agitation, synthesizing magnetic graphene-based titanium dioxide composite, comprises the steps:
1)RGOFe3O4The preparation of composite
Weigh 1.35gFeCl3·6H2O, is dissolved in 40ml ethylene glycol, obtains yellow transparent solution by ultrasonic.It is subsequently adding 100mg graphite oxide (GO), ultrasonic 1h, is eventually adding 3.6g anhydrous sodium acetate, after ultrasonic 30min, solution is proceeded in stainless steel cauldron, put into baking oven crystallization 12h at 200 DEG C.Taking out reactor after reaction and be cooled to room temperature, resulting materials 30ml ethanol is washed 6 times, vacuum drying 12h at 60 DEG C.
Fig. 1-a is the SEM picture of magnetic graphene, it can be seen that prepared Graphene is lamellar structure, and uniform magnetic microsphere is uniformly dispersed in the surface of graphene film.Fig. 1-b is the TEM picture of magnetic graphene, Fe3O4When magnetic microsphere success load is on Graphene, there are a lot of folds and has certain ripple in graphenic surface, and this is perhaps the electronics coupled effect between the graphene-based end and ferroso-ferric oxide.
2)RGOFe3O4The preparation of C composite
First 0.05gFe is weighed3O4RGO, in the nitric acid of 2M (30ml) ultrasonic 10 minutes, then uses deionized water wash.The Fe that will process3O4RGO microsphere is dispersed in 0.5M (40ml) dextrose hydrate solution, and adds cetyl trimethylammonium bromide, ultrasonic half an hour in glucose solution.After being stirred vigorously (stirring paddle) then through 10 minutes, suspension is transferred to autoclave, and reacts 4 hours at 180 DEG C.After reaction, by autoclave natural cooling in atmosphere, under the help of Magnet, suspension is separated, and wash three times respectively with deionized water and ethanol.RGOFe is obtained after dry about 4 hours at 80 DEG C in baking oven3O4C composite.
3)RGOFe3O4TiO2The preparation of composite photo-catalyst
Butyl titanate (5ml) is dissolved in ethanol (35ml), to form the solution of clarification.Then within 5 minutes, RGOFe is made by ultrasonic Treatment3O4C composite (about 50mg) is dispersed in the solution of just preparation.The mixed liquor of water (5ml) that volume ratio is 1: 5 and ethanol (25ml) is added dropwise to RGOFe3O4In the suspension of C composite, and with the strong agitation of about 15min.Hereafter, suspension is stirred for 2 hours, rear separation of ethanol and washing.With separation of ethanol, washing, redispersion, processing 5 times, the powder obtained dries in an oven, finally calcines 3 hours under 500 DEG C of nitrogen atmospheres.
Fig. 2 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of magnetic graphene based titanium dioxide composite prepared by magnetic graphene.Finding out after the outside being coated with one layer of carbon is coated with layer of titanium dioxide again from Fig. 2-c scanning electron microscope (SEM) photograph, the magnetic spherolite footpath of graphenic surface significantly increases, and by 2-d transmission electron microscope picture it can be seen that obvious surrounding layer.
Fig. 3 is GO, RGOFe3O4、RGOFe3O4C and RGOFe3O4TiO2X-ray diffraction spectrogram, it will be seen that occur in that the lattice peak of graphite oxide at about 12 ° places in the XRD figure of a graphene oxide in Fig. 3, illustrate that the original lattice structure of graphite powder is destroyed, complete oxidation is graphene oxide.When adopting solvent-thermal method by graphene oxide and FeCl3·6H2O is reduced to Fe simultaneously3O4During RGO, the characteristic peak of graphene oxide disappears, and occurs in that Fe simultaneously3O4In 2 θ=30.23 °, 35.58 °, 43.22 °, 53.54 °, 57.15 °, the characteristic diffraction peak of 62.91 °, with Fe3O4Three-dimensional crystal face: (220), (311), (400), (422), (511) and (440) are corresponding, and this illustrates Fe3O4Successfully load to graphenic surface, consistent with the characterization result of transmission electron microscope.Due to Fe3O4Diffraction maximum stronger so that the characteristic peak of Graphene is discernable hardly, in Fig. 3 shown in b.And through the RGOFe of bag carbon step synthesis3O4In X-ray diffraction spectrogram such as Fig. 3 of C shown in c, all of Fe in this figure3O4The intensity of diffraction maximum all decreases, and the successful compound of this carbon just is to magnetic Fe3O4The shielding action produced.TiO shown in d in Fig. 32In 2 θ=25.2 °, 38.56 °, 48.06 °, 55.04 °, 68.84 °, 70.39 °, the characteristic diffraction peak of the anatase crystal at 75.04 ° of places, the TiO having anatase is described2Load is at RGOFe3O4The surface of C.Compared with b in Fig. 3, Fe3O4The position of diffraction maximum is not because of carbon and TiO2Cladding and change, synthesized RGOFe is described3O4TiO2Still Fe is retained3O4Good magnetic.
A kind of prepared magnetic graphene based titanium dioxide composite, is applied to the application of photocatalytic degradation rhodamine B, and concrete grammar is: the rhodamine B solution of 6 parts of 20mL variable concentrations of preparation, concentration is 0.0005mM respectively, 0.001mM, 0.002mM, 0.005mM, 0.01mM, 0.02mM；RGOFe3O4TiO2The addition of photocatalyst is 0.25g/L.In the dark after absorption 30min, open high pressure xenon lamp (350W), be centrifuged separating every 5min or 10min sampling, test rhodamine B solution absorbance change.
Fig. 4 is the trendgram weighing magnetic graphene based titanium dioxide composite degradation rhodamine B prepared by the magnetic graphene of certain mass.Figure shows: the rhodamine B solution of variable concentrations photocatalysis efficiency (A-F:5 × 10 under finite concentration catalyst-7, 1 × 10-6, 2 × 10-5, 5 × 10-6, 1 × 10-5, 2 × 10-5mol/LofRhB；) through identical light application time, initial concentration respectively 5 × 10-7Mol/L and 1 × 10-6The photocatalytic degradation curve of the rhodamine B solution of mol/L is very close to, and the degradation rate of the rhodamine B solution obviously higher than other concentration.This illustrates when rhodamine B initial concentration solution is relatively low, and the difference of its photocatalytic degradation efficiency is little, namely initial concentration is less on photocatalysis effect impact；When rhodamine B initial concentration solution continues to increase, degradation rate then decreases.
Claims (5)
1. a preparation method for magnetic graphene based titanium dioxide composite, first passes through solvent structure different size Fe3O4The magnetic graphene composite that Nano microsphere is modified, then with magnetic graphene and butyl titanate for raw material, by mechanical agitation, synthesizing magnetic graphene-based titanium dioxide composite, comprises the steps:
1)RGOFe3O4The preparation of composite
Weigh FeCl3·6H2O, is dissolved in ethylene glycol, obtains yellow transparent solution by ultrasonic；It is subsequently adding graphite oxide (GO), ultrasonic 1h, it is eventually adding anhydrous sodium acetate, after ultrasonic 30min, solution is proceeded in stainless steel cauldron, put into baking oven crystallization 12h at 200 DEG C, take out reactor after reaction and be cooled to room temperature, resulting materials ethanol is washed 6 times, vacuum drying 12h at 60 DEG C；
2)RGOFe3O4The preparation of C composite
First Fe is weighed3O4RGO, in the nitric acid of 2M (30ml) ultrasonic 10 minutes, then with deionized water wash, the Fe that will process3O4RGO microsphere is dispersed in dextrose hydrate solution, and in glucose solution, add cetyl trimethylammonium bromide, ultrasonic half an hour, after being stirred vigorously (stirring paddle) then through 10 minutes, suspension is transferred to autoclave, and react 4 hours at 180 DEG C, after reaction, by autoclave natural cooling in atmosphere, under the help of Magnet, suspension is separated, and wash respectively three times with deionized water and ethanol, in baking oven, obtain RGOFe after dry about 4 hours at 80 DEG C3O4C composite；
3)RGOFe3O4TiO2The preparation of composite photo-catalyst
Butyl titanate (5 milliliters) is dissolved in ethanol (35 milliliters), to form the solution of clarification；Then within 5 minutes, RGOFe is made by ultrasonic Treatment3O4C composite (about 50 milligrams) is dispersed in the solution of just preparation, by water and the mixed liquor of ethanol be added dropwise to RGOFe3O4In the suspension of C composite, and with the strong agitation of about 15min；Hereafter, being stirred for by suspension 2 hours, rear separation of ethanol and washing, with separation of ethanol/washing/redispersion, process 5 times, the powder obtained dries in an oven, finally calcines 3 hours under 500 DEG C of nitrogen atmospheres.
2. the preparation method of magnetic graphene based titanium dioxide composite according to claim 1, it is characterised in that: described FeCl3·6H2The amount ratio of O, ethylene glycol, graphene oxide, anhydrous sodium acetate and ethanol is 1-5g: 20-50ml: 50-200mg: 2-5g: 20-50mL.
3. the preparation method of magnetic graphene based titanium dioxide composite according to claim 1, it is characterised in that: described Fe3O4RGO, nitric acid, deionized water, glucose solution, cetyl trimethylammonium bromide amount ratio be 10-100mg: 20-50ml: 50-200ml: 20-60ml: 10-100mg.
4. the preparation method of magnetic graphene based titanium dioxide composite according to claim 1, it is characterised in that: described butyl titanate, ethanol, RGOFe3O4C, deionized water/ethanol amount ratio be 5-10mg: 20-50mol: 20-50mg: 1: 5.
5. the application of the magnetic graphene based titanium dioxide composite prepared by a claim 1, it is characterized in that: be applied to photocatalytic degradation rhodamine B, concrete grammar is: the rhodamine B solution of 6 parts of 20mL variable concentrations of preparation, concentration is 0.0005mM respectively, 0.001mM, 0.002mM, 0.005mM, 0.01mM, 0.02mM；RGOFe3O4TiO2The addition of photocatalyst is 0.25g/L, in the dark after absorption 30min, opens high pressure xenon lamp (350W), is centrifuged separating every 5min or 10min sampling, test rhodamine B solution absorbance change.
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| CN201510771399.8A CN105749915A (en) | 2015-11-12 | 2015-11-12 | Method for preparing magnetic graphene-based titanium dioxide composite |
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| CN106076337A (en) * | 2016-07-14 | 2016-11-09 | 中国科学院生态环境研究中心 | A kind of composite photocatalyst material and preparation method thereof |
| CN106475083A (en) * | 2016-09-08 | 2017-03-08 | 东北大学秦皇岛分校 | The preparation method of graphene oxide/optically catalytic TiO 2 composite material precursor |
| CN107552082A (en) * | 2017-09-29 | 2018-01-09 | 河海大学 | A kind of quaternary multifunction magnetic nano composite material and preparation method thereof |
| CN108993540A (en) * | 2018-09-03 | 2018-12-14 | 天津工业大学 | A kind of novel photocatalyst Agx-Au1-x/ZnIn2S4/rGO/TiO2The preparation method of nanotube |
| CN109954518A (en) * | 2018-11-09 | 2019-07-02 | 成都禾木源环保科技有限公司 | A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method and device |
| CN110127678A (en) * | 2019-05-20 | 2019-08-16 | 天津市职业大学 | A kind of preparation method of magnetic graphene |
| CN110404506A (en) * | 2019-07-12 | 2019-11-05 | 中国科学院东北地理与农业生态研究所 | Magnetic oxygenated graphene/sodium titanate composite material preparation method and application |
| CN113976093A (en) * | 2021-08-24 | 2022-01-28 | 南京信息工程大学 | Nano carbon/TiO2Composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106076337A (en) * | 2016-07-14 | 2016-11-09 | 中国科学院生态环境研究中心 | A kind of composite photocatalyst material and preparation method thereof |
| CN106475083A (en) * | 2016-09-08 | 2017-03-08 | 东北大学秦皇岛分校 | The preparation method of graphene oxide/optically catalytic TiO 2 composite material precursor |
| CN107552082A (en) * | 2017-09-29 | 2018-01-09 | 河海大学 | A kind of quaternary multifunction magnetic nano composite material and preparation method thereof |
| CN108993540A (en) * | 2018-09-03 | 2018-12-14 | 天津工业大学 | A kind of novel photocatalyst Agx-Au1-x/ZnIn2S4/rGO/TiO2The preparation method of nanotube |
| CN109954518A (en) * | 2018-11-09 | 2019-07-02 | 成都禾木源环保科技有限公司 | A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method and device |
| CN109954518B (en) * | 2018-11-09 | 2022-02-15 | 成都禾木源环保科技有限公司 | Magnetic graphene-TiO2Photochemical biological sewage treatment method and device |
| CN110127678A (en) * | 2019-05-20 | 2019-08-16 | 天津市职业大学 | A kind of preparation method of magnetic graphene |
| CN110127678B (en) * | 2019-05-20 | 2022-04-29 | 天津市职业大学 | Preparation method of magnetic graphene |
| CN110404506A (en) * | 2019-07-12 | 2019-11-05 | 中国科学院东北地理与农业生态研究所 | Magnetic oxygenated graphene/sodium titanate composite material preparation method and application |
| CN110404506B (en) * | 2019-07-12 | 2022-04-29 | 中国科学院东北地理与农业生态研究所 | Preparation method and application of magnetic graphene oxide/sodium titanate composite material |
| CN113976093A (en) * | 2021-08-24 | 2022-01-28 | 南京信息工程大学 | Nano carbon/TiO2Composite material and preparation method thereof |
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