CN104128183B - Nanoscale magnetic graphene composite material for efficient degradation of microcystic toxins and preparation and application thereof - Google Patents
Nanoscale magnetic graphene composite material for efficient degradation of microcystic toxins and preparation and application thereof Download PDFInfo
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- CN104128183B CN104128183B CN201410305227.7A CN201410305227A CN104128183B CN 104128183 B CN104128183 B CN 104128183B CN 201410305227 A CN201410305227 A CN 201410305227A CN 104128183 B CN104128183 B CN 104128183B
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Abstract
The invention discloses a nanoscale magnetic graphene composite material and preparation and application thereof, and belongs to the technical field of nanotechnology and photocatalytic technology; the nanoscale magnetic graphene composite material is applied to adsorption and photocatalytic degradation of microcystic toxins in water. The preparation method is as follows: 1, mixing an ethylene glycol solution dissolved with graphene oxide with ethylenediamine or ethylene glycol dissolved with sodium acetate and ferric chloride hexahydrate for high temperature hydrothermal reaction to prepare magnetic graphene; and 2, dispersing the in obtained magnetic graphene in an ethanol water solution, heating, adjusting pH, and adding into butyl titanate to obtain a composite precursor; and 3, calcining at high temperature to obtain TiO2-graphene @ Fe3O4 magnetic composite material. The composite material is prepared by compounding anatase titanium dioxide and the magnetic graphene, compared with a traditional titanium dioxide photocatalyst, the composite material has larger specific surface area, has high photocatalytic activity and good adsorption properties on objects, has the advantages of convenient separation and repeated use, and has great significance in the application of the aspects of natural light catalytic degradation of pollutants in water.
Description
Technical field:
The present invention relates to a kind of novel nanocomposite materials tio2-graphene@fe3o4And preparation method thereof, and in fall
The application of Microcystin aspect in Xie Shui, belongs to field of nanometer technology and photocatalysis technology field.
Background technology:
Microcystin (mcs) is one group of monocyclic heptapeptide compound, is most common and toxicity is the strongest with mc-lr.Due to it
To liver kidney and other organs toxicity and strong carcinogenicity, Microcystin has been considered as seriously threatening wild animals and plants and the mankind to be good for
The environmental contaminants of health simultaneously receive significant attention, and some countries existing have promulgated the associated safety mark of Algae toxins content in water body
Accurate.The method being presently used for degraded Microcystins in Water mainly has membrane filtration, charcoal absorption, ultraviolet irradiation, ultrasonic wave
Effect, redox, the physics such as strains for degrading, chemistry, biological treating measure.But still there is many defects in them, such as condition
Harshness, has side effect, and degradation efficiency is low even to cause secondary pollution it is difficult to recycle.Therefore, photocatalytic degradation is high with it
The features such as effect, green is considered as a kind of water purification technology with application prospect.
In numerous semiconductor light-catalysts, titanium dioxide is due to stable chemical nature, nontoxic, wide to organic matter application
General, greatly paid attention to the advantages of cheap, but the limitation due to itself, hinder the raising of photocatalysis performance.
Graphene is the Two-dimensional Carbon nanometer low-dimensional materials finding in 2004, and a lot of researchs show tio2It is combined with Graphene, can be with
By means of Graphene and tio2The synergy producing reduces photo-generate electron-hole to recombination probability, expands photoresponse scope, and by
In the characterization of adsorption to object for the Graphene, can further improve photocatalysis efficiency.But magnetic material is combined with titanium dioxide to be made
Not yet there is report for photocatalytic applications.
Magnetic graphene is to be embedded with magnetic nanoparticle fe using what solvent-thermal method simply synthesized3o4Graphene composite wood
Material, the high adsorption of Graphene and magnetic material are facilitated detached feature to combine by it, have larger specific surface area and very
Good characterization of adsorption, and there is convenient separation, recyclable nonexpondable advantage, it is that one kind has modifiable basis again
Condensation material, has a wide range of applications meaning.
Content of the invention:
It is an object of the present invention to provide a kind of titanium dioxide-magnetic graphene composite photocatalyst material (tio2-graphene@
fe3o4)；
The present invention another object is that offer titanium dioxide-magnetic graphene composite photocatalyst material (tio2-graphene@
fe3o4) degrading microcystic toxins (mc-lr) purposes.
Titanium dioxide of the present invention-magnetic graphene composite photocatalyst material (tio2-graphene@fe3o4) for not
It is dissolved in the red-brown powder of water, titanium dioxide is uniformly distributed in magnetic graphene upper and lower surface and edge, and has Detitanium-ore-type
Crystal structure, is the composite photocatalyst material that a kind of nanoscale has special crystal formation.
The preparation method of this composite photocatalyst material includes three steps:
Step one by graphene oxide all be dispersed in ethylene glycol solution, separately by sodium acetate, ferric chloride hexahydrate is dissolved in
Ethylenediamine or ethylene glycol.Mix two solution and ultrasonic uniformly after injection autoclave in, in 180-220 DEG C of pyroreaction
Obtain black solid after 10-20 hour, after being dried with ultra-pure water and absolute ethanol washing, obtain magnetic graphene.
The magnetic graphene of step one gained is distributed in 14: 1 ethanol water step 2, is heated to 60-80 DEG C,
Add the concentrated sulfuric acid to adjust ph, be then slowly added dropwise butyl titanate, continued mechanical stirring is lower to react 20-24 hour, obtains complex light and urges
Change material precursor.
After the washing of step 2 gained composite photocatalyst material precursor is dried by step 3, it is transferred in Muffle furnace, 400-500
DEG C high-temperature calcination 2-4h, can get the tio of rufous2-graphene@fe3o4Composite photocatalyst material.
In the present invention, in step one, Graphene, ferric chloride hexahydrate, sodium acetate, ethylene glycol, the rate of charge of ethylenediamine are
10mg: 0.1g: 0.3g: 5ml: 1ml or 10mg: 0.1g: 0.3g: 6ml: 0ml.In step 2, every 10mg magnetic graphene adds 1ml
Butyl Phthalate.
Photocatalytic degradation application example: add the standard specimen Microcystin of 20ml500 μ g/ml in 100ml small beaker
(mc-lr) solution, adjusts ph value for 6 with 1%tfa, adds 2mg～20mg tio2-graphene@fe3o4Composite, in ultraviolet
Under light (λ=365nm) or sunlight, more than 99% is reached to mc-lr degraded.
Solution mc-lr concentration high performance liquid chromatography tracking and measuring during light degradation:
High performance liquid chromatograph is measured using agilent1260hplc.Detection wavelength 238nm.Using anti-phase c18Post
(waters, 150mm × 4.6mm, 5 μm of particle diameters) carry out separating, 40 DEG C of column temperature.Mobile phase is 65: 35 0.1%tfa methanol solutions
With the 0.1%tfa aqueous solution, flow velocity 0.8ml/min.Sample size 50 μ l.
Use tio of the present invention2-graphene@fe3o4After composite photocatalytic degradation mc-lr, by externally-applied magnetic field to anti-
Separation of solid and liquid should be carried out by rear solution, reclaim catalysis material, after multiple washing and separating and dry, can repeatedly carry out to micro-
The photocatalytic degradation of capsule Algae toxins.
With the made titanium dioxide of the present invention-magnetic graphene composite photocatalyst material, can be to micro- in nature river
Capsule Algae toxins are adsorbed and photocatalytic degradation, and also have a certain degree of absorption to other pollutants, will not be subject to cloudy in water
The impact of the impurity such as ion and organic matter.
The purposes of described titanium dioxide-magnetic graphene composite photocatalyst material, for microcystin in water body of degrading
Element.Compared with anatase titanium dioxide pure with commercially available Degussa p25, this composite has specific surface area greatly, photocatalytic activity
Height, high adsorption capacity, the advantages of degradation rate is fast, and there is during multiple degrading microcystic good stability, side
Just separate, can reuse.
Brief description:
Magnetic graphene (a) and titanium dioxide-magnetic graphene composite photocatalyst material (b) transmission electricity in Fig. 1 embodiment 1
Sub- microphotograph.
Fig. 2 is the xrd spectrogram of titanium dioxide of the present invention-magnetic graphene composite photocatalyst material.
Fig. 3 be embodiment 1 described under the conditions of titanium dioxide-magnetic graphene composite photocatalyst material to Microcystin
Photocatalytic degradation curve, and with standard items p25tio2The comparison of degradation effect.
Fig. 4 is hysteresis curve and the Magnetic Isolation design sketch of described titanium dioxide-magnetic graphene composite photocatalyst material.
Specific embodiment:
The following examples are that the present invention is further illustrated, and the unrestricted scope of the invention.
Embodiment 1
The synthesis of titanium dioxide-magnetic graphene composite photocatalyst material:
50mg graphene oxide is dispersed in 25ml ethylene glycol solution step one, separately by 1.5g sodium acetate, 0.5g six water
Close iron chloride and be dissolved in 5ml ethylenediamine.Mix two solution and ultrasonic uniformly after injection autoclave in, anti-in 180 DEG C of high temperature
Obtain black solid after answering 16 hours, after being dried with ultra-pure water and absolute ethanol washing, obtain magnetic graphene.As Fig. 1 a, display layer
Ferroso-ferric oxide microballoon is uniformly modified on shape Graphene, particle diameter is 10-20nm.
Above-mentioned for 30mg magnetic graphene is distributed in 150ml14: 1 ethanol water step 2, is heated to 70 DEG C,
Add the 1ml concentrated sulfuric acid, be then slowly added dropwise 3ml butyl titanate, the lower reaction of continued mechanical stirring 20 hours, obtain composite photocatalyst
Material precursor.
After the washing of step 3 gained composite photocatalyst material precursor is dried, it is transferred in Muffle furnace, 450 DEG C of high-temperature calcinations
2h, can get the tio of rufous2-graphene@fe3o4Composite photocatalyst material.As Fig. 1 b, display is by titanium dioxide microballoon sphere bag
By after sheet-like magnetic Graphene.The titanium dioxide modified thereon is the crystal structure with Detitanium-ore-type, as shown in Figure 2.
Photocatalysis is tested: adds the standard specimen Microcystin (mc-lr) of 20ml500 μ g/ml molten in 100ml small beaker
Liquid, adjusts ph value for 6 with 1%tfa, adds 10mg said method gained tio2-graphene@fe3o4Composite is purple in 125w
Under outer light (λ=365nm) is irradiated, 30min is to mc-lr degraded completely.As Fig. 3, pure anatase titanium dioxide enters with commercially available p25
The characteristic of the row contrast efficient degradation to mc-lr for the visible composite catalyzing material.
Embodiment 2
The synthesis of titanium dioxide-magnetic graphene composite photocatalyst material:
50mg graphene oxide is dispersed in 25ml ethylene glycol solution step one, separately by 1.5g sodium acetate, 0.5g six water
Close iron chloride and be dissolved in 5ml ethylene glycol.Mix two solution and ultrasonic uniformly after injection autoclave in, anti-in 180 DEG C of high temperature
Obtain black solid after answering 16 hours, after being dried with ultra-pure water and absolute ethanol washing, obtain magnetic graphene.
Above-mentioned for 30mg magnetic graphene is distributed in 150ml14: 1 ethanol water step 2, is heated to 70 DEG C,
It is slowly added dropwise 3ml butyl titanate, the lower reaction of continued mechanical stirring 20 hours, obtain composite photocatalyst material precursor.
After the washing of step 3 gained composite photocatalyst material precursor is dried, it is transferred in Muffle furnace, 450 DEG C of high-temperature calcinations
2h, can get the tio of rufous2-graphene@fe3o4Composite photocatalyst material.Sheet after being coated by titanium dioxide microballoon sphere
Magnetic graphene, be inlaid with thereon 150nm about ferroso-ferric oxide microballoon.
Photocatalysis is tested: adds the standard specimen Microcystin (mc-lr) of 20ml500 μ g/ml molten in 100ml small beaker
Liquid, adjusts ph value for 6 with 1%tfa, adds 10mg said method gained tio2-graphene@fe3o4Composite is purple in 125w
Under outer light (λ=365nm) is irradiated, 50min is to mc-lr degraded completely.
Embodiment 3
Preparation method is with embodiment 1.
Photocatalysis is tested: adds the standard specimen Microcystin (mc-lr) of 20ml500 μ g/ml molten in 100ml small beaker
Liquid, adjusts ph value for 6 with 1%tfa, adds 10mg embodiment 1 gained tio2-graphene@fe3o4Composite, in 125w ultraviolet
Under light (λ=365nm) irradiates, 30min is to mc-lr degraded completely.After degraded completely, externally-applied magnetic field carries out magnetic to composite catalyst
Property separate, through the 1%tfa aqueous solution, absolute ethyl alcohol repeatedly wash separate dry after, carry out above-mentioned light-catalyzed reaction again, 40min
To mc-lr degraded completely.After material reuses ten times, still can in 50min to mc-lr degraded completely.Fig. 4 is described
The hysteresis curve of material, and its Contrast on effect after carrying out separation of solid and liquid with magnet is it is seen that material has good separation property
Matter.And composite shows high stability in being used for multiple times, verify that its surface crystal structure does not change substantially through xrd collection of illustrative plates
Become.
Embodiment 4
Preparation method is with embodiment 1.
Photocatalysis test: in 100ml small beaker add 20ml modulated ph value for 6 dissolved with 50 μ g/ml standard specimen micro-capsule
The natural river of Algae toxins (mc-lr), adds 10mg embodiment 1 gained tio2-graphene@fe3o4Composite, in the sun
Under light irradiation, 50min is to mc-lr degraded completely.Disappear from the peak of the directly visible mc-lr of hplc spectrogram, and originally exist
Some other impurity also have certain minimizing.
Claims (4)
1. a kind of titanium dioxide-magnetic graphene composite photocatalyst material, wherein titanium dioxide is uniformly distributed in magnetic graphene
The upper and lower surface of material and edge, form a kind of Nano titanium dioxide and are dispersed in the composite photocatalyst in magnetic graphene
Material, and there is anatase crystal structure it is characterised in that its preparation method is:
Step one by graphene oxide all be dispersed in ethylene glycol solution, separately by sodium acetate, ferric chloride hexahydrate is dissolved in second two
Amine or ethylene glycol, mixing two solution and ultrasonic uniformly after injection autoclave in, in 180-220 DEG C of pyroreaction 10-20
Obtain black solid after hour, after being dried with ultra-pure water and absolute ethanol washing, obtain magnetic graphene；
The magnetic graphene of step one gained is distributed in 14: 1 ethanol water step 2, is heated to 60-80 DEG C, adds
The concentrated sulfuric acid adjusts ph, is then slowly added dropwise butyl titanate, and continued mechanical stirring is lower to react 20-24 hour, obtains composite photocatalyst material
Material precursor；
After the washing of step 2 gained composite photocatalyst material precursor is dried by step 3, it is transferred in Muffle furnace, 400-500 DEG C high
Temperature calcining 2-4h, can get the tio of rufous2-graphene@fe3o4Composite photocatalyst material.
2. the preparation method of titanium dioxide-magnetic graphene composite photocatalyst material according to claim 1, its feature exists
In in step one, Graphene, ferric chloride hexahydrate, sodium acetate, ethylene glycol, the rate of charge of ethylenediamine are 10mg: 0.1g: 0.3g:
(5-6)ml∶(0-1)ml.
3. the preparation method of titanium dioxide-magnetic graphene composite photocatalyst material according to claim 1, its feature exists
In in step 2, every 10mg magnetic graphene adds 1ml Butyl Phthalate.
4. a kind of purposes of titanium dioxide as claimed in claim 1-magnetic graphene composite photocatalyst material, its feature exists
In, under conditions of natural light, Microcystin in nature river can be adsorbed and photocatalytic degradation, and adsorbable its
Its pollutant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104667929B (en) * | 2015-02-10 | 2016-11-30 | 湖南大学 | A kind of magnetic nanometer photocatalyst |
| CN106468681B (en) * | 2015-08-20 | 2018-12-04 | 同济大学 | A kind of selective light electrochemical analysis method of Microcystins in Water MC-LR |
| CN106172394B (en) * | 2016-06-28 | 2018-10-12 | 南京大学 | A kind of graphene oxide/quaternary ammoniated polyethylene imine nanometer composite material and preparation method and application |
| CN106166483B (en) * | 2016-07-22 | 2019-03-19 | 国家粮食局科学研究院 | A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2And its preparation method and application |
| CN106732356A (en) * | 2016-12-19 | 2017-05-31 | 中南林业科技大学 | A kind of preparation method and application of graphene oxide-loaded titanium dioxide coupling material |
| CN108285534A (en) * | 2018-01-09 | 2018-07-17 | 西安工业大学 | A kind of polyaniline nano-rod/graphene/Fe3O4The preparation method of absorbing material |
| CN114130397B (en) * | 2021-11-26 | 2022-10-21 | 哈尔滨工业大学（深圳） | ZnO-based heterojunction photocatalytic composite material and preparation and application thereof |
| CN114146708A (en) * | 2021-11-26 | 2022-03-08 | 哈尔滨工业大学（深圳） | Magnetic TiO2Matrix modified photocatalyst and preparation and application thereof |
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Non-Patent Citations (2)
| Title |
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| Facile preparation of graphene/Fe3O4/TiO2 multifunctional composite for highly selective and sensitive enrichment of phosphopeptides;Yulu Liang et al;《RSC Advances》;20140407;第4卷;18132-18135 * |
| Synthesis of Fe3O4-graphene-TiO2 ternary composite networks for enhanced capture of phosphopeptides;Qianhao Min et al;《Chemical Communication》;20111231;第47卷;11709-11711 * |
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