CN104128183A - 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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- CN104128183A CN104128183A CN201410305227.7A CN201410305227A CN104128183A CN 104128183 A CN104128183 A CN 104128183A CN 201410305227 A CN201410305227 A CN 201410305227A CN 104128183 A CN104128183 A CN 104128183A
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- graphite alkene
- titanium dioxide
- composite photocatalyst
- photocatalyst material
- magnetic graphite
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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 nano composite TiO
2-grapheneFe
3o
4and preparation method thereof, and the application aspect Microcystin in degradation water, belong to field of nanometer technology and photocatalysis technology field.
Background technology:
Microcystin (MCs) is one group of monocycle seven peptide compounds, with MC-LR for the most common and toxicity is the strongest.Because it is to liver kidney and other organs toxicity and strong carcinogenicity, Microcystin has been considered to the environmental contaminants of serious threat wild animals and plants and human health and has been subject to extensive concern, and more existing countries have promulgated the associated safety standard of algae content of toxins in water body.At present, the method for the Microcystins in Water of degrading mainly contains membrane filtration, charcoal absorption, ultraviolet irradiation, ul-trasonic irradiation, redox, the physics such as strains for degrading, chemistry, biological treating measure.But still there is many defects in them, as harsh in condition, there is side effect, degradation efficiency is low, is difficult to recycle even cause secondary pollution.Therefore, photocatalytic degradation is considered to a kind of water purification technology with application prospect with its feature such as efficient, green.
In numerous semiconductor light-catalysts, titanium dioxide is due to stable chemical nature, nontoxic, and organic matter is widely used, cheap etc., and advantage is subject to great attention, but due to itself limitation, has hindered the raising of photocatalysis performance.Graphene is the Two-dimensional Carbon nanometer low-dimensional materials of finding in 2004, and a lot of research shows TiO
2compound with Graphene, can rely on Graphene and TiO
2the synergy producing reduces light induced electron-hole to recombination probability, expands photoresponse scope, and due to the characterization of adsorption of Graphene to object, can further improve photocatalysis efficiency.But magnetic material and titanium dioxide are compound, as photocatalytic applications, also not yet there is report.
Magnetic graphite alkene be utilize solvent-thermal method simply synthetic be embedded with magnetic nanoparticle Fe
3o
4graphene composite material, it facilitates separated feature to combine the high adsorption of Graphene and magnetic material, there is larger specific area and good characterization of adsorption, and have convenient separated, recyclable nonexpondable advantage, be a kind of modifiable basic composite material that has, have a wide range of applications meaning.
Summary of the invention:
The object of the invention is to provide a kind of titanium dioxide-magnetic graphite alkene composite photocatalyst material (TiO
2-grapheneFe
3o
4);
Another object of the present invention is to provide titanium dioxide-magnetic graphite alkene composite photocatalyst material (TiO
2-grapheneFe
3o
4) purposes of degrading microcystic toxins (MC-LR).
Titanium dioxide-magnetic graphite alkene composite photocatalyst material (TiO of the present invention
2-grapheneFe
3o
4) be water-fast rufous powder, titanium dioxide is uniformly distributed in magnetic graphite alkene 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 comprises three steps:
Step 1 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 ultrasonic injection autoclave after evenly, after 180-220 ℃ of pyroreaction 10-20 hour, obtain black solid, with ultra-pure water and absolute ethanol washing after dry magnetic graphite alkene.
Step 2 is distributed to the magnetic graphite alkene of step 1 gained in the ethanol water of 14: 1, is heated to 60-80 ℃, adds the concentrated sulfuric acid to adjust pH, then slowly drips butyl titanate, continues to react 20-24 hour under mechanical agitation, obtains composite photocatalyst material precursor.
After step 3 is dry by step 2 gained composite photocatalyst material precursor washing, be transferred in Muffle furnace, 400-500 ℃ of high-temperature calcination 2-4h, can obtain the TiO of rufous
2-grapheneFe
3o
4composite photocatalyst material.
In the present invention, in step 1, the rate of charge of Graphene, ferric chloride hexahydrate, sodium acetate, ethylene glycol, ethylenediamine is 10mg: 0.1g: 0.3g: 5mL: 1mL or 10mg: 0.1g: 0.3g: 6mL: 0mL.In step 2, every 10mg magnetic graphite alkene adds 1mL Butyl Phthalate.
Photocatalytic degradation application example: add standard specimen Microcystin (MC-LR) solution of 20mL500 μ g/mL in 100mL small beaker, take 1%TFA adjust pH as 6, add 2mg～20mg TiO
2-grapheneFe
3o
4composite, under ultraviolet light (λ=365nm) or solar light irradiation, to MC-LR, degraded reaches more than 99%.
Solution MC-LR concentration high performance liquid chromatography tracking and measuring in light degradation process:
High performance liquid chromatograph uses Agilent1260HPLC to measure.Detect wavelength 238nm.Adopt anti-phase C
18post (Waters, 150mm * 4.6mm, 5 μ m particle diameters) carries out separation, 40 ℃ of column temperatures.Mobile phase is 65: 35 0.1%TFA methanol solutions and the 0.1%TFA aqueous solution, flow velocity 0.8mL/min.Sample size 50 μ L.
Use TiO of the present invention
2-grapheneFe
3o
4after composite photocatalytic degradation MC-LR, by externally-applied magnetic field, to reacting rear solution, carry out Separation of Solid and Liquid, reclaim catalysis material, through repeatedly washing after separated and oven dry, can repeatedly carry out the photocatalytic degradation to Microcystin.
With the made titanium dioxide-magnetic graphite alkene composite photocatalyst material of the present invention, can adsorb and photocatalytic degradation Microcystin in nature river, and other pollutants are also had to absorption to a certain degree, can not be subject to the impact of the impurity such as anion and organic matter in water.
The purposes of described titanium dioxide-magnetic graphite alkene composite photocatalyst material, for the Microcystins in Water of degrading.Compare with the pure anatase titanium dioxide of commercially available Degussa P25, it is large that this composite has specific area, and photocatalytic activity is high, high adsorption capacity, the advantage such as degradation rate is fast, and repeatedly in degrading microcystic process, there is good stability, convenient separated, can reuse.
Accompanying drawing explanation:
Magnetic graphite alkene (a) and titanium dioxide-magnetic graphite alkene composite photocatalyst material (b) transmission electron microscope photo in Fig. 1 embodiment 1.
Fig. 2 is the XRD spectra of titanium dioxide-magnetic graphite alkene composite photocatalyst material of the present invention.
Fig. 3 be described in embodiment 1 under condition titanium dioxide-magnetic graphite alkene composite photocatalyst material to Microcystin photocatalytic degradation curve, and with standard items P25TiO
2the contrast of degradation effect.
Fig. 4 is hysteresis curve and the Magnetic Isolation design sketch of described titanium dioxide-magnetic graphite alkene composite photocatalyst material.
The specific embodiment:
The following examples are to further illustrate of the present invention, and the unrestricted scope of the invention.
Embodiment 1
Synthesizing of titanium dioxide-magnetic graphite alkene composite photocatalyst material:
Step 1 is dispersed in 50mg graphene oxide in 25mL ethylene glycol solution, and separately by 1.5g sodium acetate, 0.5g ferric chloride hexahydrate is dissolved in 5mL ethylenediamine.Mix two solution ultrasonic injection autoclave after evenly, 180 ℃ of pyroreactions, after 16 hours, obtain black solid, with ultra-pure water and absolute ethanol washing after dry magnetic graphite alkene.As Fig. 1 a, show on stratiform Graphene and evenly modify tri-iron tetroxide microballoon, particle diameter is 10-20nm.
Step 2 is distributed to 150mL14 by the above-mentioned magnetic graphite alkene of 30mg: in 1 ethanol water, be heated to 70 ℃, add the 1mL concentrated sulfuric acid, then slowly drip 3mL butyl titanate, continue to react 20 hours under mechanical agitation, obtain composite photocatalyst material precursor.
After step 3 gained composite photocatalyst material precursor washing is dry, be transferred in Muffle furnace, 450 ℃ of high-temperature calcination 2h, can obtain the TiO of rufous
2-grapheneFe
3o
4composite photocatalyst material.As Fig. 1 b, show the sheet magnetic graphite alkene after being coated with by titanium dioxide microballoon sphere.The titanium dioxide of modifying on it is the crystal structure with Detitanium-ore-type, as shown in Figure 2.
Photocatalysis experiment: add standard specimen Microcystin (MC-LR) solution of 20mL500 μ g/mL in 100mL small beaker, take 1%TFA adjust pH as 6, add 10mg said method gained TiO
2-grapheneFe
3o
4composite, under 125W ultraviolet light (λ=365nm) irradiates, 30min to MC-LR degraded completely.As Fig. 3, contrast the characteristic of visible compound catalyze material to the efficient degradation of MC-LR with the pure anatase titanium dioxide of commercially available P25.
Embodiment 2
Synthesizing of titanium dioxide-magnetic graphite alkene composite photocatalyst material:
Step 1 is dispersed in 50mg graphene oxide in 25mL ethylene glycol solution, and separately by 1.5g sodium acetate, 0.5g ferric chloride hexahydrate is dissolved in 5mL ethylene glycol.Mix two solution ultrasonic injection autoclave after evenly, 180 ℃ of pyroreactions, after 16 hours, obtain black solid, with ultra-pure water and absolute ethanol washing after dry magnetic graphite alkene.
Step 2 is distributed to 150mL14 by the above-mentioned magnetic graphite alkene of 30mg: in 1 ethanol water, be heated to 70 ℃, slowly drip 3mL butyl titanate, continue to react 20 hours under mechanical agitation, obtain composite photocatalyst material precursor.
After step 3 gained composite photocatalyst material precursor washing is dry, be transferred in Muffle furnace, 450 ℃ of high-temperature calcination 2h, can obtain the TiO of rufous
2-grapheneFe
3o
4composite photocatalyst material.Sheet magnetic graphite alkene after being coated with by titanium dioxide microballoon sphere, is inlaid with the tri-iron tetroxide microballoon about 150nm on it.
Photocatalysis experiment: add standard specimen Microcystin (MC-LR) solution of 20mL500 μ g/mL in 100mL small beaker, take 1%TFA adjust pH as 6, add 10mg said method gained TiO
2-grapheneFe
3o
4composite, under 125W ultraviolet light (λ=365nm) irradiates, 50min to MC-LR degraded completely.
Embodiment 3
Preparation method is with embodiment 1.
Photocatalysis experiment: add standard specimen Microcystin (MC-LR) solution of 20mL500 μ g/mL in 100mL small beaker, take 1%TFA adjust pH as 6, add 10mg embodiment 1 gained TiO
2-grapheneFe
3o
4composite, under 125W ultraviolet light (λ=365nm) irradiates, 30min to MC-LR degraded completely.After degraded completely, externally-applied magnetic field carries out Magnetic Isolation to composite catalyst, and through the 1%TFA aqueous solution, absolute ethyl alcohol repeatedly washs after separated oven dry, again carries out above-mentioned light-catalyzed reaction, and 40min to MC-LR degraded completely.Material is reused after ten times, still can be in 50min to MC-LR degraded completely.Fig. 4 is the hysteresis curve of described material, and is carrying out the Contrast on effect after Separation of Solid and Liquid with magnet, and visible material has good separating property.And composite shows high stability in repeatedly using, through XRD collection of illustrative plates, verify that its surface crystal structure does not have to change substantially.
Embodiment 4
Preparation method is with embodiment 1.
Photocatalysis experiment: add the natural river of the 20mL standard specimen Microcystin (MC-LR) that is dissolved with 50 μ g/mL that adjust pH has been 6 in 100mL small beaker, add 10mg embodiment 1 gained TiO
2-grapheneFe
3o
4composite, under solar light irradiation, 50min to MC-LR degraded completely.From the peak of the directly visible MC-LR of HPLC spectrogram, disappear, and some other impurity that originally exist also have certain minimizing.
Claims (5)
1. titanium dioxide-magnetic graphite alkene composite photocatalyst material, it is characterized in that: titanium dioxide is uniformly distributed in upper and lower surface and the edge of magnetic graphite alkene material, form a kind of Nano titanium dioxide and be dispersed in the composite photocatalyst material in magnetic graphite alkene, and there is Detitanium-ore-type crystal structure.
2. titanium dioxide-magnetic graphite alkene composite photocatalyst material (TiO
2-grapheneFe
3o
4) preparation method, its feature is as follows:
Step 1 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 ultrasonic injection autoclave after evenly, after 180-220 ℃ of pyroreaction 10-20 hour, obtain black solid, with ultra-pure water and absolute ethanol washing after dry magnetic graphite alkene.
Step 2 is distributed to the magnetic graphite alkene of step 1 gained in the ethanol water of 14: 1, is heated to 60-80 ℃, adds the concentrated sulfuric acid to adjust pH, then slowly drips butyl titanate, continues to react 20-24 hour under mechanical agitation, obtains composite photocatalyst material precursor.
After step 3 is dry by step 2 gained composite photocatalyst material precursor washing, be transferred in Muffle furnace, 400-500 ℃ of high-temperature calcination 2-4h, can obtain the TiO of rufous
2-grapheneFe
3o
4composite photocatalyst material.
3. the preparation method of titanium dioxide-magnetic graphite alkene composite photocatalyst material according to claim 2, it is characterized in that, in step 1, the rate of charge of Graphene, ferric chloride hexahydrate, sodium acetate, ethylene glycol, ethylenediamine is 10mg: 0.1g: 0.3g: (5-6) mL: (0-1) mL.
4. the preparation method of titanium dioxide-magnetic graphite alkene composite photocatalyst material according to claim 2, is characterized in that, in step 2, every 10mg magnetic graphite alkene adds 1mL Butyl Phthalate.
5. the purposes of titanium dioxide-magnetic graphite alkene composite photocatalyst material as claimed in claim 1 or 2, it is characterized in that, under the condition of natural daylight, can adsorb and photocatalytic degradation Microcystin in nature river, and adsorbable other pollutant.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667929A (en) * | 2015-02-10 | 2015-06-03 | 湖南大学 | Magnetic nanometer photocatalyst |
| CN106166483A (en) * | 2016-07-22 | 2016-11-30 | 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 |
| CN106172394A (en) * | 2016-06-28 | 2016-12-07 | 南京大学 | A kind of graphene oxide/quaternary ammoniated polyethylene imine nanometer composite and preparation method and application |
| CN106468681A (en) * | 2015-08-20 | 2017-03-01 | 同济大学 | A kind of selective light electrochemical analysis method of Microcystins in Water MC-LR |
| 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 |
| CN114130397A (en) * | 2021-11-26 | 2022-03-04 | 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 |
-
2014
- 2014-06-27 CN CN201410305227.7A patent/CN104128183B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| QIANHAO MIN ET AL: "Synthesis of Fe3O4-graphene-TiO2 ternary composite networks for enhanced capture of phosphopeptides", 《CHEMICAL COMMUNICATION》 * |
| YULU LIANG ET AL: "Facile preparation of graphene/Fe3O4/TiO2 multifunctional composite for highly selective and sensitive enrichment of phosphopeptides", 《RSC ADVANCES》 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667929A (en) * | 2015-02-10 | 2015-06-03 | 湖南大学 | Magnetic nanometer photocatalyst |
| CN106468681A (en) * | 2015-08-20 | 2017-03-01 | 同济大学 | A kind of selective light electrochemical analysis method of Microcystins in Water MC-LR |
| 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 |
| CN106172394A (en) * | 2016-06-28 | 2016-12-07 | 南京大学 | A kind of graphene oxide/quaternary ammoniated polyethylene imine nanometer composite and preparation method and application |
| 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 |
| CN106166483A (en) * | 2016-07-22 | 2016-11-30 | 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 |
| CN114130397A (en) * | 2021-11-26 | 2022-03-04 | 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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| CN104128183B (en) | 2017-01-18 |
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