CN106166483B - A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2And its preparation method and application - Google Patents
A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2And its preparation method and application Download PDFInfo
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- CN106166483B CN106166483B CN201610582809.9A CN201610582809A CN106166483B CN 106166483 B CN106166483 B CN 106166483B CN 201610582809 A CN201610582809 A CN 201610582809A CN 106166483 B CN106166483 B CN 106166483B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 230000015556 catabolic process Effects 0.000 claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002636 mycotoxin Substances 0.000 claims abstract description 34
- 231100000678 Mycotoxin Toxicity 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000002356 single layer Substances 0.000 claims abstract description 8
- 239000003053 toxin Substances 0.000 claims abstract description 7
- 231100000765 toxin Toxicity 0.000 claims abstract description 7
- 241000233866 Fungi Species 0.000 claims abstract description 5
- LINOMUASTDIRTM-QGRHZQQGSA-N deoxynivalenol Chemical compound C([C@@]12[C@@]3(C[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 LINOMUASTDIRTM-QGRHZQQGSA-N 0.000 claims description 23
- LINOMUASTDIRTM-UHFFFAOYSA-N vomitoxin hydrate Natural products OCC12C(O)C(=O)C(C)=CC1OC1C(O)CC2(C)C11CO1 LINOMUASTDIRTM-UHFFFAOYSA-N 0.000 claims description 23
- 229930002954 deoxynivalenol Natural products 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229930195730 Aflatoxin Natural products 0.000 claims description 4
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005409 aflatoxin Substances 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 4
- BXFOFFBJRFZBQZ-QYWOHJEZSA-N T-2 toxin Chemical compound C([C@@]12[C@]3(C)[C@H](OC(C)=O)[C@@H](O)[C@H]1O[C@H]1[C@]3(COC(C)=O)C[C@@H](C(=C1)C)OC(=O)CC(C)C)O2 BXFOFFBJRFZBQZ-QYWOHJEZSA-N 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 229930183344 ochratoxin Natural products 0.000 claims description 2
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- 230000000694 effects Effects 0.000 abstract description 13
- 239000011941 photocatalyst Substances 0.000 abstract description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- MBMQEIFVQACCCH-UHFFFAOYSA-N trans-Zearalenon Natural products O=C1OC(C)CCCC(=O)CCCC=CC2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-UHFFFAOYSA-N 0.000 description 3
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 206010029155 Nephropathy toxic Diseases 0.000 description 1
- ITCSWEBPTQLQKN-UHFFFAOYSA-N Nivalenol Natural products CC1=CC2OC3C(O)C(O)C(C2(CO)CC1=O)C34CO4 ITCSWEBPTQLQKN-UHFFFAOYSA-N 0.000 description 1
- UKOTXHQERFPCBU-YQPARWETSA-N Nivalenol Chemical compound C([C@]12[C@@]3([C@H](O)[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 UKOTXHQERFPCBU-YQPARWETSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 101710157310 Tegument protein UL47 homolog Proteins 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 241000082085 Verticillium <Phyllachorales> Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 231100000026 common toxicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JKKCSFJSULZNDN-UHFFFAOYSA-N gonyautoxin v Chemical compound N=C1NC(COC(=O)NS(O)(=O)=O)C2NC(=N)NC22C(O)(O)CCN21 JKKCSFJSULZNDN-UHFFFAOYSA-N 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007694 nephrotoxicity Effects 0.000 description 1
- 231100000417 nephrotoxicity Toxicity 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- RWQKHEORZBHNRI-BMIGLBTASA-N ochratoxin A Chemical compound C([C@H](NC(=O)C1=CC(Cl)=C2C[C@H](OC(=O)C2=C1O)C)C(O)=O)C1=CC=CC=C1 RWQKHEORZBHNRI-BMIGLBTASA-N 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
- 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—
Abstract
The invention discloses a kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2, hybrid material graphene/TiO2It mainly include TiO2Nano particle and its surface coated single-layer or multi-layer graphene film, it is by graphene oxide and TiO2Nano particle is according to the ratio that mass ratio is 0.1-10:100 by made from hydrothermal synthesis method；In addition, the present invention has investigated hybrid material graphene/TiO by the conditions such as graphene modified amount and light degradation time2Influence to photocatalytic degradation mycotoxin.The present invention has the hybrid material graphene/TiO of high activity by hydro-thermal method preparation2, simple process is suitable for industrial mass production, and Photocatalyst is applied to degradative fungi toxin field has very high application prospect and practical value.
Description
Technical field
The invention belongs to analytical chemistry fields, and in particular to a kind of hybrid material of photocatalytic degradation mycotoxin
graphene/TiO2And its preparation method and application
Background technique
Mycotoxin is some fungies, and such as aspergillus, Penicillium and Fusarium, what is generated during the growth process easily causes people
It is very high to humans and animals toxicity with the secondary metabolite of animal pathological change and physiology metamorphosis.Existing 300 kinds of discovery so far true
Verticillium toxin, wherein representative mycotoxin has Trichothecenes toxin (such as DON), zearalenone (ZEN), volt
Horse toxin B1(FB1), aflatoxin (AFT), ochratoxin A (OTA) and T-2 toxin etc..Mycotoxin pollutes grain and feeding
After material, into food chain, to influence breeding performonce fo animals and health of people.Due to mycotoxin chemistry, biology and toxicity
It is varied to learn property, therefore its toxic effect difference is also very big, depends on it and take in level, exposure duration, animal species, body
Synergistic effect etc. between mycotoxin is existed simultaneously in body situation and feed or food.But its common toxicity mainly causes DNA damage
Two aspects of wound and cytotoxicity；Specifically, the effect of mycotoxin major toxicity includes carcinogenesis, genetoxic, teratogenesis
Effect, hepatotoxicity, nephrotoxicity, genital disorders and immunosupress.The method effect of existing processing mycotoxin
It is ideal not enough, it mainly include physical method, chemical method, absorption method and bioanalysis etc..Physical method detoxification is not thorough, Environmental costs
It is high；Chemical method is fast rapid, but is easy residual noxious material, influences quality；Absorption method needs to carry out desorption processing, is also easy to produce two
Secondary pollution；Biochemical method takes a long time, and cost is excessively high, and metabolite toxicity is unclear.Therefore, a kind of letter green to be developed is high
The forward position detoxification technology of effect is expected to increase substantially the abatement effect of vomitoxin, reduces treatment cost.For ensureing national grain
Food safety and human health have great importance.
Directly in-depth study has been obtained in terms of depth degradation organic pollutant using solar energy in photocatalysis technology,
It is mild with reaction condition, solar energy can be made full use of, without secondary pollution, the advantages such as processing cost is low.Currently, photocatalysis technology
Existing Main Scientific Issues are that quantum efficiency is not high and visible light activity is poor.It, must be anti-from photocatalysis more than solving the problems, such as
The essence answered considers, first is that how to further suppress the recombination probability in light induced electron and hole, improves light-catalysed quantum efficiency
Problem；Second is that how further to expand sun light absorption wave band, developing has the visible light even photocatalysis body of infrared optical response
System.In photocatalytic system, the separation of charge and the migration of photo-generated carrier are the rate determining steps of reaction, but due to the loss of heat,
The presence of the extraneous factors such as the defect of surface and body phase can be such that photoinduced electron and hole occurs compound.Therefore, it is urged to improve light
The quantum efficiency for changing reaction selects suitable method of modifying to reduce electron-hole recombination rate and become the key point of research.
TiO2It is a kind of conventional ultra-violet photosensitiveness catalyst, since forbidden bandwidth (3.2eV) is wider, wave can only be absorbed in principle
The long ultraviolet light for being shorter than 387nm, optical response range is narrow cannot be high using visible light, electron hole pair recombination rate, quantum efficiency compared with
It is low, limit TiO2Large-scale application and development of the nano particle as photochemical catalyst.Therefore to TiO2Modified by nano particles is to mention
Its high photocatalytic activity.But existing main problem includes: that quantum yield is relatively low, and spectral response range is narrow, point of photochemical catalyst
It is difficult from recycling.Therefore, a kind of more efficient system is constructed to improve TiO2The activity and stability of nano particle are especially
It is important.The present invention obtains a kind of hybrid material of photocatalytic degradation mycotoxin by simple, green preparation method
graphene/TiO2, photocatalysis performance can be greatly improved.It will be expected to the removing neck in mycotoxin by means of the present invention
Domain introduces a kind of new method, facilitates the mixing together for pushing mycotoxin control and field of functional materials, drops for mycotoxin
Solution method provides part foundation and new approaches.
Summary of the invention
The first purpose of this invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
TiO2。
Second object of the present invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
TiO2Preparation method.
Third object of the present invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
TiO2Application in photocatalytic degradation mycotoxin.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2, hybrid material graphene/TiO2
It mainly include TiO2Nano particle and its surface coated single-layer or multi-layer graphene film, it is by graphene oxide and TiO2It receives
Rice grain is according to the ratio that mass ratio is 0.1-10:100 by made from hydrothermal synthesis method.
A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2Preparation method, include the following steps:
1) graphene oxide dispersion is first subjected to first time ultrasonic treatment, then by the graphene oxide after ultrasonic treatment
Dispersion liquid carries out low-speed centrifugal processing, removes sub-cloud aggregation after centrifugal treating, obtains upper solution；The upper solution is carried out
Then upper solution after ultrasonic treatment is carried out high speed centrifugation processing, removes upper layer after centrifugal treating by second of ultrasonic treatment
Unstripped graphene oxide obtains the graphene oxide of removing；It disperses the graphene oxide after removing in deionized water, after
It is continuous to carry out third time ultrasonic treatment, obtain the graphene oxide dispersion in single or multi-layer structure；
It 2) will be in the graphene oxide dispersion and TiO of single or multi-layer structure2Nano particle is mixed, and then carries out
4th time ultrasonic treatment makes TiO2Nano particle forms uniform nano-dispersed state, obtains mixture；Stone is aoxidized in the mixture
Black alkene and TiO2The mass ratio of nano particle is 0.1-10:100；
3) mixture is subjected to hydro-thermal reaction, obtains hybrid material graphene/TiO after reaction2。
Further, the actual conditions of the first time ultrasonic treatment do not limit, and graphene oxide dispersion can be made by referring to
Form uniform dispersion liquid；The condition of second of ultrasonic treatment does not limit, and referring to can make to aoxidize in the upper solution
Graphene is removed；The condition of the third time ultrasonic treatment does not limit, and refers to that the graphene oxide after capable of making removing is equal
Even dispersion in deionized water, and removes graphene oxide after removing again；The condition of 4th ultrasonic treatment
It does not limit, TiO can be made by referring to2Nano particle forms uniform nano-dispersed state；
Further, after hydro-thermal reaction, graphene oxide is reduced to graphene.
Graphene oxide and TiO is added by adjusting in the present invention2The mass ratio of nano particle, to adjust hybrid material
graphene/TiO2The modification amount of surface graphene.
Further, the revolving speed of the low-speed centrifugal processing is 2000-5000r/min；The revolving speed of the high speed centrifugation processing
For 8000-20000r/min.
Further, the concentration of the graphene oxide solution is 0.1-10mg/mL.
Further, the temperature of the hydro-thermal reaction is 160-180 DEG C.
Further, the time of the hydro-thermal reaction be 4-10h (such as: 4,5,6,7,8,9 or 10 h).
Further, single-layer graphene oxide with a thickness of 0.78nm.
Further, the TiO2The partial size of nano particle is 10-21nm；Preferably, the TiO2The partial size of nano particle is
21nm。
Further, multilayer of the present invention refers to the multilayer within five layers and five layers be made of single layer
The present invention is combined by ultrasonic treatment and centrifugal treating, and graphene oxide is carried out to the removing of layer structure, shape
At the graphene oxide of single or multi-layer structure, then by hydro-thermal method in TiO2The stone of nano grain surface cladding layer structure
Black alkene piece, to be prepared into hybrid material graphene/TiO2。
A kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2In photocatalytic degradation mycotoxin
Using.
Further, the mycotoxin is deoxynivalenol, zearalenone, aflatoxin, volt horse
Toxin, ochratoxin or T-2 toxin.
Further, a kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2In photocatalytic degradation fungi
Application in toxin, it is realized by the following method:
1) by the hybrid material graphene/TiO2It is added in mycotoxin sample, is ultrasonically treated 0.5-1 h, then
0.5-1h is stirred, the first mixed liquor is obtained；
2) first mixed liquor is subjected to light degradation.
Further, light degradation is irradiated using the light source of wavelength X < 1000nm.
Further, the light degradation time is 120-300min.
Further, in the mycotoxin sample mycotoxin concentration >=0.1 μ g/kg.
It is further noted that if not otherwise specified, any range documented by the present invention includes end value and end value
Between any numerical value and any subrange for being constituted with any number between end value or end value.
Beneficial effects of the present invention are as follows:
1, graphene oxide is carried out to the removing of layer structure by means of the present invention, then by hydro-thermal method in TiO2
Nano grain surface coats single-layer or multi-layer graphene film, to be prepared into hybrid material graphene/TiO2。
2, the present invention has visible light-responded hybrid material graphene/TiO by hydro-thermal method preparation2, simple process,
It is suitable for industrial mass production, and Photocatalyst is applied to degradative fungi toxin field there is very high answer
With prospect and practical value.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1: (a) scheme for the SEM of GP0.3；(b) scheme for the TEM of GP0.3.
Fig. 2 is GP0.1, GP3.0, TiO2The FTIR of nano particle (P25) and graphene oxide (GO) figure.
Fig. 3 is experimental group, control group and blank group photocatalytic degradation deoxidation under conditions of ultraviolet wavelength λ=365nm
The curve graph of nivalenol.
Fig. 4 be under conditions of ultraviolet wavelength λ=365nm, GP0.1, GP0.3, GP3.0, GP5.0, GP8.0 and
The bar chart of GP10.0 photocatalytic degradation deoxynivalenol degradation rate.
Fig. 5 is the height of GP0.3 photocatalytic degradation deoxynivalenol when the light degradation time is extended to 300min
Effect liquid phase chromatogram figure.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, it should not be with this
It limits the scope of the invention.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.The present invention
Used in reactant sodium nitrate, the concentrated sulfuric acid, potassium permanganate, multi-oxygen water, hydrochloric acid, acetonitrile, methanol etc. be pure, the mesh of commercially available analysis
The standard items that degradation product mycotoxin is the purchase of Sigma company are marked, deionized water is homemade.
Using Flied emission LEO-1530 type scanning electron microscope and HITACHI HT7700 type transmission electron microscope observing graphene hydridization
The pattern of material.
The analysis of structure of functional groups, the wave of scanning are carried out using the infrared spectrometer of German 700 type of Bruker VERTEX
Number range is 4000-600cm-1, scanning resolution is set as 4cm-1。
High performance liquid chromatography detection conditioned reference national standard " deoxynivalenol in GB/T 23503-2009 food
Measurement immunoaffinity chromatography purify high performance liquid chromatography ", specific chromatographic condition can are as follows:: chromatographic column: C18 column (250mm ×
4.6mm, 5 μm, xbridge)；Mobile phase: methanol/water=20/80 (V/V)；Flow velocity 1.0mL/min；25 DEG C of column temperature；Sample volume
10μL；UV detector, Detection wavelength 218nm.
Embodiment 1
1) hybrid material graphene/TiO2Preparation
The graphene oxide solution that concentration is 5mg/mL is taken out from 4 DEG C of refrigerator, is first carried out first time ultrasonic treatment, is made
Graphene oxide dispersion forms uniform dispersion liquid；Then by the graphene oxide dispersion after ultrasonic treatment with 5000r/
The revolving speed of min carries out centrifugal treating, removes sub-cloud aggregation after centrifugal treating, obtains upper solution；The upper solution is carried out
Second of ultrasonic treatment, removes graphene oxide in the upper solution；Then by the upper solution after ultrasonic treatment
Centrifugal treating is carried out with the revolving speed of 10000r/min, the unstripped graphene oxide in upper layer is removed after centrifugal treating, obtains removing
Graphene oxide；Graphene oxide 200mg after taking removing is scattered in 100mL deionized water, continues third time ultrasound
Processing, the graphene oxide after making removing is evenly dispersed in deionized water, and shells the graphite oxide after removing again
From；Obtain the graphene oxide dispersion in single or multi-layer structure that concentration is 2mg/mL；
It 2) is 2mg/mL in the graphene oxide dispersion of single or multi-layer structure and the TiO of 13g by 20mL concentration2
Nano particle is mixed, and stirring is to can't see big bulk TiO2Then the aggregation of nano particle carries out the 4th ultrasound
Processing makes TiO2Nano particle forms uniform nano-dispersed state；By the mixture in 180 DEG C of progress hydro-thermal reaction 6h, reef knot
Temperature fall is carried out after beam, obtains linen solid powder, and the linen solid powder is hybrid material graphene/
TiO2, i.e. (" 0.3 " in GP0.3 refers to the graphene oxide and TiO of addition to GP0.32The mass ratio of nano particle is 0.3:
100)。
In conjunction with Fig. 1 it is found that the micro details of (a) are shown, TiO2Nano grain surface has coated single-layer or multi-layer graphene
Nanometer sheet, it is corresponding with the pattern details of GP0.3 of (b) reflection, it provides and finishes for the raising of the Photocatalytic Degradation Property of GP0.3
Advantage on structure.
Embodiment 2
Except by " the TiO of 13g in 1 step 3) of embodiment2Nano particle " is changed to " TiO of 0.5g2Nano particle " obtains
Except GP8.0, other modes same as Example 1 prepare hybrid material graphene/TiO2。
Embodiment 3
Except by " the TiO of 13g in 1 step 3) of embodiment2Nano particle " is changed to " TiO of 40g2Nano particle " obtains
Except GP0.1；Other modes same as Example 1 prepare hybrid material graphene/TiO2。
Embodiment 4
Except by " the TiO of 13g in 1 step 3) of embodiment2Nano particle " is changed to " TiO of 1.3g2Nano particle " obtains
Except GP3.0, other modes same as Example 1 prepare hybrid material graphene/TiO2。
Embodiment 5
Except by " the TiO of 13g in 1 step 3) of embodiment2Nano particle " is changed to " TiO of 0.8g2Nano particle " obtains
Except GP5.0, other modes same as Example 1 prepare hybrid material graphene/TiO2。
In conjunction with Fig. 2 it is found that in wave number 1734cm-1、1400cm-1、1230cm-1、1061cm-1With 1624 cm-1It is right respectively to locate
It should be in the flexible vibration of C=O deformation vibration, OH deformation vibration, the stretching vibration of C-OH, the stretching vibration of C-O-C and its ring skeleton
It is dynamic；In 1580cm-1Place corresponds to the skeletal vibration peak of graphene sheet layer structure, and the surface hydridization of graphene makes to be located at 900cm-1
Within two position 720cm-1With 675 cm-1TiO2Feature peak position, which dies down, to broaden；In addition, intensity and the position of usually characteristic peak
The intensity for corresponding to chemical bond is moved, if characteristic peak remitted its fury, illustrates the remitted its fury of chemical bond, it is on the contrary then enhance.If feature
Red shift occurs for peak, illustrates the remitted its fury of chemical bond；Conversely, if blue shift, the enhanced strength of chemical bond occur for characteristic peak；Cause
This, the surface hybridism of graphene weakens the vibration of Ti-O key, graphene and TiO2Between the mutual of chemical bond has occurred
Effect.
Embodiment 6
Except by " the TiO of 13g in 1 step 3) of embodiment2Nano particle " is changed to " nano particle of 0.4g ", obtain GP10 it
Outside, other modes same as Example 1 prepare hybrid material graphene/ TiO2。
7 hybrid material graphene/TiO of embodiment2To the shadow of photocatalytic degradation deoxynivalenol (DON)
It rings
Experimental group: 1) GP0.3 of 25mg is added in DON aqueous solution that 50mL concentration be 15ppm, is first ultrasonically treated
0.5h is stirred for 0.5h, and GP0.3 is made to reach adsorption equilibrium, obtains the first mixed liquor；
2) using first mixed liquid concentration as initial concentration, then using wavelength X=365nm ultraviolet light to described
First mixed liquor carries out light degradation 120min.It is sampled after degradation, centrifugal treating is carried out to sample, it is upper after taking centrifugation
Clear liquid is put into brown liquid phase bottle, and brown liquid phase bottle is put into 4 DEG C of refrigerators and saves backup, and is examined using high performance liquid chromatography
It surveys.
In conjunction with Fig. 3 it is found that GP0.3 is in light degradation 15min, degradation rate reaches 95%, as the light degradation time extends
When to 30min, degradation rate reaches 100%, and without the P25 of hydridization in light degradation 30min, degradation rate is only 12%.
Control group 1: except by " the hybrid material graphene/TiO in experimental group2" change " nano particle TiO into2", except,
Other modes identical with experimental group carry out, nano particle TiO2In light degradation 30min, degradation rate 12%.
Control group 2: except by " the hybrid material graphene/TiO in experimental group2" change " g-C into3N4" except, it is other with
The identical mode of experimental group carries out, g-C3N4In light degradation 30min, degradation rate is only 3%.
Control group 3: except by " the hybrid material graphene/TiO in experimental group2" change into except " ZnO ", it is other with reality
It tests the identical mode of group to carry out, for ZnO in light degradation 30min, degradation rate is only 6%.
Blank group: it takes in the DON aqueous solution that 50mL concentration is 15ppm, is first ultrasonically treated 0.5h, is stirred for 0.5h, then
Pure photodissociation (Photolysis) 120min is carried out to DON aqueous solution using wavelength X=365nm ultraviolet light.Degradation terminates laggard
Row sampling carries out centrifugal treating to sample, and the supernatant after taking centrifugation is put into brown liquid phase bottle, and brown liquid phase bottle is put into
4 DEG C of refrigerators save backup, and are detected using high performance liquid chromatography, and when light degradation 30min, degradation rate is only 45%.
The different hybrid material graphene/TiO of embodiment 82To photocatalytic degradation deoxynivalenol (DON)
It influences
1) by the hybrid material graphene/TiO of 25mg2It is added in the DON aqueous solution that 50mL concentration is 15ppm, first
It is ultrasonically treated 0.5h, 0.5h is stirred for, makes hybrid material graphene/TiO2Reach adsorption equilibrium, obtains the first mixed liquor；
2) using first mixed liquid concentration as initial concentration, then using wavelength X=365nm ultraviolet light to described
First mixed liquor carries out light degradation 120min.It is sampled after degradation, centrifugal treating is carried out to sample, it is upper after taking centrifugation
Clear liquid is put into brown liquid phase bottle, and brown liquid phase bottle is put into 4 DEG C of refrigerators and saves backup, and is examined using high performance liquid chromatography
It surveys, testing result such as Fig. 4.
The hybrid material graphene/TiO2For prepared in embodiment 1 to 6 GP0.1, GP0.3, GP3.0,
GP5.0, GP8.0 and GP10.0.
In conjunction with Fig. 4 it is found that illustrating suitable graphene modified TiO2Nano particle can promote TiO2The electronics of nano particle
With the migration and separating rate in hole, to improve the ability of Visible Light Induced Photocatalytic deoxynivalenol；When the oxygen of addition
When the mass ratio of graphite alkene and nano-photocatalyst is 0.3:100, the Photocatalytic activity of GP0.3 is best, works as light degradation
When time is to 10min, GP0.3 photocatalytic activity has reached 96.4%, when increasing to 8% with the dosage of graphene,
Apparent reduction occurs for GP8.0 Photocatalytic activity, and when ratio reaches 10%, the suction-operated of graphene increases, and makes to assist
Show to enhance the effect of GP10.0 sample removal DON with effect.It can be seen that although graphene surface hydridization has
Conducive to hybrid material graphene/TiO2The light induced electron on surface shifts, but excessive dosage will hinder TiO2Light inhale
It receives, but promotes the enhancing of suction-operated.Therefore may determine that, graphene promote separation of charge and reduce optical absorption intensity it
Between there are an equalization points.
Influence of the different light degradation times of embodiment 9 to GP0.3 photocatalytic degradation deoxynivalenol
1) GP0.3 prepared by the embodiment of 25mg 1 is added in the DON aqueous solution that 50mL concentration is 15ppm, is first surpassed
Sonication 0.5h, is stirred for 0.5h, and GP0.3 is made to reach adsorption equilibrium, obtains the first mixed liquor；
2) using first mixed liquid concentration as initial concentration, then using wavelength X=365nm ultraviolet light to described
First mixed liquor carries out light degradation, is sampled after degradation, carries out centrifugal treating to sample, the supernatant after taking centrifugation is put
Enter in brown liquid phase bottle, brown liquid phase bottle is put into 4 DEG C of refrigerators and saves backup, and then investigates the different light degradation times pair
The influence of GP0.3 photocatalytic degradation DON, is detected using high performance liquid chromatography.
The light degradation time be 0min, 5min, 10min, 15min, 30min, 60min, 120 min, 180min,
240min and 300min.
In conjunction with Fig. 5 it is found that GP0.3 is to DON significant effect under wavelength X=365nm ultraviolet light, in light degradation 15min
Interior, degradation is complete, degradation rate 100%；DON intermediate product at 1.8min gradually increases with the extension of light degradation time
Add；DON intermediate product at 5.2min when the light degradation time extends to 10min with completely disappearing.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (8)
1. a kind of hybrid material graphene/TiO of photocatalytic degradation mycotoxin2, which is characterized in that the hybrid material
graphene/TiO2It mainly include TiO2Nano particle and its surface coated single-layer or multi-layer graphene film；
The hybrid material graphene/TiO2Preparation method, include the following steps: 1) that graphene oxide dispersion is advanced
Row is ultrasonically treated for the first time, and graphene oxide dispersion is made to form uniform dispersion liquid；Then low-speed centrifugal processing, centrifugation are carried out
Sub-cloud aggregation is removed after processing, obtains upper solution；The upper solution is carried out second to be ultrasonically treated, keeps the upper layer molten
Graphene oxide is removed in liquid, then carries out high speed centrifugation processing again, the unstripped oxidation in upper layer is removed after centrifugal treating
Graphene obtains the graphene oxide of removing；It disperses the graphene oxide of removing in deionized water, it is super to continue third time
Sonication keeps the graphene oxide of removing evenly dispersed in deionized water, and is removed again, obtains in single-layer or multi-layer knot
The graphene oxide dispersion of structure；Wherein, the revolving speed of the low-speed centrifugal processing is 2000-5000 r/min；The high speed from
The revolving speed of heart processing is 8000-20000 r/min；
It 2) will be in the graphene oxide dispersion and TiO of single or multi-layer structure2Nano particle is mixed, and then carries out the 4th
Secondary ultrasonic treatment makes TiO2Nano particle forms uniform nano-dispersed state, obtains mixture；Graphene oxide in the mixture
And TiO2The mass ratio of nano particle is 0.1-10:100；
3) mixture is subjected to hydro-thermal reaction, obtains hybrid material graphene/TiO after reaction2。
2. hybrid material graphene/TiO according to claim 12, which is characterized in that the graphene oxide dispersion
Concentration be 0.1-10 mg/mL, the TiO2The partial size of nano particle is 10-21nm.
3. hybrid material graphene/TiO according to claim 12, which is characterized in that the temperature of the hydro-thermal reaction is
160-180 DEG C, the time of the hydro-thermal reaction is 4-10 h.
4. the hybrid material graphene/TiO of photocatalytic degradation mycotoxin as described in claim 12In photocatalytic degradation fungi
Application in toxin.
5. application according to claim 4, which is characterized in that the mycotoxin is deoxynivalenol, jade
Zearlenone, aflatoxin, fumonisin, ochratoxin or T-2 toxin.
6. application according to claim 4 or 5, which is characterized in that it is realized by the following method:
1) by the hybrid material graphene/TiO2It is added in mycotoxin sample, is ultrasonically treated 0.5-1 h, is stirred for
0.5-1 h obtains the first mixed liquor；
2) first mixed liquor is subjected to light degradation.
7. application according to claim 6, which is characterized in that the light degradation using 1000 nm of wavelength X < light source into
Row irradiation；The light degradation time is 120-300 min.
8. application according to claim 6, which is characterized in that the concentration of mycotoxin in the mycotoxin sample >=
0.1μg/kg。
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