CN106311303B - A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4And its preparation method and application - Google Patents
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4And its preparation method and application Download PDFInfo
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- CN106311303B CN106311303B CN201610582810.1A CN201610582810A CN106311303B CN 106311303 B CN106311303 B CN 106311303B CN 201610582810 A CN201610582810 A CN 201610582810A CN 106311303 B CN106311303 B CN 106311303B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 39
- 239000002636 mycotoxin Substances 0.000 claims abstract description 34
- 231100000678 Mycotoxin Toxicity 0.000 claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 31
- 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 30
- 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 30
- 229930002954 deoxynivalenol Natural products 0.000 claims description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 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
- 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
- 238000000703 high-speed centrifugation Methods 0.000 claims description 4
- 239000002356 single layer Substances 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
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 229930183344 ochratoxin Natural products 0.000 claims description 2
- 239000003008 fumonisin Substances 0.000 claims 1
- 239000010977 jade Substances 0.000 claims 1
- 241000233866 Fungi Species 0.000 abstract description 6
- 239000003053 toxin Substances 0.000 abstract description 6
- 231100000765 toxin Toxicity 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000003413 degradative effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000006303 photolysis reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 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
- 241000894006 Bacteria Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 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
- 238000013508 migration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 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
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 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
- 241000228143 Penicillium Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000082085 Verticillium <Phyllachorales> Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 231100000026 common toxicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000000227 grinding Methods 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 230000003287 optical effect Effects 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
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 208000017443 reproductive system disease Diseases 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000000527 sonication 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
- 230000002588 toxic effect Effects 0.000 description 1
- 229930013292 trichothecene Natural products 0.000 description 1
- 150000003327 trichothecene derivatives Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention discloses a kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4, it is by graphene oxide and nano-photocatalyst g-C3N4According to the ratio that mass ratio is 0.1-10:100 by having the hybrid material graphene/C of layer assembly structure made from hydrothermal synthesis method3N4；In addition, the present invention has investigated hybrid material graphene/C by the conditions such as graphene modified amount and light degradation time3N4Influence to photocatalytic degradation mycotoxin.The present invention has visible light-responded hybrid material graphene/C by hydro-thermal method preparation3N4, 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/C3N4And 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.
Class graphitic nitralloy carbon (g-C3N4), low cost, nontoxic visible light type semiconductor light-catalyst efficient as one kind,
It is widely used in the research in terms of photocatalysis degradation organic contaminant, but there are visible light utilization efficiency is not high, quantum efficiency is low etc.
Problem.Therefore, a kind of more efficient system is constructed to improve nano-photocatalyst g-C3N4Visible light activity, expand light ring
Answer range and stability particularly important.The present invention obtains a kind of photocatalytic degradation fungi poison by simple, green preparation method
The hybrid material graphene/C of element3N4, photocatalysis performance can be greatly improved.It will be expected in fungi by means of the present invention
The removing field of toxin introduces a kind of new method, facilitates the mixing together for pushing mycotoxin control and field of functional materials,
Part foundation and new approaches are provided for mycotoxin biodegrading process.
Summary of the invention
The first purpose of this invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
C3N4。
Second object of the present invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
C3N4Preparation method.
Third object of the present invention is to provide a kind of hybrid material graphene/ of photocatalytic degradation mycotoxin
C3N4Application in photocatalytic degradation mycotoxin.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4, it is by graphene oxide and nanometer light
Catalyst g-C3N4According to the ratio that mass ratio is 0.1-10:100 by having layer assembly structure made from hydrothermal synthesis method
Hybrid material graphene/C3N4。
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4Preparation 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 nano-photocatalyst g-C of single or multi-layer structure3N4It is mixed, so
The 4th ultrasonic treatment is carried out afterwards, obtains mixture；Graphene oxide and nano-photocatalyst g-C in the mixture3N4Quality
Than for 0.1-10:100 (such as: 0.1:100,0.3:100,3.0:100,5.0:100,8.0:100 or 10.0:100 etc.).
3) mixture is subjected to hydro-thermal reaction, obtains hybrid material graphene/C after reaction3N4。
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, nano-photocatalyst g-C can be made by referring to3N4Form the nanometer sheet of uniform single or multi-layer structure；
Further, after hydro-thermal reaction, graphene oxide is reduced to graphene.
Graphene oxide and nano-photocatalyst g-C is added by adjusting in the present invention3N4Mass ratio, to adjust hydridization
Material graphene/C3N4The 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；Single layer nano-photocatalyst g-C3N4With a thickness of
0.325nm。
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, by graphene oxide and nano-photocatalyst g-C3N4Into
The removing of row layer structure forms the graphene oxide and nano-photocatalyst g-C of single or multi-layer structure3N4, then pass through water
Thermal method carries out structure layer by layer and assembles, to be prepared into the hybrid material graphene/C with layer assembly structure3N4。
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4In 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/C of photocatalytic degradation mycotoxin3N4In photocatalytic degradation fungi poison
Application in element, it is realized by the following method:
1) by the hybrid material graphene/C3N4It is added in mycotoxin sample, is ultrasonically treated 0.5-1h, then stir
0.5-1h is mixed, 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 photodegradative 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, by means of the present invention respectively by graphene oxide and nano-photocatalyst g-C3N4Carry out the stripping of layer structure
From forming the graphene oxide and nano-photocatalyst g-C of single or multi-layer structure3N4, to be prepared into layer assembly knot
The hybrid material graphene/C of structure3N4。
2, the present invention has visible light-responded hybrid material graphene/C by hydro-thermal method preparation3N4, simple process,
It is suitable for industrial mass production, and photocatalysis technology is applied to degradative fungi toxin field with before very high application
Scape 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) scanning electron microscope (SEM) figure for being GC0.3；(b) transmission electron microscope (TEM) figure for being GC0.3.
Fig. 2 is GC3.0, GC0.1, nano-photocatalyst g-C3N4Scheme with the FTIR of graphene oxide (GO).
Fig. 3 is nano-photocatalyst g-C under conditions of visible wavelength λ >=420nm3N4, pure photodissociation
(Photolysis), the rate constant bar chart of ZnO and GC0.3 photocatalytic degradation deoxynivalenol.
Fig. 4 is the height of GC0.3 photocatalytic degradation deoxynivalenol when the light degradation time is extended to 300min
Imitate liquid phase 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 dicyandiamide, sodium nitrate, the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide, hydrochloric acid, acetonitrile, methanol etc. be commercially available point
The standard items pure, target degradation product mycotoxin is bought for Sigma company are analysed, 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 10
μL；UV detector, Detection wavelength 218nm.
Embodiment 1
1) nano-photocatalyst g-C3N4Preparation
The dicyandiamide solid powder of 2g is ground into uniformly tiny powder, is then placed in the crucible of 50mL；By institute
It states crucible to be placed in Muffle furnace, the Muffle furnace is then warming up to 550 DEG C with 2.3 DEG C/min speed；The horse of crucible will be housed
Not furnace calcination reaction 4h under conditions of 550 DEG C, carries out Temperature fall after reaction, obtains flaxen solid；It will be described light
The solid of yellow carries out grinding to obtain loose powder, and the loose powder is nano-photocatalyst g-C3N4。
2) hybrid material graphene/C3N4Preparation
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 3) is 2mg/mL in the graphene oxide dispersion of single or multi-layer structure and the nanometer of 13g by 20mL concentration
Photochemical catalyst g-C3N4It is mixed, stirring is to can't see big blocky nano-photocatalyst g-C3N4, then carry out the 4th time
Ultrasonic treatment, makes nano-photocatalyst g-C3N4Form the nanometer sheet of uniform single or multi-layer structure；By the mixture in
180 DEG C of progress hydro-thermal reaction 6h carry out Temperature fall after reef knot beam, obtain the solid powder of dark yellow, the solid of the dark yellow
Powder is hybrid material graphene/C3N4, i.e. (" 0.3 " in GC0.3 refers to the graphene oxide and nanometer of addition to GC0.3
Photochemical catalyst g-C3N4Mass ratio be 0.3:100).
In conjunction with Fig. 1 it is found that the micro details of (a) are shown, the nano-photocatalyst g-C of lamellar structure3N4With lamellar structure
Graphene forms the effect of layer assembly, corresponding with the pattern details of GC0.3 of (b) reflection, and the photocatalysis for being GC0.3 is dropped
Solve the advantage of performance provided in structure.
Embodiment 2
Except by " the nano-photocatalyst g-C of 13g in 1 step 3) of embodiment3N4" it is changed to " the nano-photocatalyst of 0.5g
g-C3N4", it obtains except GC8.0, other modes same as Example 1 prepare hybrid material graphene/C3N4。
Embodiment 3
Except by " the nano-photocatalyst g-C of 13g in 1 step 3) of embodiment3N4" it is changed to " the nano-photocatalyst of 40g
g-C3N4", it obtains except GC0.1；Other modes same as Example 1 prepare hybrid material graphene/C3N4。
Embodiment 4
Except by " the nano-photocatalyst g-C of 13g in 1 step 3) of embodiment3N4" it is changed to " the nano-photocatalyst of 1.3g
g-C3N4", it obtains except GC3.0, other modes same as Example 1 prepare hybrid material graphene/C3N4。
In conjunction with as shown in Figure 2, the characteristic absorption peak of GC3.0 and GC0.1 are still with nano-photocatalyst g-C3N4The spy of functional group
It levies based on absorption peak, it may be possible to due to nano-photocatalyst g-C3N4Functional group it is abundant and vibration is stronger, mask graphene
Partial vibration, so could not obviously reflect the characteristic absorption peak of graphene from FTIR spectrogram.But in wave number 1580cm-1Place
Skeletal vibration peak corresponding to graphene sheet layer structure；In wave number 1235cm-1And 1319cm-1Place is the surface hydridization of graphene
The characteristic absorption peak for acting on the C-NH-C formed, in wave number 1313cm-1Place is C (sp2)-N stretching vibration at chemical bond vibration
It is dynamic, as a result illustrate, graphene and nano-photocatalyst g-C3N4Between the interaction of chemical bond has occurred, form more extensively
Conjugated system.
Embodiment 5
Except by " the nano-photocatalyst g-C of 13g in 1 step 3) of embodiment3N4" it is changed to " the nano-photocatalyst of 0.8g
g-C3N4", it obtains except GC5.0, other modes same as Example 1 prepare hybrid material graphene/C3N4。
Embodiment 6
Except by " the nano-photocatalyst g-C of 13g in 1 step 3) of embodiment3N4" it is changed to " the nano-photocatalyst of 0.4g
g-C3N4", it obtains except GC10, other modes same as Example 1 prepare hybrid material graphene/C3N4。
7 hybrid material graphene/C of embodiment3N4Photocatalytic degradation deoxynivalenol (DON)
Experimental group: 1) GC0.3 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 GC0.3 is made to reach adsorption equilibrium, obtains the first mixed liquor；
2) using first mixed liquid concentration as initial concentration, then using wavelength X >=420nm visible 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.
Control group 1: except by " the hybrid material graphene/C in experimental group3N4" change " nano-photocatalyst g-C into3N4",
Except, other modes identical with experimental group carry out.
Control group 2: except by " the hybrid material graphene/C in experimental group3N4" change into except " ZnO ", it is other with reality
The identical mode of group is tested to carry out.
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 >=420nm visible 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.
Reaction rate constant is bigger, hybrid material graphene/C3N4Photocatalytic degradation deoxynivalenol
(DON) activity is bigger.In conjunction with Fig. 3 it is found that above-mentioned experimental group, control group 1, control group 2 and blank group photocatalytic degradation deoxidation
The sequence of the rate constant of nivalenol follows: GC0.3 > ZnO > Photolysis > g-C3N4；GC0.3 wavelength X >=
Under the visible light of 420nm, the activity of photocatalytic degradation deoxynivalenol is best, the degradation rate constant of GC0.3
For 0.0095min-1, it is 10.0 times of pure photolysis；Show that the appropriate hydridization of graphene can promote photochemical catalyst g-C3N4
The migration and separating rate of electrons and holes, to improve hybrid material graphene/C3N4Visible light photocatalytic degradation deoxidation snow
The ability of rotten sickle-like bacteria enol.
The different hybrid material graphene/C of embodiment 83N4Photocatalytic degradation deoxynivalenol (DON)
1) by the hybrid material graphene/C of 25mg3N4It 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/C3N4Reach 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.
The hybrid material graphene/C3N4For prepared in embodiment 1 to 6 GC0.3, GC8.0, GC0.1, GC3.0,
GC5.0 or GC10.0.
It is obtained by experimental verification is repeated several times, different hybrid material graphene/C3N4Photocatalytic degradation deoxynivalenol
The sequence of the rate constant of bacterium enol (DON) follows: GC0.3 > GC8.0 > GC0.1 > GC3.0 > GC5.0 > GC10.0；Work as graphite
When the additional amount of alkene is 0.3%, under wavelength X=365nm ultraviolet light, the activity of GC0.3 photocatalytic degradation DON is best,
The deoxynivalenol that concentration is 15ppm is degraded 16% in 10min, rate constants k 0.1572min-1。
Under the different illumination degrading times of embodiment 9, GC0.3 photocatalytic degradation deoxynivalenol
1) GC0.3 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 GC0.3 is made to reach adsorption equilibrium, obtains the first mixed liquor；
2) using first mixed liquid concentration as initial concentration, then using wavelength X >=420nm visible 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 different degradation times to GC0.3
The influence of photocatalytic degradation DON, is detected using high performance liquid chromatography.
The degradation time is 0min, 5min, 10min, 15min, 30min, 60min, 120min, 180min, 240min
And 300min.
In conjunction with Fig. 4 it is found that GC0.3 has apparent degradation effect to DON, and at 1.80min, with the light degradation time
Extension, intermediate product peak appearance the phenomenon that gradually enhancing of GC0.3 photocatalytic degradation DON, DON is observed at 7.49min
The process that the main peak area of intermediate product is obviously reduced, when the light degradation time extending to 180min, DON degradation rate reaches
30% or so, as the light degradation time is when extending to 300min, DON degradation rate has been finally reached 56%, the results showed that, graphite
The surface hydridization of alkene can significantly improve g-C3N4The activity of Visible Light Induced Photocatalytic mycotoxin.
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 (9)
1. a kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4, which is characterized in that the hybrid material
graphene/C3N4It is to be combined by ultrasonic treatment and centrifugal treating, by graphene oxide and nano-photocatalyst g-C3N4
The removing for carrying out layer structure, forms the graphene oxide and nano-photocatalyst g-C of single or multi-layer structure3N4Afterwards, then
It carries out structure layer by layer by hydro-thermal method to assemble, so that the hybrid material graphene/ with layer assembly structure be prepared
C3N4；
Wherein, graphene oxide and nano-photocatalyst g-C3N4Mass ratio is 0.1-10:100；
The multilayer refers to the multilayer within five layers be made of single layer.
2. a kind of hybrid material graphene/C as described in claim 13N4Preparation method, which is characterized in that including as follows
Step:
1) graphene oxide dispersion is first subjected to first time ultrasonic treatment, graphene oxide dispersion is made to form uniform dispersion
Liquid；Then low-speed centrifugal processing is carried out, sub-cloud aggregation is removed after centrifugal treating, obtains upper solution；By the upper solution into
Second of ultrasonic treatment of row, removes graphene oxide in the upper solution, then carries out high speed centrifugation processing again, from
The unstripped graphene oxide in upper layer is removed after heart processing, obtains the graphene oxide of removing；The graphene oxide of removing is dispersed
In deionized water, continues third time and be ultrasonically treated, keep the graphene oxide of removing evenly dispersed in deionized water, and
It is removed again, obtains the graphene oxide dispersion in single or multi-layer structure；
It 2) will be in the graphene oxide dispersion and nano-photocatalyst g-C of single or multi-layer structure3N4Be mixed, then into
The 4th ultrasonic treatment of row makes nano-photocatalyst g-C3N4The nanometer sheet for forming uniform single or multi-layer structure, obtains mixture；
Graphene oxide and nano-photocatalyst g-C in the mixture3N4Mass ratio be 0.1-10:100；
3) mixture is subjected to hydro-thermal reaction, obtains hybrid material graphene/ C after reaction3N4；
Wherein, the revolving speed of the low-speed centrifugal processing is 2000-5000 r/min；The revolving speed of high speed centrifugation processing is
8000-20000 r/min。
3. preparation method according to claim 2, which is characterized in that the concentration of the graphene oxide dispersion is 0.1-
10 mg/mL 。
4. preparation method according to claim 2, 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.
5. a kind of hybrid material graphene/ C of photocatalytic degradation mycotoxin as described in claim 13N4Application, it is special
Sign is, its application in photocatalytic degradation mycotoxin.
6. application according to claim 5, which is characterized in that the mycotoxin is deoxynivalenol, jade
Zearlenone, aflatoxin, fumonisin, ochratoxin or T-2 toxin.
7. application according to claim 5 or 6, which is characterized in that it is realized by the following method:
1) by the hybrid material graphene/C3N4It 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.
8. application according to claim 7, which is characterized in that light degradation is shone using the light source of 1000 nm of wavelength X <
It penetrates；The photodegradative time is 120-300 min.
9. application according to claim 7, which is characterized in that the concentration of mycotoxin in the mycotoxin sample >=
0.1μg/kg。
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