CN106311303A - Hybrid material graphene/C3N4 for photocatalytically degrading fungaltoxin and preparation method and application thereof - Google Patents
Hybrid material graphene/C3N4 for photocatalytically degrading fungaltoxin and preparation method and application thereof Download PDFInfo
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- CN106311303A CN106311303A CN201610582810.1A CN201610582810A CN106311303A CN 106311303 A CN106311303 A CN 106311303A CN 201610582810 A CN201610582810 A CN 201610582810A CN 106311303 A CN106311303 A CN 106311303A
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- graphene oxide
- mycotoxin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000002636 mycotoxin Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 14
- 230000000593 degrading effect Effects 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 claims abstract description 37
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 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
- 231100000678 Mycotoxin Toxicity 0.000 claims description 27
- 230000015556 catabolic process Effects 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 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
- 238000012545 processing 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
- 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
- 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
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000007970 homogeneous dispersion Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229930183344 ochratoxin Natural products 0.000 claims description 2
- 239000003008 fumonisin Substances 0.000 claims 1
- 239000010977 jade Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 239000000126 substance Substances 0.000 description 6
- 241000233866 Fungi Species 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003053 toxin Substances 0.000 description 5
- 231100000765 toxin Toxicity 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 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
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 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 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000223218 Fusarium Species 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
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 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
- 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
- 239000007787 solid Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 2
- 241000228212 Aspergillus Species 0.000 description 1
- 241000894006 Bacteria 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000082085 Verticillium <Phyllachorales> Species 0.000 description 1
- 230000002159 abnormal effect Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 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
- 230000003413 degradative effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229960003444 immunosuppressant agent Drugs 0.000 description 1
- 230000001861 immunosuppressant effect Effects 0.000 description 1
- 239000003018 immunosuppressive agent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002207 metabolite Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 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
- 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
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hybrid material graphene/C3N4 for photocatalytically degrading fungaltoxin. The hybrid material graphene/C3N4 with a layer-layer-layer assembly structure is prepared from graphene oxide and a nanometer photocatalyst g-C3N4 according to the mass ratio being (0.1-10):100 through a hydro-thermal synthesis method. In addition, the influence of the hybrid material graphene/C3N4 on photocatalytic degradation of the fungaltoxin is inspected through the conditions of the graphene modifying amount, photodegradation time and the like. The high-activity hybrid material graphene/C3N4 with visible-light responses is prepared through the hydrothermal method, the process is simple, the hybrid material graphene/C3N4 is suitable for industrial volume production, the photocatalytic degradation technology is applied to the field of fungaltoxin degrading, and high application prospects and practical value are achieved.
Description
Technical field
The invention belongs to analytical chemistry field, be specifically related to the hybrid material of a kind of photocatalytic degradation mycotoxin
graphene/C3N4And its preparation method and application
Background technology
Mycotoxin is some funguses, and such as aspergillus, Penicillium and Fusarium, produce in growth course easily causes people
The secondary metabolite abnormal with animal pathological change and physiology is the highest to humans and animals toxicity.Find to have 300 kinds so far true
Verticillium toxin, the most representative mycotoxin has Trichothecenes toxin (such as DON), 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone (ZEN), volt
Horse toxin B1(FB1), aflatoxin (AFT), ochratoxin A (OTA) and T-2 toxin etc..Mycotoxin pollutes grain and raises
After material, enter food chain, thus affect breeding performonce fo animals and health of people.Due to mycotoxin chemistry, biology and toxicity
Character is varied, and therefore its toxic action difference is the biggest, depends on its absorption level, open-assembly time, animal species, body
There is synergism etc. between mycotoxin in body situation and feedstuff or food simultaneously.But its common toxicity mainly causes DNA damages
Wound and two aspects of cytotoxicity；Specifically, the effect of mycotoxin major toxicity includes carcinogenesis, genetoxic, teratogenesis
Effect, hepatotoxicity, nephrotoxicity, genital disorders and immunosuppressant.The method effect of existing process mycotoxin
Preferable not enough, mainly include Physical, chemical method, absorption method and bioanalysis etc..Physical detoxification is not thorough, Environmental costs
High；Chemical method is fast rapid, but easily remains noxious substance, affects quality；Absorption method needs to carry out desorption process, is easily generated two
Secondary pollution；Biochemical method is the longest, and high cost, metabolite toxicity is unclear.Therefore, letter is to be developed a kind of green 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.
Photocatalysis technology directly utilizes solar energy and has been obtained for in-depth study in terms of depth degradation organic pollution,
There is reaction condition gentle, solar energy, non-secondary pollution, the advantages such as processing cost is low can be made full use of.At present, photocatalysis technology
The Main Scientific Issues existed is that quantum efficiency is the highest and visible light activity is poor.Solve above problem, must be anti-from photocatalysis
The essence consideration answered, one is the recombination probability suppressing light induced electron and hole the most further, improves light-catalysed quantum efficiency
Problem；Two is to expand sunlight absorption bands the most further, and exploitation has the visible ray even photocatalysis body of infrared optical response
System.In photocatalysis system, the separation of electric charge and the migration of photo-generated carrier be reaction rate determining step, but due to heat loss,
The existence of the extraneous factors such as the defect of surface and body phase, can make photoinduced electron and hole occur compound.Therefore, want to improve light to urge
Change the quantum efficiency of reaction, select suitable method of modifying to become the key point of research to reduce electron-hole recombination rate.
Class graphitic nitralloy carbon (g-C3N4) as a kind of efficient, low cost, nontoxic visible light type semiconductor light-catalyst,
Being widely used in the research in terms of photocatalysis degradation organic contaminant, but it is the highest to there is visible ray utilization rate, quantum efficiency is low
Problem.Therefore, the more efficient system of one is constructed to improve nano-photocatalyst g-C3N4Visible light activity, expand light ring
Answer scope and stability particularly important.The present invention obtains a kind of photocatalytic degradation fungus poison by simple, green preparation method
The hybrid material graphene/C of element3N4, photocatalysis performance can be greatly improved.To be expected to fungus by the method for the present invention
The removing field of toxin introduces a kind of new method, contributes to promoting mycotoxin to control and the mixing together of field of functional materials,
Part foundation and new approaches is provided for mycotoxin biodegrading process.
Summary of the invention
First purpose of the present invention is to provide the hybrid material graphene/ of a kind of photocatalytic degradation mycotoxin
C3N4。
Second object of the present invention is to provide the hybrid material graphene/ of a kind of photocatalytic degradation mycotoxin
C3N4Preparation method.
Third object of the present invention is to provide the hybrid material graphene/ of a kind of photocatalytic degradation mycotoxin
C3N4Application in photocatalytic degradation mycotoxin.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4, it is by graphene oxide and nanometer light
Catalyst g-C3N4Through what hydrothermal synthesis method prepared, there is layer assembly structure according to ratio that mass ratio is 0.1-10:100
Hybrid material graphene/C3N4。
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4Preparation method, comprise the steps:
1) graphene oxide dispersion is first carried out supersound process for the first time, then by the graphene oxide after supersound process
Dispersion liquid carries out low-speed centrifugal process, removes lower floor's aggregation, obtain upper solution after centrifugal treating；Described upper solution is carried out
Supersound process for the second time, then carries out high speed centrifugation process by the upper solution after supersound process, removes upper strata after centrifugal treating
Unstripped graphene oxide, obtains the graphene oxide of stripping；Graphene oxide after peeling off is scattered in deionized water, continues
Continue and carry out third time supersound process, must be in the graphene oxide dispersion of single or multiple lift structure；
2) by the graphene oxide dispersion in single or multiple lift structure and nano-photocatalyst g-C3N4Mix and blend, so
After carry out the 4th supersound process, obtain mixture；Graphene oxide and nano-photocatalyst g-C in described mixture3N4Quality
Ratio is 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) described mixture carrying out hydro-thermal reaction, reaction obtains hybrid material graphene/C after terminating3N4。
Further, the actual conditions of described first time supersound process does not limit, and refers to make graphene oxide dispersion
Form homogeneous dispersion liquid；The condition of described second time supersound process does not limit, and refers to make to aoxidize in described upper solution
Graphene is peeled off；The condition of described third time supersound process does not limit, and refers to the graphene oxide after making stripping equal
Even dispersion in deionized water, and makes stripping rear oxidation Graphene again peel off；The condition of described 4th supersound process
Do not limit, refer to make nano-photocatalyst g-C3N4Form the nanometer sheet of homogeneous single or multiple lift structure；
Further, after hydro-thermal reaction, graphene oxide is reduced to Graphene.
The present invention adds graphene oxide and nano-photocatalyst g-C by regulation3N4Mass ratio, thus regulate hydridization
Material graphene/C3N4The modification amount of surface Graphene.
Further, the rotating speed that described low-speed centrifugal processes is 2000-5000r/min；The rotating speed that described high speed centrifugation processes
For 8000-20000r/min.
Further, the concentration of described graphene oxide solution is 0.1-10mg/mL.
Further, the temperature of described hydro-thermal reaction is 160-180 DEG C.
Further, the time of described hydro-thermal reaction is 4-10h (such as: 4,5,6,7,8,9 or 10h).
Further, the thickness of single-layer graphene oxide is 0.78nm；Monolayer nano-photocatalyst g-C3N4Thickness be
0.325nm。
Further, the multilamellar within multilamellar of the present invention refer to be made up of monolayer five layers and five layers.
The present invention is combined by supersound process and centrifugal treating, by graphene oxide and nano-photocatalyst g-C3N4Enter
The stripping of row layer structure, forms graphene oxide and the nano-photocatalyst g-C of single or multiple lift structure3N4, then pass through water
Full-boiled process carries out structure layer by layer and assembles, thus is prepared as the hybrid material graphene/C with layer assembly structure3N4。
A kind of hybrid material graphene/C of photocatalytic degradation mycotoxin3N4In photocatalytic degradation mycotoxin
Application.
Further, described mycotoxin is deoxynivalenol, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone, aflatoxin, volt horse
Toxin, ochratoxin or T-2 toxin.
Further, the hybrid material graphene/C of a kind of photocatalytic degradation mycotoxin3N4At photocatalytic degradation fungus poison
Application in element, it realizes by the following method:
1) by described hybrid material graphene/C3N4Join in mycotoxin sample, supersound process 0.5-1h, then stir
Mix 0.5-1h, obtain the first mixed liquor；
2) described first mixed liquor is carried out light degradation.
Further, light degradation uses the light source of wavelength X ＜ 1000nm to be irradiated.
Further, the described photodegradative time is 120-300min.
Further, the concentration >=0.1 μ g/kg of mycotoxin in described mycotoxin sample.
It is further noted that, if not otherwise specified, any scope described in the present invention includes end value and end value
Between any numerical value and the anyon scope that constituted with any number between end value or end value.
Beneficial effects of the present invention is as follows:
1, by the method for the present invention respectively by graphene oxide and nano-photocatalyst g-C3N4Carry out the stripping of layer structure
From, form graphene oxide and the nano-photocatalyst g-C of single or multiple lift structure3N4, thus it is prepared as that there is 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, technique is simple,
It is suitable for industrialized mass, and photocatalysis technology is applied to before degradative fungi toxin field has the highest application
Scape and practical value.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1: (a) is scanning electron microscope (SEM) figure of GC0.3；B () is transmission electron microscope (TEM) figure of GC0.3.
Fig. 2 is GC3.0, GC0.1, nano-photocatalyst g-C3N4Scheme with the FTIR of graphene oxide (GO).
Fig. 3 is under conditions of visible wavelength λ >=420nm, nano-photocatalyst g-C3N4, pure photodissociation
(Photolysis), the speed constant bar diagram of ZnO and GC0.3 photocatalytic degradation deoxynivalenol.
When Fig. 4 is by light degradation time lengthening to 300min, the height of GC0.3 photocatalytic degradation deoxynivalenol
Effect liquid phase figure.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is done further
Bright.It will be appreciated by those skilled in the art that following specifically described content is illustrative and be not restrictive, should be with this
Limit the scope of the invention.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.The present invention
The reactant dicyandiamide of middle use, sodium nitrate, concentrated sulphuric acid, potassium permanganate, hydrogen peroxide, hydrochloric acid, acetonitrile, methanol etc. are commercially available point
Analysing pure, target degradation product mycotoxin is the standard substance that Sigma company buys, and deionized water is homemade.
Use Flied emission LEO-1530 type scanning electron microscope and HITACHI HT7700 type transmission electron microscope observing Graphene hydridization
The pattern of material.
The infrared spectrometer using Germany's Bruker VERTEX 700 type carries out the analysis of structure of functional groups, the ripple of scanning
Number scope is 4000-600cm-1, scanning resolution is set to 4cm-1。
High performance liquid chromatography testing conditions is with reference to GB " deoxynivalenol in GB/T 23503-2009 food
Mensuration immunoaffinity chromatography purify high performance liquid chromatography ", concrete chromatographic condition can be: chromatographic column: C18 post (250mm ×
4.6mm, 5 μm, xbridge)；Flowing phase: methanol/water=20/80 (V/V)；Flow velocity 1.0mL/min；Column temperature 25 DEG C；Sample size 10
μL；UV-detector, detects wavelength 218nm.
Embodiment 1
1) nano-photocatalyst g-C3N4Preparation
The dicyandiamide pressed powder of 2g is ground to form the most tiny powder, is then placed in the crucible of 50mL；By institute
State crucible to be placed in Muffle furnace, then described Muffle furnace is warming up to 550 DEG C with 2.3 DEG C/min speed；Will be equipped with the horse of crucible
Not stove calcination reaction 4h under conditions of 550 DEG C, reaction carries out Temperature fall after terminating, obtains flaxen solid；By described light
The solid of yellow is ground obtaining loose powder, and described loose powder is nano-photocatalyst g-C3N4。
2) hybrid material graphene/C3N4Preparation
Taking out concentration from the refrigerator of 4 DEG C is the graphene oxide solution of 5mg/mL, first carries out supersound process for the first time, makes
Graphene oxide dispersion forms homogeneous dispersion liquid；Then by the graphene oxide dispersion after supersound process with 5000r/
The rotating speed of min is centrifuged processing, and removes lower floor's aggregation, obtain upper solution after centrifugal treating；Described upper solution is carried out
Supersound process for the second time, makes graphene oxide in described upper solution peel off；Then by the upper solution after supersound process
It is centrifuged processing with the rotating speed of 10000r/min, removes the graphene oxide that upper strata is unstripped after centrifugal treating, obtain stripping
Graphene oxide；Take the graphene oxide 200mg after stripping to be scattered in 100mL deionized water, proceed third time ultrasonic
Process, make the graphene oxide after stripping dispersed in deionized water, and make the graphite oxide after stripping again shell
From；Obtain the graphene oxide dispersion in single or multiple lift structure that concentration is 2mg/mL.
3) by the graphene oxide dispersion in single or multiple lift structure that 20mL concentration is 2mg/mL and the nanometer light of 13g
Catalyst g-C3N4Carrying out mix and blend, stirring to can't see big block nano-photocatalyst g-C3N4, then carry out the 4th time and surpass
Sonication, makes nano-photocatalyst g-C3N4Form the nanometer sheet of homogeneous single or multiple lift structure；By described mixture in 180
DEG C carry out hydro-thermal reaction 6h, carry out Temperature fall after reef knot bundle, obtain luteotestaceous pressed powder, described luteotestaceous pressed powder
For hybrid material graphene/C3N4, i.e. (" 0.3 " in GC0.3 refers to graphene oxide and the nano-photo catalytic added to GC0.3
Agent g-C3N4Mass ratio be 0.3:100).
Understanding in conjunction with Fig. 1, the micro details of (a) shows, the nano-photocatalyst g-C of lamellar structure3N4With lamellar structure
Graphene defines the effect of layer assembly, and the pattern details of the GC0.3 reflected with (b) is corresponding, and the photocatalysis for GC0.3 is dropped
The raising solving performance provides the advantage in structure.
Embodiment 2
Except by embodiment 1 step 3) in " the nano-photocatalyst g-C of 13g3N4" make " nano-photocatalyst of 0.5g into
g-C3N4", obtain outside GC8.0, other mode the most same as in Example 1 prepares hybrid material graphene/C3N4。
Embodiment 3
Except by embodiment 1 step 3) in " the nano-photocatalyst g-C of 13g3N4" make " the nano-photocatalyst g-of 40g into
C3N4", obtain outside GC0.1；Other mode the most same as in Example 1 prepares hybrid material graphene/C3N4。
Embodiment 4
Except by embodiment 1 step 3) in " the nano-photocatalyst g-C of 13g3N4" make " nano-photocatalyst of 1.3g into
g-C3N4", obtain outside GC3.0, other mode the most same as in Example 1 prepares hybrid material graphene/C3N4。
In conjunction with as shown in Figure 2, the characteristic absorption peak of GC3.0 and GC0.1 is still with nano-photocatalyst g-C3N4The spy of functional group
It is main for levying absworption peak, it may be possible to due to nano-photocatalyst g-C3N4Functional group abundant and vibration is relatively strong, mask Graphene
Partial vibration, so could not substantially reflect the characteristic absorption peak of Graphene from FTIR spectrogram.But, in wave number 1580cm-1Place
Skeletal vibration peak corresponding to graphene film Rotating fields；In wave number 1235cm-1And 1319cm-1Place is the surface hydridization of Graphene
The characteristic absorption peak of the C-NH-C that effect is formed, in wave number 1313cm-1Place is C (sp2)-N stretching vibration at chemical bond shake
Dynamic, result illustrates, Graphene and nano-photocatalyst g-C3N4Between there occurs the interaction of chemical bond, define more extensive
Conjugated system.
Embodiment 5
Except by embodiment 1 step 3) in " the nano-photocatalyst g-C of 13g3N4" make " nano-photocatalyst of 0.8g into
g-C3N4", obtain outside GC5.0, other mode the most same as in Example 1 prepares hybrid material graphene/C3N4。
Embodiment 6
Except by embodiment 1 step 3) in " the nano-photocatalyst g-C of 13g3N4" make " nano-photocatalyst of 0.4g into
g-C3N4", obtain outside GC10, other mode the most same as in Example 1 prepares hybrid material graphene/C3N4。
Embodiment 7 hybrid material graphene/C3N4Photocatalytic degradation deoxynivalenol (DON)
Experimental group: 1) GC0.3 of 25mg is joined in the DON aqueous solution that 50mL concentration is 15ppm, first supersound process
0.5h, is stirred for 0.5h, makes GC0.3 reach adsorption equilibrium, obtains the first mixed liquor；
2) using described first mixed liquid concentration as initial concentration, then utilize the visible ray of wavelength X >=420nm to described
First mixed liquor carries out light degradation 120min.Degraded is sampled after terminating, and is centrifuged sample processing, take centrifugal after upper
Clear liquid is put in brown liquid phase bottle, and it is standby that 4 DEG C of Refrigerator stores put into by brown liquid phase bottle, uses high performance liquid chromatography to examine
Survey.
Matched group 1: except by " the hybrid material graphene/C in experimental group3N4" change " nano-photocatalyst g-C into3N4",
Outside, other all identical with experimental group mode is carried out.
Matched group 2: except by " the hybrid material graphene/C in experimental group3N4" change into outside " ZnO ", other is all with real
Test the identical mode of group to carry out.
Blank group: take in the DON aqueous solution that 50mL concentration is 15ppm, first supersound process 0.5h, it is stirred for 0.5h, then
The visible ray utilizing wavelength X >=420nm carries out pure photodissociation (Photolysis) 120min to DON aqueous solution.Degraded terminates laggard
Row sampling, is centrifuged sample processing, and takes the supernatant after being centrifuged and puts in brown liquid phase bottle, and brown liquid phase bottle is put into
4 DEG C of Refrigerator stores are standby, use high performance liquid chromatography to detect.
Reaction rate constant is the biggest, hybrid material graphene/C3N4Photocatalytic degradation deoxynivalenol
(DON) activity is the biggest.Understand in conjunction with Fig. 3, above-mentioned experimental group, matched group 1, matched group 2 and the photocatalytic degradation deoxidation of blank group
The order of the speed constant of nivalenol is followed: GC0.3 > ZnO > Photolysis > g-C3N4；GC0.3 wavelength X >=
Under the visible ray of 420nm, the activity of its 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 photocatalyst g-C3N4
Electronics and the migration in hole and separating rate, thus improve hybrid material graphene/C3N4Visible light photocatalytic degradation deoxidation snow
The ability of rotten Fusarium spp. enol.
The different hybrid material graphene/C of embodiment 83N4Photocatalytic degradation deoxynivalenol (DON)
1) by the hybrid material graphene/C of 25mg3N4Join in the DON aqueous solution that 50mL concentration is 15ppm, first surpass
Sonication 0.5h, is stirred for 0.5h, makes hybrid material graphene/C3N4Reach adsorption equilibrium, obtain the first mixed liquor；
2) using described first mixed liquid concentration as initial concentration, then utilize the ultraviolet light of wavelength X=365nm to described
First mixed liquor carries out light degradation 120min.Degraded is sampled after terminating, and is centrifuged sample processing, take centrifugal after upper
Clear liquid is put in brown liquid phase bottle, and it is standby that 4 DEG C of Refrigerator stores put into by brown liquid phase bottle, uses high performance liquid chromatography to examine
Survey.
Described hybrid material graphene/C3N4For in embodiment 1 to 6 preparation GC0.3, GC8.0, GC0.1, GC3.0,
GC5.0 or GC10.0.
Obtain through experimental verification is repeated several times, different hybrid material graphene/C3N4Photocatalytic degradation deoxynivalenol
The order of the speed constant of bacterium enol (DON) is followed: GC0.3 > GC8.0 > GC0.1 > GC3.0 > GC5.0 > GC10.0；Work as Graphene
Addition when being 0.3%, under the ultraviolet light of wavelength X=365nm, the activity of GC0.3 photocatalytic degradation DON preferably,
In 10min, the deoxynivalenol that concentration is 15ppm being degraded 16%, its rate constants k is 0.1572min-1。
Under the embodiment 9 different illumination degrading time, GC0.3 photocatalytic degradation deoxynivalenol
1) GC0.3 prepared by the embodiment 1 of 25mg is joined in the DON aqueous solution that 50mL concentration is 15ppm, the most ultrasonic
Process 0.5h, be stirred for 0.5h, make GC0.3 reach adsorption equilibrium, obtain the first mixed liquor；
2) using described first mixed liquid concentration as initial concentration, then utilize the visible ray of wavelength X >=420nm to described
First mixed liquor carries out light degradation, and degraded is sampled after terminating, and is centrifuged sample processing, and takes the supernatant after being centrifuged and puts
Entering in brown liquid phase bottle, it is standby that 4 DEG C of Refrigerator stores put into by brown liquid phase bottle, then investigates different degradation time to GC0.3
The impact of photocatalytic degradation DON, uses high performance liquid chromatography to detect.
Described degradation time is 0min, 5min, 10min, 15min, 30min, 60min, 120min, 180min, 240min
And 300min.
Understanding in conjunction with Fig. 4, GC0.3 has obvious degradation effect to DON, and at 1.80min, along with the light degradation time
Prolongation, there is the phenomenon progressively strengthened, observes DON at 7.49min in the intermediate product peak of GC0.3 photocatalytic degradation DON
The process that the main peak area of intermediate product is obviously reduced, when light degradation time lengthening to 180min, DON degradation rate reaches
About 30%, along with when extending to 300min of light degradation time, DON degradation rate has been finally reached 56%, and result shows, 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 is only for clearly demonstrating example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, the most also may be used
To make other changes in different forms, cannot all of embodiment be given exhaustive here, every belong to this
What bright technical scheme was extended out obviously changes or changes the row still in protection scope of the present invention.
Claims (10)
1. the hybrid material graphene/C of a photocatalytic degradation mycotoxin3N4, it is characterised in that it is by graphite oxide
Alkene and nano-photocatalyst g-C3N4Have layer by layer through what hydrothermal synthesis method prepared according to the ratio that mass ratio is 0.1-10:100
The hybrid material graphene/C of package assembly3N4。
2. a hybrid material graphene/C as claimed in claim 13N4Preparation method, it is characterised in that include as follows
Step:
1) graphene oxide dispersion is first carried out supersound process for the first time, makes graphene oxide dispersion form homogeneous dispersion
Liquid；Then carry out low-speed centrifugal process, remove lower floor's aggregation after centrifugal treating, obtain upper solution；Described upper solution is entered
Row second time supersound process, makes graphene oxide in described upper solution peel off, carries out high speed centrifugation process the most again, from
The heart removes, after processing, the graphene oxide that upper strata is unstripped, obtains the graphene oxide of stripping；The graphene oxide dispersion that will peel off
In deionized water, proceeding third time supersound process, the graphene oxide making stripping is dispersed in deionized water, and
Again peel off, obtain the graphene oxide dispersion in single or multiple lift structure；
2) by the graphene oxide dispersion in single or multiple lift structure and nano-photocatalyst g-C3N4Mix and blend, then enters
The 4th supersound process of row makes nano-photocatalyst g-C3N4Form the nanometer sheet of homogeneous single or multiple lift structure, obtain mixture；
Graphene oxide and nano-photocatalyst g-C in described mixture3N4Mass ratio be 0.1-10:100；
3) described mixture carrying out hydro-thermal reaction, reaction obtains hybrid material graphene/C after terminating3N4。
Preparation method the most according to claim 2, it is characterised in that the rotating speed that described low-speed centrifugal processes is 2000-
5000r/min；The rotating speed that described high speed centrifugation processes is 8000-20000r/min.
Preparation method the most according to claim 2, it is characterised in that the concentration of described graphene oxide dispersion is 0.1-
10mg/mL。
Preparation method the most according to claim 2, it is characterised in that the temperature of described hydro-thermal reaction is 160-180 DEG C, institute
The time stating hydro-thermal reaction is 4-10h.
6. the hybrid material graphene/C of a photocatalytic degradation mycotoxin as claimed in claim 13N4Application, it is special
Levy and be, its application in photocatalytic degradation mycotoxin.
Application the most according to claim 6, it is characterised in that described mycotoxin is deoxynivalenol, jade
Zearlenone, aflatoxin, fumonisin, ochratoxin or T-2 toxin.
8. according to the application described in claim 6 or 7, it is characterised in that it realizes by the following method:
1) by described hybrid material graphene/C3N4Join in mycotoxin sample, supersound process 0.5-1h, it is stirred for
0.5-1h, obtains the first mixed liquor；
2) described first mixed liquor is carried out light degradation.
Application the most according to claim 8, it is characterised in that light degradation uses the light source of wavelength X ＜ 1000nm to shine
Penetrate；The photodegradative time is 120-300min.
Application the most according to claim 8, it is characterised in that the concentration of mycotoxin in described mycotoxin sample >=
0.1μg/kg。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861746A (en) * | 2017-03-22 | 2017-06-20 | 北京师范大学 | A kind of carbonitride loads the preparation method of single dispersing oxidation state metal atom catalysis material |
| CN109668864A (en) * | 2018-12-14 | 2019-04-23 | 福建中医药大学 | Azotized carbon nano piece couples the ochratoxin A fluorescence detection method of aptamers sensing |
| CN110465316A (en) * | 2018-10-17 | 2019-11-19 | 黑龙江大学 | A kind of photochemical catalyst g-C3N4/ GO composite material and preparation method |
| CN111569792A (en) * | 2020-05-08 | 2020-08-25 | 中南大学 | Aerogel composite material and preparation method and application thereof |
| CN114939404A (en) * | 2022-07-01 | 2022-08-26 | 丽水市农林科学研究院 | Be used for degrading aflatoxin B 1 And a method for preparing the same |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769187A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | Preparation method of graphene/g-C3N4 compound photocatalyst |
| CN105028436A (en) * | 2015-07-09 | 2015-11-11 | 东南大学 | Novel application of graphite-phase carbon nitride as antibacterial material |
-
2016
- 2016-07-22 CN CN201610582810.1A patent/CN106311303B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769187A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | Preparation method of graphene/g-C3N4 compound photocatalyst |
| CN105028436A (en) * | 2015-07-09 | 2015-11-11 | 东南大学 | Novel application of graphite-phase carbon nitride as antibacterial material |
Non-Patent Citations (3)
| Title |
|---|
| GUIQIANG WANG ET AL.: "Enhanced Electrocatalytic Performance of a Porous g-C3N4/Graphene Composite as a Counter Electrode for Dye-Sensitized Solar Cells", 《CHEM. EUR. J》 * |
| 中国环境科学学会环境工程分会: "《2003（第三届）中国水污染防治与废水资源化技术交流会论文集》", 31 December 2003, 《环境工程》编辑部 * |
| 张芬 等: "RGO/C3N4复合材料的制备及可见光催化性能", 《无机化学学报》 * |
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| CN106861746B (en) * | 2017-03-22 | 2020-02-04 | 北京师范大学 | Preparation method of carbon nitride supported monodisperse oxidation state metal atom catalytic material |
| CN110465316A (en) * | 2018-10-17 | 2019-11-19 | 黑龙江大学 | A kind of photochemical catalyst g-C3N4/ GO composite material and preparation method |
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| CN115634680B (en) * | 2022-09-26 | 2024-02-20 | 北京建筑大学 | GO-induced MXene hydrogel as well as preparation method and application thereof |
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