CN107142616A - A kind of preparation method of the nanofiber packaging material of degradable residues of pesticides - Google Patents
A kind of preparation method of the nanofiber packaging material of degradable residues of pesticides Download PDFInfo
- Publication number
- CN107142616A CN107142616A CN201710256118.4A CN201710256118A CN107142616A CN 107142616 A CN107142616 A CN 107142616A CN 201710256118 A CN201710256118 A CN 201710256118A CN 107142616 A CN107142616 A CN 107142616A
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- fibrous membrane
- packaging material
- nano fibrous
- residues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 34
- 239000002121 nanofiber Substances 0.000 title claims abstract description 20
- 239000005022 packaging material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 16
- 235000012055 fruits and vegetables Nutrition 0.000 claims abstract description 14
- 238000011160 research Methods 0.000 claims abstract description 12
- 238000009832 plasma treatment Methods 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 13
- 239000003905 agrochemical Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 claims description 5
- 229950001664 phoxim Drugs 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 235000013311 vegetables Nutrition 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000004202 carbamide Substances 0.000 abstract description 6
- 239000000447 pesticide residue Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 11
- 235000010469 Glycine max Nutrition 0.000 description 10
- 244000068988 Glycine max Species 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000003851 corona treatment Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000003953 Solanum lycopersicum var cerasiforme Nutrition 0.000 description 7
- 240000003040 Solanum lycopersicum var. cerasiforme Species 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000004083 survival effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003987 organophosphate pesticide Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- DJRLIRRZVVGJSP-RGMNGODLSA-N C(CC)N[C@@H](CCO)C(=O)O.[Mo] Chemical class C(CC)N[C@@H](CCO)C(=O)O.[Mo] DJRLIRRZVVGJSP-RGMNGODLSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- XEKPEQLEUMZAQO-UHFFFAOYSA-N antimony;2,3-dihydroxybutanedioic acid;potassium Chemical compound [K].[Sb].OC(=O)C(O)C(O)C(O)=O XEKPEQLEUMZAQO-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical class [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000000152 carbamate pesticide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- -1 chlopyrifos Chemical compound 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of g C of degradable garden stuff pesticide residue3N4The preparation method of nanofiber packaging material.It is of the invention that g C are first synthesized by calcination method by urea3N4, then by electrostatic spinning by g C3N4Nano fibrous membrane is spun into, then g C are handled with high pressure plasma under nitrogen protection3N4Nano fibrous membrane, g C are improved with this3N4The effect of nano fibrous membrane Researches on Photocatalytic Degradation of Pesticide Using.Electrostatic spinning technique of the present invention, plasma treatment technique and g C3N4Preparation technology all relative maturities, it is plasma treated after g C3N4Nano fibrous membrane is used for wrapping up fruits and vegetables, and the effect of degrading pesticide residues is significantly improved, with higher market application value.
Description
Technical field
The invention belongs to field of food safety, and in particular to g-C3N4The preparation of nano fibrous membrane, plasma are to g-C3N4
The processing of nano fibrous membrane and g-C3N4The application that nano fibrous membrane is degraded to garden stuff pesticide residue.
Background technology
With the increasingly raising of people's living standard, food-safety problem turns into the focus of current social.Agricultural chemicals
Environmental pollution and food poisoning happen occasionally caused by residual, have seriously threatened the healthy and life of consumer to pacify
Entirely, the stabilization and harmony of society are influenceed.Residues of pesticides refer in agricultural production applying pesticides rear portion agricultural chemicals directly or
Connect the phenomenon remained in cereal, fruits and vegetables, fruit, livestock products, aquatic products and soil and water body.The agricultural chemicals used at present some
Innocuous substance can be turned into by biodegradation within a short period of time, and some organophosphors, Organic fluoride, organic chlorine agriculture chemicals are difficult
It is the strong agricultural chemicals of residual to degrade.Current method both at home and abroad to pesticide residual degradation, conventional has biological, physics and chemistry drop
Solution, these methods easily damage fruits and vegetables or cause secondary pollution.In consideration of it, researching and developing safe and efficient photocatalytic degradation
The method of residues of pesticides has turned into one of vital task of raising China food security.
The country has a lot on Researches on Photocatalytic Degradation of Pesticide Using, the patent application of plasma and electrostatic spinning：
CN102962046A discloses a kind of method of Researches on Photocatalytic Degradation of Pesticide Using, utilizes ZnO/TiO2Composite nano materials are to residues of pesticides
Carry out photocatalytic degradation.CN102442711A discloses a kind of method of light catalytic degrading carbamate pesticide in water.
The method that CN102120631A discloses pyrethroid pesticide in a kind of photocatalytic degradation water, available for degraded grain, water
The Practice for Pesticide Residue in Agricultural Products such as fruit.CN103839748A discloses plasma processing apparatus and method of plasma processing.
CN103041714A discloses a kind of Compound Ultrafiltration of modification of chitosan composite electrostatic spinning nanofiber and preparation method thereof；
CN102776709A discloses a kind of electrostatic spinning and prepares polyvinylpyrrolidone/chitosan composite nano fibre film.
Researches on Photocatalytic Degradation of Pesticide Using residual with its energy-conservation, it is efficient, easy to operate, have a wide range of application, contaminant degradation thoroughly, without choosing
The advantages of selecting property, non-secondary pollution, is as study hotspot in recent years.g-C3N4As a kind of new photochemical catalyst, due to it
The driven band gap of visible ray, high heat endurance, chemical stability and the characteristic such as easily prepared, are widely used.But by
In g-C3N4The high coincidence factor and low surface area in light induced electron cave, are subject to certain restrictions its photocatalytic activity.And g-
C3N4Directly appearance is easy to when food surface sprays assembles and declines phenomenon to nano particle, reduces the biology of encapsulated substance
Activity.Therefore can be by g-C3N4Nano particle is loaded into nanofiber, so that nano particle is fixed on tunica fibrosa.It is quiet
Electrospun is at present can be continuously to prepare nanofiber and the relatively mild mode of mode of operation, and its nano fibrous membrane prepared has
Specific surface area is big, the high packaging effects of nanoscale hole and reactive compound the advantages of.Many polymer such as PEO, poly- breast
Acid and polyvinyl alcohol have been widely used for preparing nano fibrous membrane because of its excellent performance.
Then corona treatment g-C is recycled3N4Nano fibrous membrane, reduces the coincidence factor in its light induced electron cave, improves
Its surface area, so as to improve g-C3N4The ability of Researches on Photocatalytic Degradation of Pesticide Using.The concept of plasma be earliest nineteen twenty-eight first
Be suggested, and point out that plasma is the aggregate of approximate electroneutral, be made up of ion with electronic population, and can to electric field and
Magnetic field is responded.Surface plasma photocatalysis is also a kind of emerging technology, and surface plasma photocatalysis in 2008 is also just
Formula is suggested, and a series of research all demonstrates superperformance of the surface plasma in photocatalysis.
The g-C of urea calcining synthesis of the present invention3N4Nano-particle is combined with electrostatic spinning and plasma, research experiment
Composition of raw materials and its technological parameter, improve g-C3N4Photocatalytic activity, has important meaning for the active food packaging for developing new
Justice.
The content of the invention
The purpose of the present invention is to disclose a kind of g-C of degradable garden stuff pesticide residue3N4The preparation of nanofiber packaging material
Method, the g-C prepared by urea3N4G-C is obtained by electrostatic spinning technique3N4Nano fibrous membrane, then by corona treatment
It is used for wrapping up fruits and vegetables afterwards, the effect of its stability and Researches on Photocatalytic Degradation of Pesticide Using is significantly improved, and the residual of fruits and vegetables Pesticides is big
Width is reduced, and reaches the purpose of the agricultural product edible safety such as fruits and vegetables.
The present invention prepares g-C in vacuum tube furnace by urea by calcination method3N4, heating rate is 5 DEG C/min, calcining
Temperature is 550~600 DEG C, and calcination time is 4~5h.
G-C of the present invention3N4The preparation method of nanofiber antibacterial film：Polyethylene glycol oxide is added into g-C3N4It is made in solution
Electrostatic spinning solution, ultrasound degassing obtains spinning precursor solution after stirring at normal temperature is stayed overnight.Then syringe draws spinning forerunner
Liquid solution carries out electrostatic spinning, and electrostatic spinning voltage is 5kV~30kV, and propulsion speed is 0.1~3mL/h, and it is 10 to receive distance
~20cm, air humidity is controlled below 35%, using flat panel collector method, obtains g-C3N4Nano fibrous membrane.
The g-C3N4The concentration of solution is 0.1~0.5% (W/V, g/mL).
The concentration of polyethylene glycol oxide is 6~8wt% (g/g) in the electrostatic spinning solution.
The degasification process 10min.
Plasma treatment of the present invention is under conditions of nitrogen protection, by g-C3N4It is cold that nano fibrous membrane is placed on high voltage electric field
4~5min is handled in source plasma equipment, processing power is in 500~600W.Then by the g-C after plasma treatment3N4Nanometer
Tunica fibrosa parcel fruits and vegetables are placed in light-catalyzed reaction instrument, and the reaction of Researches on Photocatalytic Degradation of Pesticide Using, light source work(are carried out under simulated visible light
Rate is 300~350W.
Brief description of the drawings
G-C after the processing of Fig. 1 green soy beans plasma3N4Nano fibrous membrane is to Rogor solution degradation.
G-C after the processing of Fig. 2 cherry tomatos plasma3N4Nano fibrous membrane is to Rogor solution degradation.
G-C after Fig. 3 corona treatments3N4Nano fibrous membrane is to four kinds of organophosphorus pesticide photocatalytic degradations.
Embodiment
Illustrate the embodiment of the present invention, but the protection content of the present invention by Examples below, be not only limited to this.
G-C after the corona treatment of embodiment 13N4Degradation rate of the nano fibrous membrane to garden stuff pesticide residue
1 experiment material
2 experimental methods
1)g-C3N4Preparation
1. 10g urea is weighed, is placed in crucible, and is closed the lid, is placed in vacuum tube furnace；
2. calcining heat and time are adjusted：550 DEG C are raised to 5 DEG C/min heating rate, then 4 are calcined at 550 DEG C
Hour, room temperature is cooled to, the g-C for faint yellow solid is obtained3N4, grind into powder is standby.
2)g-C3N4The preparation of nano-particle electrospun fibers film
1. by the g-C of the above-mentioned preparations of 50mg3N4Nano-particle, which is dissolved in 50mL Wahaha Pure Water, to be mixed evenly,
It is configured to 0.1% (W/V, g/ml) g-C3N4The solution of nano-particle.
2. the polyethylene glycol oxide for weighing 600mg is slowly added to the g-C that 1. 9.4g steps are prepared3N4In nano-particle solution
It is stirred overnight, prepares 6wt% (g/g) spinning precursor solution.
3. by spinning precursor solution ultrasound degassing 10min.
4. syringe draws 5mL spinning precursor solutions and assembles and start spinning, and electrostatic spinning voltage is 20kV, is promoted
Speed is 0.6mL/h, and it is 15.5cm to receive distance, and air humidity is controlled below 35%, is carrier with transparent plastic sheeting,
Using flat panel collector method, nano fibrous membrane is obtained after 3h.
3) corona treatment g-C3N4Nano fibrous membrane
1. obtained nano fibrous membrane is placed in culture dish；
2. culture dish is placed in plasma apparatus and handled, processing power is 600W, processing time is 5 minutes；
4)g-C3N4Residues of pesticides in nano fibrous membrane photocatalytic degradation fruits and vegetables
1. the green soy bean and cherry tomato for weighing 5g are immersed in the Rogor solution that concentration is 500mg/L, soak 30min；
2. above-mentioned 5g green soy beans and 5g cherry tomatos are taken out from Rogor solution and dried, then with after above-mentioned corona treatment
g-C3N4Nano fibrous membrane (is abbreviated as g-C3N4NM-plasma) wrapped up；
3. then by the green soy bean and cherry tomato after parcel be placed in photocatalysis instrument react half an hour reach adsorption equilibrium；
4. light source is opened, power is taking-up after 350W, 4h, removes the nano fibrous membrane of parcel；
5. above-mentioned green soy bean and cherry tomato are separately immersed in 50ml Wahaha Pure Water, soak 30min；
6. 9mL solution and then is therefrom taken to be centrifuged, 13000rpm, 20min take 5mL supernatant liquid；
7. handled by national standard GB 11893-89 molybdenum propylhomoserins spectrophotometer method：
A. acid adjustment：Respectively toward 5mL supernatant liquids and 5mL steps 4) the step of the Rogor solution 1. prepared (without g-C3N4Place
The Rogor solution of reason) the middle addition 10uL concentrated sulfuric acids, is fitted into after concussion is uniform in tool plug test tube.
B. clear up：800uL potassium peroxydisulfates (50g/L) are added into the sample after above-mentioned acid adjustment, tool plug test tube is stoppered into use
One napkin and line tighten glass stopper, are placed in large beaker and are placed in autoclave, treat that pressure reaches 1.1kg/
cm2, when relevant temperature is 120 DEG C, keep stopping heating after 30min.After pressure gauge reading is down to zero, taking-up lets cool and then used
Water is diluted to 10mL.
C. molybdate solution is prepared：13g ammonium molybdates are dissolved in 100mL water.0.35g potassium antimony tartrates are dissolved in 100mL
In water, 300mL sulfuric acid solutions (V is added to being stirred continuously lower ammonium molybdate solution is blown slowlyThe concentrated sulfuric acid：VWater=1:1) in, plus tartaric acid
Antimony potassium solution and it is well mixed.
D. color development：200uL ascorbic acid solutions (100g/L) are added into above-mentioned digestion solution to mix, and add 400uL to match somebody with somebody after 30s
The dimolybdate salt solution of system is fully mixed.
8. measured under spectrophotometer：Place at room temperature after 15min, using light path 30mm cuvettes, in 700nm wavelength
Under, determine absorbance.
9. secondly, g-C is used after the sample of any photochemical catalyst, immersion agricultural chemicals are not added with after immersion agricultural chemicals3N4Carried out again after processing
Not plasma-treated g-C is used after the sample and immersion agricultural chemicals of light-catalyzed reaction3N4Nano fibrous membrane (is abbreviated as g-
C3N4NM the sample of light-catalyzed reaction is carried out after) wrapping up again, this three is according to step 4) 5. -7. the step of carry out identical
Processing, as a control group；
5) calculating of degradation rate
C0：The absorbance (absorbance of the Rogor solution without any processing) of blank control group
C：The absorbance of experimental group (passes through g-C3N4Or g-C3N4Nanometer after nano fibrous membrane or plasma treatment
The absorbance of Rogor solution after fiber film process)
3 experimental results
As shown in figure 1, the green soy bean of light-catalyzed reaction is carried out in photocatalysis instrument, after 4 hours, through g-C3N4After effect,
OD700nmValue drop to the survival rate of Rogor solution on 0.88123, green soy bean by 100% by 1.0243211 and drop to 86.03%.
And through g-C3N4The green soy bean of nano fibrous membrane parcel, OD700nmValue drop to 0.495422 by 1.0243211, Rogor solution
Survival rate drops to 48.37% by 100%.The g-C of effect most preferably after plasma treatment3N4Nano fibrous membrane is wrapped up
Green soy bean, after 4 hours, OD700nmValue drop to 0.25069 by 1.0243211, the survival rate of Rogor solution is declined by 100%
To 24.47%.Fig. 2 is the degraded situation of residues of pesticides on cherry tomato after photocatalysis treatment.Substantially with the situation one of green soy bean
Cause, be all to utilize the g-C after plasma treatment3N4The Rogor of final residue is minimum on the cherry tomato of nano fibrous membrane parcel, degraded
Preferably, Rogor survival rate drops to 23.73% to effect by 100%.G-C after plasma treated in summary3N4Nanofiber
Film, the effect of Researches on Photocatalytic Degradation of Pesticide Using residual is significantly improved.It follows that plasma and electrostatic spinning technique can improve g-
C3N4Photocatalysis effect, reach the effect of efficient degradation agricultural chemicals, and can be widely applied among packaging for foodstuff.
G-C after the corona treatment of embodiment 23N4Degraded of the nano fibrous membrane to common organophosphorus pesticide
1 experiment material
2 experimental methods
1)g-C3N4Preparation
1. 10g urea is weighed, is placed in crucible, and is closed the lid, is placed in vacuum tube furnace；
2. calcining heat and time are adjusted：550 DEG C are raised to 5 DEG C/min heating rate, then 4 are calcined at 550 DEG C
Hour, room temperature is cooled to, the g-C for faint yellow solid is obtained3N4, grind into powder is standby.
2)g-C3N4The preparation of nano-particle electrospun fibers film
1. by 50mg g-C3N4Nano-particle, which is dissolved in 50mL Wahaha Pure Water, to be mixed evenly, and is configured to
0.1% (W/V, g/ml) g-C3N4The solution of nano-particle.
2. the polyethylene glycol oxide for weighing 600mg is slowly added to the g-C that 1. 9.4g steps are prepared3N4In nano-particle solution
It is stirred overnight, prepares 6wt% (g/g) spinning precursor solution.
3. by spinning precursor solution ultrasound degassing 10min.
4. syringe draws 5mL spinning precursor solutions and assembles and start spinning, and electrostatic spinning voltage is 20kV, is promoted
Speed is 0.6mL/h, and it is 15.5cm to receive distance, and air humidity is controlled below 35%, is carrier with transparent plastic sheeting,
Using flat panel collector method, nano fibrous membrane is obtained after 3h.
3) corona treatment g-C3N4Nano fibrous membrane
1. obtained nano fibrous membrane is placed in culture dish；
2. culture dish is placed in plasma apparatus and handled, processing power is 600W, processing time is 5 minutes；
4) corona treatment g-C3N4Nano fibrous membrane photocatalytic degradation common are machine phosphorus insecticide
1. respectively by 70mg orthene, phoxim, chlopyrifos and Rogor are dissolved in 200mL Wahaha Pure Water
In, ultrasonically treated 10 minutes, reach and be completely dissolved；
2. the g-C after 4 parts of 50mg above-mentioned plasma treatment is weighed respectively3N4Nano fibrous membrane；
3. respectively by 50mL orthene, phoxim, chlopyrifos, Rogor, 4 parts of 50mg g-C3N4Nano fibrous membrane
Be put into 4 rotors in 4 test tubes, be subsequently placed in photocatalysis instrument react half an hour reach adsorption equilibrium；
4. light source is opened, power is 350W, 9mL solution is drawn respectively from above-mentioned 4 test tubes after 4 hours；
5. 9mL solution is centrifuged, 13000rpm, 20min, takes 5mL supernatant liquid；
6. handled by national standard GB 11893-89 molybdenum propylhomoserins spectrophotometer method：
A. acid adjustment：Respectively toward 5mL supernatant liquids and 5mL steps 4) the step of the Rogor solution 1. prepared (without g-C3N4Place
The Rogor solution of reason) the middle addition 10uL concentrated sulfuric acids, is fitted into after concussion is uniform in tool plug test tube.
B. clear up：800uL potassium peroxydisulfates (50g/L) are added into the sample after above-mentioned acid adjustment, tool plug test tube is stoppered into use
One napkin and line tighten glass stopper, are placed in large beaker and are placed in autoclave, treat that pressure reaches 1.1kg/
cm2, when relevant temperature is 120 DEG C, keep stopping heating after 30min.After pressure gauge reading is down to zero, taking-up lets cool and then used
Water is diluted to 10mL.
C. molybdate solution is prepared：13g ammonium molybdates are dissolved in 100mL water.0.35g potassium antimony tartrates are dissolved in 100mL
In water, 300mL sulfuric acid solutions (V is added to being stirred continuously lower ammonium molybdate solution is blown slowlyThe concentrated sulfuric acid：VWater=1:1) in, plus tartaric acid
Antimony potassium solution and it is well mixed.
D. color development：200uL ascorbic acid solutions (100g/L) are added into above-mentioned digestion solution to mix, and add 400uL to match somebody with somebody after 30s
The dimolybdate salt solution of system is fully mixed.
7. it will be measured under spectrophotometer：Place at room temperature after 15min, using light path 30mm cuvettes, in 700nm wavelength
Under, determine absorbance.
5) calculating of degradation rate
C0：The starting absorbance of all kinds of the pesticide solutions
C：The absorbance of the pesticide solution after photocatalysis
3 experimental results
With the nano fibrous membrane g-C after plasma treatment3N4To orthene, phoxim, chlopyrifos and Rogor these four
Organophosphorus pesticide carries out photocatalytic degradation experiment, as a result as shown in figure 3, after light-catalyzed reaction in 4 hours, although the relative original matched somebody with somebody
Solution, OD700nmValue has all declined, and survival rate is 61.6%, 65.66%, 21.68% and 37.5% respectively, and survival rate is all low
In 100%, but degradation effect still has significance difference.As seen from the figure, g-C3N4- plasma to the degradation effect of chlopyrifos most
It is good, next to that Rogor.It is not notable to the degradation effect of orthene and phoxim.
Claims (9)
1. a kind of nanofiber packaging material of degradable residues of pesticides, it is characterised in that：The nanofiber packaging material is
g-C3N4Nano fibrous membrane, is to first pass through electrostatic spinning technique nano fibrous membrane, then plasma treated parcel fruit is made
Vegetable, is placed under visible ray the residues of pesticides for fruits and vegetables of degrading, improves the stability of nano fibrous membrane and the effect of Researches on Photocatalytic Degradation of Pesticide Using
Really.
2. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 1, it is characterised in that described
First passing through the step of nano fibrous membrane is made in electrostatic spinning technique is：Polyethylene glycol oxide is added into g-C3N4Electrostatic is made in solution
Spinning solution, ultrasound degassing obtains spinning precursor solution after stirring at normal temperature is stayed overnight；Then syringe absorption spinning presoma is molten
Liquid carry out electrostatic spinning, electrostatic spinning voltage be 5kV~30kV, propulsions speed be 0.1~3mL/h, receive distance be 10~
20cm, air humidity is controlled below 35%, using flat panel collector method, obtains g-C3N4Nano fibrous membrane.
3. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 2, it is characterised in that described
g-C3N4The concentration of solution is 0.1~0.5% (W/V, g/mL).
4. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 2, it is characterised in that described
The concentration of polyethylene glycol oxide is 6~8wt% (g/g) in electrostatic spinning solution；The degasification process 10min.
5. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 1, it is characterised in that described
Plasma treatment is under conditions of nitrogen protection, by g-C3N4Nano fibrous membrane is placed on high voltage electric field low-temperature receiver plasma apparatus
4~5min of middle processing, processing power is in 500~600W.
6. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 1, it is characterised in that described
The residues of pesticides for being placed under visible ray fruits and vegetables of degrading refer to：By the g-C after plasma treatment3N4Nano fibrous membrane parcel fruits and vegetables are placed in
In light-catalyzed reaction instrument, the reaction of Researches on Photocatalytic Degradation of Pesticide Using is carried out under simulated visible light, light source power is 300~350W.
7. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 1, it is characterised in that described
Fruits and vegetables agricultural chemicals is orthene, phoxim, chlopyrifos or Rogor.
8. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 7, it is characterised in that described
Fruits and vegetables agricultural chemicals is chlopyrifos or Rogor.
9. the nanofiber packaging material of a kind of degradable residues of pesticides according to claim 1, it is characterised in that described
Fruits and vegetables agricultural chemicals is chlopyrifos.
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