CN106215858B - A kind of preparation method and applications of the functionalization graphene of the adsorbable mycotoxin of high activity - Google Patents
A kind of preparation method and applications of the functionalization graphene of the adsorbable mycotoxin of high activity Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the functionalization graphene of adsorbable mycotoxin of high activity, it will be mixed in the graphene oxide dispersion of single or multi-layer structure and surfactant, then the 4th ultrasonic treatment is carried out, and 24-48h is stirred at room temperature, obtains uniform mixed liquor；The mixed liquor is stirred into 6-10h at 70-95 DEG C, obtains functionalization graphene.The present invention is using graphene oxide as raw material, using amphiphilic surfactant as modifying agent, it is modified that covalent functionalization is carried out to graphene by ion exchange and amidation process, the functionalization graphene with good dissolution dispersity has been obtained, and the absorption property of functionalization graphene is improved.Functionalization graphene of the invention is significant to the adsorption effect of mycotoxin, has very high practical value and application prospect.
Description
Technical field
The invention belongs to analytical chemistry fields, and in particular to a kind of functionalization graphene of the adsorbable mycotoxin of high activity
Preparation method and applications.
Background technique
Mycotoxin is toxic secondary metabolite caused by fungi grows in food or feed, to human body and animal
Health have great harm, have the function of teratogenesis, it is carcinogenic, cause cell mutation.The mycotoxin being currently known has more than 300
Kind, it mainly include aspertoxin class, fusarium toxin class, penicillic toxin class etc..Common is serious to human health damage
Mycotoxin mainly includes aflatoxin, vomitoxin, fumonisin, zearalenone, ochratoxin, Penicillium patulum
Element, citrinin etc..Mycotoxin also results in quality of agricultural product decline in addition to endangering human and livestock health, hinders the export of farm produce, right
Peasant household and agricultural economy bring about great losses.In China, the influence of climate factor and peasant household's individual planting patterns, grain and oil crop
And its product by mycotoxin contamination phenomenon than more serious.Therefore, the control research for reinforcing mycotoxin in agricultural product very must
It wants.But this is one and covers agricultural product from field, storage, transport, processing, sale up to dining table whole-process control " system work
Journey ".Current investigative technique is far unable to satisfy the requirement of people, therefore various countries have formulated the limitation of mycotoxin in food and feed
Standard, to ensure human food's safety.
In agricultural production, prevention and treatment grain is polluted by mycotoxin, it may include two aspect contents: is prevented before gathering in true
Bacterium is to seed infection；Cereal is well saved after harvesting；Or detoxification processing is carried out to slight pollution crop.Present invention is generally directed to
Grain detoxicating method is polluted, mycotoxin method has physical method, chemical method and biological skill in the grain that now removes and degrade
Art.Mainly for the cereal of contaminant toxin, processing method has physical method: reject (rejecting appearance has damage part),
It washes, shell, being heat-treated, milling, irradiating, adsorbent absorption and autoclaving etc..Chemical method is the chemistry knot using toxin itself
Structure and chemical property, therefore can be with active strong or chemical reaction substance can occur therewith and be converted into other materials, to reach
Degradation removes malicious purpose.Biological removal method mainly utilizes certain micro-organisms to can decompose specific mycotoxin, and then changes poison
The chemical structure of plain molecule reaches degradation removal mycotoxin purpose.The selected adsorbent in physical method is for mould poison at present
Element removal aspect, involved adsorbent species are various, the active charcoal of common adsorbent, concave convex rod and atlapulgite etc.,
Its absorption principle is to rely primarily on the advantage of itself pore structure to be adsorbed, although having good removal effect to mycotoxin,
But due to containing a large amount of impurities, the rate of adsorption is slow, regeneration efficiency is low, limits its application prospect.It integrates, all kinds of adsorbents
Generally existing defect is: 1. adsorption function is single, cannot adsorb a variety of different types of mould poison present in grain and oil simultaneously
Element；2. additive amount is big, excessive formulation space is occupied；3. while absorbing mycotoxin, with vitamin, the minerals etc. in grain and oil
Nutritional ingredient combines, and interferes nutrient utilization；4. other pollutants may be contained, grain and oil quality is reduced to a certain extent.
Therefore, finding and develop the adsorbent that the rate of adsorption is fast, absorption property is good, can be recycled is still absorption research field
One of important directions.For this purpose, the adsorbent of selection: 1. must have high absorption capacity；2. selective absorption；3. wide spectrum adsorbs；
4. with good stability；5. usage amount wants low and effective, non-toxic；6. must have laboratory and the dual money of animal experiment
Material can prove effectively.
The conjugation carbon nanomaterial graphene oxide (GO) of Recent study hot topic, it has unique two-dimensional structure and height
Specific surface area, suction-operated can be carried out on surface by lamellar structure itself, be also helped while improving absorption property
Desorption and regeneration；In addition, being easy and adsorbate point since surface of graphene oxide contains the oxygen-containing groups such as great amount of hydroxy group, carboxyl
Son forms hydrogen bond and then is adsorbed and removed, therefore graphene oxide will have important researching value in adsorbing domain and answer
Use prospect.For the application value for improving graphene, need to carry out its surface modification and functionalization, to promote the dispersion of graphene
Property, or even can also assign graphene new performance.In most cases, when organic molecule and graphene surface are covalently attached
When, the original conjugated structure of graphene is destroyed, energy band is opened, can effective its structure of modulation and Electronic Performance.Organic molecule
The position for generating covalent bond with graphene can be the carbon-carbon double bond in graphene, the oxygen-containing group being also possible on graphene oxide
Group's (such as hydroxyl, carboxyl, epoxy group).It is covalent that the present invention synthesizes amphiphile, amphiphilic molecule didodecyldimethylammbromide bromide (DDAB)
The graphene of functionalization.Using graphene oxide as raw material, with didodecyldimethylammbromide bromide introduce amino group, then with carboxylic
The graphene oxide molecule of base carries out amidation, has obtained the functionalization graphene material of good dissolution dispersity, and
So that the absorption property of functionalization graphene is further promoted.So far, graphene oxide is to heavy metal ion, dyestuff
Molecule and antibiotic all show excellent absorption property, and the research for this functionalization graphene material for absorption has no
Report, especially there are no the researchs that pertinent literature and patent report are used to adsorb mycotoxin.
Summary of the invention
The first purpose of this invention is to provide a kind of system of the functionalization graphene of adsorbable mycotoxin of high activity
Preparation Method.
Second object of the present invention is to provide a kind of answering for the functionalization graphene of adsorbable mycotoxin of high activity
With.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of the functionalization graphene of the adsorbable mycotoxin of high activity, includes the following steps:
1) graphene oxide dispersion is first subjected to first time ultrasonic treatment, forms graphene oxide dispersion uniform
Dispersion liquid；Then low-speed centrifugal processing is carried out, sub-cloud aggregation is removed after centrifugal treating, obtains upper solution；The upper layer is molten
Liquid carries out second and is ultrasonically treated, and graphene oxide in the upper solution is completely exfoliated, then carry out again high speed from
The heart is handled, and the unstripped graphene oxide in upper layer is removed after centrifugal treating, obtains the graphene oxide of removing；By the oxidation stone of removing
Black alkene is scattered in deionized water, continue third time be ultrasonically treated, make removing graphene oxide be dispersed in from
In sub- water, the graphene oxide dispersion in single or multi-layer structure is obtained；
2) it will mix in the graphene oxide dispersion of single or multi-layer structure and surfactant, then carry out the 4th time
Ultrasonic treatment, and 24-48h is stirred at room temperature, obtain uniform mixed liquor；
3) mixed liquor is stirred at 70-95 DEG C 6-10h, obtains functionalization 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 surfactant is the amphiphilic surfactant with 1-4 alkyl chain.
Further, the surfactant: the mass ratio of graphene oxide is 0.2-5:1.
Further, the amphiphilic surfactant with 1-4 alkyl chain is cetrimonium bronmide
(CTAB), didodecyldimethylammbromide bromide (DDAB) or tetrabromo dodecyl ammonium (TAB) etc..
Further, amphiphilic surfactant's is hydrophilic terminal modified in graphene surface, and amphiphilic surfactant's dredges
Water end (W.E.) is towards water phase, when being added in mycotoxin sample and acutely rock, amphiphilic surfactant by functionalization graphene
Fully dispersed in graphene film layer surface, to effectively prevent the aggregation of graphene, this is increased for the raising of absorption property
Reaction site, and then it is improved functionalization graphene to the absorption property of mycotoxin.
Further, the concentration of the graphene oxide dispersion is 0.1-10mg/mL.
A kind of application of the functionalization graphene of the adsorbable mycotoxin of high activity, the functionalization graphene are true in absorption
Application in verticillium toxin.
Further, the mycotoxin is zearalenone, vomitoxin, aflatoxin, fumonisin or reddish brown song
Mould toxin.
A kind of application of the functionalization graphene of the adsorbable mycotoxin of high activity, it is realized by the following method:
1) functionalization graphene is dispersed in water, carries out ultrasound and stirring, obtain the function that concentration is 1-5mg/mL
Graphite alkene dispersion liquid；
2) the mycotoxin sample that the functionalization graphene dispersion liquid and concentration are >=0.1 μ g/kg is mixed, so
After carry out adsorption reaction, after adsorption reaction intermediate reaction liquid；The pH value for adjusting the intermediate reaction liquid, is then taken
Sample and detection.
Further, the temperature of adsorption reaction is 60-95 DEG C (such as: 60 DEG C, 80 DEG C, 90 DEG C or 95 DEG C etc.).
Further, the time of adsorption reaction is 1-10h (such as: 1h, 2h, 3h, 4h, 6h, 7h, 8h or 10h etc.).
Further, adjusted using HCl and NaOH aqueous solution the pH value of the intermediate reaction liquid to 9.0-12.6 (such as: 9,
10,11,12 or 12.6 etc.).
In some embodiments, it is promoted using the modified functionalization graphene of didodecyldimethylammbromide bromide
The formation of micellar solution the corn oil containing zearalenone is added in functionalization graphene solution, by adequately shaking
It swings, disperses the aggregation of functionalization graphene again, come into full contact with the zearalenone in organic phase, this is adsorptivity
The raising of energy increases reaction site, and then is improved functionalization graphene to the absorption property of mycotoxin.But when double
When the modified amount of Dodecydimethylammonium bronides is increased to a certain extent, the space contact steric hindrance of functionalization graphene molecule becomes
Greatly, it is reduced with the adsorption site of zearalenone, to make adsorption effect that downward trend be presented.
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, the present invention is using graphene oxide as raw material, using amphiphilic surfactant as modifying agent, by ion exchange and
Amidation process carries out covalent functionalization to graphene and is modified, and has obtained having the function of good dissolution dispersity graphite
Alkene, and the absorption property of functionalization graphene is improved.
2, the present invention is that functionalization graphene is prepared in pure aquatic system, is not necessarily to any organic solvent, and preparation process letter
List, raw material are inexpensive, are easy to large-scale production；Functionalization graphene of the invention is significant to the adsorption effect of mycotoxin, has
Very high practical value and application prospect.
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: being (a) transmission electron microscope picture of functionalization graphene；It (b) is graphene hydrogel (SGH) transmission electron microscope picture；
It (c) is the transmission electron microscope picture of concave convex rod (ATTP)；It (d) is the transmission electron microscope picture of active carbon (AC).
Fig. 2 is bar chart of the functionalization graphene to zearalenone desorption rate.
Fig. 3 is the bar chart of functionalization graphene, control group and blank group to zearalenone adsorption rate.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, it should not be with this
It limits the scope of the invention.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.The present invention
Used in reactant sodium nitrate, the concentrated sulfuric acid, potassium permanganate, multi-oxygen water, hydrochloric acid, acetonitrile, methanol etc. be pure, the mesh of commercially available analysis
The standard items that degradation product mycotoxin is the purchase of Sigma company are marked, deionized water is homemade.
Using Hitachi HT-7700 type transmission electron microscope (TEM), beam voltage 100kV；Using Waters public affairs
The adsorbance for taking charge of the Water E2695 high performance liquid chromatography detection zearalenone of production, with reference to " GB/T 23504-2009
The measurement immunoaffinity chromatography of zearalenone purifies high performance liquid chromatography in food ", and do appropriate amendment.Specific chromatography
Condition are as follows: chromatographic column: C18 column (250mm × 4.6mm, 5 μm, xbridge)；Mobile phase: water/acetonitrile=50/50 (V/V)；Flow velocity
1.0mL/min；25 DEG C of column temperature；10 μ L of sample volume；Fluorescence detector: excitation wavelength (Ex)=274nm, launch wavelength (Em)=
440nm。
In some embodiments, influence of the search time to absorption property is to utilize pseudo-first-order kinetics equation and standard two
Grade two kinds of models of kinetics equation carry out simulated dynamics data.
Pseudo-first-order kinetic model equation formula are as follows:
ln(qe-qt)=lnqe-k1t
Q in formulaeAnd qtFunctionalization graphene is respectively represented under equilibrium state and different time state t to mycotoxin
Adsorbance (mgg-1), k1Refer to pseudo-first-order kinetics equation adsorbing filament technique (min-1)；By with ln (qe-qt) map to t
Linear fit obtains straight line, acquires q by the intercept and slope of straight lineeAnd qt。
Pseudo-second order kinetic model includes all stages in adsorption process: outside diffusion, absorption, intra-particle diffusion, side
Formula are as follows:
Q in formulaeAnd qtFunctionalization graphene is respectively represented under equilibrium state and different time state t to mycotoxin
Adsorbance (mgg-1), k2Refer to pseudo-second order kinetic equation adsorbing filament technique (gmg-1·min-1)；By with t/qtT is made
Linear fit obtains straight line, acquires q by the slope and intercept of straight lineeAnd k2。
Embodiment 1
1) 5mg/mL graphene oxide dispersion is first subjected to first time ultrasonic treatment, forms graphene oxide dispersion
Uniform dispersion liquid；Then centrifugal treating is carried out with 5000r/min speed, removes sub-cloud aggregation after centrifugal treating, obtains upper layer
Solution；The upper solution is carried out second to be ultrasonically treated, graphene oxide in the upper solution is completely exfoliated,
Then centrifugal treating is carried out with 10000r/min speed, the unstripped graphene oxide in upper layer is removed after centrifugal treating, must be removed
Graphene oxide；It disperses the graphene oxide of removing in deionized water, continues third time and be ultrasonically treated, make to remove
Graphene oxide it is evenly dispersed in deionized water, obtain concentration be 1mg/mL the graphene oxide in single or multi-layer structure
Dispersion liquid；
It 2) will be in the graphene oxide dispersion of single or multi-layer structure and double dimethyls of 7.5mg described in 20mL
The mixing of base ammonium bromide, then carries out ultrasonic treatment 30min, and 48h is stirred at room temperature, obtains uniform mixed liquor；
3) mixed liquor is placed in heat-collecting magnetic stirring device and is stirred to react 6h at 90 DEG C, carried out after reaction
Natural cooling obtains grey black product, and the grey black product is washed with deionized water and ethyl alcohol respectively, and dry in 60 DEG C
The dry 12h of dry case, is ground after dry, obtains functionalization graphene.
Embodiment 2
" didodecyldimethylammbromide bromide of 7.5mg " in embodiment 1 is changed into " double dimethyls of 3.8mg
Base ammonium bromide ", other modes same as Example 1 carry out.
Embodiment 3
" didodecyldimethylammbromide bromide of 7.5mg " in embodiment 1 is changed into " double dodecyl dimethyls of 20mg
Ammonium bromide ", other modes same as Example 1 carry out.
Embodiment 4
" didodecyldimethylammbromide bromide of 7.5mg " in embodiment 1 is changed into " double dodecyl dimethyls of 50mg
Ammonium bromide ", other modes same as Example 1 carry out.
Embodiment 5
" didodecyldimethylammbromide bromide of 7.5mg " in embodiment 1 is changed into " double dimethyls of 100mg
Base ammonium bromide ", other modes same as Example 1 carry out.
6 functionalization graphene of embodiment evaluates the absorption property of zearalenone
The extracting method of zearalenone is with reference to " SN/T 1745-2006 imports and exports soybean, rapeseed and edible plant
The method of inspection of zearalenone in object oil " and do appropriate amendment.
The preparation of zearalenone sample: it is red that the ethyl acetate of 4mL by syringe is injected into the corn containing 25mg
In mould ketenes standard items bottle, fullys shake, make it completely dissolved, obtain mixed liquor；By the corn oil of the mixed liquor and 1000mL
Mixing, and ultrasound and concussion are carried out, obtaining concentration is 25mg/L zearalenone sample, and the zearalenone sample is put
Enter spare in 4 DEG C of refrigerators.
Experimental group: dispersing the functionalization graphene in 20mL water, carries out ultrasonic treatment 60min, and stir
30min, obtaining concentration is 2.4mg/mL functionalization graphene dispersion liquid；It is by the functionalization graphene dispersion liquid and concentration
The zearalenone sample of 25mg/L is mixed, then in 95 DEG C of progress adsorption reaction 6h, after adsorption reaction in
Between reaction solution；The pH to 9-12 of the intermediate reaction liquid is adjusted, carries out cooling and centrifugal treating after reaction, takes upper layer oily
Sample extracts the zearalenone in sample, monitors and analyzes to liquid phase.
The results show that functionalization graphene is 95.1% to the adsorption rate of zearalenone, equilibrium adsorption capacity is
23.75mg/g。
Control group 1: " functionalization graphene " in experimental group being changed into " active carbon (AC) ", other identical with experimental group
Mode carries out, and active carbon is 8.0% to the adsorption rate of zearalenone
Control group 2: " functionalization graphene " in experimental group being changed into " concave convex rod (ATTP) ", other identical as experimental group
Mode carry out, concave convex rod is 10.1% to the adsorption rate of zearalenone.
Control group 3: " functionalization graphene " in experimental group being changed into " graphene hydrogel (SGH) ", it is other with experiment
The identical mode of group carries out, and graphene hydrogel is 37.6% to the adsorption rate of zearalenone
Control group 4: " functionalization graphene " in experimental group is changed to " didodecyldimethylammbromide bromide (DDAB) " into:,
Other modes identical with experimental group carry out, and DDAB is 15.5% to the adsorption rate of zearalenone.
Control group 5: by " functionalization graphene " in experimental group change into embodiment 1 preparation " in single or multi-layer structure
Graphene oxide (GO) dispersion liquid ", other modes identical with experimental group carry out, in the graphite oxide of single or multi-layer structure
Alkene dispersion liquid is 0% to the adsorption rate of zearalenone.
Blank group: the zearalenone sample that concentration is 25mg/L is subjected to reaction 6h in 95 DEG C, adsorption reaction terminates
Intermediate reaction liquid is obtained afterwards；The pH to 9-12 of the intermediate reaction liquid is adjusted, cooling and centrifugal treating is carried out after reaction, takes
Layer oil sample, extracts the zearalenone in oil sample, monitors and analyzes to liquid phase.Adsorption rate is 10.18%.
Adsorption-desorption merit rating of 7 functionalization graphene of embodiment to zearalenone
It disperses the functionalization graphene in 20mL water, carries out ultrasonic treatment 60min, and stir 30min, obtain concentration
For 2.4mg/mL functionalization graphene dispersion liquid；The Gibberella zeae for being 25mg/L by the functionalization graphene dispersion liquid and concentration
Ketenes sample is mixed, then in 95 DEG C of progress adsorption reaction 6h, by the function fossil of adsorption saturation after adsorption reaction
Black alkene is separated by the method being centrifuged；Then the functionalization graphene of milli-Q water adsorption saturation is first used, then with 5mL body
Fraction carries out concussion 3min for the functionalization graphene after 90% acetonitrile solution and washing, will washing and concussion operation weight
It is 4 times multiple, supernatant liquor is then centrifuged to obtain；The concentration of supernatant liquor measurement zearalenone is taken, examination difference is washed
De- influence of the number to the desorption effect of zearalenone.
In conjunction with Fig. 2 it is found that as washing steps N=1, the desorption rate of zearalenone is 59.4%；As washing steps N
When=2, the desorption rate of zearalenone is 92.9%；When the desorption rate of washing steps N=4, zearalenone are
96.1%；The experiment of adsorption-desorption shows that functionalization graphene of the invention pierces mould ketenes to corn and not only has good absorption
Performance, and there is functionalization graphene good regeneration to use ability.
Embodiment 8 adjusts influence of the pH value to functionalization graphene absorption zearalenone
It disperses the functionalization graphene in 20mL water, carries out ultrasonic treatment 60min, and stir 30min, obtain concentration
For the functionalization graphene dispersion liquid of 2.4mg/mL；The corn for being 25mg/L by the functionalization graphene dispersion liquid and concentration is red
Mould ketenes sample is mixed, and then in 95 DEG C of progress adsorption reaction 6h, intermediate reaction liquid is obtained after adsorption reaction；Adjust institute
The pH to 9-12.6 (such as pH value is 9,10,11,12 or 12.6) for stating intermediate reaction liquid, is cooled down after reaction and is centrifuged
Processing takes upper layer oil sample, extracts the zearalenone in oil sample, monitors and analyzes to liquid phase.
By test display is repeated several times, with the increase of pH value, functionalization graphene adsorbs the suction of zearalenone
Attached rate increases rapidly, and as pH=12.6, adsorption rate reaches maximum, adsorption rate 95%, and continuing growing with pH value of solution,
The adsorption rate of functionalization graphene absorption zearalenone reduces therewith.
Embodiment 9 adjusts influence of the adsorption temp to functionalization graphene absorption zearalenone
It disperses the functionalization graphene in 20mL water, carries out ultrasonic treatment 60min, and stir 30min, obtain concentration
For the functionalization graphene dispersion liquid of 2.4mg/mL；The corn for being 25mg/L by the functionalization graphene dispersion liquid and concentration is red
Mould ketenes sample is mixed, and then in 60-95 DEG C (for example, 60 DEG C, 80 DEG C, 90 DEG C or 95 DEG C) progress adsorption reaction 6h, is inhaled
Intermediate reaction liquid is obtained after reaction enclosure；Adjust the pH to 12.6 of the intermediate reaction liquid, carry out after reaction it is cooling and from
Heart processing, takes upper layer oil sample, extracts the zearalenone in oil sample, monitors and analyzes to liquid phase.
By test display is repeated several times, with the increase of adsorption temp, functionalization graphene is to zearalenone
Adsorption rate increases with it.When temperature reaches 90 DEG C, absorption is maximum, but the trend adsorbed at 95 DEG C becomes more gentle, inhales
It is attached to progressively reach balance.This is because accelerating the fortune of zearalenone molecule in the solution with the raising of solution temperature
Dynamic and diffusion, although also accelerate zearalenone molecule from functionalization graphene surface desorption to solution in rate,
It is that the competitive reaction rate of absorption is apparently higher than the rate of desorption reaction.Therefore, it controls suitable temperature condition and is more advantageous to suction
The progress of reaction enclosure.
Embodiment 10 adjusts influence of the adsorption time to functionalization graphene absorption zearalenone
It disperses the functionalization graphene in 20mL water, carries out ultrasonic treatment 60min, and stir 30min, obtain concentration
For the functionalization graphene dispersion liquid of 2.4mg/mL；It is 25mg/L containing corn by the functionalization graphene dispersion liquid and concentration
The corn oil samples of zeranol are mixed, then in 95 DEG C of progress adsorption reaction 1-10h (for example, 1h, 2h, 3h, 4h,
6h, 7h, 8h or 10h), intermediate reaction liquid is obtained after adsorption reaction；Adjust the pH to 12.6 of the intermediate reaction liquid, reaction knot
Cooling and centrifugal treating is carried out after beam, takes upper layer oil sample, extracts the zearalenone in oil sample, is monitored and is analyzed to liquid phase.
By test display is repeated several times, functionalization graphene is to the adsorption rate of zearalenone with adsorption time
Extend and increase, and over time, reaches adsorption equilibrium；Reach 6h in adsorption time, functionalization graphene is to corn
The adsorption rate of zeranol reaches 95%, then tends to adsorption equilibrium,
The dynamics of 11 functionalization graphene of embodiment absorption zearalenone
Table 2 is the dynamics fitting result that functionalization graphene adsorbs zearalenone
Table 2 lists the functionalization graphene absorption Gibberella zeae that two kinds of models fittings of pseudo-first-order and quasi- second level are calculated
The dynamics fitting result of ketenes, it can be seen that, related coefficient (R undesirable with pseudo-first-order kinetics equation fitting result2) be
0.770, correlation is poor, and under the equilibrium state fitted adsorbance calculated value (qe,cal) and experiment value
(qe,exp) between have a long way to go；In comparison, pseudo-second order kinetic model is more satisfactory to the fitting result of experimental data, related
Coefficient (R2) close to 0.99, and under the equilibrium state fitted adsorbance calculated value (qe,cal) and experiment value (qe,exp)
Between it is very close, deviation is within 3%, adsorption dynamics adsorption kinetics process ratio of this functions graphite alkene to zearalenone
Relatively meet pseudo-second order kinetic model.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of the functionalization graphene of the adsorbable mycotoxin of high activity, which is characterized in that including walking as follows
It is rapid:
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, is completely exfoliated graphene oxide in the upper solution, then carries out at high speed centrifugation again
It manages, the unstripped graphene oxide in upper layer is removed after centrifugal treating, obtains the graphene oxide of removing；By the graphene oxide of removing
It is scattered in deionized water, continues third time and be ultrasonically treated, the graphene oxide of removing is made to be dispersed in deionized water
In, obtain the graphene oxide dispersion in single or multi-layer structure；
2) it will be mixed in the graphene oxide dispersion of single or multi-layer structure and surfactant, then carry out the 4th ultrasound
Processing, and 24-48h is stirred at room temperature, obtain uniform mixed liquor；
3) mixed liquor is stirred at 70-95 DEG C 6-10h, obtains functionalization graphene；
Wherein, the surfactant is the amphiphilic surfactant with 1-4 alkyl chain；It is described that there is 1-4 alkyl
The amphiphilic surfactant of chain be cetrimonium bronmide (CTAB), didodecyldimethylammbromide bromide (DDAB) or
Tetrabromo dodecyl ammonium (TAB)；
The revolving speed of the low-speed centrifugal processing is 2000-5000 r/min；The revolving speed of the high speed centrifugation processing is 8000-
20000 r/min。
2. preparation method according to claim 1, which is characterized in that the surfactant: the quality of graphene oxide
Than for 0.2-5:1.
3. preparation method according to claim 1, which is characterized in that the concentration of the graphene oxide dispersion is 0.1-
10 mg/mL。
4. the functionalization graphene that preparation method according to claim 1 is prepared answering in absorption mycotoxin
With.
5. application according to claim 4, which is characterized in that the mycotoxin be zearalenone, vomitoxin,
Aflatoxin, fumonisin or ochratoxin.
6. application according to claim 4 or 5, which is characterized in that it is realized by the following method:
1) functionalization graphene is dispersed in water, carries out ultrasound and stirring, obtain the function fossil that concentration is 1-5mg/mL
Black alkene dispersion liquid；
2) the mycotoxin sample that the functionalization graphene dispersion liquid and concentration are >=0.1 μ g/kg is mixed, then into
Row adsorption reaction obtains intermediate reaction liquid after adsorption reaction；The pH value for adjusting the intermediate reaction liquid, be then sampled and
Detection.
7. application according to claim 6, which is characterized in that the temperature of adsorption reaction be 60-95 DEG C, adsorption reaction when
Between be 1-10h.
8. application according to claim 6, which is characterized in that the pH value for adjusting the intermediate reaction liquid is 9.0-12.6.
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| Elif Çalışkan Salihi et al..Enhanced removal of nickel(II) ions from aqueous solutions by SDS-functionalized graphene oxide.《SEPARATION SCIENCE AND TECHNOLOGY》.2016,第51卷(第8期), |
| Monomer emission from pyrene adsorbed in surfactant-intercalated graphite oxide;Yoshiaki Matsuo et al.;《Chem. Commun.》;19991231;第43-44页 |
| Preparation of Cationic Surfactant Intercalated Graphene Oxide and Quantitative Determination of the Interlamellar Spacing;Yu Liu et al.;《Fullerenes, Nanotubes and Carbon Nanostructures》;20140904;第23卷;第196-202页 |
| 氧化石墨烯对黄曲霉毒素B1的吸附性能研究;喻理 等;《中国油料作物学报》;20131031;第432-435页 |
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