CN106984276A - Metal-organic framework material, its preparation method and application - Google Patents
Metal-organic framework material, its preparation method and application Download PDFInfo
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- CN106984276A CN106984276A CN201710317094.9A CN201710317094A CN106984276A CN 106984276 A CN106984276 A CN 106984276A CN 201710317094 A CN201710317094 A CN 201710317094A CN 106984276 A CN106984276 A CN 106984276A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
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Abstract
A kind of metal-organic framework material, its preparation method and application, are related to technical field of material.A kind of preparation method of metal-organic framework material, including：Magnetic oxygenated graphene/Tanabe Seiyoku the composite being composited by magnetic oxygenated grapheme material and Tanabe Seiyoku is reacted with organic ligand, metallic compound.This method preparation technology is simple, and controllability is strong, with low cost, easy scale.A kind of metal-organic framework material, is prepared from by the above method.The stability of material is good, and resistance to acids and bases is strong, anti-matrix interference, it is easy to preserve, and absorption flux is high, and financial cost is low, can be achieved to carry out fast enriching and removal to insecticide pollution.
Description
Technical field
The present invention relates to technical field of material, and more particularly to a kind of metal-organic framework material, its preparation method
And application.
Background technology
Anabasine pesticide is the general name of the insecticide of the class neural activity related to nicotine.Anabasine pesticide
Active ingredient is made into hundreds of product in more than 100 country's sale.But most anabasine pesticide is high poison to honeybee
, and the riot of honeycomb can be caused, finally honeycomb is disintegrated.Anabasine pesticide also has an impact to the health of human body.Due to new
Nicotinoids agricultural chemicals is spectroscopic system insecticide, therefore has in food residual.Human body intake largely contains anabasine agriculture
The fruit and tea of medicine residual, easily cause headache, fatigue, finger is trembled, transience is lost memory, have a fever, cough, palpitaition, pectoralgia, stomach
Bitterly, powerless, rhythm abnormality of muscle cramp etc..Anabasine pesticide over time, can be rich in surface water and groundwater
Collection, causes harm, and cause the ecosystem to be disintegrated to terrestrial and aquatic insect.
At present, anabasine material residue detection technology for example high performance liquid chromatography, gas chromatography, thin-layered chromatography,
Gas chromatography-mass spectrometry, Liquid Chromatography-Mass Spectrometry and capillary electrophoresis etc., these methods need to use solid phase extraction
Take, SPME, the pretreatment technology such as liquid-liquid extraction.But traditional pesticide sample pretreatment technology operation is often more numerous
Trivial, detection sensitivity and the degree of accuracy are easily disturbed by matrix effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of metal-organic framework material, this method preparation technology letter
Single, controllability is strong, with low cost, easy scale.
Another object of the present invention is to provide a kind of metal-organic framework material, the stability of material is good, resistance to acids and bases
By force, anti-matrix interference, it is easy to preserve, absorption flux is high, and financial cost is low, can be achieved to carry out insecticide pollution fast enriching and
Remove.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of metal-organic framework material, including：Will be by magnetic oxygenated grapheme material
Magnetic oxygenated graphene/Tanabe Seiyoku the composite being composited with Tanabe Seiyoku and organic ligand, metallic compound
Reaction.
The present invention proposes a kind of metal-organic framework material, is prepared from by the above method.
A kind of metal-organic framework material, the beneficial effect of its preparation method of the embodiment of the present invention be：
Metal-organic framework material is made with Tanabe Seiyoku reaction using magnetic oxygenated grapheme material in the present invention, by magnetic
Property the fast enriching separation of graphene oxide and the selective absorption of the hydrophobic cavity of Tanabe Seiyoku and loose structure
The high flux absorption property of metal framework material is combined together, realize quick, high flux absorption to anabasine pesticide and
Remove.Preparation method is simple, and controllability is strong, with low cost.The metal-organic framework material recognition performance of preparation is good, stability
Good, resistance to acids and bases is strong, anti-matrix interference, it is easy to preserve, and absorption flux is high, and financial cost is low, with good application prospect.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the scanning electron microscope diagram of the metal-organic framework material of the embodiment of the present invention 5；
Fig. 2 is the examination of infrared spectrum figure of the metal-organic framework material of the embodiment of the present invention 5；
Fig. 3 is the Fe of the embodiment of the present invention 53O4Particle, magnetic oxygenated grapheme material, magnetic oxygenated graphene/amino ring
The XRD diffraction patterns of dextrin composite, metal-organic framework material；
Fig. 4 is the Fe of the embodiment of the present invention 53O4Particle, magnetic oxygenated grapheme material, magnetic oxygenated graphene/amino ring
The hysteresis curve figure of dextrin composite, metal-organic framework material；
Fig. 5 inhales for the metal-organic framework material of the embodiment of the present invention 5 to the static of anabasine pesticide under various concentrations
Attached effect curves；
Fig. 6 makees for the metal-organic framework material of the embodiment of the present invention 5 to the Dynamic Adsorption of 10 μ g/mL anabasine pesticides
Use curve；
Fig. 7 mixes target TIC figures for 100ng/mL anabasine pesticide；
The TIC of supernatant after Fig. 8 adsorbs for the metal-organic framework material of the embodiment of the present invention 5 to anabasine pesticide
Figure.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
A kind of metal-organic framework material of the embodiment of the present invention, its preparation method and application are carried out specifically below
It is bright.
A kind of preparation method of metal-organic framework material provided in an embodiment of the present invention, including：
Prepare magnetic oxygenated grapheme material.
Graphene oxide is dispersed in water, it is abundant in order to be uniformly dispersed, react, under conditions of mechanical agitation, add
FeCl3、FeCl2.Due to FeCl3、FeCl2Moisture is easily absorbed in atmosphere, in embodiments of the present invention, specifically, is added
FeCl3·6H2O and FeCl2·4H2O.Preferably, the speed of stirring is 600~1200rpm, and reaction temperature is 60~90 DEG C, instead
It is 0.5~1h between seasonable.Ammoniacal liquor is added to continue to react 0.5~1.5h.Preferably, the mass percent of ammoniacal liquor is 25%.At this
In invention other embodiment, the mass percent of ammoniacal liquor can be 28%.In the course of reaction, graphene oxide deposits to generation
Fe3O4Particle surface.
Preferably, prevent the oxygen in air from influenceing reaction, reaction is carried out in the absence of oxygen, in the implementation of the present invention
In example, nitrogen deoxygenation is used.
Further, in preferred embodiment of the present invention, graphene oxide, FeCl3、FeCl2, 25wt% ammoniacal liquor consumption
Than for 0.2~0.4mg:1.08g:0.48~0.61g:10~15mL.Preferably, graphene oxide, water, FeCl3·6H2O、
FeCl2·4H2The amount ratio of O, 25wt% ammoniacal liquor is 0.2~0.4mg:240mL:1.8g:0.75~0.96g:10~15mL.
After reaction terminates, purified reaction product is washed.Specifically, reaction product is suspended in ethanol, vibration vortex 1~
3min；The precipitation that Magneto separate is obtained is suspended in water, vibration 1~3min of vortex, washes the hydrotrope and unreacted ammoniacal liquor off.Will
Above-mentioned steps are repeated 2~4 times, and vacuum drying produces magnetic oxygenated grapheme material.Preferably, wash every time with second alcohol and water
Volume ratio is 1:2~4.
Prepare magnetic oxygenated graphene/Tanabe Seiyoku composite.
By Tanabe Seiyoku and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC), N- hydroxysuccinimidyls
Acid imide (NHS) mixing is dissolved in solvent solution.In order that reaction is more abundant, alkaline environment is provided for reaction.In the present invention
In embodiment, solvent is PBS cushioning liquid, and its concentration is 0.01M, and pH value is 7.4.Specifically, mixed solution under the conditions,
0.5~1.5h of priming reaction.After priming reaction terminates, mixed solution is mixed with the magnetic oxygenated grapheme material through ultrasonic disperse
Close uniform, 20~24h of oscillating reactions.
In embodiments of the present invention, magnetic oxygenated grapheme material is prepared from by the above method.In other of the present invention
In embodiment, magnetic oxygenated grapheme material can also be obtained by other approach, such as be bought, and the present invention is not limited it.
Further, in preferred embodiment of the present invention, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material,
The amount ratio of PBS cushioning liquid is 4mg:12~16mg:3mg:12~29mg:8~12mL.
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
Prepare metal-organic framework material.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
0.1~1h of oscillating reactions, makes magnetic oxygenated graphene/Tanabe Seiyoku composite contain carboxyl, after Magneto separate and washing,
Washed product is suspended in water.Preferably, washing methods is to be washed with ethanol three times.In the basic conditions, sulfydryl second is passed through
Acid is conducive to the formation of metal-organic framework material by carboxyl modified to composite.
Specifically, added into the above-mentioned aqueous solution containing magnetic oxygenated graphene/Tanabe Seiyoku composite dissolved with
Dimethylformamide (DMF), the alcohol mixed solution of organic ligand.It is anti-under conditions of mechanical agitation in order to react fully
Answer 0.1~1h.Preferably, the volume ratio of DMF and ethanol is 1:1.Wherein, organic ligand includes trimesic acid (H3BTC it is) or right
Phthalic acid, the present invention is not limited it.
Specifically, the aqueous solution dissolved with metallic compound is added, 3~6h is reacted.In order to react fully, add phase and turn
Shifting catalyst-triethylamine continues to react 2~4h.Specifically, the metallic compound in the embodiment of the present invention is a water acetic acid copper.
Metallic compound can also be iron, aluminium, the compound of cobalt, and the present invention is not limited it.
Further, in preferred embodiment of the present invention, magnetic oxygenated graphene/Tanabe Seiyoku composite,
H3BTC, copper acetate, the amount ratio of triethylamine are 0.12~0.2g:500~750mg:1200mg:2.4~4.2mL.
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Preferably, in washing process, washing 2~3 times is replaced with ethanol with DMF.
Present invention also offers a kind of metal-organic framework material, it is prepared from by above-mentioned preparation method.
A kind of metal-organic framework material that the present invention is provided has the effect for being enriched with and removing insecticide pollution, can be used for
Detection, removal agricultural chemicals.
Further, in preferred embodiment of the present invention, agricultural chemicals is anabasine pesticide.
Further, in preferred embodiment of the present invention, anabasine pesticide includes Diacloden, imidacloprid, Acetamiprid, alkene
Pyridine worm amine, MTI-446, clothianidin, thiacloprid.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of metal-organic framework material and preparation method thereof is present embodiments provided, including：
Tanabe Seiyoku and EDC, NHS are dissolved in PBS cushioning liquid, 0.5h is activated.Again with magnetic oxygenated graphene material
Material is well mixed, oscillating reactions 20h.
Wherein, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material, the amount ratio of PBS cushioning liquid are 4mg:
12mg:3mg:12mg:8mL。
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
React 0.1h.Add dissolved with H3BTC DMF, alcohol mixed solution.After reaction 0.1h under conditions of mechanical agitation, add
Acetic acid copper liquor, reacts 5h.Triethylamine is added to continue to react 3h.
Wherein, magnetic oxygenated graphene/Tanabe Seiyoku composite, H3BTC, copper acetate, the amount ratio of triethylamine are
0.12g:500mg:1200mg:4.2mL。
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Embodiment 2
A kind of metal-organic framework material and preparation method thereof is present embodiments provided, including：
Graphene oxide is dispersed in water, under conditions of mechanical agitation, under the protection of nitrogen, FeCl is added3·
6H2O and FeCl2·4H2O, at 60 DEG C, reacts 0.5h.Reaction completion adds ammoniacal liquor and continues to react 0.5h.
Wherein, graphene oxide, water, FeCl3·6H2O、FeCl2·4H2O, the amount ratio of ammoniacal liquor are 0.2mg:240mL:
1.8g:0.75g:10mL。
After reaction terminates, respectively with ethanol and hydromagnetic adsorbing separation, washing purified reaction product, vacuum drying, magnetic is obtained
Property graphene oxide composite material.
Tanabe Seiyoku and EDC, NHS are dissolved in PBS cushioning liquid, 0.5h is activated.Again with the magnetic through ultrasonic disperse
Graphene oxide composite material is well mixed, oscillating reactions 20h.
Wherein, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material, the amount ratio of PBS cushioning liquid are 4mg:
12mg:3mg:12mg:8mL。
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
Oscillating reactions 0.1h.Add dissolved with H3BTC DMF, alcohol mixed solution.After reaction 0.1h under conditions of mechanical agitation, then
Acetic acid copper liquor is added, 3h is reacted.Triethylamine is added to continue to react 2h.
Wherein, magnetic oxygenated graphene/Tanabe Seiyoku composite, H3BTC, copper acetate, the amount ratio of triethylamine are
0.12g:500mg:1200mg:2.4mL。
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Embodiment 3
A kind of metal-organic framework material and preparation method thereof is present embodiments provided, including：
Graphene oxide is dispersed in water, under conditions of mechanical agitation, under the protection of nitrogen, FeCl is added3·
6H2O and FeCl2·4H2O, at 90 DEG C, reacts 1h.The ammoniacal liquor that reaction completes to add 25wt% continues to react 1.5h.
Wherein, graphene oxide, water, FeCl3·6H2O、FeCl2·4H2The amount ratio of O, 25wt% ammoniacal liquor is 0.4mg:
240mL:1.8g:0.96g:15mL。
After reaction terminates, respectively with ethanol and hydromagnetic adsorbing separation, washing purified reaction product, vacuum drying, magnetic is obtained
Property graphene oxide composite material.
Tanabe Seiyoku and EDC, NHS are dissolved in PBS cushioning liquid, 1.5h is activated.Again with the magnetic through ultrasonic disperse
Graphene oxide composite material is well mixed, oscillating reactions 24h.
Wherein, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material, the amount ratio of PBS cushioning liquid are 4mg:
16mg:3mg:29mg:12mL。
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
Oscillating reactions 1h.Add dissolved with H3BTC DMF, alcohol mixed solution.After reaction 1h under conditions of mechanical agitation, add
Acetic acid copper liquor, reacts 6h.Triethylamine is added to continue to react 4h.
Wherein, magnetic oxygenated graphene/Tanabe Seiyoku composite, H3BTC, copper acetate, the amount ratio of triethylamine are
0.2g:750mg:1200mg:4.2mL。
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Embodiment 4
A kind of metal-organic framework material and preparation method thereof is present embodiments provided, including：
Graphene oxide is dispersed in water, under conditions of mechanical agitation, under the protection of nitrogen, FeCl is added3·
6H2O and FeCl2·4H2O, at 80 DEG C, reacts 0.6h.The ammoniacal liquor that reaction completes to add 25wt% continues to react 1.2h.
Wherein, graphene oxide, water, FeCl3·6H2O、FeCl2·4H2The amount ratio of O, 25wt% ammoniacal liquor is 0.3mg:
240mL:1.8g:0.85g:12mL。
After reaction terminates, respectively with ethanol and hydromagnetic adsorbing separation, washing purified reaction product, vacuum drying, magnetic is obtained
Property graphene oxide composite material.
Tanabe Seiyoku and EDC, NHS are dissolved in PBS cushioning liquid, 1h is activated.Again with the magnetic oxygen through ultrasonic disperse
Graphite alkene material is well mixed, oscillating reactions 22h.
Wherein, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material, the amount ratio of PBS cushioning liquid are 4mg:
12mg:3mg:12mg:12mL。
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
Oscillating reactions 0.6h.Add dissolved with H3BTC DMF, alcohol mixed solution.After reaction 0.3h under conditions of mechanical agitation, then
Acetic acid copper liquor is added, 5h is reacted.Triethylamine is added to continue to react 2h.
Wherein, magnetic oxygenated graphene/Tanabe Seiyoku composite, H3BTC, copper acetate, the amount ratio of triethylamine are
0.16g:625mg:1200mg:4.2mL。
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Embodiment 5
A kind of metal-organic framework material and preparation method thereof is present embodiments provided, including：
Graphene oxide is dispersed in water, under conditions of mechanical agitation, under the protection of nitrogen, FeCl is added3·
6H2O and FeCl2·4H2O, at 75 DEG C, reacts 0.8h.The ammoniacal liquor that reaction completes to add 25wt% continues to react 1h.
Wherein, graphene oxide, water, FeCl3·6H2O、FeCl2·4H2The amount ratio of O, 25wt% ammoniacal liquor is 0.3mg:
240mL:1.8g:0.85g:12mL。
After reaction terminates, respectively with ethanol and hydromagnetic adsorbing separation, washing purified reaction product, vacuum drying, magnetic is obtained
Property graphene oxide composite material.
Tanabe Seiyoku and EDC, NHS are dissolved in PBS cushioning liquid, 1h is activated.Again with the magnetic oxygen through ultrasonic disperse
Graphite alkene material is well mixed, oscillating reactions 22h.
Wherein, Tanabe Seiyoku, EDC, NHS, magnetic oxygenated grapheme material, the amount ratio of PBS cushioning liquid are 4mg:
14mg:3mg:20mg:10mL。
After reaction terminates, reaction product is separated through magnetic suck, washed, is dried in vacuo and obtains magnetic oxygenated graphene/ammonia
Cyclodextrin composite.
By in the TGA for magnetic oxygenated graphene/Tanabe Seiyoku composite is suspended in, the mixed solution of ethanol,
Oscillating reactions 0.5h.Add dissolved with H3BTC DMF, alcohol mixed solution.After reaction 0.5h under conditions of mechanical agitation, then
Acetic acid copper liquor is added, 4.5h is reacted.Triethylamine is added to continue to react 3h.
Wherein, magnetic oxygenated graphene/Tanabe Seiyoku composite, H3BTC, copper acetate, the amount ratio of triethylamine are
0.16g:625mg:1200mg:3.3mL。
After reaction terminates, magnetic suck separation, washing are carried out to reaction product and metal-organic framework material is obtained after drying.
Test example 1
Metal-organic framework material progress performance detection prepared by embodiment 1~5 is chosen, method is as follows：
The metal-organic framework material of 5mg embodiments 1~5 is added to the water that 1mL imidacloprid concentrations are 50 μ g/mL respectively
In solution, supernatant is separated by externally-applied magnetic field, is determined with HPLC-MS/MS and calculates adsorbance.Test result is such as
Under：
Adsorbance of the metal-organic framework material of table 1 to imidacloprid
As shown in Table 1, the adsorbance of the metal-organic framework material of embodiment 1~5 is all higher, wherein, the gold of embodiment 5
The adsorbance for belonging to organic framework materials is maximum, illustrates that the metal-organic framework material has better performance.
Test example 2
Choose metal-organic framework material progress Morphology analysis prepared by embodiment 5.Scanning electron microscopy such as Fig. 1
It is shown.As shown in Figure 1, the metal-organic framework material that prepared by embodiment 5 is into loose porous block structure.The structure contributes to
Agricultural chemicals is enriched with and removed.
Test example 3
Metal-organic framework material progress examination of infrared spectrum prepared by embodiment 5 is chosen, Fig. 2 is as a result seen.
As shown in Figure 2,576cm-1The absworption peak at place is Fe-O characteristic absorption peak, while in 1571cm-1Place occurs in that-
CONH- characteristic absorption peak, illustrates that Tanabe Seiyoku molecule has been coupled to surface of graphene oxide.1391cm-1Place is occurred in that
One strong vibration peak, this peak is H3- COOH stretching vibration peak, 1502cm in BTC-1The vibration peak at place is H3Substituted benzene in BTC
The characteristic peak of ring, above analytic explanation is successfully prepared magnetic oxygenated graphene/Tanabe Seiyoku metal-organic framework material.
Test example 4
Choose the Fe in embodiment 53O4Particle, magnetic oxygenated grapheme material, magnetic oxygenated graphene/Tanabe Seiyoku
Composite, metal-organic framework material carry out X-ray diffraction test, and test result is shown in Fig. 3.
In Fig. 3, a curves are Fe3O4The XRD curves of particle, b curves are the XRD curves of magnetic oxygenated grapheme material, and c is bent
Line is the XRD curves of magnetic oxygenated graphene/Tanabe Seiyoku composite, and d curves are bent for the XRD of metal-organic framework material
Line.Fe3O4The XRD curves of particle contain 5 characteristic diffraction peaks, with Fe3O4Three-dimensional minute surface mutually coincide, with X-ray diffraction number
According to Fe in storehouse3O4The data of standard card are consistent.From the figure 3, it may be seen that Fe3O4In modification graphene oxide and metal-organic framework material
The crystal structure of spinelle is remained in that during cladding.But with modification and the progress of cladding, shell thickness increases,
Fe3O4The intensity of 5 characteristic diffraction peaks gradually weaken, but still maintain preferable magnetic.
Test example 5
Choose the Fe in embodiment 53O4Particle, magnetic oxygenated grapheme material, magnetic oxygenated graphene/Tanabe Seiyoku
Composite, metal-organic framework material carry out hysteresis curve test, and test result is shown in Fig. 4.Wherein, a curves are Fe3O4Particle
Curve of Magnetic Hysteresis Loop, b curves be magnetic oxygenated grapheme material Curve of Magnetic Hysteresis Loop, c curves be magnetic oxygenated graphene/
The Curve of Magnetic Hysteresis Loop of Tanabe Seiyoku composite, d curves are the Curve of Magnetic Hysteresis Loop of metal-organic framework material.
By Fig. 4, Fe3O4Particle has higher magnetic saturation intensity, is 67.7emu/g, but is due to the surface effect of particle
Should, Fe3O4Particle magnetic saturation intensity is significantly less than the theoretical strength 92emu/g of large volume magnet.Because with decorative material
Increase, magnetic response reduces therewith.The remanent magnetization of a, b, c curve and remaining coercivity all level off to 0, illustrate these three
Magnetic material all has superparamagnetism.In the presence of externally-applied magnetic field, it is only necessary to about 20s time, magnetic metal is organic
Frame material rapidly can just be assembled from solution to be separated.After externally-applied magnetic field disappearance, magnetic metal organic frame
Material can be uniformly dispersed in solution again.Fe3O4It is good that metal-organic framework material can be assigned as magnetic core and carrier
Superparamagnetism, can avoid the steps such as centrifugation, greatly save time and cost, the insecticide pollution of realization rapidly and efficiently
Absorption and removal.
Test example 6
It is respectively 0.5 μ that the metal-organic framework material of 5mg embodiments 5 is added into 1mL anabasine pesticide concentration respectively
In g/mL, 1 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ g/mL, the 100 μ g/mL aqueous solution, wherein every part of anabasine
In class agricultural chemicals, Diacloden, imidacloprid, Acetamiprid, Nitenpyram, MTI-446, clothianidin, the concentration all same of thiacloprid.Absorption
Supernatant is filtrated to get after 2h, supernatant is determined with HPLC-MS/MS and calculates adsorbance.Test result such as Fig. 5.
As shown in Figure 5, it is that metal-organic framework material is to seven in the range of 0.5~50 μ g/mL in anabasine pesticide concentration
The adsorbance for planting anabasine pesticide is continuously increased with the rise of initial soln concentration, in 50~100 μ g/mL concentration ranges
Interior, metal-organic framework material becomes gentle to the adsorbance increase trend of anabasine pesticide, basically reaches adsorption equilibrium.Although
Metal-organic framework material has certain absorption (can be described as class specificity) to seven kinds of anabasine agricultural chemicals, but to thiacloprid
Adsorption capacity outline is higher than other several agricultural chemicals, wherein the adsorption capacity to MTI-446 is worst.Its possible cause is that metal is organic
Active force between frame material and anabasine agricultural chemicals do not have based on π-πconjugation and hydrophobic effect, in MTI-446 phenyl ring and
Double bond structure, causes metal-organic framework material to function power decrease, adsorbance reduction.
Test example 7
The metal-organic framework material of 5mg embodiments 5 is added to 1mL anabasine pesticides concentration for 10 μ g/mL respectively
The aqueous solution in, be filtrated to get supernatant after absorption 2h, determine supernatant with HPLC-MS/MS and calculate adsorbance.Test result
Such as Fig. 6.
It will be appreciated from fig. 6 that metal-organic framework material to the adsorbance of seven kinds of anabasine pesticides with the increase of time
It is incremented by, but advancing the speed for its adsorbance is but gradually reduced.In preceding 30min, the adsorbance of metal-organic framework material is fast
Speed increase；In 60min, the adsorbance of metal-organic framework material is maximum；The metal-organic framework material in 60~120min
Adsorbance starts reduction, it may occur however that dynamic absorption-resolving.
Test example 8
Anabasine agriculture in anabasine pesticide and test example 7 to 100ng/mL after metal-organic framework material absorption
The supernatant of aqueous solution carries out liquid chromatography mass spectrometric test.As a result such as Fig. 7 and Fig. 8.
Seven kinds of anabasine pesticides contains in Fig. 7 and Fig. 8, the supernatant after being adsorbed through metal-organic framework material
Amount declines, wherein, the adsorbance to thiacloprid is maximum.Illustrate that metal-organic framework material prepared by embodiment 5 can be realized pair
The enrichment and removal of anabasine pesticide.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of metal-organic framework material, it is characterised in that including：Will by magnetic oxygenated grapheme material with
Magnetic oxygenated graphene/Tanabe Seiyoku the composite and organic ligand, metallic compound that Tanabe Seiyoku is composited are anti-
Should.
2. the preparation method of metal-organic framework material according to claim 1, it is characterised in that the magnetic oxygenated stone
Black alkene/Tanabe Seiyoku composite contains carboxyl.
3. the preparation method of metal-organic framework material according to claim 2, it is characterised in that the organic ligand bag
Terephthalic acid (TPA) or trimesic acid are included, the metallic compound includes copper acetate.
4. the preparation method of metal-organic framework material according to claim 3, it is characterised in that the magnetic oxygenated stone
Black alkene/Tanabe Seiyoku composite, the trimesic acid, the amount ratio of the copper acetate are 0.12~0.2g:500~
750mg:1200mg。
5. the preparation method of metal-organic framework material according to claim 1, it is characterised in that the magnetic oxygenated stone
The preparation method of black alkene/Tanabe Seiyoku composite includes：By the Tanabe Seiyoku and 1- (3- dimethylamino-propyls) -3-
Ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide admixture activation, then mixed instead with the magnetic oxygenated grapheme material
Should.
6. the preparation method of metal-organic framework material according to claim 5, it is characterised in that the amino ring paste
Smart, described 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, the n-hydroxysuccinimide, the magnetic
The amount ratio of graphene oxide composite material is 4mg:12~16mg:3mg:12~29mg.
7. the preparation method of metal-organic framework material according to claim 5, it is characterised in that the magnetic oxygenated stone
The preparation method of black alkene material includes：Under conditions of 60~90 DEG C, anaerobic, by graphene oxide and FeCl3、FeCl2Reaction
After 0.5~1h, add ammoniacal liquor and continue to react 0.5~1.5h.
8. the preparation method of metal-organic framework material according to claim 7, it is characterised in that the graphite oxide
Alkene, the FeCl3, the FeCl2Amount ratio be 0.2~0.4mg:1.08g:0.48~0.61g.
9. a kind of metal-organic framework material, it is characterised in that as the metal organic frame described in any one of claim 1~8
The preparation method of material is prepared from.
10. application of the metal-organic framework material as claimed in claim 9 in terms of detection, removal agricultural chemicals.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467490A (en) * | 2018-03-29 | 2018-08-31 | 中国农业科学院蔬菜花卉研究所 | Functional metal organic frame porous material and its preparation method and application |
| CN109453746A (en) * | 2018-11-13 | 2019-03-12 | 北京化工大学 | A kind of high-specific surface area COFs nano adsorption material, preparation method and application |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551197A (en) * | 2013-11-11 | 2014-02-05 | 北京化工大学 | Magnetic metal-organic framework material with pocket-channel structure and preparation and reaction for acylation thereof |
| CN103549635A (en) * | 2013-11-01 | 2014-02-05 | 西南大学 | Preparation method of resistant starch nutritional carrier based on metal-organic framework as well as product thereof |
| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104138746A (en) * | 2014-07-22 | 2014-11-12 | 华南理工大学 | Copper-based metal-organic framework porous material and preparation method and application thereof |
-
2017
- 2017-05-08 CN CN201710317094.9A patent/CN106984276B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103549635A (en) * | 2013-11-01 | 2014-02-05 | 西南大学 | Preparation method of resistant starch nutritional carrier based on metal-organic framework as well as product thereof |
| CN103551197A (en) * | 2013-11-11 | 2014-02-05 | 北京化工大学 | Magnetic metal-organic framework material with pocket-channel structure and preparation and reaction for acylation thereof |
| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104138746A (en) * | 2014-07-22 | 2014-11-12 | 华南理工大学 | Copper-based metal-organic framework porous material and preparation method and application thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467490A (en) * | 2018-03-29 | 2018-08-31 | 中国农业科学院蔬菜花卉研究所 | Functional metal organic frame porous material and its preparation method and application |
| CN109453746A (en) * | 2018-11-13 | 2019-03-12 | 北京化工大学 | A kind of high-specific surface area COFs nano adsorption material, preparation method and application |
| CN109796005A (en) * | 2019-03-27 | 2019-05-24 | 中国农业大学 | Application of the cyclodextrin metal organic frame carbon material in water process and fertilizer slow release |
| CN110749667A (en) * | 2019-09-20 | 2020-02-04 | 青岛理工大学 | Analysis and detection method of four neonicotinoid insecticides in water |
| CN110749667B (en) * | 2019-09-20 | 2022-07-15 | 青岛理工大学 | Analysis and detection method of four neonicotinoid insecticides in water |
| CN111740093A (en) * | 2020-06-11 | 2020-10-02 | 扬州大学 | Method for preparing reduced graphene/aminated column [5] arene/sulfur serving as lithium-sulfur positive electrode material |
| CN111999276A (en) * | 2020-08-26 | 2020-11-27 | 北京大学 | Method for preparing luminous europium-based metal organic framework probe and application thereof |
| CN111999276B (en) * | 2020-08-26 | 2021-06-08 | 北京大学 | Method for preparing luminous europium-based metal organic framework probe and application thereof |
| CN114618444A (en) * | 2021-12-16 | 2022-06-14 | 南京工业大学 | Modified metal organic polyhedral material, preparation method and application thereof |
| CN114618444B (en) * | 2021-12-16 | 2023-09-01 | 南京工业大学 | Modified metal organic polyhedral material, preparation method and application thereof |
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