CN110339823A - A kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application - Google Patents
A kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, preparation including Eichhornia crassipes activated feedstock, the preparation of Eichhornia crassipes base magnetism multi-stage porous carbon and the preparation of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, Eichhornia crassipes is strong with its reproductive capacity, it is easily obtained, the advantages such as carbon element content is abundant and surface functional group is abundant are as the good raw material for preparing multi-stage porous carbon material, multi-stage porous carbon material is prepared as molecular engram host material using Eichhornia crassipes, it not only can effectively alleviate shortage of resources problem but also being capable of mitigating circumstances pollution problem.
Description
Technical field
It is utilized the present invention relates to water plant and Treatment process field, more particularly to a kind of Eichhornia crassipes base is magnetic
Multi-stage porous carbon surface imprinted material and its preparation method and application.
Background technique
Ciprofloxacin belongs to third generation fluoroquinolone antibiotics, has that has a broad antifungal spectrum, antibacterial activity be strong, haemoconcentration
Height, bioavailability are high, can decompose the features such as each tissue rapidly and be widely used.Due to the suction of antibiotic in vivo
The property received is lower, and most of drug used enters environment after draining with parent drug form, causes potential threat to environment.
Studies have shown that about 25%-75% in the antibiotic medicine that animal uses by from excrement with the shape of parent drug or metabolin
Formula excretes, therefore enters the antibiotic of soil or aquatic environment by excreta, generates far-reaching influence to environment.
Eichhornia crassipes also known as water hyacinth, fertility is strong, grows in flakes, can not only block river, influence field irrigation and water
Upper transport can also fight for illumination, nutrient and growing space with other aquatiles in water body, and the biology for seriously threatening water body is more
Sample, prepares biological carbon materials then using Eichhornia crassipes and can effectively reduce environmental hazard caused by it and realize and change harmful to treasure.
Molecularly imprinted polymer is that have specific recognition and selectivity to target molecule by molecular imprinting technology synthesis
The polymer of absorption.Surface molecule print technology is by establishing molecular recognition site on the surface of host material, and the technology is very
It is good solve conventional bulk polymerization it is highly cross-linked caused by target molecule binding ability is small, cannot completely remove, active site
Embed the disadvantages of too deep, mass transfer is slow and the dynamic performance of adsorption-desorption is bad.
Multi-stage porous carbon material refers to while having micropore, mesoporous and three kinds of aperture structures of macropore carbon material, due to its tool
The features such as having higher specific surface area, good chemical stability, the cellular structure of prosperity, becomes a kind of ideal surface molecular
Blotting matrix material, being applied to environmental improvement is current research hotspot.
Therefore, how cheap biomass resource is utilized, prepares the trace that adsorption capacity is big, selective recognition capability is strong and inhales
Enclosure material, and then effectively identifying and separate traces of antibiotic from Complex Water Environment system using trace adsorbent material is this field
The problem of technical staff's urgent need to resolve.
Summary of the invention
In view of this, the present invention prepares multi-stage porous carbon material as molecular engram host material using Eichhornia crassipes, not only may be used
Effectively to alleviate shortage of resources problem and being capable of mitigating circumstances pollution problem.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, comprising the following steps:
(1) preparation of Eichhornia crassipes activated feedstock
Eichhornia crassipes is salvaged from lake and is come, cauline leaf is removed, retains root, is cleaned Water Hyacinth Root with distilled water, is dried
And crushed, be sieved, grind into powder, the Eichhornia crassipes powder is added in phosphoric acid solution, is heated while stirring, is dissolved
Vacuum drying obtains Eichhornia crassipes activated feedstock after completely；
(2) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon
The Eichhornia crassipes activated feedstock is uniformly mixed with the ethanol solution of iron chloride, the vacuum in 90-100 DEG C of baking oven
Drying to constant weight is placed in tube furnace, and cooling after high temperature cabonization magnetization under inert gas protection, washing, drying obtain phoenix eyes
Lotus base magnetism multi-stage porous carbon；
(3) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material
Successively Ciprofloxacin, methacrylic acid are added in the mixed solution of methanol and water, under inert gas protection
Then glycol methacrylate is added in ultrasonic 40min, it is magnetic more that stirring continuously adds Eichhornia crassipes base to after being thoroughly mixed
The mixed solution of grade hole carbon and the first alcohol and water containing polyvinylpyrrolidone, ultrasound 60min, continues under inert gas protection
2,2 ' azo diisobutyl amidine dihydrochlorides are added, products therefrom collected with permanent magnet, washed, extract, be dried in vacuo
To Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material.
In the above-mentioned technical solutions, glycol methacrylate plays the role of crosslinking agent, polyvinylpyrrolidone
Due to that above-mentioned several substances can be dissolved well with excellent solubility property, 2,2 ' azo diisobutyl amidine, two hydrochloric acid
Salt is water soluble starter, during polymer polymerizing from initiation.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in drying temperature be 100-120 DEG C, time 12-24h；The passing-screen size is 100 mesh.
The beneficial effect of above-mentioned technical proposal is: the restriction of above-mentioned numerical value, can be good at for next step chemical activation with
And the preparation of multi-stage porous carbon material is prepared.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (1)
The mass ratio of middle Eichhornia crassipes powder and phosphoric acid solution is 1:1-4, and wherein the concentration of phosphoric acid solution is 10-20%.
The beneficial effect of above-mentioned technical proposal is: phosphoric acid plays the role of activator, for manufacturing micropore and increasing hole
Gap rate.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in be heated to be 60-70 DEG C under the conditions of heating water bath 1-3h.
The beneficial effect of above-mentioned technical proposal is: heating water bath process can promote the activation of material.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in it is dry be 100-120 DEG C under the conditions of be dried in vacuo 12-24h.
The beneficial effect of above-mentioned technical proposal is: the phoenix eyes in above-mentioned temperature and drying in the period, after guaranteeing activation
The drying of lotus powder.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (2)
The mass ratio of the ethanol solution of middle Eichhornia crassipes activated feedstock and iron chloride is 3:20, and wherein the concentration of the ethanol solution of iron chloride is
0.02-0.1g/mL。
The beneficial effect of above-mentioned technical proposal is: the purpose of ethanol solution of iron chloride is added is to prepare magnetic multi-stage porous
Carbon.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (2)
Described in high temperature cabonization magnetization be to be warming up to 600-800 DEG C with the rate of 5-8 DEG C/min, carbonization magnetization 2-3h.
The beneficial effect of above-mentioned technical proposal is: by the control to the temperature and time in carbonisation, realizing to carbon
Change the control of material pass structure, synthesizes the activated carbon with high-specific surface area and pore volume, and make it have good machinery
Stability, thermal stability and regenerability.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (2)
Described in washing for be 1:1 with volume ratio ethyl alcohol/distilled water washed product.
The beneficial effect of above-mentioned technical proposal is: can guarantee that the impurity for being dissolved in water with being dissolved in ethyl alcohol is dry by thorough washing
Only.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
The molar ratio of middle Ciprofloxacin and methacrylic acid is 1:3-4.
The beneficial effect of above-mentioned technical proposal is: methacrylic acid here functions as the effect of function monomer.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
The concentration of middle Ciprofloxacin is 20-30mol/L.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
The molar ratio of middle Ciprofloxacin and glycol methacrylate is 1:8-10.
The beneficial effect of above-mentioned technical proposal is: glycol methacrylate plays the role of crosslinking agent.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
Described in Eichhornia crassipes base magnetism multi-stage porous carbon material concentration control in 0.2-0.4g/100mL.
The beneficial effect of above-mentioned technical proposal is: Eichhornia crassipes base magnetism multi-stage porous carbon material is in surface imprinted adsorbent material
It is matrix in preparation, above-mentioned concentration is successfully to prepare the precondition of surface imprinted material.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
The ratio of middle Ciprofloxacin and 2,2 ' azo diisobutyl amidine dihydrochlorides is 1mmol:0.6g.
Preferably, in a kind of above-mentioned preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, step (3)
Described in extract be with methanol and acetic acid volume ratio be 9:1 mixed liquor Soxhlet extraction for 24 hours, until can't detect ring in eluent
Third husky star.
The beneficial effect of above-mentioned technical proposal is: with methanol and acetic acid volume ratio be 9:1 mixed liquor Soxhlet extraction for 24 hours,
It is thorough to guarantee that template molecule extracts.
The invention also discloses a kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted materials that the above method is prepared；
And a kind of application for the Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material that the above method is prepared, it is described surface imprinted
Material for Ciprofloxacin in environment Selective recognition with separate.
It can be seen via above technical scheme that compared with prior art, the present invention uses Eichhornia crassipes for raw material, numerous using its
Grow the advantages such as power is strong, be easily obtained, carbon element content is abundant and surface functional group is abundant multi-stage porous carbon material is prepared,
And be used as molecular engram host material, not only can effectively alleviate shortage of resources problem and also can mitigating circumstances pollution
Problem.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing be surface imprinted material of the present invention (MMIPs) suspension in water (left side) and under the action of an external magnetic field
The photo on (the right)；
Fig. 2 attached drawing is the hysteresis loop figure of magnetic Eichhornia crassipes multi-stage porous carbon and surface imprinted material (MMIPs) in room temperature；
Fig. 3 attached drawing is the infrared spectroscopy of Eichhornia crassipes powder of the present invention and Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material
Figure；
Fig. 4 attached drawing is the adsorption isotherm map that imprinted material of the present invention and non-imprinted material adsorb Ciprofloxacin；
Fig. 5 attached drawing is the adsorption dynamics adsorption kinetics figure that imprinted material of the present invention and non-imprinted material adsorb Ciprofloxacin；
Fig. 6 attached drawing is imprinted material of the present invention and non-imprinted material respectively in non-template molecule sulphadiazine (SD), Fourth Ring
The adsorption energy that absorption template molecule Ciprofloxacin is striven in the presence of plain (TC) is tried hard to.
Fig. 7 attached drawing is absorption of the imprinted material of the present invention in the mixed solution of single CIP solution and antibiotic molecule to CIP
Capacity schematic diagram.
Specific embodiment
Below in conjunction with the attached drawing of the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a kind of preparation methods of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, including
Following steps:
(1) preparation of Eichhornia crassipes activated feedstock
Eichhornia crassipes is salvaged from lake and is come, cauline leaf is removed, retains root；Water Hyacinth Root is cleaned with distilled water, is dried
And crushed, it is sieved with 100 mesh sieve；100 DEG C -120 DEG C of Eichhornia crassipes drying temperature, time 12-24h, grind into powder,
It is spare；
Above-mentioned material is added in the phosphoric acid solution that concentration is 10%-20% and is stirred, water hyacinth powder and phosphoric acid solution
The mass ratio of (activator) is 1:1-4, under the conditions of -70 DEG C of temperature 60 C, heating water bath 1-3h；It is 100 DEG C -120 in temperature
Under the conditions of DEG C, it is dried in vacuo 12-24h, obtains Eichhornia crassipes activated feedstock；
(2) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon
It is the ethanol solution of 0.02-0.1g/ml iron chloride according to matter by Eichhornia crassipes activated feedstock obtained above and concentration
Amount is mixed than the ratio for being 3:20, is thoroughly mixed uniformly, vacuum drying is to constant weight in 90-100 DEG C of baking oven, by above-mentioned material
Material is fitted into tube furnace, under inert gas argon gas shielded, gas flow rate 40-90mL/min, with 5-8 DEG C/min heating rate
600-800 DEG C of heating, carbonization magnetizing time is 3h, is 1:1 with volume ratio by the product taking-up in tube furnace after natural cooling
Ethyl alcohol/distilled water washed product, drying obtain Eichhornia crassipes base magnetism multi-stage porous carbon.
(3) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material
According to Ciprofloxacin: methacrylic acid molar ratio is 1:(3-4) (mol/mol), successively by Ciprofloxacin, methyl-prop
Olefin(e) acid is added in the mixed liquor of the methanol that volume ratio is 3:1 and water, and the concentration of Ciprofloxacin is controlled in 20-30moL/L, on
State mixed liquor ultrasound 40min under nitrogen protection；Then in above-mentioned mixed liquor according to molar ratio Ciprofloxacin: the double first of ethylene glycol
Glycol methacrylate (EGDMA) is added for the ratio of 1:(8-10) (mol/mol) in base acrylate (EGDMA), machine
Tool stirring continuously adds Eichhornia crassipes base magnetism multi-stage porous carbon material and polyvinylpyrrolidone containing 0.02g after being thoroughly mixed
(PVP) mixed solution of first alcohol and water, wherein methanol and water volume ratio are 3:1, wherein control Eichhornia crassipes base magnetism multi-stage porous
Concentration of the carbon material in entire solution system is 0.2-0.4g/100mL, and above-mentioned mixed system is ultrasonic under nitrogen protection
60min, then to 2,2 ' azo diisobutyl amidine dihydrochlorides (AIBA) are added in above-mentioned solution, according to Ciprofloxacin: 2,2 '
Azo diisobutyl amidine dihydrochloride (AIBA) usage ratio is 1:0.6 (mmol/g), above-mentioned mixed liquor room under nitrogen protection
Temperature reaction 15h；
Above-mentioned products therefrom is collected with Nd-Fe-B permanent magnet, is repeatedly washed with dehydrated alcohol and distilled water, is then used first
Pure and mild acetic acid be the mixed liquor Soxhlet extraction of 9:1 (V/V) for 24 hours, to can't detect Ciprofloxacin molecule into eluent, 60 DEG C are very
Sky is dry to constant weight.
The preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface non-imprinted material is same as above, and cyclopropyl sand is only not added in the process
Star.
It is to be carried out to the Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material that the present invention is prepared referring to attached drawing 1-3
It detects as follows:
Fig. 1 is that molecularly imprinted material on surface (MMIPs) suspends in water (left side) and under the action of an external magnetic field (the right)
Photo, it can be seen from the figure that MMIPs has good dispersibility and Magneto separate efficiency in water, MMIPs is dispersed in water
In, under the action of externally-applied magnetic field in 20s can by it from water quick separating, show that MMIPs has good reclaiming
Energy.
Fig. 2 is the hysteresis loop of magnetic Eichhornia crassipes multi-stage porous carbon and MMIPs in room temperature, as can be seen from Figure 2 two songs
The shape and variation tendency of line are similar, and are all to show magnetic Eichhornia crassipes multi-stage porous carbon and surface print about origin symmetry
Mark material (MMIPs) all has superparamagnetism, the saturation magnetization (Ms) of room temperature magnetic Eichhornia crassipes multi-stage porous carbon and MMIPs
Respectively 12.285emu.g-1With 7.466 emu.g-1。
Fig. 3 is the infrared spectrogram of Eichhornia crassipes (a), Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material (b), Eichhornia crassipes
(a), the corresponding infrared signature peak of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material (b) can be used to verify some existing
Functional group.From Fig. 3 (a) it is found that in 3410cm-1And 1628cm-1The absorption peak at place is the peak Eichhornia crassipes hydroxyl (- OH) and CH, CH2
Middle c h bond stretching absorbance peak, 1422cm-1And 1050cm-1The absorption peak at place is Eichhornia crassipes C=O stretching vibration peak；From Fig. 3 (b)
In it is found that 595cm-1And 520cm-1All there is Fe in place3O4The Fe-O key characteristic absorption peak of nanoparticle, in 1710cm-1With
1210 cm-1The absorption peak at place be the stretching vibration of C=O in carboxyl, in EGDMA ester group C-O symmetric vibration.
The surface imprinted material of Eichhornia crassipes base magnetism multi-stage porous carbon that the present invention is prepared below with reference to specific embodiment
The application of material is described further:
Absorption property evaluation is completed using Static Adsorption test in specific embodiment in the present invention.
10mL ciprofloxacin solution is added in centrifuge tube, 5.0mg Ciprofloxacin molecular engram material is added thereto respectively
Material and non-imprinted material, it is static in room-temperature water bath, initial concentration solution and time of contact are investigated to Ciprofloxacin adsorption capacity
It influences, up to after balancing, imprinted material (MMIPs) or non-imprinted material (MNIPs) are separated with Nd-Fe-B permanent magnet for absorption, are inhaled
Remaining Ciprofloxacin Concentration is measured at wavelength 276nm with ultraviolet-uisible spectrophotometer in attached solution.Calculate to obtain absorption
Capacity (q)
Q=[(C0-Ce)V]/W
C0(mmol/L) and Ce(mmol/L) be respectively Ciprofloxacin initial concentration and balance when concentration, V (mL) and W
(mg) be respectively liquor capacity and adsorbent material dosage.
Test example 1: take 10mL initial concentration the ciprofloxacin solution of 0.0005mmol/L-0.1mmol/L be added to from
In heart pipe, it is separately added into 5.0mg Ciprofloxacin molecular engram material and non-imprinted material, test solution is placed in room temperature water bath
Middle standing for 24 hours, with the concentration of remaining Ciprofloxacin molecule in solution after ultraviolet-uisible spectrophotometer measurement absorption, is calculated and is inhaled
Attached capacity.
Show that adsorption capacity increases with the raising of concentration shown in Fig. 4, molecular engram material and non-imprinted material are to ring
Third husky star saturated adsorption capacity is respectively 2850 μ g/g and 1550 μ g/g, studies have shown that compared with non-imprinted material, Ciprofloxacin
Molecular engram material has bigger adsorption capacity, shows good specific recognition performance, illustrate in imprinted material exist with
The active site that Ciprofloxacin molecule matches.
Test example 2: taking 10mL initial concentration is that the ciprofloxacin solution of 0.05mmol/L is added in centrifuge tube, is added
Test solution is placed in quiet respectively in water-bath under room temperature by 5.0mg Ciprofloxacin molecular engram material and non-imprinted material
5,10,30,45,60,90,120 and 150min is set, the concentration of Ciprofloxacin in solution after adsorbing then is measured, calculates absorption
Capacity.
As can be known from Fig. 5, with the increase of adsorption time, adsorption capacity increases sharply, and absorption reaches balance after 50min,
In entire Longer absorption times, Ciprofloxacin molecular engram material is greater than non-imprinted material pair to the adsorption capacity of Ciprofloxacin
Ciprofloxacin adsorption capacity, the results showed that, imprinted material shows higher adsorption capacity than non-imprinted material and passes faster
Mass-energy power.
Test example 3: antibiotic compound (such as the sulphadiazine SD, Fourth Ring similar with Ciprofloxacin (CIP)) structure are chosen
Plain TC) as competition substance evaluate the selectivity of Ciprofloxacin molecular engram material.It is husky to single 0.2mmol/L cyclopropyl respectively
The sulphadiazine of 0.2mmol/L is added in star solution, forms two-constituent solution in tetracycline, while being separately added into 10.0mg
Ciprofloxacin molecular engram material and non-imprinted material, temperature is room temperature, when adsorption time reaches balance for 24 hours, to adsorb, trace
Material (MMIPs) or non-trace (MNIPs) are separated with Nd-Fe-B permanent magnet, remaining every kind of antibiotic in solution after absorption
The concentration of class compound is measured with HPLC.
Fig. 6 is the present invention importance that further research formwork structure combines molecular engram material target, is inhaled with competition
Attached experiment is to investigate, there is shown in two-constituent solution, the adsorption capacity of imprinted material and non-imprinted material to Ciprofloxacin.
It can be seen from the figure that imprinted material still shows higher absorption to Ciprofloxacin under the conditions of competing existing for antibiotic
Capacity, the results showed that imprinted material still has template Ciprofloxacin molecule (CIP) under conditions of structure is interfered similar to antibiotic
Higher selectivity adsorption capacity.
Test example 4: the regenerability Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material of surface molecule print adsorbs CIP
After reaching balance, imprinted material is separated with permanent magnet from solution, supernatant is removed, with the mixed solution of methanol and acetic acid
(9:1, V/V) is used as eluant, eluent, and 60min under 10.0mL eluant, eluent ultrasound condition is taken to elute imprinted material.According to above-mentioned
Five attached circulations of adsorption/desorption of method.
From figure 7 it can be seen that the imprinted material after five regeneration is in single CIP solution and the similar antibiotic point of structure
12.11% and 18.76% are reduced respectively to the adsorption capacity of CIP in the mixed solution of son, show preparation this is surface imprinted
Material has excellent regenerability.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material, which comprises the following steps:
(1) preparation of Eichhornia crassipes activated feedstock
Eichhornia crassipes is salvaged from lake and is come, cauline leaf is removed, retains root, is cleaned Water Hyacinth Root with distilled water, drying is gone forward side by side
Row crushes, is sieved, grind into powder, and the Eichhornia crassipes powder is added in phosphoric acid solution, is heated while stirring, and dissolution is complete
Vacuum drying obtains Eichhornia crassipes activated feedstock afterwards；
(2) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon
The Eichhornia crassipes activated feedstock is uniformly mixed with the ethanol solution of iron chloride, the vacuum drying in 90-100 DEG C of baking oven
It is placed in tube furnace to constant weight, cooling after high temperature cabonization magnetization under inert gas protection, washing, drying obtain Eichhornia crassipes base
Magnetic multi-stage porous carbon；
(3) preparation of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material
Successively Ciprofloxacin, methacrylic acid are added in the mixed solution of methanol and water, it is ultrasonic under inert gas protection
40min, is then added glycol methacrylate, and stirring continuously adds Eichhornia crassipes base magnetism multi-stage porous to after being thoroughly mixed
The mixed solution of carbon and the first alcohol and water containing polyvinylpyrrolidone, ultrasound 60min, continuously adds under inert gas protection
2,2 ' azo diisobutyl amidine dihydrochlorides, products therefrom are collected with permanent magnet, and washed, extraction, vacuum drying obtain phoenix
Eye lotus base magnetism multi-stage porous carbon surface imprinted material.
2. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that the mass ratio of Eichhornia crassipes powder and phosphoric acid solution is 1:1-4 in step (1), and wherein the concentration of phosphoric acid solution is 10-
20%.
3. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that the mass ratio of the ethanol solution of Eichhornia crassipes activated feedstock and iron chloride is 3:20 in step (2), wherein the second of iron chloride
The concentration of alcoholic solution is 0.02-0.1g/mL.
4. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that the magnetization of high temperature cabonization described in step (2) is that 600-800 DEG C is warming up to the rate of 5-8 DEG C/min, carbonization magnetization 2-
3h。
5. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that the molar ratio of Ciprofloxacin and methacrylic acid is 1:3-4 in step (3).
6. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is, the concentration of Ciprofloxacin is 20-30mol/L in step (3), and the Eichhornia crassipes base magnetism multi-stage porous carbon material
Concentration is controlled in 0.2-0.4g/100mL.
7. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that the molar ratio of Ciprofloxacin and glycol methacrylate is 1:8-10 in step (3).
8. a kind of preparation method of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material according to claim 1, special
Sign is that Ciprofloxacin and 2 in step (3), the ratio of 2 ' azo diisobutyl amidine dihydrochlorides is 1mmol:0.5-0.8g.
9. a kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface that method according to claim 1-8 is prepared print
Mark material.
10. a kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface that method according to claim 1-8 is prepared
The application of imprinted material, which is characterized in that the surface imprinted material is used for the Selective recognition of Ciprofloxacin in environment and divides
From.
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