CN107961764A - A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon - Google Patents

A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon Download PDF

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CN107961764A
CN107961764A CN201711226995.3A CN201711226995A CN107961764A CN 107961764 A CN107961764 A CN 107961764A CN 201711226995 A CN201711226995 A CN 201711226995A CN 107961764 A CN107961764 A CN 107961764A
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beta
cyclodextrin
sio
carboxymethyl
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CN107961764B (en
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李柏林
杨琴
邹楠
李晔
高雪洁
卢忆灵
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Wuhan University of Technology WUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
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Abstract

The present invention provides a kind of preparation method of carboxymethyl beta cyclodextrin functional magnetic mesoporous silicon microballoon, includes the following steps：Coprecipitation prepares Fe3O4；Prepare SiO2The Fe of parcel3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@SiO2；Prepare mesoporous SiO2The Fe of parcel3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；Using wet method or dry process carboxymethyl beta cyclodextrin, CM β CD are denoted as；Carboxymethyl beta cyclodextrin functional magnetic mesoporous silicon microballoon is prepared, is denoted as Fe3O4@SiO2@SiO2‑CM‑β‑CD.The present invention is with Fe3O4For object, using chemical coprecipitation technique and the magnetic mesoporous silicon complex microsphere of Stober method complex functionalityizatioies, preparation process is simple, processing is efficient, of low cost, provides new thinking for the preparation and application of magnetic absorption microballoon, can improve Fe3O4To the removal effect of heavy metal in water.

Description

A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon
Technical field
The present invention relates to water treatment materials manufacturing technology field, and in particular to a kind of carboxymethyl-beta-cyclodextrin functionalization The preparation method of magnetic mesoporous silicon microballoon.
Background technology
Fe3O4Magnetic nanoparticle possesses the advantageous property (such as particle diameter is small, surface area is big) of nano material, also with it The characteristic of itself, when grain diameter is less than 20nm, shows superparamagnetism at normal temperatures；In addition easily repaiied by functional group Decorations, can occur specific affinity with object and adsorb, can be by object from multigroup time-sharing environment under the oriented control of externally-applied magnetic field Middle quick separating comes out；With preparation process is easy, inexpensive, less toxic, 26S Proteasome Structure and Function the predictability of price is strong, Modulatory character The advantages that so that it has very high application value in adsorbing separation, catalysis and carrier etc..But exposed Fe3O4Particle is in sky Easily aoxidized in gas, perishable in sour environment and reunion, and then the distinctive property of nano material can be lost, make its absorption Effect is deteriorated with adsorptive selectivity.To make Fe3O4Magnetic Nano material can more effectively, optionally heavy-metal ion removal, palpus Modification is modified to it.
On the one hand, using inorganic material to Fe3O4Coated, obtained composite material can be provided simultaneously with magnetism and receive The performance of rice grain and covering material.Since mesoporous silicon oxide has orderly meso-hole structure, it is widely used in ADSORPTION OF GOLD Belonging to ion, dyestuff and other organic compounds, high-specific surface area causes it, and chemically and physically adsorption process ratio is very fast, in addition, The easy functionalization of mesoporous silicon oxide and there is special performance.With coated with silica Fe3O4Magnetic Fe can be protected3O4 Intragranular core, and silica possesses good compatibility and dispersiveness, it is easy to be modified and functionalization, can obtain wider Application range, the thickness of clad can be adjusted by varying the dosage of reactant.Patent No. The Chinese invention patent of CN200910219335.1 (it is CN101707106 B to authorize public number)《A kind of titanium dioxide of core shell structure The preparation method of silicon magnetic composite microsphere》In disclose a kind of preparation method of silicon dioxide magnetic composite microballoon, prepare Magnetic Nano microsphere includes a magnetic iron oxide kernel and the silica shells of one layer of dense non-porous.Inert dense non-porous A critical function of silica shells be that protection has high chemism iron oxide, but also result in silica magnetic Property complex microsphere specific surface area it is low so that absorption point position decline, cause adsorption efficiency to reduce, limit its application.The patent No. The Chinese invention patent of CN201310222225.7 (it is CN103310935 A to authorize public number)《Silicon dioxide nano magnetic microsphere And preparation method thereof》Disclose a kind of preparation method of the magnetic nanoparticle of double-deck coated with silica, obtained titanium dioxide Silicon nano-magnetic microsphere has multi-layer core-shell structure, and kernel is the magnetic nano-particle of monodispersity, and monodispersity can make middle level Compact silicon dioxide be closely coated on magnetic nano-particle surface so that guarantor unit's quality nano-magnetic microsphere magnetism is more By force, outer layer is mesoporous silicon oxide, and specific surface area is high, but removes template using the method for high temperature sintering in preparation process, So that meso-hole structure is easily destroyed and reduces performance, it is therefore desirable to finds milder and effective release method.
On the other hand, organo-functional group modification can also be carried out, passes through specific chemicals reaction such as silanization coupling reaction, network Reaction or esterification etc. are closed, by the surface of various Organic ligand modifications to magnetic-particle, so as to prepare containing difference in functionality The magnetic composite adsorbent of group.It is different from the mode of action between heavy metal ion according to different organo-functional groups, counterweight can be synthesized Metal ion has the compound adsorbent of Selective recognition ability.(authorize public number is patent No. CN201310222225.7 CN103310935 A) Chinese invention patent《Silicon dioxide nano magnetic microsphere and preparation method thereof》Disclose a kind of bilayer The preparation method of the magnetic nanoparticle of coated with silica, prepares the nano-magnetic microsphere with double-deck silicon dioxide structure, Specific surface area is increased by the porous silicon dioxide layer of outer layer, has the function that to improve heavy metal adsorption efficiency, but only rely on two The effect of silicon oxide layer is bad to the removal effect of heavy metal ion, need to find the method for further improving its adsorption efficiency.Specially Profit number is the Chinese invention patent of 201410714076.0 (it is CN104353431A to authorize public number)《A kind of beta-cyclodextrin modified The preparation of magnetic nano-particle》In, there is provided a kind of preparation method of the magnetic nanoparticle of beta-cyclodextrin modified, is prepared Magnetic nanoparticle have good recognition capability to guest molecule after beta-cyclodextrin modified, but due to magnetic core surfaces Fine and close SiO2The presence of layer makes the reduction of its specific surface area, causes the reduction of absorption property.Patent No. CN201410208552.1 Chinese invention patent《The preparation method of cyclodextrin modified magnetic nanometer adsorbent and its answering in haemodialysis adsorption system With》In, it is proposed that a kind of cyclodextrin modified magnetic nanometer adsorbent Fe3O4The preparation method of-β-CD, and Fe in the method3O4 Do not protect, be easily oxidised, and manufacturing cycle is longer, limits its application, it is therefore desirable to such magnetic-particle preparation side Method is improved, and expands its application range.
The content of the invention
The object of the present invention is to provide a kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon, With Fe3O4For object, functional magnetic mesoporous silicon complex microsphere, preparation process letter are formed using chemical coprecipitation technique and Stober methods List, processing are efficient, of low cost, enhance traditional Fe3O4Adsorbent is that magnetic absorption is micro- to the removal effect of heavy metal in water The preparation and application of ball provide new thinking.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon, includes the following steps：
1) coprecipitation prepares Fe3O4：
The NaOH solution for measuring 300~500mL, 1.5~2mol/L is placed in three-necked flask, is passed through high pure nitrogen, water-bath It is heated to 80 DEG C；With molar ratio 2:1 ratio weighs 0.02~0.04mol FeCl respectively3·6H2O and 0.01~0.02mol FeCl24H2O is dissolved in the HCl of 0.5~1mol/L of 50ml, is then slowly added in NaOH solution, and adjusting pH to 9.0~ 10.0, reaction generation black particle, stops stirring, natural cooling, isolates solid product, replace successively after reacting 0.5~1h Solid product is washed with deionized water and ethanol 3~5 times, is placed in vacuum drying chamber drying, grinding, obtains black crystalline body Fe3O4 Particle, envelope preserve；
2) magnetic silicon is prepared：
Weigh the Fe of 0.1~0.5g steps 1) preparation3O4Particle, is scattered in 30~300mL ethanol, 10 by being ultrasonically treated In the mixed solution of the concentrated ammonia solution of~100mL deionized waters and 1~6mL28wt% composition, be uniformly mixed liquid；To mixed Close and 0.2~2mL tetraethyl orthosilicates be added dropwise in liquid, after mechanical agitation, be collected into black product, successively alternately with ethanol and go from Sub- water washing 3~8 times, is placed in vacuum drying chamber drying, obtains SiO2The Fe of parcel3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@ SiO2；
3) magnetic mesoporous silicon is prepared：
Weigh the Fe of 0.1~0.5g steps 2) preparation3O4@SiO2Particle, be uniformly dispersed by ultrasonic wave added be scattered in 40~ In 400mL ethanol, the concentrated ammonia liquor of 1~6mL28wt% is added, forms solution A；By 0.2~0.5g templates cetyl three Ammonium methyl is dispersed in 70~400mL deionized waters, is carried out 0.5~1h of mechanical agitation with the rotating speed of 200~500rpm, is formed molten Liquid B；By solution B and solution A 4~8h of mechanical agitation under the rotating speed of 200~500rpm, mixed liquor C is obtained；With rubber head dropper to 0.2~2mL tetraethyl orthosilicates are added dropwise in mixed liquor C dropwise, high speed machine stirs 3~8h under the rotating speed of 500~600rpm, With the separating obtained particulate matter D of magnet, and it is washed with deionized 3~5 times；Weigh the particulate matter D and 40 of 0.2~0.6g synthesis ~100mL acetone and ammonium nitrate mixed solution are placed in centrifuge tube together, under conditions of 40~60 DEG C at ultrasound on extracting Natural cooling after reason, with the separating obtained product of magnet, collects bottom solidliquid mixture, is washed with acetone and ammonium nitrate mixed solution 1~2 time, vacuum drying chamber drying is placed in, up to mesoporous SiO2The Fe of parcel3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) wet method or dry process carboxymethyl-beta-cyclodextrin are used, is denoted as CM- β-CD；
5) carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon is prepared：
Weigh 0.1~0.5g Fe3O4@SiO2@SiO2In the aqueous solution of 10~50mL, with buffer solution of sodium phosphate by pH Value is adjusted to 6~8, the cyanamide of 0.1~0.5gCM- β-CD and 0.1~0.5ml is then added, under 80~90 DEG C of water bath condition With mechanical agitation 2~4 under the rotating speed of 200~500rpm it is small when, obtain the coated Fe of carboxymethyl-beta-cyclodextrin3O4@SiO2@SiO2 Magnetic composite microsphere, is washed 3~5 times with sodium phosphate buffer, at 60 DEG C be dried in vacuo 10~15h, get product carboxymethyl- Beta-cyclodextrin functional magnetic mesoporous silicon microballoon, is denoted as Fe3O4@SiO2@SiO2-CM-β-CD。
According to above scheme, the volumetric concentration of nitrogen is more than 99.999% in high pure nitrogen in the step 1), flow velocity For 30~50mL/min；The drying temperature of vacuum drying chamber is 60 DEG C, and drying time is 20~25h.
According to above scheme, when being ultrasonically treated in the step 2), the frequency of ultrasonic wave is 30kHz, sonication treatment time For 0.5~1.5h；Churned mechanically rotating speed is 200rpm, mixing time is 3~10h；The drying temperature of vacuum drying chamber is 60 DEG C, drying time is 8~10h.
According to above scheme, in the step 3) during ultrasonic wave added decentralized processing, the frequency of ultrasonic wave is 30kHz, ultrasound Processing time is 0.5~2.0h；In acetone and ammonium nitrate mixed solution, the volume ratio 1 of acetone and ammonium nitrate:1, ammonium nitrate it is dense Spend for 80mmol/L；During ultrasound on extracting processing, the frequency of ultrasonic wave is 30kHz, sonication treatment time is 0.8~1.2h； The drying temperature of vacuum drying chamber is 60 DEG C, and drying time is 12~14h.
According to above scheme, the method that the wet method prepares carboxymethyl-beta-cyclodextrin is：
Beta-cyclodextrin (β-CD), NaOH and chloroacetic acid are weighed in proportion, and the beta-cyclodextrin weighed and NaOH are dissolved in In ionized water, heating water bath is to 50 DEG C, and 0.5~0.6h of mechanical agitation, makes beta-cyclodextrin alkalize under the rotating speed of 200~500rpm And it is completely dissolved；Add chloroacetic acid, 60 DEG C of waters bath with thermostatic control, 200~500rpm rotating speed under mechanical agitation processing 5h；Cooling After to room temperature 14h is stored at room temperature to 5~7 with salt acid for adjusting pH；Methanol is added, produces white precipitate, is filtered, it is solid to obtain white Body, is dissolved in water, and recycles methanol to carry out repeated precipitation and filter 3~5 times；The vacuum that white solid is finally placed in 60 DEG C is done Dry case dries 5~10h, obtains carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, is denoted as CM- β-CD.
According to above scheme, the molar ratio of the NaOH and chloroacetic acid are 3.6:1, the chloroacetic acid and beta-cyclodextrin Molar ratio be 7.2:1.
According to above scheme, the method for the dry process carboxymethyl-beta-cyclodextrin is：
Weigh beta-cyclodextrin, NaOH and chloroacetic acid in proportion, beta-cyclodextrin is placed in it is finely ground in mortar, add NaOH it is equal Even mixing, is added dropwise absolute ethyl alcohol and water uniform mixed grinding again, and adding chloroacetic acid after the 0.8~1.2h that alkalizes grinds 0.5~1h, It is put into 40 DEG C of baking ovens and dries 0.5h, 0.5h is ground in taking-up again, and 2~6h of etherification reaction is so repeated, finally washs 2 with ethanol ~3 times, be put into 60 DEG C of baking ovens and dry, obtain carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, be denoted as CM- β- CD。
According to above scheme, the molar ratio of the NaOH and chloroacetic acid are 3:1, the chloroacetic acid and beta-cyclodextrin Molar ratio is 6:1.
According to above scheme, bath temperature is 80~90 DEG C in the step 5), mechanical agitation speed for 200~ 400rpm, mixing time are 2~4h；The buffer solution of sodium phosphate by 87.7mL0.003mol/L NaH2PO4With 12.3mL0.003mol/L Na2HPO4It is formulated.
The advantages of step 2) of the present invention, is：By fine and close SiO2It is wrapped in Fe3O4Particle surface, can effectively prevent substrate Material is leached into mother system, to internal Fe3O4Particle plays the role of stablizing and protects, and overcomes Patent No. (CN201410208552.1) Chinese invention patent《The preparation method of cyclodextrin modified magnetic nanometer adsorbent and its in blood Application in adsorption system of dialysing》Middle internal magnetization particle is not protected, it is oxidizable or be contaminated and interference system it is normal The problem of function.In addition, can be to SiO by varying the additive amount of TEOS in this step2The thickness of layer is adjusted, to meet Difference needs, and has widened its application range.
The advantages of step 3) of the present invention, is：In Fe3O4Surface compact SiO2On the basis of layer, then to wrap up one layer of tool mesoporous The SiO of structure2, increase the specific surface area of particle, increase load capacity, and further being modified beneficial to the later stage so that magnetic Property nano particle has wider application prospect, overcomes the Chinese invention patent of Patent No. CN200910219335.1 《A kind of preparation method of the silicon dioxide magnetic composite microballoon of core shell structure》In and Patent No. 201410714076.0 Chinese invention patent《A kind of preparation of the magnetic nano-particle of beta-cyclodextrin modified》In, fine and close SiO2Layer is so that silica The problems such as specific surface area of magnetic composite microsphere is relatively low, and the molecular amounts of absorption are limited.In addition, ultrasound is utilized in this step first The method removed template method of auxiliary extraction, removal effect is good and mild condition, meso-hole structure is destroyed seldom, solves high temperature Calcination method destroys the problem of larger to meso-hole structure, and advantage is more apparent compared with conventional calcination method, overcomes the patent No. The Chinese invention patent of CN201310222225.7 (it is CN103310935 A to authorize public number)《Silicon dioxide nano magnetic microsphere And preparation method thereof》The method of high temperature calcination removes template and meso-hole structure is easily destroyed and reduces its performance Problem, while it is more also to solve common solvent extraction consumption quantity of solvent, ineffective, the shortcomings that cost is higher.
The advantages of step 4) of the present invention, is：Usual β-CD solubility is low (about 18.5/L), influences it and forms bag with object The water solubility of compound, limits its application range, and-COOH is linked to cyclodextrin cavity side by the method for the present invention by ehter bond Edge, destroys the original hydrogen bond network of cyclodextrin molecular, and the oxygen atom in carboxyl can form hydrogen bond with the hydrogen in hydrone, Greatly improve the water solubility of cyclodextrin；In addition, the carboxyl at cyclodextrin cavity edge is anionic group, in faintly acid or alkalescence It is dissociable into-COO in environment-, complex compound can be formed with metal ion, therefore be grafted and can increased greatly with magnetic material surface Its strong removal ability to heavy metal ion.In addition, the carboxymethyl-beta-cyclodextrin purity prepared by wet method is higher.
The beneficial effects of the invention are as follows：
1) present invention is using bilayer SiO2Wrap up Fe3O4, internal layer SiO2Effectively prevent base material from leaching into mother system, To internal Fe3O4Particle plays the role of stablizing and protects, and the normal function for solving internal particle pollution or interference system is asked Topic；Outer layer SiO at the same time2Abundant gap is brought, increases the specific surface area of particle, there is good absorption property, load capacity Height, and beneficial to further being modified, there is wider application prospect；
2) SiO in the present invention2The thickness of layer is flexibly adjustable, is adjusted by varying the additive amount of reactant to meet not Stack pile SiO2The needs of layer；
3) present invention using extraction method removed template method, can effective removed template method, and mild condition, to mesoporous Structure is destroyed seldom, it is larger to solve the problems, such as that high-temperature calcination destroys meso-hole structure, extraction is compared with conventional calcination method Advantage is more apparent；
4) extraction of the present invention does not destroy the structure of template so that the template of abjection, which is recycled, to be used for multiple times, and is saved Cost, it is economical and eco-friendly, solve the problems, such as the template that higher price is directly destroyed in high-temperature calcination and cannot reuse；
5) present invention removes CTAB templates using ultrasound on extracting method, can improve removal efficiency, reduces extraction times, Extractant is saved, and ultrasonic energy consumption is relatively low, meets the principle of green production, it is excellent compared with conventional calcination method and general extraction Gesture is more apparent；
6) present invention is grafted magnetic microsphere using carboxymethyl-beta-cyclodextrin, since it contains abundant carboxyl, energy Complexing occurs with heavy metal ion in water, substantially increases magnetic microsphere heavy-metal ion removal ability；
7) magnetic mesoporous the silicon dioxide microsphere structure and regular appearance of carboxymethyl-beta-cyclodextrin functionalization of the invention, Mesopore size and structure are adjustable, and functional, can be recycled；
8) preparation process of the invention is simple, and raw material is common, is adapted to industrialized production, in adsorbing separation, catalysis and medicine The fields such as carrier have good prospect.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is X-ray diffraction (XRD) figure of 1 intermediate products of the embodiment of the present invention and finished product；
Fig. 3 is infrared spectrum (FT-IR) figure of 1 intermediate products of the embodiment of the present invention and finished product；
Fig. 4 be 1 finished product of the embodiment of the present invention to the adsorbance of different heavy metal ion with pH change curves.
Embodiment
Technical scheme is illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1, is shown in Fig. 1-4：
The present invention provides a kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon, including as follows Step (see Fig. 1)：
1) coprecipitation prepares Fe3O4：
The NaOH solution for measuring 500mL 1.5mol/L is placed in three-necked flask, is passed through high pure nitrogen (30mL/min), water Bath is heated to 80 DEG C；With molar ratio 2:1 ratio weighs 0.04mol FeCl respectively3·6H2O and 0.02mol FeCl2·4H2O It is dissolved in the HCl of 50ml 0.5mol/L, is then slowly added in NaOH solution, adjusts pH to 9.0, reaction generation black Grain, stops stirring after reacting 0.5h, and natural cooling, isolates solid product, is alternately washed successively with deionized water and ethanol solid State product 3~5 times, is placed in vacuum drying chamber drying, grinding, obtains black crystalline body Fe3O4Particle, envelope preserve；
2) magnetic silicon is prepared:
Weigh the Fe of 0.1g steps 1) preparation3O4Particle, by being ultrasonically treated, (30kHz) is scattered in 40mL ethanol, 10mL is gone In the mixed solution of the concentrated ammonia solution of ionized water and 1.2mL28wt% composition, be uniformly mixed liquid；It is added dropwise into mixed liquor 0.4mL tetraethyl orthosilicates, after mechanical agitation (200rpm) 6h, are collected into black product, alternately use ethanol and deionization successively Water washing 3 times, is placed in the dry 8h of (60 DEG C) of vacuum drying chamber, obtains SiO2The Fe of parcel3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@SiO2；
3) magnetic mesoporous silicon is prepared：
Weigh the Fe of 0.1g steps 2) preparation3O4@SiO2Particle, handles (30kHz) 1h by ultrasonic wave added, makes its uniform It is scattered in 60mL ethanol, adds the concentrated ammonia liquor of 1.2mL28wt%, forms solution A；By 0.3g template cetyl front threes Base ammonium is dispersed in 80mL deionized waters, is carried out mechanical agitation 0.5h with the rotating speed of 200rpm, is formed solution B；By solution B with it is molten Liquid A mechanical agitation 6h under the rotating speed of 300rpm, obtain mixed liquor C；0.43mL is added dropwise dropwise into mixed liquor C with rubber head dropper Tetraethyl orthosilicate, high speed machine stirs 6h under the rotating speed of 500rpm, with the separating obtained particulate matter D of magnet, and uses deionization Water washing 3 times；Weigh the particulate matter D and acetone (20mL) and ammonium nitrate (20mL, 80mmol/l) mixed solution of 0.2g synthesis (extractant) is placed in centrifuge tube together, and the natural cooling after ultrasound on extracting processing (30kHz) 1h under conditions of 60 DEG C, is used Magnet separation product and extractant, collect product, are washed with acetone (20mL) and ammonium nitrate (20mL, 80mmol/l) mixed solution 2 times, the dry 13h of (60 DEG C) of vacuum drying chamber is placed in, up to SiO2The Fe of parcel3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) carboxymethyl-beta-cyclodextrin is prepared using wet method：
Weigh 10g β-CD and 8g NaOH to be dissolved in water (37mL), heating water bath is to 50 DEG C, mechanical agitation (100rpm) 15min makes it alkalize and be completely dissolved.7.49g chloroacetic acids (16.3%) are added, mechanical agitation is handled at 60 DEG C of water bath with thermostatic control 5h, 14h is stored at room temperature after being cooled to room temperature with salt acid for adjusting pH to 5~7；Methanol (50mL) is added to resulting solution to produce in vain Color precipitates, and is filtered, obtains white solid, is dissolved in water, and recycles methanol to carry out repeated precipitation and filter 3 times, most postposition In (60 DEG C) dry 7h of vacuum drying chamber, carboxymethylated β-CD are obtained, are denoted as CM- β-CD；
5) carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon is prepared：
Weigh 0.1g Fe3O4@SiO2@SiO2In the aqueous solution of 10mL, pH value is adjusted to 6 with buffer solution of sodium phosphate, Then the cyanamide of 0.1gCM- β-CD and 0.1ml are added, with mechanical agitation 4 under the rotating speed of 400rpm under 80 DEG C of water bath condition Hour, obtain the coated Fe of carboxymethyl-beta-cyclodextrin3O4@SiO2@SiO2Magnetic composite microsphere, 3 are washed with sodium phosphate buffer It is secondary, 12h is dried in vacuo at 60 DEG C, is got product, is denoted as Fe3O4@SiO2@SiO2-CM-β-CD。
Further, the buffer solution of sodium phosphate is the NaH by 87.7mL0.003mol/L2PO4And 12.3mL The Na of 0.003mol/L2HPO4It is formulated.
Intermediate products and finished product to the present embodiment have carried out corresponding characterization and finished product inhales heavy metal ion in water The research that attached amount changes with solution ph, the result is shown in Fig. 2~4.
Fig. 2 is the Fe prepared by the embodiment of the present invention 13O4、Fe3O4@SiO2@SiO2、Fe3O4@SiO2@SiO2-CM-β-CD X-ray diffraction (XRD) photo.It is seen that Fe3O4、Fe3O4@SiO2@SiO2, carboxymethyl-beta-cyclodextrin functionalization magnetic Property mesoporous silicon microsphere sample shows strong diffraction maximum on 220,311,400,422,511 and 440 diffraction surfaces, with JCPDS (No.85-1436) Plays cubic spinel structure is consistent, shows the Fe of synthesis3O4、Fe3O4@SiO2@SiO2, carboxylic first Group-beta-cyclodextrin functional magnetic mesoporous silicon microballoon is pure face-centered cubic crystalline form.
Fig. 3 is the Fe prepared by the embodiment of the present invention 13O4、Fe3O4@SiO2@SiO2、Fe3O4@SiO2@SiO2-CM-β-CD Infrared spectrum (FT-IR) photo.From curve (a) as can be seen that unmodified Fe3O4Magnetic-particle mainly has 3 characteristic absorptions Peak.Wherein, wave number 3417cm-1And 1592cm-1Neighbouring absworption peak corresponds respectively to Fe3O4Magnetic-particle surface-OH's is flexible And flexural vibrations, 568cm-1Neighbouring strong absworption peak corresponds to the flexural vibrations of Fe-O, and other positions do not occur obvious miscellaneous Mass peak.
From curve (b) as can be seen that through double-deck SiO2The Fe of cladding3O4Magnetic-particle is in wave number 1090cm-1、960cm-1、 798cm-1、465cm-1There is new absworption peak in place, corresponds to the antisymmetric stretching vibration of Si-O-Si respectively, Si-OH vibrations, The symmetrical stretching vibration peak of Si-O-Si and the flexural vibrations peak of Si-O-Si, show SiO2Layer is successfully coated to Fe304Particle table Face.
From curve (c) as can be seen that the Fe modified through carboxymethyl-beta-cyclodextrin3O4Magnetic-particle is in wave number 2860cm-1、 2927cm-1、1633cm-1、1402cm-1Occur new absworption peak Deng many places, correspond to respectively C-H antisymmetric stretching vibration and The symmetrical stretching vibration of symmetrical stretching vibration, the antisymmetric stretching vibration of COOH and C-O, shows carboxymethyl-beta-cyclodextrin success Magnetic-particle surface has been arrived in ground modification.
Carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoons of the Fig. 4 prepared by the embodiment of the present invention 1 is to different heavy The adsorbance of metal ion is with pH change curves.It can be seen from the figure that at lower ph, H+Ion passes through ion exchange Mechanism effectively with M2+Ion competition is used for the adsorption site of-COOH, reduces Metal absorption ability, molten with the increase of pH H in liquid+The concentration of ion reduces, while the increase of adsorbent surface negative electrical charge, is conducive to the absorption of metal ion, when pH is 7, Its adsorption capacity reaches maximum.When pH is more than 7, since part metals ion removes in a manner of precipitating, cause synthetic material The adsorption capacity of metal ion is reduced.
Embodiment 2：
The present embodiment presses basic embodiment 1, and difference is：The amount of TEOS increases to 1mL in step 2).This is found through characterization Fe obtained by case study on implementation3O4@SiO2@SiO2Coated with silica layer thickness increases to 50nm in-CM- β-CD particles.
Embodiment 3：
The present embodiment presses basic embodiment 1, and difference is：The amount of TEOS is reduced to 0.2mL in step 2).Found through characterization Fe obtained by the implementation case3O4@SiO2@SiO2Coated with silica layer thickness is reduced to 10nm in-CM- β-CD particles.
Embodiment 4 (comparative example)：
The present embodiment presses basic embodiment 1, and difference is：Extractant in step 3) uses 40mL acetone solns, warp Characterization finds that template removal rate is only 82% in the implementation case, and 14% is reduced compared with embodiment 1.
Embodiment 5：
The present embodiment presses basic embodiment 1, and difference is：β-CD in step 4) use dry process, take 6g β-CD in It is finely ground in mortar, add 1.26g NaOH and uniformly mix, absolute ethyl alcohol (5mL) and water (5mL) uniform mixed grinding again, alkali is added dropwise Chloroacetic acid (4.49g, 16.3%) grinding 30min is added after changing 1h, is put into 40 DEG C of baking ovens and dries 30min, taking-up is ground again 30min, is so repeated etherification reaction 4h, is finally washed 2 times with ethanol, is put into 60 DEG C of baking ovens and dries.Found through characterization The substitution value of β-CD is 1.4 in the implementation case, and the β-CD prepared compared to 1 wet method of embodiment have been raised.
Above example only to illustrative and not limiting technical scheme, although above-described embodiment to the present invention into Detailed description is gone, the related technical personnel of this area should be understood：It can modify to the present invention or replace on an equal basis, but Any modification and local replacement for not departing from spirit and scope of the invention should all be covered in scope of the presently claimed invention.

Claims (9)

1. a kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon, it is characterised in that including following step Suddenly：
1) coprecipitation prepares Fe3O4：
The NaOH solution for measuring 300~500mL, 1.5~2mol/L is placed in three-necked flask, is passed through high pure nitrogen, heating water bath To 80 DEG C；With molar ratio 2:1 ratio weighs 0.02~0.04mol FeCl respectively3·6H2O and 0.01~0.02mol FeCl24H2O is dissolved in the HCl of 0.5~1mol/L of 50ml, is then slowly added in NaOH solution, and adjusting pH to 9.0~ 10.0, reaction generation black particle, stops stirring, natural cooling, isolates solid product, replace successively after reacting 0.5~1h Solid product is washed with deionized water and ethanol 3~5 times, is placed in vacuum drying chamber drying, grinding, obtains black crystalline body Fe3O4 Particle, envelope preserve；
2) magnetic silicon is prepared：
Weigh the Fe of 0.1~0.5g steps 1) preparation3O4Particle, by be ultrasonically treated be scattered in 30~300mL ethanol, 10~ In the mixed solution of the concentrated ammonia solution of 100mL deionized waters and 1~6mL28wt% composition, be uniformly mixed liquid；To mixing 0.2~2mL tetraethyl orthosilicates are added dropwise in liquid, after mechanical agitation, are collected into black product, alternately use ethanol and deionization successively Water washing 3~8 times, is placed in vacuum drying chamber drying, obtains SiO2The Fe of parcel3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@ SiO2；
3) magnetic mesoporous silicon is prepared：
Weigh the Fe of 0.1~0.5g steps 2) preparation3O4@SiO2Particle, be uniformly dispersed by ultrasonic wave added be scattered in 40~ In 400mL ethanol, the concentrated ammonia liquor of 1~6mL28wt% is added, forms solution A；By 0.2~0.5g templates cetyl three Ammonium methyl is dispersed in 70~400mL deionized waters, is carried out 0.5~1h of mechanical agitation with the rotating speed of 200~500rpm, is formed molten Liquid B；By solution B and solution A 4~8h of mechanical agitation under the rotating speed of 200~500rpm, mixed liquor C is obtained；With rubber head dropper to 0.2~2mL tetraethyl orthosilicates are added dropwise in mixed liquor C dropwise, high speed machine stirs 3~8h under the rotating speed of 500~600rpm, With the separating obtained particulate matter D of magnet, and it is washed with deionized 3~5 times；Weigh the particulate matter D and 40 of 0.2~0.6g synthesis ~100mL acetone and ammonium nitrate mixed solution are placed in centrifuge tube together, under conditions of 40~60 DEG C at ultrasound on extracting Natural cooling after reason, with the separating obtained product of magnet, collects bottom solidliquid mixture, is washed with acetone and ammonium nitrate mixed solution 1~2 time, vacuum drying chamber drying is placed in, up to mesoporous SiO2The Fe of parcel3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) wet method or dry process carboxymethyl-beta-cyclodextrin are used, is denoted as CM- β-CD；
5) carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon is prepared：
Weigh 0.1~0.5g Fe3O4@SiO2@SiO2In the aqueous solution of 10~50mL, with buffer solution of sodium phosphate by pH value tune For 6~8, the cyanamide of 0.1~0.5gCM- β-CD and 0.1~0.5ml are then added, with 200 under 80~90 DEG C of water bath condition When mechanical agitation 2~4 is small under the rotating speed of~500rpm, the coated Fe of carboxymethyl-beta-cyclodextrin is obtained3O4@SiO2@SiO2It is magnetic Complex microsphere, is washed 3~5 times with sodium phosphate buffer, and 10~15h is dried in vacuo at 60 DEG C, gets product carboxymethyl-β-ring Dextrin functional magnetic mesoporous silicon microballoon, is denoted as Fe3O4@SiO2@SiO2-CM-β-CD。
2. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature It is, the volumetric concentration of nitrogen is more than 99.999% in high pure nitrogen in the step 1), and flow velocity is 30~50mL/min；Very The drying temperature of empty drying box is 60 DEG C, and drying time is 20~25h.
3. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature It is, when being ultrasonically treated in the step 2), the frequency of ultrasonic wave is 30kHz, sonication treatment time is 0.5~1.5h；Machinery The rotating speed of stirring is 200rpm, mixing time is 3~10h；The drying temperature of vacuum drying chamber is 60 DEG C, drying time for 8~ 10h。
4. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature Be, when being ultrasonically treated in the step 3), the frequency of ultrasonic wave is 30kHz, the ultrasonic wave added decentralized processing time be 0.5~ 2h；In acetone and ammonium nitrate mixed solution, the volume ratio 1 of acetone and ammonium nitrate:1, the concentration of ammonium nitrate is 80mmol/L；Ultrasound During auxiliary extraction, the frequency of ultrasonic wave is 30kHz, the ultrasound on extracting time is 0.8~1.2h；The dry temperature of vacuum drying chamber Spend for 60 DEG C, drying time is 12~14h.
5. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature It is, the method that the wet method prepares carboxymethyl-beta-cyclodextrin is：
Beta-cyclodextrin, NaOH and chloroacetic acid are weighed in proportion, the beta-cyclodextrin weighed and NaOH are dissolved in deionized water, water Bath is heated to 50 DEG C, and 0.5~0.6h of mechanical agitation under the rotating speed of 200~500rpm, makes beta-cyclodextrin alkalize and be completely dissolved； Add chloroacetic acid, 60 DEG C of waters bath with thermostatic control, 200~500rpm rotating speed under mechanical agitation processing 5h；Used after being cooled to room temperature Salt acid for adjusting pH is stored at room temperature 14h to 5~7；Methanol is added, produces white precipitate, is filtered, is obtained white solid, add water-soluble Solution, recycles methanol to carry out repeated precipitation and filter 3~5 times；White solid is finally placed in 60 DEG C of vacuum drying chamber drying 5 ~10h, obtains carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, is denoted as CM- β-CD.
6. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 5, its feature It is, the molar ratio of the NaOH and chloroacetic acid are 3.6:1, the molar ratio of the chloroacetic acid and beta-cyclodextrin is 7.2:1.
7. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature It is, the method for the dry process carboxymethyl-beta-cyclodextrin is：
Weigh beta-cyclodextrin, NaOH and chloroacetic acid in proportion, beta-cyclodextrin is placed in it is finely ground in mortar, add NaOH uniformly mix Close, absolute ethyl alcohol and water uniform mixed grinding again is added dropwise, adding chloroacetic acid after the 0.8~1.2h that alkalizes grinds 0.5~1h, is put into 0.5h is dried in 40 DEG C of baking ovens, taking-up grinds 0.5h, 2~6h of etherification reaction is so repeated, finally washs 2~3 with ethanol again It is secondary, it is put into 60 DEG C of baking ovens and dries, obtain carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, is denoted as CM- β-CD.
8. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 7, its feature It is, the molar ratio of the NaOH and chloroacetic acid are 3:1, the molar ratio of the chloroacetic acid and beta-cyclodextrin is 6:1.
9. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, its feature Be, bath temperature is 80~90 DEG C in the step 5), mechanical agitation speed is 200~400rpm, mixing time be 2~ 4h；The buffer solution of sodium phosphate by 87.7mL0.003mol/L NaH2PO4With the Na of 12.3mL0.003mol/L2HPO4Match somebody with somebody System forms.
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