CN107961764B - 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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CN107961764B
CN107961764B CN201711226995.3A CN201711226995A CN107961764B CN 107961764 B CN107961764 B CN 107961764B CN 201711226995 A CN201711226995 A CN 201711226995A CN 107961764 B CN107961764 B CN 107961764B
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cyclodextrin
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CN107961764A (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
    • B01J20/28009—Magnetic properties
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    • 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
    • B01J20/28—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: that coprecipitation prepares Fe3O4；Prepare SiO2The Fe of package3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@SiO2；Prepare mesoporous SiO2The Fe of package3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；Using wet process or dry process carboxymethyl-beta-cyclodextrin, it is denoted as CM- β-CD；Carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon is prepared, Fe is denoted as3O4@SiO2@SiO2-CM-β-CD.The present invention is with Fe3O4For object, functional magnetic mesoporous silicon complex microsphere is synthesized using chemical coprecipitation technique and Stober method, preparation process is simple, processing is efficient, low in 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 fields, and in particular to a kind of carboxymethyl-beta-cyclodextrin functionalization The preparation method of magnetic mesoporous silicon microballoon.
Background technique
Fe3O4Magnetic nanoparticle has the advantageous property (such as partial size is small, surface area is big) of nano material, also has it The characteristic of itself shows superparamagnetism when grain diameter is less than 20nm at normal temperature；Furthermore it is easy to be repaired by functional group Decorations can occur specific affinity with object and adsorb, can be by object from multiple groups time-sharing environment under the oriented control of externally-applied magnetic field Middle quick separating comes out；It is easy with preparation process, inexpensive, less toxic, structure and function the predictability of price is strong, Modulatory character The advantages that so that its adsorbing separation, catalysis and in terms of have very high application value.But exposed Fe3O4Particle is in sky It is easily oxidized in gas, perishable in acidic environment and reunion, and then the distinctive property of nano material can be lost, make its absorption Effect and adsorptive selectivity are deteriorated.To make Fe3O4Magnetic Nano material can it is more effective, be optionally removed heavy metal ion, palpus Modification is modified to it.
On the one hand, using inorganic material to Fe3O4It is coated, 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 makes it, and chemically and physically adsorption process ratio is very fast, in addition, Mesoporous silicon oxide is easy functionalization and has special performance.With coated with silica Fe3O4Magnetic Fe can be protected3O4 Intragranular core, and silica has good compatibility and dispersibility, it is easy to be modified and functionalization, can obtain wider Application range, the thickness of clad can be adjusted by changing the dosage of reactant.Patent No. A kind of Chinese invention patent " titanium dioxide of core-shell structure of CN200910219335.1 (authorization public number is CN101707106 B) 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 the silica shells of a magnetic iron oxide kernel and one layer of dense non-porous.Inert dense non-porous A critical function of silica shells be that protection has high chemical activity iron oxide, but also result in silica magnetic Property complex microsphere specific surface area it is low so that absorption point decline, cause adsorption efficiency to reduce, limit its application.The patent No. Chinese invention patent " the silicon dioxide nano magnetic microsphere of CN201310222225.7 (authorization public number is CN103310935 A) And preparation method thereof " disclose a kind of double-deck coated with silica magnetic nanoparticle preparation method, titanium dioxide obtained Silicon nano-magnetic microsphere has multi-layer core-shell structure, and kernel is the magnetic nano-particle of monodispersity, and monodispersity can make middle layer 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 during the preparation process, So that meso-hole structure is easy to be destroyed and reduce performance, it is therefore desirable to find milder and effective release method.
On the other hand, organo-functional group modification can also be carried out, specific chemicals reaction such as silanization coupling reaction, network are passed through Reaction or esterification etc. are closed, by the surface of various Organic ligand modifications to magnetic-particle, to prepare containing different function 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.(authorization 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 the double-deck silicon dioxide structure, Increase specific surface area by the porous silicon dioxide layer of outer layer, has the function that 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 increasing its adsorption efficiency.Specially Benefit number is a kind of Chinese invention patent " beta-cyclodextrin modified of 201410714076.0 (authorization public number is CN104353431A) The preparation of magnetic nano-particle " in, a kind of preparation method of the magnetic nanoparticle of beta-cyclodextrin modified is provided, 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, leads to the reduction of absorption property.Patent No. CN201410208552.1 Chinese invention patent " preparation method of cyclodextrin modified magnetic nanometer adsorbent and its answering in haemodialysis adsorption system With " in, propose a kind of cyclodextrin modified magnetic nanometer adsorbent Fe3O4The preparation method of-β-CD, and Fe in the method3O4 It does not protect, is easily oxidised, and manufacturing cycle is longer, limit its application, it is therefore desirable to such magnetic-particle preparation side Method improves, and expands its application range.
Summary 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 method List, processing are efficient, low in 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 the goals above, The technical solution adopted by the 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；0.02~0.04mol FeCl is weighed respectively with the ratio of molar ratio 2:13·6H2O 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 generates black particle, stops stirring after reacting 0.5~1h, natural cooling is isolated solid product, successively replaced With deionized water and ethanol washing solid product 3~5 times, it is placed in vacuum oven drying, grinding obtains black crystalline body Fe3O4 Particle, envelope save；
2) magnetic silicon is prepared:
Weigh the Fe of 0.1~0.5g step 1) preparation3O4Particle is scattered in 30~300mL ethyl alcohol, 10 by ultrasonic treatment In the mixed solution of the concentrated ammonia solution of~100mL deionized water and 1~6mL28wt% composition, be uniformly mixed liquid；To mixed Close and 0.2~2mL tetraethyl orthosilicate be added dropwise in liquid, after mechanical stirring, be collected into black product, successively alternately with ethyl alcohol and go from Sub- water washing 3~8 times is placed in vacuum oven drying, obtains SiO2The Fe of package3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@ SiO2；
3) magnetic mesoporous silicon is prepared:
Weigh the Fe of 0.1~0.5g step 2) preparation3O4@SiO2Particle, be uniformly dispersed by ultrasonic wave added be scattered in 40~ In 400mL ethyl alcohol, the concentrated ammonia liquor of 1~6mL28wt% is added, forms solution A；By 0.2~0.5g template cetyl three Methyl ammonium is dispersed in 70~400mL deionized water, is carried out 0.5~1h of mechanical stirring with the revolving speed of 200~500rpm, is formed molten Liquid B；By solution B and solution A under the revolving speed of 200~500rpm 4~8h of mechanical stirring, obtain mixed liquor C；With rubber head dropper to 0.2~2mL tetraethyl orthosilicate is added dropwise in mixed liquor C dropwise, high speed machine stirs 3~8h under the revolving 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 is collected bottom solidliquid mixture, is washed with acetone and ammonium nitrate mixed solution with the separating obtained product of magnet 1~2 time, it is dry to get mesoporous SiO to be placed in vacuum oven2The Fe of package3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) wet process or dry process carboxymethyl-beta-cyclodextrin are used, CM- β-CD is denoted as；
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 stirring 2~4 hours under the revolving speed of 200~500rpm, the coated Fe of carboxymethyl-beta-cyclodextrin is obtained3O4@SiO2@SiO2 Magnetic composite microsphere is washed 3~5 times with sodium phosphate buffer, is dried in vacuo 10~15h at 60 DEG C to get finished 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 99.999% or more in high pure nitrogen in the step 1), flow velocity For 30~50mL/min；The drying temperature of vacuum oven is 60 DEG C, and drying time is 20~25h.
According to above scheme, in the step 2) when ultrasonic treatment, the frequency of ultrasonic wave is 30kHz, sonication treatment time For 0.5~1.5h；Churned mechanically revolving speed is 200rpm, mixing time is 3~10h；The drying temperature of vacuum oven is 60 DEG C, drying time is 8~10h.
According to above scheme, in the step 3) when ultrasonic wave added decentralized processing, the frequency of ultrasonic wave is 30kHz, ultrasound The processing time is 0.5~2.0h；In acetone and ammonium nitrate mixed solution, the volume ratio 1:1 of acetone and ammonium nitrate, ammonium nitrate it is dense Degree is 80mmol/L；When ultrasound on extracting processing, the frequency of ultrasonic wave is 30kHz, sonication treatment time is 0.8~1.2h； The drying temperature of vacuum oven is 60 DEG C, and drying time is 12~14h.
According to above scheme, method that the wet process prepares carboxymethyl-beta-cyclodextrin are as follows:
Beta-cyclodextrin (β-CD), NaOH and chloroacetic acid are weighed in proportion, and weighed beta-cyclodextrin and NaOH are dissolved in In ionized water, heating water bath is to 50 DEG C, and 0.5~0.6h of mechanical stirring, makes beta-cyclodextrin alkalize under the revolving speed of 200~500rpm And it is completely dissolved；Be added chloroacetic acid, 60 DEG C of waters bath with thermostatic control, 200~500rpm revolving speed under mechanical stirring handle 5h；It is cooling 14h is stored at room temperature to 5~7 with salt acid for adjusting pH after to room temperature；Methanol is added, generates white precipitate, filters, it is solid to obtain white Body is dissolved in water, and methanol is recycled to carry out repeated precipitation and filter 3~5 times；Finally the vacuum that white solid is placed in 60 DEG C is done Dry 5~the 10h of dry case, 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 is 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 are as follows:
Weigh beta-cyclodextrin, NaOH and chloroacetic acid in proportion, beta-cyclodextrin is placed in it is finely ground in mortar, be added NaOH it is equal Dehydrated alcohol and water uniform mixed grinding again is added dropwise in even mixing, and chloroacetic acid is added after the 0.8~1.2h that alkalizes and 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, carries out 2~6h of etherification reaction repeatedly, finally uses ethanol washing 2 It~3 times, is put into 60 DEG C of baking ovens and dries, 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 is 3:1, the chloroacetic acid and beta-cyclodextrin Molar ratio is 6:1.
According to above scheme, in the step 5) bath temperature be 80~90 DEG C, mechanical stirring speed be 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 leaches into mother system, to internal Fe3O4Particle plays the role of stablizing and protect, and overcomes Patent No. (CN201410208552.1) the Chinese invention patent " preparation method of cyclodextrin modified magnetic nanometer adsorbent and its in blood Dialysis adsorption system in application " in internal magnetization particle do not protect, it is oxidizable or be contaminated and interference system it is normal The problem of function.In addition, can be to SiO by changing 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 the further progress for being conducive to the later period is modified, so that magnetic Property nano particle have wider application prospect, overcome the Chinese invention patent of Patent No. CN200910219335.1 In " a kind of preparation method of the silicon dioxide magnetic composite microballoon of core-shell structure " and Patent No. 201410714076.0 In Chinese invention patent " a kind of preparation of the magnetic nano-particle of beta-cyclodextrin modified ", fine and close SiO2Layer makes silica The problems such as specific surface area of magnetic composite microsphere is lower, and the molecular amounts of absorption are limited.In addition, ultrasound is utilized in this step for the first time The method removed template method of auxiliary extraction, removal effect is good and mild condition seldom to meso-hole structure destruction solves high temperature Calcination method destroys larger problem to meso-hole structure, and advantage is more apparent compared with conventional calcination method, overcomes the patent No. Chinese invention patent " the silicon dioxide nano magnetic microsphere of CN201310222225.7 (authorization public number is CN103310935 A) And preparation method thereof " method of high temperature calcination removes template and meso-hole structure is made to be easy to be destroyed and reduce its performance Problem, while it is more also to solve common solvent extraction consumption quantity of solvent, it is ineffective, the shortcomings that higher cost.
The advantages of step 4) of the present invention is: usual β-CD solubility is low (about 18.5/L), influences it and object is formed and wrapped The water solubility for closing object, limits its scope of application, and-COOH is linked to cyclodextrin cavity side by ehter bond by method of the invention 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 alkalinity It is dissociable at-COO in environment-, complex compound can be formed with metal ion, therefore be grafted and can increase greatly with magnetic material surface Its strong removal ability to heavy metal ion.In addition, higher by the carboxymethyl-beta-cyclodextrin purity that wet process is prepared.
The beneficial effects of the present invention are:
1) present invention uses bilayer SiO2Wrap up Fe3O4, internal layer SiO2It effectively prevent base material to leach into mother system, To internal Fe3O4Particle plays the role of stablizing and protect, and solves asking for the normal function of internal particle pollution or interference system Topic；Outer layer SiO simultaneously2Gap abundant is brought, the specific surface area of particle is increased, there is good absorption property, load capacity Height, and be conducive to further progress and modify, there is wider application prospect；
2) SiO in the present invention2The thickness of layer is flexibly adjustable, and the additive amount by changing reactant is adjusted 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, is used for multiple times, saves so that the template of abjection is recyclable Cost, it is economical and eco-friendly, it solves the problems, such as directly to destroy the higher template of price in high-temperature calcination and cannot reuse；
5) present invention removes CTAB template using ultrasound on extracting method, and removal efficiency can be improved, and reduces extraction times, Extractant is saved, and ultrasonic energy consumption is lower, 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, due to its carboxyl rich in, energy Complexing occurs with heavy metal ion in water, substantially increases magnetic microsphere heavy-metal ion removal ability；
7) the magnetic mesoporous 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 suitble to industrialized production, in adsorbing separation, catalysis and drug The fields such as carrier have good prospect.
Detailed description of the invention
Fig. 1 is process flow diagram of the 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 spectroscopy (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 curve.
Specific embodiment
Technical solution of the present invention is illustrated with embodiment with reference to the accompanying drawing.
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；0.04mol FeCl is weighed respectively with the ratio of molar ratio 2:13·6H2O and 0.02mol FeCl2·4H2O It is dissolved in the HCl of 50ml 0.5mol/L, is then slowly added in NaOH solution, adjust pH to 9.0, reaction generates black Grain stops stirring after reacting 0.5h, and natural cooling isolates solid product, successively alternately solid with deionized water and ethanol washing State product 3~5 times, it is placed in vacuum oven drying, grinding obtains black crystalline body Fe3O4Particle, envelope save；
2) magnetic silicon is prepared:
Weigh the Fe of 0.1g step 1) preparation3O4Particle, by the way that ultrasonic treatment (30kHz) is scattered in 40mL ethyl alcohol, 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 orthosilicate after mechanical stirring (200rpm) 6h, is collected into black product, successively alternately uses ethyl alcohol and deionization Water washing 3 times, (60 DEG C) of vacuum oven dry 8h are placed in, SiO is obtained2The Fe of package3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@SiO2；
3) magnetic mesoporous silicon is prepared:
Weigh the Fe of 0.1g step 2) preparation3O4@SiO2Particle handles (30kHz) 1h by ultrasonic wave added, makes it uniformly It is scattered in 60mL ethyl alcohol, the concentrated ammonia liquor of 1.2mL28wt% is added, form solution A；By 0.3g template cetyl front three Base ammonium is dispersed in 80mL deionized water, is carried out mechanical stirring 0.5h with the revolving speed of 200rpm, is formed solution B；By solution B with it is molten Liquid A mechanical stirring 6h under the revolving speed of 300rpm, obtains 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 revolving 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 natural cooling after ultrasound on extracting processing (30kHz) 1h, is used under conditions of 60 DEG C Magnet separation product and extractant collect product, are washed with acetone (20mL) and ammonium nitrate (20mL, 80mmol/l) mixed solution 2 times, (60 DEG C) of vacuum oven dry 13h are placed in get SiO2The Fe of package3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) carboxymethyl-beta-cyclodextrin is prepared using wet process:
It weighs 10g β-CD and 8g NaOH to be dissolved in water (37mL), heating water bath is to 50 DEG C, mechanical stirring (100rpm) 15min makes it alkalize and be completely dissolved.It is added 7.49g chloroacetic acid (16.3%), mechanical stirring is handled at 60 DEG C of water bath with thermostatic control 5h is stored at room temperature 14h to 5~7 with salt acid for adjusting pH after being cooled to room temperature；It is white that methanol (50mL) generation is added to acquired solution Color precipitating, is filtered, obtains white solid, be dissolved in water, and methanol is recycled to carry out repeated precipitation and filter 3 times, most postposition In (60 DEG C) of vacuum oven dry 7h, carboxymethylated β-CD is obtained, CM- β-CD is denoted as；
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 is added, with mechanical stirring 4 under the revolving speed of 400rpm under 80 DEG C of water bath condition Hour, obtain the coated Fe of carboxymethyl-beta-cyclodextrin3O4@SiO2@SiO2Magnetic composite microsphere washs 3 with sodium phosphate buffer It is secondary, 12h is dried in vacuo at 60 DEG C to get finished 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, is as a result shown in Fig. 2~4.
Fig. 2 is 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 all 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 Fe prepared by the embodiment of the present invention 13O4、Fe3O4@SiO2@SiO2、Fe3O4@SiO2@SiO2-CM-β-CD Infrared spectroscopy (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 absorption peak corresponds respectively to Fe3O4Magnetic-particle surface-OH's is flexible And bending vibration, 568cm-1Neighbouring strong absworption peak corresponds to the bending vibration of Fe-O, and other positions do not occur apparent miscellaneous Mass peak.
From curve (b) as can be seen that through the double-deck SiO2The Fe of cladding3O4Magnetic-particle is in wave number 1090cm-1、960cm-1、 798cm-1、465cm-1There is new absorption peak in place, respectively corresponds the antisymmetric stretching vibration of Si-O-Si, Si-OH vibration, 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-1There is new absorption peak in equal many places, respectively correspond C-H antisymmetric stretching vibration and Symmetrical stretching vibration, the antisymmetric stretching vibration of COOH and C-O symmetrical stretching vibration, show carboxymethyl-beta-cyclodextrin success Magnetic-particle surface has been arrived in ground modification.
Fig. 4 is carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon prepared by the embodiment of the present invention 1 to different heavy The adsorbance of metal ion is with pH change curve.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 adsorbent surface negative electrical charge increases, and is conducive to the absorption of metal ion, when pH is 7, Its adsorption capacity reaches maximum.When pH is greater than 7, since part metals ion removes in a manner of precipitating, lead to 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).Originally through characterization discovery The resulting Fe of case study on implementation3O4@SiO2@SiO2Coated with silica thickness degree increases to 50nm in-CM- β-CD particle.
Embodiment 3:
The present embodiment presses basic embodiment 1, and difference is: the amount of TEOS is reduced to 0.2mL in step 2).It is found through characterization The resulting Fe of the implementation case3O4@SiO2@SiO2Coated with silica thickness degree is reduced to 10nm in-CM- β-CD particle.
Embodiment 4 (comparative example):
The present embodiment presses basic embodiment 1, and difference is: the extractant in step 3) uses 40mL acetone soln, warp Template removal rate is only 82% in characterization discovery the implementation case, reduces 14% compared in embodiment 1.
Embodiment 5:
The present embodiment presses basic embodiment 1, and difference is: β-CD in step 4) uses dry process, take 6g β-CD in It is finely ground in mortar, 1.26g NaOH is added and uniformly mixes, dehydrated 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 carries out etherification reaction 4h repeatedly, finally uses ethanol washing 2 times, is put into 60 DEG C of baking ovens and dries.It is found through characterization The degree of substitution of β-CD is 1.4 in the implementation case, and the β-CD compared to the preparation of 1 wet process of embodiment is increased.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment to the present invention into Gone detailed description, the related technical personnel of this field it is understood that can modify to the present invention or replace on an equal basis, but Any modification and part 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, which is characterized in that including walking as follows It is rapid:
1) coprecipitation prepares Fe3O4:
The NaOH solution for measuring 300 ~ 500mL, 1.5 ~ 2 mol/L is placed in three-necked flask, is passed through high pure nitrogen, heating water bath is extremely 80℃；0.02 ~ 0.04mol FeCl is weighed respectively with the ratio of molar ratio 2:13·6H2O and 0.01 ~ 0.02mol FeCl2· 4H2O is dissolved in the HCl of 0.5 ~ 1mol/L of 50ml, is then slowly added in NaOH solution, and pH to 9.0 ~ 10.0, reaction are adjusted Black particle is generated, stops stirring after reacting 0.5 ~ 1h, natural cooling isolates solid product, successively alternately uses deionized water With ethanol washing solid product 3 ~ 5 times, be placed in that vacuum oven is dry, and grinding obtains black crystalline body Fe3O4Particle, envelope are protected It deposits；
2) magnetic silicon is prepared:
Weigh the Fe of 0.1 ~ 0.5g step 1) preparation3O4Particle is scattered in 30 ~ 300mL ethyl alcohol, 10 ~ 100mL by ultrasonic treatment In the mixed solution of the concentrated ammonia solution of deionized water and 1 ~ 6mL28wt% composition, be uniformly mixed liquid；It is dripped into mixed liquor Add 0.2 ~ 2mL tetraethyl orthosilicate, after mechanical stirring, be collected into black product, successively alternately washs 3 with ethyl alcohol and deionized water ~ 8 times, it is placed in vacuum oven drying, obtains SiO2The Fe of package3O4Particle, i.e., magnetic silicon, is denoted as Fe3O4@SiO2；
3) magnetic mesoporous silicon is prepared:
Weigh the Fe of 0.1 ~ 0.5g step 2 preparation3O4@SiO2Particle is uniformly dispersed by ultrasonic wave added and is scattered in 40 ~ 400mL In ethyl alcohol, the concentrated ammonia liquor of 1 ~ 6mL28wt% is added, forms solution A；By 0.2 ~ 0.5g template cetyl trimethyl ammonium point It is dispersed in 70 ~ 400mL deionized water, 0.5 ~ 1h of mechanical stirring is carried out with the revolving speed of 200 ~ 500rpm, forms solution B；By solution B With solution A under the revolving speed of 200 ~ 500rpm 4 ~ 8h of mechanical stirring, obtain mixed liquor C；With rubber head dropper into mixed liquor C dropwise 0.2 ~ 2mL tetraethyl orthosilicate is added dropwise, high speed machine stirs 3 ~ 8h under the revolving speed of 500 ~ 600rpm, with magnet separating obtained Grain object D, and be washed with deionized 3 ~ 5 times；Weigh the particulate matter D and 40 ~ 100mL acetone and ammonium nitrate of 0.2 ~ 0.6g synthesis Mixed solution is placed in centrifuge tube together, the natural cooling after ultrasound on extracting processing under conditions of 40 ~ 60 DEG C, with magnet point From products therefrom, bottom solidliquid mixture is collected, is washed 1 ~ 2 time with acetone and ammonium nitrate mixed solution, is placed in vacuum oven Drying is to get mesoporous SiO2The Fe of package3O4@SiO2Particle, i.e., magnetic mesoporous silicon, is denoted as Fe3O4@SiO2@SiO2；
4) wet process or dry process carboxymethyl-beta-cyclodextrin are used, CM- β-CD is denoted as；
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, pH value is adjusted to 6 with buffer solution of sodium phosphate ~ 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 200 ~ Mechanical stirring 2 ~ 4 hours under the revolving speed of 500rpm obtain the coated Fe of carboxymethyl-beta-cyclodextrin3O4@SiO2@SiO2Magnetic coupling Microballoon is washed 3 ~ 5 times with sodium phosphate buffer, is dried in vacuo 10 ~ 15h at 60 DEG C to get finished product carboxymethyl-beta-cyclodextrin function The magnetic mesoporous silicon microballoon of energyization, 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, feature It is, the volumetric concentration of nitrogen is 99.999% or more in high pure nitrogen in the step 1), and flow velocity is 30 ~ 50mL/min；Vacuum The drying temperature of 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, feature It is, when being ultrasonically treated in the step 2, the frequency of ultrasonic wave is 30 kHz, sonication treatment time is 0.5 ~ 1.5h；It is mechanical The revolving speed of stirring is 200rpm, mixing time is 3 ~ 10h；The drying temperature of vacuum oven be 60 DEG C, drying time be 8 ~ 10h。
4. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, feature It is, in the step 3) when ultrasonic wave added decentralized processing, the frequency of ultrasonic wave is 30 kHz, ultrasonic wave added decentralized processing time For 0.5 ~ 2h；In acetone and ammonium nitrate mixed solution, the volume ratio 1:1 of acetone and ammonium nitrate, the concentration of ammonium nitrate is 80mmol/ L；When ultrasound on extracting, the frequency of ultrasonic wave is 30kHz, the ultrasound on extracting time is 0.8 ~ 1.2h；Vacuum oven Drying temperature is 60 DEG C, and drying time is 12 ~ 14h.
5. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 1, feature It is, the method that the wet process prepares carboxymethyl-beta-cyclodextrin are as follows:
Beta-cyclodextrin, NaOH and chloroacetic acid are weighed in proportion, weighed beta-cyclodextrin and NaOH are dissolved in deionized water, water Bath is heated to 50 DEG C, and 0.5 ~ 0.6h of mechanical stirring under the revolving speed of 200 ~ 500rpm makes beta-cyclodextrin alkalize and be completely dissolved；Add Enter chloroacetic acid, 60 DEG C of waters bath with thermostatic control, 200 ~ 500rpm revolving speed under mechanical stirring handle 5h；Hydrochloric acid is used after being cooled to room temperature PH to 5 ~ 7 is adjusted, 14h is stored at room temperature；Methanol is added, generates white precipitate, filters, obtains white solid, be dissolved in water, then benefit Repeated precipitation is carried out with methanol and is filtered 3 ~ 5 times；Dry 5 ~ the 10h of the vacuum oven that white solid is finally placed in 60 DEG C, obtains To carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, it is denoted as CM- β-CD.
6. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 5, feature It is, the molar ratio of the NaOH and chloroacetic acid is 3.6:1, and 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, feature It is, the method for the dry process carboxymethyl-beta-cyclodextrin are as follows:
Weigh beta-cyclodextrin, NaOH and chloroacetic acid in proportion, beta-cyclodextrin is placed in it is finely ground in mortar, be added NaOH uniformly mix It closes, dehydrated alcohol and water uniform mixed grinding again is added dropwise, chloroacetic acid is added after the 0.8 ~ 1.2h that alkalizes and grinds 0.5 ~ 1h, is put into 40 0.5h is dried in DEG C baking oven, 0.5h is ground in taking-up again, carries out 2~6h of etherification reaction repeatedly, finally use ethanol washing 2~3 times, It is put into 60 DEG C of baking ovens and dries, obtain carboxymethylated beta-cyclodextrin, i.e. carboxymethyl-beta-cyclodextrin, be denoted as CM- β-CD.
8. the preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon according to claim 7, feature It is, the molar ratio of the NaOH and chloroacetic acid is 3:1, and 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, feature It is, bath temperature is 80 ~ 90 DEG C in the step 5), and mechanical stirring speed is 200 ~ 400rpm, mixing time is 2 ~ 4h；Institute Buffer solution of sodium phosphate is stated by the NaH of 87.7mL0.003mol/L2PO4With the Na of 12.3mL0.003mol/L2HPO4Prepare and At.
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