CN103182294B - Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition - Google Patents
Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition Download PDFInfo
- Publication number
- CN103182294B CN103182294B CN201310101904.9A CN201310101904A CN103182294B CN 103182294 B CN103182294 B CN 103182294B CN 201310101904 A CN201310101904 A CN 201310101904A CN 103182294 B CN103182294 B CN 103182294B
- Authority
- CN
- China
- Prior art keywords
- weight portion
- under
- magnetic
- mesoporous carbon
- mixed liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing magnetic mesoporous carbon nanoparticles with a high adsorption property for dyes under the acidic condition, relates to a method for preparing a magnetic mesoporous carbon material with a core-shell structure, and aims to solve the problem that magnetic mesoporous carbon which is prepared by a current route method under the alkaline condition and provided with the core-shell structure is small in bore diameter and specific surface area. According to the method, under the acidic condition, a solvent evaporation self-assembly method is used to synthesize a magnetic mesoporous silica material which is provided with the core-shell structure and adopts magnetic Fe3O4 as an inner core, a compact SiO2 layer as an intermediate layer and a mesoporous SiO2 layer as an outer layer; then the magnetic mesoporous silica material is used as a hard template; cane sugar is filled into a magnetic mesoporous silica material bore channel; and the SiO2 layers are removed after carbonization, and the magnetic mesoporous carbon material with the core-shell structure is obtained. The magnetic mesoporous carbon nanoparticles provided by the invention have larger mesoporous bore diameters (3.4 nm and 11.1 nm), high specific surface area (971.3 m <2>/g) and large pore volume (1.42 cm<3>/g), and the magnetic saturation is 1.73 emu/g.
Description
Technical field
The present invention relates to the preparation method of core-shell structure magnetic meso-porous carbon material.
Background technology
Core-shell structure magnetic mesoporous carbon is a kind of with magnetic Fe
3o
4for kernel, the nano material that the carbon-coating with high-specific surface area, large pore volume, larger mesoporous aperture is shell, has a wide range of applications in fields such as electrochemistry, catalysis, sewage disposal, biological medicines.Its core Fe
3o
4there is superparamagnetism, can be under additional magnetic fields fast, directional separation; The effect that the mesoporous carbon-coating of outer shell has fast, efficiently separates the pollutant in water body.The magnetic mesoporous carbon material of preparing that magnetic core is combined with mesoporous carbon-coating can be used for the fields such as wastewater treatment, biological medicine, electrochemistry, catalysis.The synthetic of core-shell structure magnetic mesoporous material generally all adopts alkali condition first to prepare the mesoporous silicon layer of MCM-41 type at present, on this basis taking it as hard template, further fills carbon source and obtains meso-porous carbon material.Owing to serving as, the mesoporous silicon layer aperture of hard template is less, surface area lowly causes the mesoporous size of synthetic meso-porous carbon material also less, surface area is lower, thereby has limited its extensive use in fields such as macromolecule contaminant and large biological molecule absorption.
Summary of the invention
The object of the invention is to prepare in order to solve existing alkali condition Path Method the problem that core-shell structure magnetic mesoporous carbon aperture is little and specific area is low, under acid condition, prepare method dyestuff to the magnetic mesoporous carbon nanometer micro ball of high absorption property and provide.
The method that preparation has the magnetic mesoporous carbon nanometer micro ball of high absorption property to dyestuff under acid condition of the present invention is carried out according to following steps:
A, magnetic Fe
3o
4the preparation of nano particle: one, take by weight 1～2 part of source of iron, join under the condition of magnetic agitation in 40～60 weight portion reducing agents and be uniformly mixed, obtain mixed solution; Two, the precipitating reagent of 2～3 weight portions and 0.8～1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, obtain mixed liquid; Three, mixed step 2 liquid being transferred in reactor, being heated to, after 200 DEG C of crystallization 8h, be cooled to room temperature, successively with distilled water with absolute ethyl alcohol is each cleans 6 times, is dry 12h in the baking oven of 60 DEG C in temperature, obtains Fe
3o
4nano particle;
B, Fe
3o
4@nSiO
2preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3o
4nano particle, is scattered in mixed liquor, ultrasonic processing 15min; Five, by ultrasonic step 4 Fe after treatment
3o
4under the effect of nano particle outside magnetic field, separate, collect solid formation, respectively wash 3 times with distilled water and absolute ethyl alcohol successively, then add 80～100 weight portion absolute ethyl alcohols, 20 weight portion distilled water and 1 weight portion concentrated ammonia liquor, under room temperature, stir 60min, obtain even mixed liquor; Six,, in the even mixed liquor obtaining to step 5, drip 0.6 weight portion silicon source with the speed of 0.1 drop/sec, under the condition that is then 800～1000rpm at rotating speed, mechanical agitation 12h; Under outside magnetic field effect, separating, collect solid formation, respectively clean 6 times successively with distilled water and absolute ethyl alcohol, is to be dried after 12h in 60 DEG C of baking ovens in temperature, obtains Fe
3o
4@nSiO
2; Wherein, the mixed liquor described in step 4 is that 0.2M hydrochloric acid solution makes by the concentration of 30～40 weight portion absolute ethyl alcohols and 5～8 weight portions;
C, Fe
3o
4@nSiO
2@mSiO
2preparation: seven, by step B gained Fe
3o
4@nSiO
2be scattered in mixed liquor ultrasonic processing 15min; Eight, the ultrasonic solution after treatment of step 7 is stirred and evenly mixed, add after 0.02 weight account polyethylene pyrrolidones, stir 2h, obtain mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in to 10～15 weight portions adds in the mixed liquor of step 8 to clarification, under room temperature, stirs 2h, obtains solution; Ten, in the solution of step 9, add 0.8 weight portion silicon source, under room temperature, stir after 2d, dry; 11, step 10 is dried to product grinding and proceed in reactor, add the distilled water of 15～20 weight portions, be placed in 100 DEG C of baking oven crystallization 24h, Magnetic Isolation goes out after solid formation, is dry 12h in 60 DEG C of baking ovens in temperature; 12, dry step 11 gained thing is proceeded in tube furnace, at N
2under atmosphere, temperature is to calcine 5～6h under 550 DEG C of conditions, is then cooled to after room temperature grinding, obtains Fe
3o
4@nSiO
2@mSiO
2; Wherein, the mixed liquor described in step 7 is to be 0.2M by absolute ethyl alcohol and the 5 weight portion concentration of 20～30 weight portions hydrochloric acid solution is made;
D, magnetic mesoporous carbon Fe
3o
4the preparation of@mC: 13, by step 12 gained Fe
3o
4@nSiO
2@mSiO
2add in mixed liquid, after stirring, be placed in 80 DEG C of baking ovens and dry after 4h, be warming up to 160 DEG C, place 12h, obtain solid; 14, the solid of step 13 is ground, then add in mixed liquor, repeating step 13 operation 1 time, obtains decorating film; 15, step 14 gained decorating film is put into tube furnace, at N
2under atmosphere, carbonization 5～6h under 900 DEG C of conditions; 16, get product after the carbonization of step 15 0.4～0.5 weight portion and grind and be placed in the NaOH solution that the quality percentage composition of 50～60 weight portions is 20%, mechanical agitation 8h, obtains solid formation; Then extremely neutral with distillation washing solid formation, then separate under outside magnetic field effect, collect solid formation, be placed in 60 DEG C of oven dryings, desciccate is magnetic mesoporous carbon Fe
3o
4@mC; Wherein, the mixed liquid described in step 13 is the distilled water by 5 weight portions, and 0.025～0.030 weight portion concentrated sulfuric acid and 0.75～1.00 weight portion carbon source make; Mixed liquor described in step 14 is by 3 weight portion distilled water, and 0.01～0.02 weight portion concentrated sulfuric acid and 0.4 weight portion carbon source make.
The present invention comprises following beneficial effect:
The present invention adopts acid condition, solvent evaporates self-assembling method synthesizing magnetic Fe
3o
4for kernel, fine and close SiO
2layer is intermediate layer, mesoporous SiO
2layer is outer field core-shell structure magnetic Metaporous silicon dioxide material, is labeled as Fe
3o
4@nSiO
2@mSiO
2.Then with Fe
3o
4@nSiO
2@mSiO
2for hard template, the carbon sources such as sucrose are inserted in its mesopore orbit, after carbonization, remove SiO
2layer, obtains the magnetic mesoporous carbon material of nucleocapsid structure.
The present invention adopts acid condition, solvent evaporates self-assembling method synthetic kernel shell structure magnetic mesoporous carbon material.The synthetic material in the more alkaline path of resulting materials has larger aperture (3.4nm, 11.1nm), high specific area (971.3m
2/ g) and large pore volume (1.42cm
3/ g), magnetic saturation is 1.73emu/g.This carbon ball has fast and high-adsorption-capacity dye of positive ion rhodamine B and anionic dye methyl orange MO, and the material after absorbing dye can separate rapidly under extraneous magnetic fields, after ethanol washing, dyestuff is dissolved in ethanol, adsorbent through Magnetic Isolation, dry after again absorbing dye and after reusing for several times adsorbance change very little.Wherein, solvent evaporates self assembly: be by the method for block macromolecular self assembly in solution of solvent evaporates induced surface activity.
Brief description of the drawings
Fig. 1 is the synthetic route chart that 1 pair of dyestuff of test has the core-shell structure magnetic mesoporous carbon of high absorption property;
Fig. 2 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the little angle XRD diffraction pattern of@mC;
Fig. 3 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the wide-angle XRD diffraction pattern of@mC;
Fig. 4 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the N of@mC
2adsorption-desorption isollaothermic chart wherein, ◆ represent desorption curve, ■ represents adsorption curve;
Fig. 5 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the graph of pore diameter distribution of@mC;
Fig. 6 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the IR figure of@mC;
Fig. 7 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the M-H curve of@mC;
Fig. 8 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the ultraviolet absorpting spectrum of@mC absorption rhodamine B; Wherein, a is 0 minute ultraviolet absorption curve, and b is 5 minutes ultraviolet absorption curves, and c is 10 minutes ultraviolet absorption curves, and d is 20 minutes ultraviolet absorption curves, and e is 30 minutes ultraviolet absorption curves;
Fig. 9 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4@mC adsorption-desorption dye well adsorbent separation process schematic diagram;
Figure 10 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4@mC is to rhodamine B absorption property loop test figure;
Figure 11 is test 1 core-shell structure magnetic meso-porous carbon material Fe
3o
4the ultraviolet absorpting spectrum of@mC absorption methyl orange; Wherein, a is 0 minute ultraviolet absorption curve, b is 5 minutes ultraviolet absorption curves, c is 10 minutes ultraviolet absorption curves, and d is 20 minutes ultraviolet absorption curves, and e is 30 minutes ultraviolet absorption curves, f is 40 minutes ultraviolet absorption curves, g is 50 minutes ultraviolet absorption curves, and h is 60 minutes ultraviolet absorption curves, and i is 120 minutes ultraviolet absorption curves.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: under a kind of acid condition of present embodiment, the preparation method of synthetic kernel shell structure magnetic mesoporous carbon material carries out according to following steps:
A, magnetic Fe
3o
4the preparation of nano particle: one, take by weight 1～2 part of source of iron, join under the condition of magnetic agitation in 40～60 weight portion reducing agents and be uniformly mixed, obtain mixed solution; Two, the precipitating reagent of 2～3 weight portions and 0.8～1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, obtain mixed liquid; Three, mixed step 2 liquid being transferred in reactor, being heated to, after 200 DEG C of crystallization 8h, be cooled to room temperature, successively with distilled water with absolute ethyl alcohol is each cleans 6 times, is dry 12h in the baking oven of 60 DEG C in temperature, obtains Fe
3o
4nano particle;
B, Fe
3o
4@nSiO
2preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3o
4nano particle, is scattered in mixed liquor, ultrasonic processing 15min; Five, by ultrasonic step 4 Fe after treatment
3o
4under the effect of nano particle outside magnetic field, separate, collect solid formation, respectively wash 3 times with distilled water and absolute ethyl alcohol successively, then add 80～100 weight portion absolute ethyl alcohols, 20 weight portion distilled water and 1 weight portion concentrated ammonia liquor, under room temperature, stir 60min, obtain even mixed liquor; Six,, in the even mixed liquor obtaining to step 5, drip 0.6 weight portion silicon source with the speed of 0.1 drop/sec, under the condition that is then 800～1000rpm at rotating speed, mechanical agitation 12h; Under outside magnetic field effect, separating, collect solid formation, respectively clean 6 times successively with distilled water and absolute ethyl alcohol, is to be dried after 12h in 60 DEG C of baking ovens in temperature, obtains Fe
3o
4@nSiO
2; Wherein, the mixed liquor described in step 4 is that 0.2M hydrochloric acid solution makes by the concentration of 30～40 weight portion absolute ethyl alcohols and 5～8 weight portions;
C, Fe
3o
4@nSiO
2@mSiO
2preparation: seven, by step B gained Fe
3o
4@nSiO
2be scattered in mixed liquor ultrasonic processing 15min; Eight, the ultrasonic solution after treatment of step 7 is stirred and evenly mixed, add after 0.02 weight account polyethylene pyrrolidones, stir 2h, obtain mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in to 10～15 weight portions adds in the mixed liquor of step 8 to clarification, under room temperature, stirs 2h, obtains solution; Ten, in the solution of step 9, add 0.8 weight portion silicon source, under room temperature, stir after 2d, dry; 11, step 10 is dried to product grinding and proceed in reactor, add the distilled water of 15～20 weight portions, be placed in 100 DEG C of baking oven crystallization 24h, Magnetic Isolation goes out after solid formation, is dry 12h in 60 DEG C of baking ovens in temperature; 12, dry step 11 gained thing is proceeded in tube furnace, at N
2under atmosphere, temperature is to calcine 5～6h under 550 DEG C of conditions, is then cooled to after room temperature grinding, obtains Fe
3o
4@nSiO
2@mSiO
2; Wherein, the mixed liquor described in step 7 is to be 0.2M by absolute ethyl alcohol and the 5 weight portion concentration of 20～30 weight portions hydrochloric acid solution is made;
D, magnetic mesoporous carbon Fe
3o
4the preparation of@mC: 13, by step 12 gained Fe
3o
4@nSiO
2@mSiO
2add in mixed liquid, after stirring, be placed in 80 DEG C of baking ovens and dry after 4h, be warming up to 160 DEG C, place 12h, obtain solid; 14, the solid of step 13 is ground, then add in mixed liquor, repeating step 13 operation 1 time, obtains decorating film; 15, step 14 gained decorating film is put into tube furnace, at N
2under atmosphere, carbonization 5～6h under 900 DEG C of conditions; 16, get product after the carbonization of step 15 0.4～0.5 weight portion and grind and be placed in the NaOH solution that the quality percentage composition of 50～60 weight portions is 20%, mechanical agitation 8h, obtains solid formation; Then extremely neutral with distillation washing solid formation, then separate under outside magnetic field effect, collect solid formation, be placed in 60 DEG C of oven dryings, desciccate is magnetic mesoporous carbon Fe
3o
4@mC; Wherein, the mixed liquid described in step 13 is the distilled water by 5 weight portions, and 0.025～0.030 weight portion concentrated sulfuric acid and 0.75～1.00 weight portion carbon source make; Mixed liquor described in step 14 is by 3 weight portion distilled water, and 0.01～0.02 weight portion concentrated sulfuric acid and 0.4 weight portion carbon source make.
The beneficial effect of present embodiment is:
Present embodiment adopts solvent evaporates self-assembling method synthesizing magnetic Fe under acid condition
3o
4for kernel, fine and close SiO
2layer is intermediate layer, mesoporous SiO
2layer is outer field core-shell structure magnetic mesoporous silicon material, is labeled as Fe
3o
4@nSiO
2@mSiO
2.Then with Fe
3o
4@nSiO
2@mSiO
2for hard template, sucrose is inserted in its mesopore orbit, after carbonization, remove SiO
2layer, obtains the magnetic mesoporous carbon material of nucleocapsid structure.
Present embodiment adopts acid condition, solvent evaporates self-assembling method synthetic kernel shell structure magnetic mesoporous carbon material.The synthetic material with carbon element in the more alkaline path of resulting materials has larger aperture: 3.4nm and 11.1nm, high specific area: 971.3m
2/ g and large pore volume: 1.42cm
3/ g, magnetic saturation is 1.73emu/g.Carbon ball prepared by the method has fast and high-adsorption-capacity dye of positive ion rhodamine B and anionic dye methyl orange MO, and the material after absorbing dye can separate rapidly under extraneous magnetic fields, after ethanol washing, adsorbent through Magnetic Isolation, dry after again absorbing dye for several times after adsorbance change very little.
Detailed description of the invention two: present embodiment is different from detailed description of the invention one: the source of iron described in steps A is FeCl
36H
2o or Fe (NO
3)
39H
2o.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is different from detailed description of the invention one or two: the reducing agent described in steps A is ethylene glycol or ammoniacal liquor.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is different from one of detailed description of the invention one to three: the precipitating reagent described in steps A is sodium acetate or NaOH.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is different from one of detailed description of the invention one to four: the silicon source described in step B and step C is tetraethyl orthosilicate.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is different from one of detailed description of the invention one to five: the surfactant described in step C is that polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 (molecular formula is EO20PO70EO20) or F127(molecular formula are EO106PO70EO106).Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is different from one of detailed description of the invention one to six: the carbon source described in step D is sucrose or phenolic resins.Other is identical with one of detailed description of the invention one to six.
By following verification experimental verification beneficial effect of the present invention:
The preparation method that dyestuff is had to a core-shell structure magnetic meso-porous carbon material of high absorption property in this test carries out according to following steps:
(1) magnetic Fe
3o
4the preparation of nano particle
One, by the FeCl of 1.08g
36H
2o is dissolved in the ethylene glycol of 40mL under the condition of magnetic agitation, then adds sodium acetate and the 0.8g polyethylene glycol of 2.88g, is at room temperature uniformly mixed 4h, proceeds in reactor, is heated to 200 DEG C of crystallization 8h; Two, after step 1 crystallization finishes, being cooled to room temperature, obtaining black particle, clean 6 times successively with distilled water and absolute ethyl alcohol, is dry 12h in 60 DEG C of baking ovens in temperature, obtains magnetic Fe
3o
4nano particle;
(2) Fe
3o
4@nSiO
2preparation
Three, get the magnetic Fe of the prepared 0.1g of step 2
3o
4nano particle, is scattered in mixed liquor, under the condition that is 40KHz in supersonic frequency, and ultrasonic dispersion 15min; Four, by the product after ultrasonic step 3 dispersion, after adopting the effect of permanent magnet outside magnetic field to separate, respectively wash 3 times with distilled water and absolute ethyl alcohol successively, proceed to 250mL tri-neck round-bottomed flasks, then add 80mL absolute ethyl alcohol, 20mL distilled water and 1mL concentrated ammonia liquor, stir 60min under room temperature, obtains even mixed liquor; Five, in the even mixed liquor obtaining in step 4, drip 0.6mL tetraethyl orthosilicate (TEOS) with the speed of 0.1 drop/sec, then with the speed of 1000rpm, mechanical agitation 12h, under external magnetic field, separate, gained black product, cleaning 6 times with distilled water and absolute ethyl alcohol successively, is dry 12h in 60 DEG C of baking ovens in temperature, obtains Fe
3o
4@nSiO
2; Wherein, the mixed liquor described in step 3 is to be that 0.2M hydrochloric acid solution makes by the absolute ethyl alcohol of 20mL and the concentration of 5mL;
(3) Fe
3o
4@nSiO
2@mSiO
2preparation
Six, by gained Fe
3o
4@nSiO
2be scattered in mixed liquor, after ultrasonic dispersion 15min, mechanical agitation makes to be uniformly dispersed; After adding 0.01g polyvinylpyrrolidone (PVP), continue to stir 2h, obtain mixed liquor; Seven, the P123 of 1g is dissolved in to 10mL absolute ethyl alcohol, after stirring to clarify, joins in the mixed liquor that step 6 obtains, at room temperature stir after 2h, drip the TEOS of 0.8mL with the speed of 0.1 drop/sec, after dropwising, at room temperature stir solvent flashing, stir after 2d, obtain grume solid formation; Eight, grume solid formation step 7 being obtained is dried after 12h in temperature is the baking oven of 60 DEG C, proceeds in 30mL reactor after grinding, adds 15mL distilled water, is placed in 100 DEG C of baking oven crystallization 24h; Nine, by the product after step 8 crystallization, adopt after Magnetic Isolation, be dry 12h in 60 DEG C of baking ovens in temperature; To obtain gray product and proceed in tube furnace, at N
2under atmosphere, temperature is under 550 DEG C of conditions, to calcine 6h to remove template, be chilled to after room temperature grinds and obtain Fe
3o
4@nSiO
2@mSiO
2; Wherein, the mixed liquor described in step 6 is made by 20mL absolute ethyl alcohol and 5mL concentration 0.2M hydrochloric acid solution;
(4) magnetic mesoporous carbon Fe
3o
4the preparation of@mC
Ten, by step 9 gained Fe
3o
4@nSiO
2@mSiO
2add containing 5mL distilled water, in the mixed liquor of the 0.025mL concentrated sulfuric acid and 0.75g sucrose, after stirring, suspension is placed in to 80 DEG C of baking oven evaporating solvents, after 4h, be warming up to 160 DEG C, place 12h, obtain solid; 11, step 10 solid is ground, again add and contain 3mL distilled water, in the mixed liquor of the 0.01mL concentrated sulfuric acid and 0.4g sucrose, after stirring, be warming up to 160 DEG C after suspension is placed in to 80 DEG C of baking oven evaporating solvent 4h, place 12h, obtain atrament; 12, step 11 gained atrament is put into tube furnace, at N
2under atmosphere, carbonization 6h under 900 DEG C of conditions; 13, the atrament 0.4g grinding after step 12 carbonization being placed on to quality percentage composition is that in 20%NaOH solution 50mL, mechanical agitation 8h, obtains solid formation; Adopt distillation washing solid formation for several times to neutral, then separate under external magnetic field, collect product, be placed in 60 DEG C of oven dryings, gained black desciccate is magnetic mesoporous carbon Fe
3o
4@mC.
The core-shell structure magnetic meso-porous carbon material that this test is made carries out following detection:
1, the little angle of XRD and wide-angle detect
The core-shell structure magnetic meso-porous carbon material that this test is obtained carries out the detection of XRD diffraction, and result as shown in Figures 2 and 3.As can be seen from Figure 2, the shell of core-shell structure magnetic meso-porous carbon material has typical two-dimentional hexagonal structure duct, but its (100) diffraction peaks broadening, and (110) and the diffraction maximum of (200) disappeared, former because long-time high temperature cabonization and the etching of follow-up NaOH strong base solution have destroyed that order mesoporous structure causes.
As shown in Figure 3, there is broad peak at 20-28 ° in 2 θ, the composition of amorphous carbon in counter structure.Be 30.1 ° at 2 θ, 35.61 °, 43.04 °, 53.7 °, 57.20 °, locate the diffraction maximum occurring, correspond respectively to Fe for 63.19 °
3o
4(220), (311), (400), (422), (511), (440) crystal face diffraction, therefore proves face-centered cubic spinel structure Fe well
3o
4existence.(101) diffraction maximum and the Fe of ° position graphitic carbon in 2 θ=43.50
3o
4(400) diffraction maximum overlap, so there is the peak type of broadening at this place.
2, nitrogen adsorption one desorption isotherm test
The core-shell structure magnetic meso-porous carbon material that this test is obtained carries out N
2adsorb a desorption and detect, result as shown in Figure 4.Nitrogen adsorption desorption curve is at P/P
0=0.4-0.8 presents hop, belongs to typical IV thermoisopleth, and H1 type hysteresis loop has shown the existence of the meso-hole structure in homogeneous duct, Fe
3o
4the BET specific area of@mC material is up to 971.3m
2/ g., the peak occurring at 3.4nm and 11.1nm place in graph of pore diameter distribution (Fig. 5) respectively corresponding outer mesoporous carbon-coating mesoporous aperture and etch away the cavity size producing after internal layer silica.Larger specific area, large aperture, large pore volume (1.42cm
3/ g) make Fe
3o
4@mC material, in the time that large molecular dye is adsorbed, has the rate of adsorption and larger adsorption capacity faster.
3, IR detects
The core-shell structure magnetic meso-porous carbon material that this test is obtained carries out IR detection, and result is as Fig. 6.At 570cm
-1place, for Fe-O stretching vibration peak, shows Fe
3o
4existence.1390 and 2950cm
-1for saturated c h bond stretching vibration peak.ν (C=C) absworption peak appears at 1565cm
-1, ν (CH
2-O-CH
2) absworption peak appears at 1162 and 1080cm
-1place.
4, M-H detects
The core-shell structure magnetic mesoporous carbon that this test is obtained is carried out magnetic saturation detection, and result as shown in Figure 7.The magnetic saturation of magnetic mesoporous carbon nanometer micro ball is 1.73emu/g, and this numerical value is enough for Magnetic Isolation.In curve, occur without any hysteresis loop, this has illustrated prepared magnetic mesoporous carbon Fe
3o
4@mC sample has superparamagnetism.Have the nano material of superparamagnetism feature, can produce response to external magnetic field rapidly, and disappear with external magnetic field, can again be scattered in solution again, this is very favourable for adsorbent subsequent recovery regeneration in practical application.
5, dyestuff rhodamine B absorption property is detected
To dye of positive ion rhodamine B absorption property, test adopts following steps to carry out: 10mg adsorbent, join in the rhodamine B solution of 100mL20PPM, in vibrating bed, adsorb, behind certain hour interval, it is a small amount of that external magnetic field is got supernatant liquor after separating, by ultraviolet spectroscopy adsorption effect, result is as Fig. 8.For Fe
3o
4@mC adsorbent, within 5 minutes, 82.24% rhodamine B is adsorbed, and by 30 minutes, absorption reached 99.45%, and absorption completes substantially, and adsorbance reaches 198.9mgg
-1.The reason of quick adsorption and high-adsorption-capacity is mainly and ascribes the high-specific surface area of mesoporous material and larger aperture and pore volume to.
For adsorbent, the performance of its recycling utilization is most important for practical application.Circulation experiment operating procedure (as shown in Figure 9) is: (1) prepares a certain amount of concentration known rhodamine B solution; (2) Fe
3o
4@mC adds water body absorbing dye; (3) under the effect of adsorbent outside magnetic field, separate; (4) clean adsorbent for several times with a small amount of absolute ethyl alcohol, make dyestuff desorption in ethanol, adsorbent is reused after Magnetic Isolation, oven dry.The circular regeneration performance test of adsorbent as shown in figure 10, can be found out prepared Fe by five adsorbances of circulation
3o
4@mC adsorbance after five circulations is 176.2mg/g, adsorbance be while using for the first time adsorbance 88.6%.Visible Fe
3o
4@mC is as the adsorbent of rhodamine B, and stable in properties, has good circular regeneration performance.
6, methyl orange absorption property is detected
Adopt following steps to carry out to the performance test of anionic dye Adsorption of Methyl Orange: 10mg adsorbent, join in the methyl orange solution of 100mL 20PPM, in vibrating bed, adsorb, behind certain hour interval, after external magnetic field centrifugation, get supernatant a small amount of, by ultraviolet spectroscopy adsorption effect, result is as Figure 11.Within 5 minutes, 72.87% methyl orange is adsorbed; After 40min, absorption reached after 95.18%, 120 minute, and 97.68% methyl orange is adsorbed, and adsorbance is 195.4mg/g.Because this meso-porous carbon material high-specific surface area and large pore volume show to methyl orange dye fast and high-adsorption-capacity.
In sum, in conjunction with the result of the test shown in Fig. 2 to 11, known test successfully prepared dyestuff had to the core-shell structure magnetic meso-porous carbon material compared with high absorption property under acid condition, is expected to be widely used in fields such as sewage disposal, biological medicine, catalysis and the energy.
Claims (4)
1. under acid condition, prepare method dyestuff to the magnetic mesoporous carbon nanometer micro ball of high absorption property, it is characterized in that its preparation method carries out according to following steps:
A, magnetic Fe
3o
4the preparation of nano particle: one, take by weight 1～2 part of source of iron, join under the condition of magnetic agitation in 40～60 weight portion reducing agents and be uniformly mixed, obtain mixed solution; Two, the precipitating reagent of 2～3 weight portions and 0.8～1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, obtain mixed liquid; Three, mixed step 2 liquid being transferred in reactor, being heated to, after 200 DEG C of crystallization 8h, be cooled to room temperature, successively with distilled water with absolute ethyl alcohol is each cleans 6 times, is dry 12h in the baking oven of 60 DEG C in temperature, obtains Fe
3o
4nano particle;
B, Fe
3o
4@nSiO
2preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3o
4nano particle, is scattered in mixed liquor, ultrasonic processing 15min; Five, by ultrasonic step 4 Fe after treatment
3o
4under the effect of nano particle outside magnetic field, separate, collect solid formation, respectively wash 3 times with distilled water and absolute ethyl alcohol successively, then add 80～100 weight portion absolute ethyl alcohols, 20 weight portion distilled water and 1 weight portion concentrated ammonia liquor, under room temperature, stir 60min, obtain even mixed liquor; Six,, in the even mixed liquor obtaining to step 5, drip 0.6 weight portion silicon source with the speed of 0.1 drop/sec, under the condition that is then 800～1000rpm at rotating speed, mechanical agitation 12h; Under outside magnetic field effect, separating, collect solid formation, respectively clean 6 times successively with distilled water and absolute ethyl alcohol, is to be dried after 12h in 60 DEG C of baking ovens in temperature, obtains Fe
3o
4@nSiO
2; Wherein, the mixed liquor described in step 4 is that 0.2M hydrochloric acid solution makes by the concentration of 30～40 weight portion absolute ethyl alcohols and 5～8 weight portions;
C, Fe
3o
4@nSiO
2@mSiO
2preparation: seven, by step B gained Fe
3o
4@nSiO
2be scattered in mixed liquor ultrasonic processing 15min; Eight, the ultrasonic solution after treatment of step 7 is stirred and evenly mixed, add after 0.02 weight account polyethylene pyrrolidones, stir 2h, obtain mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in to 10～15 weight portions adds in the mixed liquor of step 8 to clarification, under room temperature, stirs 2h, obtains solution; Ten, in the solution of step 9, add 0.8 weight portion silicon source, under room temperature, stir after 2d, dry; 11, step 10 is dried to product grinding and proceed in reactor, add the distilled water of 15～20 weight portions, be placed in 100 DEG C of baking oven crystallization 24h, Magnetic Isolation goes out after solid formation, is dry 12h in 60 DEG C of baking ovens in temperature; 12, dry step 11 gained thing is proceeded in tube furnace, at N
2under atmosphere, temperature is to calcine 5～6h under 550 DEG C of conditions, is then cooled to after room temperature grinding, obtains Fe
3o
4@nSiO
2@mSiO
2; Wherein, the mixed liquor described in step 7 is to be 0.2M by absolute ethyl alcohol and the 5 weight portion concentration of 20～30 weight portions hydrochloric acid solution is made;
D, magnetic mesoporous carbon Fe
3o
4the preparation of@mC: 13, by step 12 gained Fe
3o
4@nSiO
2@mSiO
2add in mixed liquid, after stirring, be placed in 80 DEG C of baking ovens and dry after 4h, be warming up to 160 DEG C, place 12h, obtain solid; 14, the solid of step 13 is ground, then add in mixed liquor, repeating step 13 operation 1 time, obtains decorating film; 15, step 14 gained decorating film is put into tube furnace, at N
2under atmosphere, carbonization 5～6h under 900 DEG C of conditions; 16, get product after the carbonization of step 15 0.4～0.5 weight portion and grind and be placed in the NaOH solution that the quality percentage composition of 50～60 weight portions is 20%, mechanical agitation 8h, obtains solid formation; Then extremely neutral with distillation washing solid formation, then separate under outside magnetic field effect, collect solid formation, be placed in 60 DEG C of oven dryings, desciccate is magnetic mesoporous carbon Fe
3o
4@mC; Wherein, the mixed liquid described in step 13 is the distilled water by 5 weight portions, and 0.025～0.030 weight portion concentrated sulfuric acid and 0.75～1.00 weight portion carbon source make; Mixed liquor described in step 14 is by 3 weight portion distilled water, and 0.01～0.02 weight portion concentrated sulfuric acid and 0.4 weight portion carbon source make; Wherein, the reducing agent described in steps A is ethylene glycol or ammoniacal liquor; Precipitating reagent described in steps A is sodium acetate or NaOH; Carbon source described in step D is sucrose or phenolic resins.
2. method dyestuff to the magnetic mesoporous carbon nanometer micro ball of high absorption property of preparing under acid condition according to claim 1, is characterized in that the source of iron described in steps A is FeCl
36H
2o or Fe (NO
3)
39H
2o.
3. method dyestuff to the magnetic mesoporous carbon nanometer micro ball of high absorption property of preparing under acid condition according to claim 1, is characterized in that the silicon source described in step B and step C is tetraethyl orthosilicate.
4. method dyestuff to the magnetic mesoporous carbon nanometer micro ball of high absorption property of preparing under acid condition according to claim 1, is characterized in that the surfactant described in step C is polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 or F127.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101904.9A CN103182294B (en) | 2013-03-27 | 2013-03-27 | Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101904.9A CN103182294B (en) | 2013-03-27 | 2013-03-27 | Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103182294A CN103182294A (en) | 2013-07-03 |
| CN103182294B true CN103182294B (en) | 2014-09-17 |
Family
ID=48673889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310101904.9A Expired - Fee Related CN103182294B (en) | 2013-03-27 | 2013-03-27 | Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103182294B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623788B (en) * | 2013-11-22 | 2016-04-06 | 江苏大学 | A kind of preparation method of magnetic mesoporous free radical controllable polymerization ion blotting adsorbent |
| CN104475062A (en) * | 2014-12-17 | 2015-04-01 | 武汉大学 | Amidine modified mesoporous foam material used for carbon dioxide adsorption and preparation method of amidine modified mesoporous foam material |
| CN105552354B (en) * | 2016-03-17 | 2018-09-18 | 齐鲁工业大学 | A kind of preparation method of lithium ion battery negative material |
| CN105565265B (en) * | 2016-03-17 | 2018-09-18 | 齐鲁工业大学 | A kind of preparation method of the complex microsphere lithium ion battery negative material with yolk structure |
| CN106117474B (en) * | 2016-06-24 | 2018-06-12 | 复旦大学 | A kind of covalent organic frame magnetic composite microsphere with nucleocapsid and preparation method thereof |
| CN107957455B (en) * | 2017-11-17 | 2020-03-31 | 江苏省原子医学研究所 | Method for determining EGCG palmitate by modified and modified multi-walled carbon nanotube dispersed solid phase extraction/UPLC-MS |
| CN112275278B (en) * | 2020-04-07 | 2022-05-17 | 杭州电子科技大学 | Shell-core type composite nano material with hollow silicon sphere layer as shell and nano metal oxide as core, and preparation method and application thereof |
| CN111408347A (en) * | 2020-04-24 | 2020-07-14 | 杭州楚环科技股份有限公司 | Novel Fe3O4@SiO2Preparation method and application of @ ESM mesoporous material |
| CN111760554A (en) * | 2020-08-12 | 2020-10-13 | 湖南三五二环保科技有限公司 | Preparation method of carbon material for wastewater treatment, product and application thereof |
| CN111804279A (en) * | 2020-08-19 | 2020-10-23 | 湖南三五二环保科技有限公司 | Preparation method of carbon material for dye wastewater, product and application thereof |
| CN114870798B (en) * | 2022-03-04 | 2023-06-23 | 华北电力大学 | Novel three-dimensional layered hierarchical mesoporous carbon material and preparation method thereof |
| CN114797861A (en) * | 2022-04-25 | 2022-07-29 | 国能(山东)能源环境有限公司 | Magnetic mesoporous silica microsphere and preparation method and application thereof |
| CN115872402A (en) * | 2022-07-13 | 2023-03-31 | 武汉科技大学 | Hollow mesoporous carbon sphere self-assembly porous carbon microsphere and preparation method thereof |
| CN115475597B (en) * | 2022-08-10 | 2024-03-29 | 中国地质大学（武汉） | Core-shell magnetic mesoporous silica material, method for preparing material by using iron tailings and application of material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247803A (en) * | 2011-05-04 | 2011-11-23 | 中国科学院化学研究所 | Core-shell type magnetic mesoporous nano-microsphere as well as preparation method and application thereof |
| WO2012062793A1 (en) * | 2010-11-09 | 2012-05-18 | Studiengesellschaft Kohle Mbh | Process for preparing carbon protected superparamagnetic or magnetic nanospheres |
| CN102614819A (en) * | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
| CN102649046A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院合肥物质科学研究院 | Nanometer ferroferric oxide core-carbon meso pore hollow shell complex, as well as preparation method and application thereof |
-
2013
- 2013-03-27 CN CN201310101904.9A patent/CN103182294B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012062793A1 (en) * | 2010-11-09 | 2012-05-18 | Studiengesellschaft Kohle Mbh | Process for preparing carbon protected superparamagnetic or magnetic nanospheres |
| CN102649046A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院合肥物质科学研究院 | Nanometer ferroferric oxide core-carbon meso pore hollow shell complex, as well as preparation method and application thereof |
| CN102247803A (en) * | 2011-05-04 | 2011-11-23 | 中国科学院化学研究所 | Core-shell type magnetic mesoporous nano-microsphere as well as preparation method and application thereof |
| CN102614819A (en) * | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103182294A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103182294B (en) | Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition | |
| Shi et al. | Janus particles with pH switchable properties for high-efficiency adsorption of PPCPs in water | |
| Liu et al. | Removal of pharmaceuticals by novel magnetic genipin-crosslinked chitosan/graphene oxide-SO3H composite | |
| CN104072762B (en) | The preparation method of the magnetic carbon nano-tube that the poly-Dopamine HCL in a kind of surface is modified | |
| Chen et al. | Preparation of size-controlled magnetite nanoparticles with a graphene and polymeric ionic liquid coating for the quick, easy, cheap, effective, rugged and safe extraction of preservatives from vegetables | |
| Sun et al. | Removal of patulin in apple juice based on novel magnetic molecularly imprinted adsorbent Fe3O4@ SiO2@ CS-GO@ MIP | |
| Zhang et al. | Fe3O4@ SiO2@ CCS porous magnetic microspheres as adsorbent for removal of organic dyes in aqueous phase | |
| Zhao et al. | Surfactant-modified flowerlike layered double hydroxide-coated magnetic nanoparticles for preconcentration of phthalate esters from environmental water samples | |
| CN107096494A (en) | A kind of preparation and application method of magnetic core-shell nano-compound adsorbent | |
| Gao et al. | A controlled solvethermal approach to synthesize nanocrystalline iron oxide for congo red adsorptive removal from aqueous solutions | |
| Zhang et al. | Ultrasound-enhanced adsorption of chromium (VI) on Fe3O4 magnetic particles | |
| CN103041773A (en) | Magnetic carbon nanotube composite material and preparation method and application thereof | |
| Liang et al. | The synthesis of core–shell Fe3O4@ mesoporous carbon in acidic medium and its efficient removal of dye | |
| CN105664936A (en) | Method for preparing nano composite material having core-shell structure with dopamine as carbon source | |
| Yao et al. | Fabrication and characterization of amphiphilic magnetic water purification materials for efficient PPCPs removal | |
| CN103143305A (en) | Method for synthesizing magnetic mesoporous silica nanoparticle microsphere with core-shell structure in acidic conditions | |
| CN107511132A (en) | A kind of magnetic ferroferric oxide nano-particles and its Plasma modification method and application | |
| CN105396555A (en) | Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions | |
| CN102517020B (en) | Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof | |
| CN103771429A (en) | Method using co-template agent to synthesizing porous spherical silica | |
| CN103223331A (en) | Preparation method of Ni (Co,Fe)-supported magnetic mesoporous carbon material with high adsorption performance on dyes | |
| CN109499520A (en) | A kind of amino functional manganese dioxide load nano-magnetic preparation method for bentonite and its application | |
| CN105597714A (en) | Preparation of phenyl-modified magnetic graphene/mesoporous silicon dioxide composite material and application of phenyl-modified magnetic graphene/mesoporous silicon dioxide composite material as solid-phase extracting agent | |
| CN104128163A (en) | Preparation method of microporous-mesoporous MIL-101 material and application thereof | |
| CN106040185A (en) | Method for preparing magnetic adsorbent for methylene blue wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140917 Termination date: 20160327 |