CN102110506B - Carbon-based magnetic mesoporous composite microsphere and preparation method thereof - Google Patents
Carbon-based magnetic mesoporous composite microsphere and preparation method thereof Download PDFInfo
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- CN102110506B CN102110506B CN 201010550223 CN201010550223A CN102110506B CN 102110506 B CN102110506 B CN 102110506B CN 201010550223 CN201010550223 CN 201010550223 CN 201010550223 A CN201010550223 A CN 201010550223A CN 102110506 B CN102110506 B CN 102110506B
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Abstract
The invention provides a carbon-based magnetic mesoporous composite microsphere and a preparation method thereof, belonging to the technical field of the preparation of an inorganic composite material. The diameter of the carbon-based magnetic mesoporous composite microsphere particle is 3-6 microns, the specific surface area of the microsphere is 270-315 m2/g, the pore diameter is 4-8 nanometers, and the pore volume is 0.15-0.31 cm3/g. The preparation method comprises the following steps: firstly, synthesizing an FexOy/ carbon-based composite microsphere; and then, preparing the gamma-Fe2O3/ carbon-based magnetic mesoporous composite microsphere. The invention has the following obvious advantages: the FexOy/ carbon-based composite microsphere is synthesized in one step, the activation and magnetization are synchronously carried out, and the obtained material has a simplex magnetic component, is in a mesoporous structure and has a large specific surface area. The preparation method of the mesoporous carbon-based magnetic composite microsphere is simple and easy to control magnetically, can be used as a micro adsorbent or magnetic targeted drug carrier, and has potential application value in delivery and separation processes.
Description
Technical field:
The invention belongs to field of inorganic materials, be specifically related to a kind of γ-Fe
2O
3/ carbon-based magnetic mesoporous composite microsphere and preparation method thereof.
Background technology:
Mesoporous material pore volume storage is high, surperficial condensing characteristic good, select shape separation, high-efficient characteristic catalysis, sensing and light, electricity, there is important application prospect in the magnetic field.Mesoporous carbon has the advantages that specific area is large, pore-size distribution is moderate, can replace activated carbon in the important materials of the aspect purposes such as drinking-water advanced treating, catalyst carrier.γ-Fe
2O
3Have good magnetic, catalytic performance and ultraviolet radiation absorption and screen effect, than Fe
3O
4Stability high, but in air long preservation, can be because oxidation affect magnetic, stable in the air depositing is a kind of widely used functional material, all has a good application prospect in fields such as electronics, petrochemical industry, environmental protection and biological medicines.Nanometer γ-Fe
2O
3Owing to have small-size effect, skin effect, quantum size effect and macro quanta tunnel effect etc., show many distinctive character, show more excellent performance at aspects such as catalysis, magnetic.Carbon-based material and nanometer γ-Fe
2O
3Compound performance and the application space that will further expand meso-porous carbon material.Document (1) Journal of Hazardous Materials 160 (2008) 643 has reported γ-Fe
2O
3Synthetic method with nanometer carbon pipe composite material.CN101823777A discloses a kind of take meso-porous carbon material CMK-3 as carrier, utilizes equi-volume impregnating and the method for roasting in inert gas, with Fe
3O
4Particulate load enters the method for the mesopore orbit of mesoporous carbon CMK-3.
Nearly 20, about meso-hole structure and pattern control and the existing a large amount of reports of synthetic research.Day by day deep along with to material pattern and performance study, people recognize that gradually the material with carbon element of spherical structure has many potential using values.Nanometer γ-Fe
2O
3The composite material that consists of with mesoporous carbon spheres is the various excellent properties of bi-material itself comprehensively, become a kind of advanced composite material (ACM), play a greater role at numerous areas such as sewage disposal, bioengineering, target administrations.CN101284223 discloses and has adopted resin and hydroxide colloid mixture to prepare the method for porous magnetic carbon ball.It is precursor that document (2) Adv.Mater.18 (2006) 1968 and document (3) J.Phys.Chem.C 112 (2008) 8623 adopt crosslinked resin or globular chitosan, after the load iron content component, obtain the magnetic mesoporous carbon ball through high-temperature roasting.
Report or disclosed method that with regard to the source of carbon, cost is higher, and magnetic component contains γ-Fe in the composite carbon ball
2O
3, Fe
3C, Fe form complicatedly, and contained component and each constituent content are difficult to control; With regard to the preparation of the acquisition of microballoon precursor and load iron component microballoon, need to distribute and carry out, step is comparatively loaded down with trivial details.Single-phase γ-Fe with high-ratio surface
2O
3/ carbon-based magnetic mesoporous composite microsphere there is not yet report.
Summary of the invention:
The object of the present invention is to provide a kind of carbon-based magnetic mesoporous composite microsphere and preparation method thereof.The diameter of this carbon-based magnetic mesoporous composite microsphere particle is the 3-6 micron, and the microsphere specific area is 270-315m
2/ g, aperture 4-8 nanometer, pore volume is 0.15-0.31cm
3/ g, this complex microsphere are a kind of γ-Fe with meso-hole structure, good magnetic induction
2O
3The compound micron-size spherical body of/carbon back.
Preparation method's concrete steps of described carbon-based magnetic mesoporous composite microsphere are as follows:
(1) with certain density solubility trivalent iron salt and glucose or sucrose Hydrothermal Synthesis Fe in filling the reactor of the aqueous solution
xO
y/ carbon back complex microsphere, the mass ratio of described solubility trivalent iron salt and glucose or sucrose is (0.2-1.2): 1, and reaction temperature is 160-200 ℃, behind the reaction 8-24h reactor is naturally cooled to room temperature in air, then take out feed liquid, feed liquid is made Fe through dehydration, drying
xO
y/ carbon back complex microsphere;
(2) to the synthetic Fe that obtains of step (1)
xO
y/ carbon back complex microsphere high temperature under carbon dioxide atmosphere magnetizes and activation obtains γ-Fe
2O
3The compound micron-size spherical body of/carbon back, i.e. carbon-based magnetic mesoporous composite microsphere; This high temperature magnetization and activation parameter are: the flow of carbon dioxide gas amount is 0.5-2.0L/min, and activation temperature is 650-800 ℃, and soak time is 2-4h.
Described solubility trivalent iron salt is ferric nitrate.
The heating mode that adopts in the activation process is programmed temperature method.
The beneficial effect that the present invention has is:
Take ferric nitrate and monose or disaccharides as raw material, prepare Fe under the hydrothermal condition
xO
y/ carbon back complex microsphere; And take thus obtained microsphere as presoma, magnetization and activation under carbon dioxide atmosphere.Magnetization is carried out synchronously with activation, and method is simply controlled.Be used for the removal of water pollutant, can under magnetic fields, realize Separation of Solid and Liquid.
The outstanding advantages of this material is: by having ferromagnetic γ-Fe
2O
3Compound with the active carbon-based material of high-ratio surface, all magnetic can realize the magnetic field of material is controlled, and the active carbon-based material of high-ratio surface makes it have good absorption property.This microballoon can be used as azo dyes in a kind of adsorbent adsorbing separation dyeing waste water, and adsorbent can be realized Magnetic Isolation with mother liquor, economy easy and simple to handle after using.
γ-Fe provided by the invention
2O
3/ carbon-based magnetic mesoporous composite microsphere has a good application prospect in fields such as sewage disposals for the removal of dyestuff in the dyeing waste water provides new preparation method and sorbing material.Has potential using value in fields such as bioengineering.
Description of drawings:
Fig. 1: γ-Fe
2O
3The XRD collection of illustrative plates of/carbon back composite magnetic mesoporous microsphere.
Curve a, b, c are respectively γ-Fe that activation temperature is 650 ℃, 720 ℃, 800 ℃ preparations among Fig. 1
2O
3The XRD collection of illustrative plates of/carbon back composite magnetic mesoporous microsphere.Abscissa is 2 θ among the figure, unit be (°) degree, ordinate is intensity, unit is a.u. (absolute unit).Adopt your (Sherrer) formula of Scherrer to calculate γ-Fe in the spherical compound
2O
3Grain size (D=k λ/β cos θ, D is grain size, λ is wavelength, gets 0.15418nm, θ is the angle of diffraction, β is half broad peak, k gets constant 0.89).
Fig. 2: γ-Fe
2O
3The stereoscan photograph of/carbon back composite magnetic mesoporous microsphere.
The represented stereoscan photograph of Fig. 2 is that the flow of carbon dioxide gas amount is 1L/min take glucose and ferric nitrate as raw material, and heating rate is 5 ℃/min, and 720 ℃ keep 3h, the γ-Fe that obtains
2O
3The stereoscan photograph of/carbon composite magnetic mesoporous microsphere.
Embodiment:
Embodiment 1: with 4g ferric nitrate (Fe (NO
3)
3) and 10g glucose (C
6H
12O
6) be dissolved in the 80mL water, stir and to make it to dissolve fully, be transferred in the 100mL reaction, be warming up to 200 ℃, insulation 24h, after make reactor in air, be cooled to room temperature.Then take out feed liquid, dehydration.Products therefrom is 80 ℃ of dry 6h in air, get Fe
xO
y/ carbon back complex microsphere.
Fe with the 5g drying
xO
y/ carbon back complex microsphere is inserted in the tube furnace quartz ampoule, passes into carbon dioxide, and gas flow is 1L/min.Heating rate with 5 ℃/min rises to 720 ℃.Keep 3h.And then be cooled to room temperature under the carbon dioxide atmosphere.Obtain γ-Fe of the present invention
2O
3/ carbon back composite magnetic mesoporous microsphere.
Adopt X-ray diffraction to characterize product structure with the full-automatic diffractometer of X pertMPD Philiphs, its XRD test result contains single γ-Fe as shown in Figure 1 in the product
2O
3, the SEM photo adopts JSM-6490LV, and the sample specific surface is surveyed instrument by Micromeritics ASAP 2020 type specific surfaces and is carried out low temperature N
2The adsorption-desorption test obtains.
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is as follows:
Contain γ-Fe in the XRD demonstration carbon ball sill
2O
3(seeing curve b among Fig. 1) calculates γ-Fe
2O
3Be 17 nanometers, SEM photo show sample is the spherical or subsphaeroidal particle of 3-6 micron, the visible hole texture (Fig. 2) in surface.The microsphere specific area is 315m
2/ g, aperture 6nm, average pore volume is 0.31cm
3/ g.
Embodiment 2: adopt sucrose (C
12H
22O
11) be carbon source, m (Fe (NO in mass ratio
3)
3): m (C
12H
22O
11The ratio of)=0.8: 1 is reinforced, and the consumption of ferric nitrate and sucrose is respectively 4g and 5g, hydro-thermal time 20h, and carbon dioxide gas stream is 0.5L/min during activation, and activation temperature is 800 ℃, and other is implemented such as method same among the embodiment 1 to keep 2h..
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is as follows:
Contain γ-Fe in the XRD demonstration carbon ball sill
2O
3(seeing curve c among Fig. 1) calculates γ-Fe
2O
3Be 26 nanometers, the microsphere specific area is 287m
2/ g, average pore size 8nm, pore volume are 0.26cm
3/ g.
Embodiment 3: employing glucose is carbon source, in mass ratio m (Fe (NO
3)
3): m (C
6H
12O
6The ratio of)=0.6: 1 is reinforced, and the consumption of ferric nitrate and glucose is respectively 6g and 10g, hydro-thermal time 18h; Carbon dioxide gas stream is 2L/min during activation, and activation temperature is 650 ℃, keeps 4h.Other is implemented such as method same among the embodiment 1.
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is as follows:
Contain γ-Fe in the XRD demonstration carbon ball sill
2O
3(see among Fig. 1 that curve a) calculates γ-Fe
2O
3Be 10 nanometers.The microsphere specific area is 276m
2/ g, average pore size 4nm, pore volume are 0.15cm
3/ g.
Embodiment 4: employing sucrose is carbon source, in mass ratio m (Fe (NO
3)
3): m (C
12H
22O
11The ratio of)=0.4: 1 is reinforced, and the consumption of ferric nitrate and glucose is respectively 2g and 5g, hydro-thermal time 10h; Carbon dioxide gas stream is 1L/min during activation, and activation temperature is 720 ℃, and other is implemented such as method same among the embodiment 1 to keep 3h..
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is close with example 1.
Embodiment 5: employing glucose is carbon source, in mass ratio m (Fe (NO
3)
3): m (C
6H
12O
6The ratio of)=0.2: 1 is reinforced, and the consumption of ferric nitrate and glucose is respectively 2g and 10g, hydro-thermal time 10h; Carbon dioxide gas stream is 0.5L/min during activation, and activation temperature is 800 ℃, and other is implemented such as method same among the embodiment 1 to keep 2h..
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is close with example 2.
Embodiment 6: employing sucrose is carbon source, in mass ratio m (Fe (NO
3)
3): m (C
12H
22O
11The ratio of)=1.2: 1 is reinforced, and the consumption of ferric nitrate and sucrose is respectively 6g and 5g, hydro-thermal time 10h; Carbon dioxide gas stream is 2L/min during activation, and activation temperature is 650 ℃, and other is implemented such as method same among the embodiment 1 to keep 4h..
γ-the Fe that obtains
2O
3/ carbon composite magnetic mesoporous microsphere analysis result is close with example 3.
Claims (3)
1. carbon-based magnetic mesoporous composite microsphere, it is characterized in that: the diameter of described carbon-based magnetic mesoporous composite microsphere particle is the 3-6 micron, the microsphere specific area is 270-315m
2/ g, aperture 4-8 nanometer, pore volume is 0.15-0.31cm
3/ g, this complex microsphere are a kind of γ-Fe with meso-hole structure, good magnetic induction
2O
3The compound micron-size spherical body of/carbon back.
2. a kind of preparation method of carbon-based magnetic mesoporous composite microsphere as claimed in claim 1 is characterized in that these preparation method's concrete steps are as follows:
(1) with certain density solubility trivalent iron salt and glucose or sucrose Hydrothermal Synthesis Fe in filling the reactor of the aqueous solution
xO
y/ carbon back complex microsphere, the mass ratio of described solubility trivalent iron salt and glucose or sucrose is (0.2-1.2): 1, and reaction temperature is 160-200 ℃, behind the reaction 8-24h reactor is naturally cooled to room temperature in air, then take out feed liquid, feed liquid is made Fe through dehydration, drying
xO
y/ carbon back complex microsphere;
(2) to the synthetic Fe that obtains of step (1)
xO
y/ carbon back complex microsphere high temperature under carbon dioxide atmosphere magnetizes and activation obtains γ-Fe
2O
3The compound micron-size spherical body of/carbon back, i.e. carbon-based magnetic mesoporous composite microsphere; This high temperature magnetization and activation parameter are: the flow of carbon dioxide gas amount is 0.5-2.0L/min, and activation temperature is 650-800 ℃, and soak time is 2-4h.
3. preparation method according to claim 2, it is characterized in that: described solubility trivalent iron salt is ferric nitrate.
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| CN102772366B (en) * | 2012-07-02 | 2014-10-08 | 华南理工大学 | Preparation method of water-soluble molecular microspheres encapsulated by biodegradable high molecules |
| CN104703689B (en) * | 2012-08-17 | 2019-04-12 | 拜欧科利尔列斯塔勒两合公司 | Magnetic activated carbons and the method for being used to prepare and regenerating such material |
| US9579635B2 (en) * | 2012-12-13 | 2017-02-28 | Basf Corporation | Carbon bodies and ferromagnetic carbon bodies |
| CN103495398B (en) * | 2013-10-22 | 2015-12-02 | 安徽工业大学 | A kind of preparation method carrying carbon magnetic fiber material and application thereof with one-dimensional nucleocapsid structure |
| CN108097210A (en) * | 2017-12-19 | 2018-06-01 | 海宁瑞创新材料有限公司 | A kind of preparation method of nano-metal-oxide and porous active carbon composite material |
| CN109499529A (en) * | 2018-11-01 | 2019-03-22 | 华东理工大学 | A kind of magnetic porous carbon material of N doping and its preparation method and application |
| CN109337646B (en) * | 2018-11-05 | 2021-08-10 | 西北工业大学 | Magnetic porous carbon microsphere and method for preparing same by utilizing hydroxymethyl ferrocene |
| CN110137465B (en) * | 2019-05-13 | 2022-03-01 | 江苏科技大学 | Carbon @ Fe2O3@ carbon microsphere composite material and application thereof |
| CN110787772B (en) * | 2019-11-14 | 2022-02-18 | 山东大学 | Magnetic caramelized carbon nano material and preparation method and application thereof |
| CN111635007A (en) * | 2020-06-05 | 2020-09-08 | 江苏启创环境科技股份有限公司 | Preparation method and application of water treatment magnetic carbon filler |
| WO2023094553A1 (en) | 2021-11-29 | 2023-06-01 | Radma Carbon Ab | A process for the production of magnetic activated carbon (mac) having a variety of properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007658A (en) * | 2007-01-22 | 2007-08-01 | 华东师范大学 | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
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| CN101007658A (en) * | 2007-01-22 | 2007-08-01 | 华东师范大学 | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
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