CN105460978A - Large-scale preparation method of carbon-doped ferrite porous microspheres - Google Patents
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Abstract
The invention discloses a large-scale preparation method of carbon-doped ferrite porous microspheres. The method comprises the following specific steps: using soluble sugar glucose or saccharose as a carbon source, using soluble metal salt metal salt and bivalent metal salt as a precursor of ferrite, adding soluble metal salt into an aqueous solution of soluble sugar under the condition of stirring so as to form an uniform precursor solution, transferring the precursor solution into spray-drying equipment to atomize the precursor solution, removing water to obtain metal salt/sugar powder, placing the metal salt/sugar powder into a tube furnace, heating at the heating rate of 1-5 DEG C/min in the inert atmosphere to 300-700 DEG C and calcining for 0.5-6 h, and naturally cooling to room temperature to obtain the carbon-doped ferrite porous microspheres. By the above method, large-scale preparation of the carbon-doped ferrite porous microspheres is realized. Continuous treatment process for the nano-material preparation can be realized by spray-drying. The prepared carbon-doped ferrite porous microspheres can be directly used without smashing or grinding.
Description
Technical field
The invention belongs to the synthesis technical field of nano material, be specifically related to a kind of method that carbon doping ferrite porous microsphere is prepared in mass-producing.
Background technology
Spinels ferrite nanometer particle, because of the process based prediction model of its uniqueness, makes it have different purposes from block ferrospinel material.Due to light weight and the nano magnetic effect of its uniqueness, the fields such as pharmaceutical carrier, nano-reactor, filtration, separation, photocatalyst, lithium ion battery and ultracapacitor can be applied in.Ferrite itself is nontoxic, and use procedure can not work the mischief to environment, and easy Magneto separate recycling, is thus subject to special concern in actual applications.But along with the reduction of nanometer ferrite size, the surface energy of nano particle increases rapidly, causes particle easily to be reunited, and then reduces the activity of material.In recent years, in order to make, nanoparticle is as much as possible to be exposed in residing application system, avoiding magnetic nanoparticle to reunite is main direction of studying, its main direction of studying has two kinds: one is by spinel nano particulate load on the carriers such as gac, silica gel, Graphene or carbon nanotube, stops the reunion of nano particle.Publication number is the one that patent discloses of CN102125853A is propping material with Graphene, adopt and graphite oxide is placed in ethanol ultrasonic disperse, iron nitrate and zinc nitrate join stirring and dissolving in ethanol, then by two kinds of system mixing, afterwards mixed system is transferred in water heating kettle and reacts, after reaction terminates, product, after centrifugation, washing and drying, obtains nano zinc ferrite-graphene composite photocatalyst.Publication number is that molysite and zinc salt are dissolved in deionized water by the one that patent discloses of CN104383930A, to join in solution through pretreated carbon nanotube again, supersound process, adjust pH to 7.5-11.5, proceed to after stirring in tetrafluoroethylene retort, then retort is placed in microwave dissolver, hydro-thermal reaction is carried out in 0.3-1.5MPa, filter, dry, cross 100 mesh sieves after grinding and obtain zinc ferrite load carbon nano-tube catalyst.Another kind is that nano particle is assembled into porous microsphere, changes the external morphology of particle, increases the contact of nanoparticle and application system while suppressing nanoparticle to be reunited.Publication number is that the one that patent discloses of CN1632889A adopts copolymerization organic micro-spheres as template; the organic micro-spheres compound submicron particles that the Magnetic Nanoparticle of core/shell structure is coated, then in high purity inert protective gas, calcining obtains mesoporous martial ethiops hollow microsphere particle.Document (ZhangG., LouX.W., AngewandteChemie, 2014,53 (34): 9041-9044.; LaiX, HalpertJE, WangD, Energy & EnvironmentalScience, 2012,5 (2): 5604-5618.) report with the method for carbon ball for Template preparation hollow thing microballoon, these two kinds of methods are all first adopt hydrothermal method that glucose is prepared into carbon ball template, by be immersed in carbon ball surface or inner adsorb transition metal salt be prepared into presoma, then by calcining except the oxide compound obtaining hollow structure.Publication number is that a kind of ultrasonic atomizatio method that adopts that patent discloses of CN101596435A synthesizes acid proof single dispersing carbon-metal oxide magnetic complex microsphere, as magnetic composite microspheres such as carbon-ferric oxide, carbon-cobalt oxide and carbon-cobalt ferrites.
Aforesaid method effectively prevents the reunion of nano particle, also improves performance in a certain respect.But these method preparation processes are relatively many, need to prepare template in advance, large-scale production relative difficulty, be unfavorable for the scale operation of material.In sum, research and develop the preparation method of granules that step is simple and continuous prodution degree is higher and there is wide prospects for commercial application.Meanwhile, single Ferrite Material, owing to having the reasons such as poorly conductive, is difficult to meet the application demand day by day improved.It is the study hotspot that the matrix material material of active material becomes in recent years using carbon material as conductive additive, with ferrite.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of method that carbon doping ferrite porous microsphere is prepared in mass-producing; solving nano material in prior art can not the shortcoming prepared on a large scale of serialization; the method is without the need to using template, and the product of synthesis is comparatively homogeneous, and stability is better.
The present invention adopts following technical scheme for solving the problems of the technologies described above, the method of carbon doping ferrite porous microsphere is prepared in a kind of mass-producing, it is characterized in that concrete steps are: (1) for carbon source, is made into soluble in water for soluble sugar the aqueous solution that mass concentration is 10-90g/L with soluble sugar glucose or sucrose; (2) be ferritic precursor with soluble metallic salt iron nitrate and divalent metal salt, under the condition stirred soluble metallic salt joined in the aqueous solution that step (1) obtains and form homogeneous precursor solution, wherein the total mol concentration of soluble metallic salt is 1:0.3-3 with the ratio of the volumetric molar concentration of soluble sugar, and divalent metal salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, nickelous nitrate, zinc nitrate or cupric nitrate; (3) precursor solution that step (2) obtains is proceeded in spray drying device, remove water after precursor solution is atomized and obtain metal-salt-Icing Sugar body, spray drying device intake air temperature is 180-260 DEG C, air outlet temperature is 110-140 DEG C, take nitrogen as dry gas, gained metal-salt-Icing Sugar body is by bottom drying tower and cyclone collection; (4) metal-salt-Icing Sugar body that step (3) obtains is placed in tube furnace and is warming up to 300-700 DEG C of calcining 0.5-6h with the temperature rise rate of 1-5 DEG C/min under inert atmosphere, then naturally cool to room temperature and obtain carbon doping ferrite porous microsphere, wherein inert atmosphere is nitrogen, helium or argon gas.
Preparation method of the present invention, its key is the ratio controlling soluble metal salt concn and carbon source, soluble metallic salt and carbon source form homogeneous powder, and in calcination process, suffered by spherical powder surface and inside, stress is different and form porous hollow microballoon gradually.Carbon source strength of solution is greater than 100g/L or is less than 10g/L simultaneously, and gained spheroid spherome surface in heat treatment process easily subsides.By regulating the size of precursor solution concentration, the control to particle size and carbon content after annealing, finally can be realized in an inert atmosphere.
Preparation method of the present invention, when metal-salt after spraying dry-Icing Sugar body is heat-treated, sugar is heated carbonization, spheroid shrinks, the metal-salt be doped in wherein is decomposed to form metal oxide shell simultaneously, due to sugar in carbonization process and metal oxide shell contraction rate difference and form hollow structure, the integrity degree of temperature rise rate to hollow ball of heat treatment process has material impact, if temperature rise rate is crossed slow ball surface and inside and is heated evenly and forms porous solid sphere, if the too fast meeting of temperature rise rate causes spherome surface and inside are heated seriously uneven and cause spheroid avalanche.
Carbon doping ferrite porous microsphere prepared by the present invention, its shell is formed by ferrite nanometer particle and the coke build-up be mingled with therebetween, and wherein ferrite nanometer particle is CoFe
2o
4, NiFe
2o
4, CuFe
2o
4or ZnFe
2o
4.By controlling the concentration of soluble metallic salt and the ratio of carbon source, soluble metallic salt and carbon source form homogeneous powder, for providing prerequisite in the formation of calcination process porous hollow sphere.By the size regulating the concentration of precursor solution to control carbon containing ferrite ball, the control to particle size and carbon content finally can be realized.
The invention solves two key issues: first key issue solves nanoparticle to be exposed to the less problem of residing application system.In spray-drying process, vaporization along with solvent obtains metal-salt-Icing Sugar body, it is advantageous that and first the Solution Dispersion of macroscopic view is become tiny particle, greatly reduce the possibility of particle agglomeration, and metal-salt becomes ferrite nanometer particle in calcination process, pyrolysis carbonization due to carbohydrate adds the porousness of ferrite ball, and then is exposed in application system by as much as possible for nanoparticle, increases that it is active accordingly.Second key issue is the mass-producing preparation process that step is simple, serialization is higher achieving carbon doping ferrite porous microsphere; spraying dry can realize uninterruptedly carrying out to the process of reaction raw materials liquid, thus realizes the extensive preparation of carbon doping ferrite porous microsphere.
Raw materials used cheap and easy to get, the environmental protection of the present invention, and preparation process is simple, reaction conditions is gentle, can easily carry out operate continuously, be convenient to large-scale production, easy to utilize.The present invention only needs the precursor solution concentration of regulation experiment and the granularity of controllable carbon doping ferrite porous microsphere.The carbon doping ferrite porous microsphere that the present invention obtains does not need, again through pulverizing or grinding, to disperse rear and other Material cladding, can be directly used in the fields such as sensor, photochemical catalysis, absorption, lithium cell and ultracapacitor yet in water or organic solvent.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of the carbon doping ferrite porous microsphere that the embodiment of the present invention 1 obtains;
Fig. 2 is the field emission scanning electron microscope figure of the carbon doping ferrite porous microsphere that the embodiment of the present invention 1 obtains;
Fig. 3 is the magnetic hysteresis loop of the carbon doping ferrite porous microsphere that the embodiment of the present invention 1 obtains.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Carbon doping ZnFe
2o
4the preparation of porous microsphere
(1) take 1g sucrose with electronic balance and put into 200mL beaker, add 100mL deionized water, stirring 30min formation mass concentration is the sucrose solution of 10g/L;
(2) take 4.5g Fe(NO3)39H2O respectively and 1.65g zinc nitrate hexahydrate is added in sucrose solution, vigorous stirring is until dissolve and be fully formed homogeneous precursor solution;
(3) precursor solution of gained proceeded in refined journey YC-018 spray-drier, remove water after making gained solution atomization and obtain metal-salt-Icing Sugar body, intake air temperature 230 DEG C, air outlet temperature 110 DEG C, employing nitrogen is dry gas, and flow rate pump is 2mL/min;
(4) metal-salt of gained-Icing Sugar body is placed in tube furnace, in nitrogen atmosphere, is warming up to 450 DEG C of calcining 3.5h with the temperature rise rate of 3 DEG C/min, then naturally cools to room temperature and obtain carbon doping ZnFe
2o
4porous microsphere.
Gained carbon doping ZnFe
2o
4the XRD figure of porous microsphere and SEM figure are as shown in Figures 1 and 2.The ZnFe of gained spinel type can be determined from figure
2o
4, sphere diameter is about 800nm.From carbon doping ZnFe
2o
4the magnetic hysteresis loop (accompanying drawing 3) of porous microsphere can be found out, gained carbon doping ZnFe
2o
4porous microsphere has good magnetic.
With made carbon doping ZnFe
2o
4porous microsphere photocatalytic degradation rhodamine B is tested: get the carbon doping ZnFe that 0.05g is obtained
2o
4porous microsphere, puts into the rhodamine B solution of 100mL, and the mass concentration of rhodamine B is 20mg/L.First carry out 30min stirring to mixed solution, guarantee that it reaches adsorption equilibrium, (wavelength >=420nm) gets every 5min the concentration that 1mL solution measures rhodamine B then under visible light, analyzes its palliating degradation degree.Result shows its degradation rate in 30min and reaches 90%.
Embodiment 2
Carbon doping CoFe
2o
4the preparation of porous microsphere
(1) take with electronic balance the beaker that 300mL put into by 5g sucrose, slowly add 200mL deionized water, it is the glucose solution of 25g/L that Keep agitation 1h forms mass concentration;
(2) be dissolved in glucose solution by 7.48g six nitric hydrate iron iron and 2.69g Cobaltous nitrate hexahydrate, vigorous stirring is until form homogeneous precursor solution;
(3) precursor solution of gained is proceeded in refined journey YC-018 spray-dryer, remove water after gained precursor solution is atomized and obtain metal-salt-Icing Sugar body, intake air temperature 180 DEG C, air outlet temperature 140 DEG C, employing nitrogen is dry gas, and flow rate pump is 1.5mL/min;
(4) metal-salt of gained-Icing Sugar body is placed in tube furnace, in argon gas atmosphere, is warming up to 700 DEG C of calcining 0.5h with the temperature rise rate of 1 DEG C/min, then naturally cools to room temperature and obtain the carbon doping CoFe that median size is 1245nm
2o
4porous microsphere.
Photocatalytic Degradation Property test is with method 1, and result shows its degradation rate in 30min and reaches 86%.
Embodiment 3
Carbon doping NiFe
2o
4the preparation of porous microsphere
(1) take with electronic balance the beaker that 300mL put into by 10g glucose, slowly add 200mL deionized water, it is the glucose solution of 50g/L that stirring and dissolving forms mass concentration;
(2) take 22.44g Fe(NO3)39H2O respectively and 8.09g Nickelous nitrate hexahydrate is dissolved in glucose solution, vigorous stirring is until form homogeneous precursor solution;
(3) proceed in spray drying device by the precursor solution of gained, remove water after making gained solution atomization and obtain metal-salt-Icing Sugar body, intake air temperature 220 DEG C, air outlet 130 DEG C, employing nitrogen is dry gas, and flow rate pump is 4.5mL/min;
(4) metal-salt of gained-Icing Sugar body is placed in tube furnace, in nitrogen atmosphere, is warming up to 450 DEG C of calcining 1h with the temperature rise rate of 1 DEG C/min, then naturally cools to room temperature and obtain the carbon doping NiFe that median size is 2780nm
2o
4porous microsphere.
Photocatalytic Degradation Property test is with method 1, and result shows its degradation rate in 30min and reaches 80%.
Embodiment 4
Carbon doping MgFe
2o
4the preparation of porous microsphere
(1) take beaker 9g glucose being put into 200mL with electronic balance, slowly add 100mL deionized water, it is the glucose solution of 90g/L that stirring and dissolving forms mass concentration;
(2) be dissolved in glucose solution by 13.47g six nitric hydrate iron and 4.27g magnesium nitrate hexahydrate, vigorous stirring is until form homogeneous precursor solution;
(3) precursor solution of gained proceeded in refined journey YC-018 spray drying device, remove water after making gained solution atomization and obtain metal-salt-Icing Sugar body, intake air temperature 260 DEG C, air outlet temperature 110 DEG C, employing nitrogen is dry gas, and flow rate pump is 2mL/min;
(4) gained metal-salt-Icing Sugar body is placed in tube furnace, is warming up to 300 DEG C of calcining 6h with the temperature rise rate of 5 DEG C/min in a nitrogen atmosphere, then naturally cools to room temperature and obtain the carbon doping MgFe that median size is 1920nm
2o
4porous microsphere.
Photocatalytic Degradation Property test is with method 1, and result shows its degradation rate in 30min and reaches 86%.
Embodiment 5
Carbon doping CuFe
2o
4the preparation of porous microsphere
(1) take 5g glucose with electronic balance and dissolve in the beaker putting into 200mL, slowly add 100mL deionized water, it is the glucose solution of 50g/L that stirring and dissolving forms mass concentration;
(2) be dissolved in glucose solution by 3.74g Fe(NO3)39H2O and 1.12g cupric nitrate successively, vigorous stirring is until form homogeneous precursor solution;
(3) precursor solution of gained is proceeded in refined journey YC-018 spray drying device, remove water after making gained solution atomization and obtain metal-salt-Icing Sugar body, intake air temperature 220 DEG C, air outlet temperature 110 DEG C, employing nitrogen is dry gas, and flow rate pump is 3.5mL/min;
(4) gained metal-salt-Icing Sugar body is placed in tube furnace, in nitrogen atmosphere, is warming up to 650 DEG C of calcining 3.5h with the temperature rise rate of 2 DEG C/min, then naturally cools to room temperature and obtain the carbon doping CuFe that median size is 1350nm
2o
4porous microsphere.
Photocatalysis performance test is with method 1, and result shows its degradation rate in 30min and reaches 79%.
Embodiment above describes ultimate principle of the present invention, principal character and advantage; the technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (1)
1. a method for carbon doping ferrite porous microsphere is prepared in mass-producing, it is characterized in that concrete steps are: (1) for carbon source, is made into soluble in water for soluble sugar the aqueous solution that mass concentration is 10-90g/L with soluble sugar glucose or sucrose; (2) be ferritic precursor with soluble metallic salt iron nitrate and divalent metal salt, under the condition stirred soluble metallic salt joined in the aqueous solution that step (1) obtains and form homogeneous precursor solution, wherein the total mol concentration of soluble metallic salt is 1:0.3-3 with the ratio of the volumetric molar concentration of soluble sugar, and divalent metal salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, nickelous nitrate, magnesium nitrate or cupric nitrate; (3) precursor solution that step (2) obtains is proceeded in spray drying device, remove water after precursor solution is atomized and obtain metal-salt-Icing Sugar body, the intake air temperature of spray drying device is 180-260 DEG C, air outlet temperature is 110-140 DEG C, take nitrogen as dry gas, gained metal-salt-Icing Sugar body is by bottom drying tower and cyclone collection; (4) metal-salt-Icing Sugar body that step (3) obtains is placed in tube furnace and is warming up to 300-700 DEG C of calcining 0.5-6h with the temperature rise rate of 1-5 DEG C/min under inert atmosphere, then naturally cool to room temperature and obtain carbon doping ferrite porous microsphere, wherein inert atmosphere is nitrogen, helium or argon gas.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043131A (en) * | 2017-03-21 | 2017-08-15 | 海安南京大学高新技术研究院 | The preparation method of nano-strontium ferrite |
| CN108054367A (en) * | 2017-12-12 | 2018-05-18 | 江西理工大学 | A kind of preparation method of carbon coating MgFe2O4 negative materials for sodium-ion battery |
| CN108511204A (en) * | 2018-04-02 | 2018-09-07 | 张家港博威新能源材料研究所有限公司 | A kind of preparation method of the nitrogen co-doped Porous hollow carbosphere of oxygen |
| CN108556105A (en) * | 2018-05-18 | 2018-09-21 | 大连门庭木业有限公司 | Environment-friendlycomposite composite board and preparation method thereof with function of absorbing formaldehyde |
| CN109081328A (en) * | 2018-09-08 | 2018-12-25 | 天津大学 | A method of preparing the three-dimensional porous carbon nanosheet ball of N doping |
| CN109437322A (en) * | 2018-11-05 | 2019-03-08 | 浙江工业大学 | A kind of compound carbon ball of metal oxide and preparation method thereof |
| CN109659145A (en) * | 2018-12-17 | 2019-04-19 | 上海应用技术大学 | A method of preparing porous spherical manganese oxide/carbon complex |
| CN109761284A (en) * | 2019-01-16 | 2019-05-17 | 昆明理工大学 | A kind of method and its application preparing coppe ferrite nano material using drying process with atomizing |
| CN110790254A (en) * | 2019-11-12 | 2020-02-14 | 湖南大学 | Method for preparing porous carbon materials with different morphologies by ultrasonic spray pyrolysis regulation and control |
| CN111001419A (en) * | 2019-12-25 | 2020-04-14 | 陕西国防工业职业技术学院 | Preparation method of silver-modified magnetic separable photocatalyst |
| CN111509188A (en) * | 2020-04-30 | 2020-08-07 | 石家庄铁道大学 | Anode material, anode, lithium ion battery and preparation method |
| CN112165846A (en) * | 2020-09-21 | 2021-01-01 | 山东理工大学 | Preparation method of low-frequency efficient wave-absorbing ferroferric oxide/macroporous thin-layer carbon magnetic composite material |
| CN113680291A (en) * | 2021-09-09 | 2021-11-23 | 吉林农业大学 | Preparation method of paramagnetic metal oxide/spinel/carbon composite microsphere |
| CN114618485A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院理化技术研究所 | Carbon-based hollow supported microsphere catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040028592A1 (en) * | 2002-08-07 | 2004-02-12 | Yuji Akimoto | Method for manufacturing highly-crystallized oxide powder |
| CN103435105A (en) * | 2013-08-07 | 2013-12-11 | 浙江凯恩电池有限公司 | Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof |
| CN104393244A (en) * | 2014-11-28 | 2015-03-04 | 东北林业大学 | Preparation method of hollow ZnFe2O4 nanometer anode material of lithium ion battery |
-
2015
- 2015-11-24 CN CN201510820845.XA patent/CN105460978A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040028592A1 (en) * | 2002-08-07 | 2004-02-12 | Yuji Akimoto | Method for manufacturing highly-crystallized oxide powder |
| CN103435105A (en) * | 2013-08-07 | 2013-12-11 | 浙江凯恩电池有限公司 | Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof |
| CN104393244A (en) * | 2014-11-28 | 2015-03-04 | 东北林业大学 | Preparation method of hollow ZnFe2O4 nanometer anode material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 齐海萍 等: "喷雾-焙烧法制备的Co2-Z 型铁氧体及其电磁性能", 《磁性材料及器件》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043131A (en) * | 2017-03-21 | 2017-08-15 | 海安南京大学高新技术研究院 | The preparation method of nano-strontium ferrite |
| CN107043131B (en) * | 2017-03-21 | 2019-03-15 | 海安南京大学高新技术研究院 | The preparation method of nano-strontium ferrite |
| CN108054367B (en) * | 2017-12-12 | 2020-06-09 | 江西理工大学 | Preparation method of carbon-coated MgFe2O4 negative electrode material for sodium-ion battery |
| CN108054367A (en) * | 2017-12-12 | 2018-05-18 | 江西理工大学 | A kind of preparation method of carbon coating MgFe2O4 negative materials for sodium-ion battery |
| CN108511204A (en) * | 2018-04-02 | 2018-09-07 | 张家港博威新能源材料研究所有限公司 | A kind of preparation method of the nitrogen co-doped Porous hollow carbosphere of oxygen |
| CN108511204B (en) * | 2018-04-02 | 2020-06-16 | 张家港博威新能源材料研究所有限公司 | Preparation method of oxygen-nitrogen co-doped porous hollow carbon microspheres |
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