CN103739020B - Method for preparing porous nano ferroferric oxide - Google Patents

Method for preparing porous nano ferroferric oxide Download PDF

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CN103739020B
CN103739020B CN201310533977.5A CN201310533977A CN103739020B CN 103739020 B CN103739020 B CN 103739020B CN 201310533977 A CN201310533977 A CN 201310533977A CN 103739020 B CN103739020 B CN 103739020B
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deionized water
mixing
ethanol
polyvinyl alcohol
reaction
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CN103739020A (en
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马建超
董宪姝
徐德龙
李泓锐
李晨
王玲玲
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Taiyuan University of Technology
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Abstract

The invention discloses a method for preparing porous nano ferroferric oxide. The method comprises the steps: dissolving two of FeCl2.4H2O, FeSO4.7H2O, FeCl3.6H2O and Fe2(SO4)3 in one of polyvinyl alcohol, ethanol and deionized water or a mixture thereof to obtain a mixed solution containing Fe<2+> and Fe<3+>; adding one of NaHCO3, N2H4.H2O, Na2CO3, (NH4)2CO3 and NH4HCO3 in one of polyvinyl alcohol, ethanol and deionized water or the mixture thereof to obtain an alkaline substance aqueous solution; mixing the mixed solution containing Fe<2+> and Fe<3+> with the alkaline substance aqueous solution in a reaction vessel, heating, and stirring; adjusting the pH of the stirred mixed liquid to 8-13, keeping for 0.5-3 h, gradually adjusting the temperature to 30-60 DEG C, keeping the constant temperature for 2-24 h, allowing the mixed liquid to fully undergo a reaction, and after finishing the reaction, cooling to the room temperature; and washing the precipitate product after reaction with one of anhydrous ethanol and deionized water or a mixture thereof until the pH is 7, and drying for 8-36 h. The reaction process has no need of inert gas protection, and the industrialized production doorsill is low.

Description

A kind of method preparing porousness nano ferriferrous oxide
Technical field
The invention belongs to chemical field, relate to a kind of method preparing porousness nano ferriferrous oxide.
Background technology
Porous magnetic Fe 3o 4pay close attention to greatly because being subject to people with the high-specific surface area of the magnetic property of magneticsubstance and porous material and large pore volume, be widely used in the biomedical sectors such as immobilized enzyme, cellular segregation, target drug-carrying, DNA separation, and the industrial circle such as high-density magnetic storage, magnetic fluid, catalysis.Therefore, design and synthesize magnetic porous Fe 3o 4there is significant scientific meaning and using value.
At present, the method preparing ferriferrous oxide nano-particle is a lot, as high-energy ball milling method, chemical coprecipitation, oxidation reduction process, solvent-thermal method, microemulsion method and pyrolysis method etc.But prepare multi-hole type nanometer Fe 3o 4particle effective ways report is less, as Zhejiang University on July 29th, 2006 patent " a kind of preparation method of nanometer porous magnetic composite ferroferric oxide material and the application " (application number 200610049214.3 applied for, publication number 1803634) in open report, in the atmosphere of rare gas element, add Fe at Ke Fuluoli silica 3+/ Fe 2+inorganic salt, prepare porous Fe 3o 4/ Ke Fuluoli Silica composite; Chengliang Han etc. passes through FeCl 36H 2o and Trisodium Citrate, adopt protein act to obtain one and be rich in carboxyl porous Fe 3o 4fiber.(Carboxyl Enriched Monodisperse Porous Fe 3O 4Nanoparticles with Extraordinary Sustained-Release Property)。
Existing technology mainly passes through Fe 3o 4coexist with other materials and prepare porousness magneticsubstance, and mainly under the atmosphere of rare gas element, carry out under the reaction environment of such filling with inert gas (as nitrogen) or the high temperature in autoclave, high pressure, the requirement to conversion unit will be increased like this, improve industrialization cost, be unfavorable for industrialization promotion.
Prior art, the method preparing porous Z 250 is mainly generated with other materials through solvent thermal is legal under atmosphere of inert gases medium and high temperature state together by organism, and prepared condition comparatively complex process, cost is higher.
The present invention passes through Fe 3+/ Fe 2+inorganic salt, prepare multi-hole type Z 250 through revising coprecipitation method single step reaction, its crystallization degree is high, and pore texture is flourishing, with low cost, is easy to industrialization promotion, and its product not with other materials association, there is the convenient effect utilized.
Specifically, as shown in Figure 1, concrete steps of the present invention are as follows:
Step S101: by FeCl 24H 2o, FeSO 47H 2o, FeCl 36H 2o, Fe 2(SO 4) 3wherein both are dissolved in one of polyvinyl alcohol, ethanol, deionized water or mixing, are prepared into Fe 2+with Fe 3+mixing solutions.
Wherein, among this step, described Fe 2+with Fe 3+in mixing solutions, Fe 2+with Fe 3+between mol ratio (n (Fe 2+): n (Fe 3+))=1 ~ 3.
In other words, Fe 2+compound can comprise FeCl 24H 2o, FeSO 47H 2o, Fe 3+compound comprise FeCl 36H 2o, Fe 2(SO 4) 3, these four kinds of materials, at satisfied (n (Fe 2+): n (Fe 3+)) under=prerequisite of 1 ~ 3, can the mutual mixing of independent assortment and reaction.
Wherein, in time selecting the mixing of polyvinyl alcohol, ethanol, deionized water, select the mixing of polyvinyl alcohol and deionized water or deionized water and ethanol, wherein, the blending ratio of polyvinyl alcohol and deionized water or deionized water and ethanol is 10 ~ 50% (v/v).
Step S102: add NaHCO in one of polyvinyl alcohol, ethanol, deionized water or mixing 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3one of them, be made into alkaline substance solution, wherein, and NaHCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3, they mainly play a part as precipitation agent;
Step S103: by Fe 2+with Fe 3+mixing solutions and alkaline substance solution mix and heat and stir in reaction vessels;
In order to avoid side reaction, affect Fe 3o 4the generation of crystallite, in this step by Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and before heating and stirring, also comprise the oxygen step dispelled in reaction vessels, comprising in reaction vessels:
In reaction vessels, add deionized water, and add precipitation agent NaHCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3one of them, be heated to 40 ~ 80 DEG C, keeps 10 ~ 40 minutes.
Wherein, in this step, by Fe 2+with Fe 3+mixing solutions and alkaline substance solution mix and heat and in the process that stirs, need to keep Heating temperature 60 ~ 100 DEG C, stirring velocity remains on 500 ~ 200r/min.
Step S104: the later mixed solution of stirring is adjusted to pH=8 ~ 13, keeps 0.5 ~ 3h, progressively adjust the temperature to 30 ~ 60 DEG C, constant temperature keeps 2 ~ 24h, above-mentioned mixed solution is fully reacted, and is cooled to room temperature after the completion of reaction;
Step S105: use dehydrated alcohol and the reacted precipitated product of deionized water wash to pH=7, and precipitated product is placed in the dry 8 ~ 36h of 40 ~ 100 DEG C of vacuum drying ovens, obtain the finished product porousness ferriferrous oxide nano-particle.
Can be seen by above-mentioned steps, describedly to prepare in the method for porousness nano ferriferrous oxide, be prepared under the Working environment of inert-free gas.
Wherein, as shown in Figure 2,3, 4, the various chemical sex character figure of its finished product, as XRD figure (X-raydiffraction, X-ray diffractogram), SEM figure (Scanning ElectronMicroscope, sweep electron microscope) of Fig. 3, BET figure (Brunauer, Emmett, Teller, BET specific surface area method of testing) of Fig. 4 of Fig. 2.、
Can see that the crystal grain of Z 250 is about 10.8nm from the XRD spectra above-described embodiment;
The grain morphology of Z 250 can be seen from the SEM spectrogram above-described embodiment;
From the known specific surface area 286.9m of BET result above-described embodiment 2/ g, pore volume 0.6928cm 3/ g, mean pore size , can see that the intra-die pore structure of Z 250 is mesopore pore structure from BET spectrogram.The present invention passes through Fe 3+/ Fe 2+mixed solution, after after chemical reaction, prepare multi-hole type Z 250, its crystallization degree is high, pore texture is flourishing, with low cost, be easy to industrialization promotion, and participate in without complicated organism or inorganics in reaction process, reaction process is simple, raw material sources are conveniently easy to get, and crystal formation is easy to control, and suitability for industrialized production threshold is low.
Summary of the invention
The present invention is directed to the defect of prior art, by chemical feedstocks cheap and easy to get, through correlated response, prepare porousness nanometer Fe 3o 4magneticsubstance, final gained porousness nanometer Fe 3o 4magneticsubstance not with other materials association.
It is as follows that the present invention solves the problems of the technologies described above taked technical scheme:
Prepare a method for porousness nano ferriferrous oxide, comprising:
By FeCl 24H 2o, FeSO 47H 2o, FeCl 36H 2o, Fe 2(SO 4) 3wherein both are dissolved in one of polyvinyl alcohol, ethanol, deionized water or mixing, are prepared into Fe 2+with Fe 3+mixing solutions;
NaHCO is added in one of polyvinyl alcohol, ethanol, deionized water or mixing 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3one of them, be made into alkaline substance solution;
By Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and heating and stir in reaction vessels;
The later mixed solution of stirring is adjusted to pH=8 ~ 13, keeps 0.5 ~ 3h, and progressively adjust the temperature to 30 ~ 60 DEG C, and constant temperature keeps 2 ~ 24h, above-mentioned mixed solution is fully reacted, and is cooled to room temperature after the completion of reaction;
With one of dehydrated alcohol and deionized water or the above-mentioned reacted precipitated product of mixing, washing to pH=7, and precipitated product is placed in the dry 8 ~ 36h of 40 ~ 100 DEG C of vacuum drying ovens, obtains the finished product porousness nano ferriferrous oxide.
Preferred method is, described Fe 2+with Fe 3+in mixing solutions, Fe 2+with Fe 3+between mol ratio (n (Fe 2+): n (Fe 3+))=1 ~ 3.
Preferred method is, by Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and before heating and stirring, also comprise the oxygen step dispelled in reaction vessels, comprising in reaction vessels:
In reaction vessels, add deionized water, and add precipitation agent NaHCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3one of them, be heated to 40 ~ 80 DEG C, keeps 10 ~ 40 minutes.
Preferred method is, the concentration of described alkaline substance solution is 0.5 ~ 10mol/L.
Preferred method is, in time selecting the mixing of polyvinyl alcohol, ethanol, deionized water, select the mixing of polyvinyl alcohol and deionized water or deionized water and ethanol, wherein, the blending ratio of polyvinyl alcohol, deionized water or deionized water and ethanol is 10 ~ 50% (v/v).
Preferred method is, by Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and heat and stir in reaction vessels, and Heating temperature remains on 60 ~ 100 DEG C, stirring velocity remains on 500 ~ 200r/min.
The present invention passes through Fe 3+/ Fe 2+mixed solution, after after chemical reaction, prepare simple monodispersity multi-hole type Z 250, its crystallization degree is high, pore texture is flourishing, with low cost, be easy to industrialization promotion, and participate in without complicated organism or inorganics in reaction process, reaction process is simple, raw material sources are conveniently easy to get, and crystal formation is easy to control, and suitability for industrialized production threshold is low.
Other features and advantages of the present invention will be set forth in the following description, and, partly become apparent from specification sheets, or understand by implementing the present invention.Object of the present invention and other advantages realize by structure specifically noted in write specification sheets, claims and accompanying drawing and obtain.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in detail, to make above-mentioned advantage of the present invention definitely.Wherein,
Fig. 1 is the schematic flow sheet that the present invention prepares the method for porousness nano ferriferrous oxide;
Fig. 2 is the XRD figure of Z 250 prepared by the present invention;
Fig. 3 is the SEM figure of Z 250 prepared by the present invention;
Fig. 4 is the BET figure of Z 250 prepared by the present invention.
Embodiment
Describe embodiments of the present invention in detail below with reference to drawings and Examples, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.It should be noted that, only otherwise form conflict, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the technical scheme formed is all within protection scope of the present invention.
Embodiment two:
Step 201: (n (Fe in molar ratio 2+): n (Fe 3+))=1 ~ 3 take Fe 2+(FeCl 24H 2o, FeSO 47H 2and Fe O) 3+(FeCl 36H 2o, Fe 2(SO4) 3), be dissolved in 50 ~ 300mL polyvinyl alcohol/ethanol/deionized water, be prepared into Fe 2+with Fe 3+mixing solutions;
Step 202: the precipitation agent NaHCO of configuration 0.5 ~ 10mol/L 3/ Na 2cO 3/ NH 4hCO 3etc. the alkaline matter polyvinyl alcohol/ethanol/deionized water solution being easy to molysite generation precipitation.
In the there-necked flask of step 203:500mL, the deionized water of 100mL, adds NaHCO 3, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3easy decomposability generate non-oxygen mineral compound one of them, be heated to 40 DEG C, keep 20 minutes, this step is the oxygen of dispelling in reaction vessels;
Step 204: 201 and 202 are transferred in there-necked flask, under the condition that temperature rises to 70 DEG C of constant temperature, 200r/min Quick mechanical stirs, dropping liquid is to certain pH=8, keep 0.5h, be progressively cooled to 30 DEG C, constant temperature keeps 12h, after reaction terminates, be cooled to room temperature.
Wherein, with CO 3 2-for precipitation agent is example, its chemical reaction is as follows:
Fe 2++ 2Fe 3++ 4CO 3 2-=FeCO 3/ Fe 2(CO 3) 3(formation co-precipitation)
FeCO 3+Fe 2(CO 3) 3+4H 2O＝Fe(OH) 2+2Fe(OH) 3+4CO 2↑
Fe(OH) 2+Fe(OH) 3＝y FeOOH+Fe 3O 4
FeOOH+Fe 2+＝yFe 3O 4+H +
Step 205: with dehydrated alcohol/deionized water difference cleaning product to pH=7, product is placed in 40 ~ 100 DEG C of dry 36h of vacuum drying oven, obtains porousness ferriferrous oxide nano-particle.
Embodiment three:
Step 301: mol ratio (n (Fe 2+): n (Fe 3+))=1 ~ 3 take Fe 2+(FeCl 24H 2o, FeSO 47H 2and Fe O) 3+(FeCl 36H 2o, Fe 2(SO4) 3), be dissolved in 100mL polyvinyl alcohol/ethanol/deionized water, be prepared into Fe 2+with Fe 3+mixing solutions;
Step 302: the precipitation agent NaHCO of configuration 0.5 ~ 10mol/L 3/ Na 2cO 3/ NH 4hCO 3etc. the alkaline matter polyvinyl alcohol/ethanol/deionized water solution being easy to molysite generation precipitation.
In the there-necked flask of step 303:500mL, the deionized water of 100mL, adds NaHCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3etc. easy decomposability generate non-oxygen mineral compound one of them, be heated to 80 DEG C, keep 20 minutes;
Step 304: 301 and 302 are transferred in there-necked flask, under the condition that temperature rises to 60 DEG C of constant temperature, 500r/min Quick mechanical stirs, dropping liquid is to certain pH=10, keep 2h, be progressively cooled to 30 DEG C, constant temperature keeps 2h, after reaction terminates, be cooled to room temperature.
Step 305: with dehydrated alcohol/deionized water difference cleaning product to pH=7, product is placed in the dry 8 ~ 36h of 40 ~ 100 DEG C of vacuum drying ovens, obtains porousness ferriferrous oxide nano-particle.
Embodiment four:
Step 401: mol ratio (n (Fe 2+): n (Fe 3+))=1 ~ 3 take Fe 2+(FeCl 24H 2o, FeSO 47H 2and Fe O) 3+(FeCl 36H 2o, Fe 2(SO4) 3), be dissolved in 300mL polyvinyl alcohol/ethanol/deionized water, be prepared into Fe 2+with Fe 3+mixing solutions;
Step 402: the precipitation agent NaHCO of configuration 10mol/L 3/ Na 2cO 3/ NH 4hCO 3etc. the alkaline matter polyvinyl alcohol/ethanol/deionized water solution being easy to molysite generation precipitation.
In the there-necked flask of step 403:500mL, the deionized water of 100mL, adds NaHCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3etc. easy decomposability generate non-oxygen mineral compound one of them, be heated to 80 DEG C, keep 40 minutes;
Step 404: 401 and 402 are transferred in there-necked flask, under the condition that temperature rises to 80 DEG C of constant temperature, 200r/min Quick mechanical stirs, dropping liquid is to certain pH=12, keep 3h, be progressively cooled to 60 DEG C, constant temperature keeps 2h, after reaction terminates, be cooled to room temperature.
Step 405: with deionized water difference cleaning product to pH=7, product is placed in 40 ~ 100 DEG C of dry 24h of vacuum drying oven, obtains porousness ferriferrous oxide nano-particle.
The present invention passes through Fe 3+/ Fe 2+mixed solution, after after chemical reaction, prepare multi-hole type Z 250, its crystallization degree is high, pore texture is flourishing, with low cost, be easy to industrialization promotion, and participate in without complicated organism or inorganics in reaction process, reaction process is simple, raw material sources are conveniently easy to get, and crystal formation is single, be easy to control, and suitability for industrialized production threshold is low.
It should be noted that, for aforesaid method embodiment, in order to simple description, therefore it is all expressed as a series of combination of actions, but those skilled in the art should know, the application is not by the restriction of described sequence of operation, because according to the application, some step can adopt other orders or carry out simultaneously.Secondly, those skilled in the art also should know, the embodiment described in specification sheets all belongs to preferred embodiment, and involved action might not be that the application is necessary.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (5)

1. prepare a method for porousness nano ferriferrous oxide, it is characterized in that, comprising:
By F ecl 24H 2o, F esO 4.7H 2o, F ecl 36H 2o, Fe 2(SO 4) 3wherein both are dissolved in one of polyvinyl alcohol, ethanol, deionized water or mixing, are prepared into Fe 2+with Fe 3+mixing solutions;
NaHCO is added in one of polyvinyl alcohol, ethanol, deionized water or mixing 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3, NH 4hCO 3one of them, be made into alkaline substance solution;
Dispel the oxygen step in reaction vessels, comprising:
In reaction vessels, add deionized water, and add precipitation agent N ahCO 3, N 2h 4h 2o, Na 2cO 3, (NH 4) 2cO 3one of them, be heated to 40 ~ 80 DEG C, keeps 10 ~ 40 minutes;
By Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and heat, stir in reaction vessels;
The later mixed solution of stirring is adjusted to pH=8 ~ 13, keeps 0.5 ~ 3h, and progressively adjust the temperature to 30 ~ 60 DEG C, and constant temperature keeps 2 ~ 24h, above-mentioned mixed solution is fully reacted, and is cooled to room temperature after the completion of reaction;
With one of dehydrated alcohol and deionized water or the above-mentioned reacted precipitated product of mixing, washing to pH=7, and precipitated product is placed in the dry 8 ~ 36h of 40 ~ 100 DEG C of vacuum drying ovens, obtains the finished product porousness nano ferriferrous oxide.
2. the method preparing porousness nano ferriferrous oxide according to claim 1, is characterized in that, described Fe 2+with Fe 3+in mixing solutions, Fe 2+with Fe 3+between mol ratio (n (Fe 2+): n (Fe 3+))=1 ~ 3.
3. the method preparing porousness nano ferriferrous oxide according to claim 1 and 2, is characterized in that, the concentration of described alkaline substance solution is 0.5 ~ 10mol/L.
4. the method preparing porousness nano ferriferrous oxide according to claim 1, it is characterized in that, in time selecting the mixing of polyvinyl alcohol, ethanol, deionized water, select the mixing of polyvinyl alcohol deionized water or deionized water and ethanol, wherein, the blending ratio of polyvinyl alcohol, deionized water or deionized water and ethanol is 10 ~ 50% (v/v).
5. the method preparing porousness nano ferriferrous oxide according to claim 1, is characterized in that, by Fe 2+with Fe 3+mixing solutions and alkaline substance solution carry out mixing and heat and stir in reaction vessels, and Heating temperature remains on 60 ~ 100 DEG C, stirring velocity remains on 500 ~ 200r/min.
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CN110683587A (en) * 2019-10-21 2020-01-14 中国科学院山西煤炭化学研究所 Method for preparing mesoporous nano ferroferric oxide particles from titanium dioxide byproduct ferrous sulfate
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