CN101555042A - Method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction - Google Patents
Method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction Download PDFInfo
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- CN101555042A CN101555042A CNA2009100277066A CN200910027706A CN101555042A CN 101555042 A CN101555042 A CN 101555042A CN A2009100277066 A CNA2009100277066 A CN A2009100277066A CN 200910027706 A CN200910027706 A CN 200910027706A CN 101555042 A CN101555042 A CN 101555042A
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Abstract
The invention relates to a method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction. The method adds trivalent iron salt and one or more divalent metal salts into a mortar according to the proportioning by weight of 2: 1, then adds inorganic acid according to 0-5 percent of the weight of inorganic salt, grinds for 10 minutes-1 hour, then obtains a precursor of paste compound metal salt, adds a solid base, the exothermic reaction which is often accompanied by releasing water vapor from the reaction is carried out immediately, continues the grinding for 10 minutes-1 hour till the reaction is completed, adds water for washing, separates centrifugally and dries to obtain the deep color spinel type iron oxide-containing nano-materials with different sizes and shapes. As the reaction is carried out in the absence of solvent at room temperature or low temperature, in the method, the solvent does not need to be recycled or processed, ,thereby having low energy consumption and being conductive to environmental protection; the operation is simple, the reaction is easy to realize; the method can be used for large-scale industrial production, thereby facilitating the promotion; and the method has no organic solvent participating in the reaction, thereby being a relatively green chemical process technology.
Description
Technical field
The present invention relates to the preparation method of the nanometer spinel type oxides-containing iron of a kind of controllable appearance and structure.Specifically, relate to the method that low fever solid phase reaction prepares the nanometer spinel type oxide compound of controllable appearance and structure.
Background technology
Spinel type iron-containing oxide is a kind of nontoxic inorganic materials.For example: because great majority have excellent magnetism and biocompatibility, spinel type iron-containing oxide can be used for making gas sensor, magnetic memory device, effective catalyst, efficient water sanitising agent or the like [referring to: 1.N.Z.Bao, L.M.Shen, Y.H.Wang, P.Padhan, A.Gupta, Journal of the American Chemical Society 129,12374 (OCT 17,2007); 2.Q.Chen, Z.J.Zhang, Applied Physics Letters 73,3156 (NOV 23,1998); 3.T.Hyeon et al., Journal ofPhysical Chemistry B 106,6831 (JUL 11,2002); 4.E.Kang et al., Journal of PhysicalChemistry B 108,13932 (SEP 16,2004); 5.O.Song, Z.J.Zhang, Journal of the AmericanChemical Society 126,6164 (MAY 19,2004); 6.O.Masala, R.Seshadri, Journal of theAmerican Chemical Society 127,9354 (JUL 6,2005); 7.K.Parekh, R.V.Upadhyay, L.Belova, K.V.Rao, Nanotechnology 17,5970 (DEC 28,2006)].
Discover that recently spinel type iron-containing oxide can be used for the nuclear magnetic resonance of living things system and the target of medicine discharges.Utilize the semiconductor property of some spinel oxides, can also design the high-performance gas sensor.Spinel type iron-containing oxide can also be used as effective catalyst or sorbent material, and the organic and inorganic pollutant in the degraded removal water [referring to: 1.C.T.Yavuz et al., Science 314,964 (NOV 10,2006); 2.S.Yean et al., Journal of MaterialsResearch 21,1862 (JUL, 2006); 3.A.B.M.Giasuddin, S.R.Kanel, H.Choi, Environmental Science ﹠amp; Technology 41,2022 (MAR 15,2007); 4.J.Gimenez, M.Martinez, J.de Pablo, M.Rovira, L.Duro, Journal of Hazardous Materials 141,575 (MAR 22,2007); 5.J.T.Mayo et al., Science and Technology of Advanced Materials 8,71 (JAN-MAR, 2007); 6.O.L.Zhang, N.Y.Gao, Y.C.Lin, B.Xu, L.S.Le, Water Environment Research 79,931 (AUG, 2007); 7.Q.L.Zhang, Y.C.Lin, X.Chen, N.Y.Gao, Journal of Hazardous Materials148,671 (SEP 30,2007); 8.G.Morin et al., Environmental Science ﹠amp; Technology 42,2361 (APR 1,2008); 9.C.M.Su, R.W.Puls, Water Air and Soil Pollution 193,65 (SEP, 2008) .].Simultaneously, the pattern of nano material and size also may cause the huge change of their performances.
Because the nanometer spinel type oxide compound has the performance of many excellences, about studying and use the extensive concern that is subjected to entrepreneur and scientists.Wherein about the research of how to control and to produce nanometer spinel type oxides-containing iron efficiently Showed Very Brisk especially with definite shape and size.The preparation method of nanometer spinel type oxides-containing iron is a lot, and still, present most of synthetic methods are all carried out in water or oil phase.
Summary of the invention
The invention provides a kind of new, and spinel oxides nanometer particle process method easily and effectively.
Method of the present invention comprises the nano particle that adopts tensio-active agent to synthesize the spinel oxides with definite shape and size under low-heat condition.
Technical scheme of the present invention is as follows:
A kind of method of preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction, it comprises the steps:
Step 1. prescription: trivalent iron salt and ratio 2: 1 the ratio of one or more divalent metal salts in amount of substance are added in mortar or the ball mill, and the 0-5% that presses the inorganic salt quality subsequently adds mineral acid;
Step 3. is reacted: add solid alkali in containing composite metal salt precursor mortar or ball mill, thermopositive reaction takes place at once and often emits from reaction with aqueous vapor, continues to grind extremely to react in 10 minutes-1 hour and finishes.The ratio of the amount of substance of solid alkali and metal-salt is 2: 1-10: 1;
Step 4. aftertreatment: add water washing, centrifugation, drying obtains the dark spinel type iron-containing oxide nano-materials of different size and shape.
In described step 1, can add tensio-active agent.Described tensio-active agent can be anion surfactant, cats product or nonionogenic tenside, anion surfactant preferably, and the consumption of tensio-active agent is the 10-100% of metal-salt weight.Add the precursor of tensio-active agent preparation, continue step 3 reaction and can obtain size than uniform spherical spinel oxides nanoparticle.
In described step 1, trivalent iron salt and divalent metal salt comprise the vitriol that contains crystal water and do not contain crystal water, hydrochloride, nitrate and their double salt.Divalent metal salt can be main group metal or transition metal ionic salt, as: Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+And Ni
2+Deng.
In described step 1, the 0-5% that presses inorganic salt weight adds mineral acid, as: concentrated hydrochloric acid (35M), concentrated nitric acid (65%), the vitriol oil (98%), acetic acid (100%), or their 1-10 times dilute aqueous, to suppress the hydrolysis of metal-salt when preparing precursor.When not adding mineral acid (0%), simply grind precursor and the solid alkali reaction that trivalent iron salt and divalent metal salt obtain and also can obtain the spinel oxides nanoparticle.But,, generally have dephasign to exist wherein because metal-salt can partial hydrolysis.
In described step 3, solid alkali can be NaOH, KOH, NaHCO
3Or Na
2CO
3The time of grinding generally is less than 15 minutes.
Between above-mentioned steps 3 and 4, can increase the crystallization growth step:
Crystallization growth: different colours mashed prod or meal that step 3 obtains were grown 2 hours-6 days in room temperature-1100 a ℃ following crystallization again; The growth of high temperature crystallization can obtain the nanocrystalline product of large-size.
The principle of invention is as follows:
According to the ultimate principle of solid state chemistry, in the solid state reaction process between solid metal salt and the solid alkali through having four steps all through the ages: diffusion, reaction, nucleation and growth.If solid state reaction takes place for metal-salt A and solid alkali B, generated nanoparticle C and by-product salt D:
A (s)+B (s) → C (nanoparticle)+D (salt)+nH
2O (l+g)
By above-mentioned reaction formula, after system begins reaction, there are 5 kinds of things to coexist mutually, be respectively A, B, C, D, H
2O, the wherein small amount of H of Sheng Chenging
2O plays lubrication, all the other four kinds of solid matter A, B, C, D molecular structure difference.Because the difference of species crystal force of cohesion, product C and by-product salt D can automatic agglomeration separation.Nucleation after product C reaches a certain size.The resultant D that follows is generally Na salt or K salt, with small amount of H
2After dissolving each other, O grows up to crystalline phase.Among the by product phase D that product phase C high dispersing after the nucleation forms at the same time.Therefore by product phase D has hindered the growth of C.After C and D came off from A, B surface, A, B had produced new interface again, constantly ground, and constantly reacted, and finished obtaining nano material until reaction.
Excellent results of the present invention is:
1) owing to be reflected at room temperature or low temperature and do not have and carry out under the condition of solvent, there are not the recovery and the processing of solvent, so energy consumption is low and help environmental protection;
2) simple to operate, reaction is easy to realize;
3) but large-scale industrial production be convenient to promote;
4) not having organic solvent to participate in reaction, is green chemical technique technology.
Description of drawings
Fig. 1: room temperature solid state reaction synthetic spinel type CoFe
2O
4The TEM photo of nanoparticle.
Fig. 2: spinel type CoFe after 400 ℃ of roastings
2O
4The SEM photo of nanoparticle.
Fig. 3: the room temperature solid state reaction is synthesized (a), and 200 ℃ (b), 400 ℃ (c), 600 ℃ (d) and 800 ℃ of (e) roastings spinel type CoFe after 2 hours
2O
4The XRD figure spectrum of nanoparticle.
Fig. 4: the sodium stearate protection is room temperature solid state reaction synthetic spinel type CoFe down
2O
4The TEM photo of nanoparticle.
Fig. 5: room temperature solid state reaction synthetic spinel type Fe
3O
4The TEM photo of nanoparticle.
Fig. 6: room temperature solid state reaction synthetic spinel type MgFe
2O
4The TEM photo of nanoparticle.
Fig. 7: room temperature solid state reaction synthetic spinel type MnFe
2O
4The TEM photo of nanoparticle.
Fig. 8: room temperature solid state reaction synthetic spinel type NiFe
2O
4The TEM photo of nanoparticle.
Embodiment
Embodiment 1: spinel type CoFe
2O
4Nanoparticle synthetic
Concrete steps are as follows:
1. with 0.02 mole of FeCl
36H
2O and 0.01 mole of CoCl
26H
2O is added in mortar or the ball mill, presses 0.5% of inorganic salt quality subsequently and adds concentrated hydrochloric acid.
2. acutely grind and obtain safran pasty state composite metal salt precursor after 0.5 hour, drying for standby or directly apply to the preparation of step 3 nano material.
3. add solid NaOH (0.08 mole) and contain in composite metal salt precursor mortar or the ball mill in step 2, thermopositive reaction takes place at once and emits from reactor with aqueous vapor.Continue to grind extremely to react in 0.5 hour and finish.
4. the black color mashed prod that obtains adds water washing, centrifugation, and drying obtains the black solid product.
5. product can be dispersed in the water.
6. obtain nano particle in irregular shape, mean diameter is about 10 nanometers (seeing accompanying drawing 1).
Embodiment 2: as described in embodiment 1, different is:
In step 1, do not add mineral acid.The CoFe that reaction obtains
2O
4Nanoparticle similar to the nanoparticle pattern of gained among the embodiment 1 (seeing accompanying drawing 2).But, have dephasign to exist in the product.
Embodiment 3: as described in embodiment 1, different is:
In step 3, add KOH, NaHCO
3Or Na
2CO
3To substitute NaOH.The CoFe that reaction obtains
2O
4Nanoparticle is similar to the nanoparticle of gained among the embodiment 1.
Embodiment 4: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
Add NaOH (0.06 mole) in step 3, other step is constant, the CoFe that obtains
2O
4Nanoparticle is similar to the nanoparticle of gained among the embodiment 1, still, has dephasign to exist in the product.Equally, adding excessive NaOH (0.3 mole) in step 3 can obtain similar to the nanoparticle of gained among the embodiment 1.
Embodiment 5: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
The black color mashed prod that step 4 obtains can obtain the nanoparticle of about 30 nanometers 400 ℃ of roastings 6 hours.
Embodiment 6: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
The black color mashed prod that step 4 obtains can obtain the nanoparticle of about 200 nanometers 1100 ℃ of roastings 2 hours.Improve the crystallization growth temperature or prolong growth time and can obtain larger-size nanoparticle.The XRD figure spectrum of the nanoparticle that the differing temps roasting obtains is seen accompanying drawing 3.
Embodiment 7: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
Add sodium stearate as tensio-active agent in step 1, consumption is that 1 part of metal-salt adds 1 part of (being mass parts) tensio-active agent.Can obtain diameter is 13 nanometer spherical nanoparticles (seeing accompanying drawing 4).
Embodiment 8: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
Be to add Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, or four octyl group brometo de amonios are as tensio-active agent, and consumption is that 1 part of metal-salt adds the tensio-active agent of 0.1 part (being mass parts).Can obtain the nano spherical particle similar to embodiment 4.
Embodiment 9: spinel type CoFe
2O
4Nanoparticle synthetic
As described in embodiment 1, different is:
Use vitriol instead, or nitrate is reactant.The mineral acid of Jia Ruing also makes corresponding vitriol oil acid or concentrated nitric acid into simultaneously, obtains the nanoparticle that particle diameter is about 10 nanometers.By muriate, vitriol, or the precursor of nitrate preparation and solid alkali react the nanoparticle that obtains and have size and the pattern similar to embodiment 1.
Embodiment 10: spinel type Fe
3O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of FeCl
2Substitute CoCl
2, other step is constant, obtains spinel type Fe
3O
4Nanoparticle, about 8 nanometers of median size (seeing accompanying drawing 5).
Embodiment 11: spinel type MgFe
2O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of MgCl
2Substitute CoCl
2, other step is constant, obtains irregular sheet spinel type MgFe
2O
4Nanoparticle, the thickness of platy particle are about 2 nanometers (seeing accompanying drawing 6).
Embodiment 12: spinel type ZnFe
2O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of ZnCl
2Substitute CoCl
2, other step is constant, obtains ZnFe
2O
4Nanoparticle, about 15 nanometers of median size.
Embodiment 13: spinel type MnFe
2O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of MnCl
2Substitute CoCl
2, other step is constant, obtains MnFe
2O
4Nanoparticle, about 6 nanometers of median size (seeing accompanying drawing 7).
Embodiment 14: spinel type NiFe
2O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of NiCl
2Substitute CoCl
2, other step is constant, obtains NiFe
2O
4Nanoparticle, about 2 nanometers of median size (seeing accompanying drawing 8).
Embodiment 15: spinel type CoFe
2O
4Nanoparticle synthetic,
As described in embodiment 1, different is:
In step 1, add 0.01 mole of ZnCl
2Substitute CoCl
2, other step is constant, obtains ZnFe
2O
4Nanoparticle, about 15 nanometers of median size.
Claims (7)
1. a low fever solid phase reaction prepares the method for spinel oxides nano material, it is characterized in that it comprises the steps:
Step 1. prescription: trivalent metal salt and the ratio of one or more divalent metal salts in 2: 1 are added in mortar or the ball mill, and the 0-5% that presses the inorganic salt quality subsequently adds mineral acid acid;
Step 2. precursor preparation: acutely grind after 10 minutes-1 hour and obtain pasty state composite metal salt precursor, drying for standby or directly apply to the preparation of nano material;
Step 3. reaction: add solid alkali in containing composite metal salt precursor mortar or ball mill, thermopositive reaction takes place at once and often emits from reaction with aqueous vapor, continue to grind extremely to react in 10 minutes-1 hour and finish, the mol ratio of solid alkali and metal-salt is 2: 1-10: 1;
Step 4. aftertreatment: add water washing, centrifugation, drying obtains the dark spinel type iron-containing oxide nano-materials of different size and shape.
2. method for making according to claim 1 is characterized in that: in above-mentioned steps 1, add tensio-active agent, the consumption of tensio-active agent is the 10-100% of metal-salt quality.
3. method for making according to claim 1 is characterized in that: in described step 1, trivalent iron salt or divalent metal salt comprise vitriol, hydrochloride or the nitrate that contains crystal water or do not contain crystal water, perhaps their double salt.
4. method for making according to claim 1, the metal ion of divalent metal salt is Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+Or Ni
2+
5. method for making according to claim 1 is characterized in that: in step 1, described mineral acid is concentrated hydrochloric acid, concentrated nitric acid or the vitriol oil, or their 1-10 times of dilute aqueous.
6. method for making according to claim 1 is characterized in that: in step 3, described solid alkali is NaOH, KOH, NaHCO
3Or Na
2CO
3The time of grinding generally is no less than 15 minutes.
7. method for making according to claim 1 is characterized in that: between above-mentioned steps 3 and 4, increase the crystallization growth step:
The crystallization growth: different colours mashed prod or meal that step 3 obtains were grown 2 hours-6 days in room temperature-1100 a ℃ following crystallization again, and the growth of high temperature crystallization can obtain the nanocrystalline product of large-size.
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CN102863028A (en) * | 2012-09-11 | 2013-01-09 | 吉林大学 | Method of preparing water-soluble iron oxide under room temperature condition |
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2009
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CN102863028A (en) * | 2012-09-11 | 2013-01-09 | 吉林大学 | Method of preparing water-soluble iron oxide under room temperature condition |
CN103771538A (en) * | 2014-01-27 | 2014-05-07 | 石家庄铁道大学 | Low-temperature solid-phase reaction preparation method of nano CoFe2O4 powder |
WO2019004755A1 (en) * | 2017-06-30 | 2019-01-03 | 주식회사 엘지화학 | Method for preparing nickel oxide nanoparticle and nickel oxide nanoparticle prepared using same |
KR20190003138A (en) * | 2017-06-30 | 2019-01-09 | 주식회사 엘지화학 | METHOD FOR FABRICATING NiO NANO PARTICLES AND NiO NANO PARTICLES FABRICATED BY THE SAME |
CN110446687A (en) * | 2017-06-30 | 2019-11-12 | 株式会社Lg化学 | For producing the method for nickel oxide nano particle and using the nickel oxide nano particle of its production |
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CN110446687B (en) * | 2017-06-30 | 2022-04-05 | 株式会社Lg化学 | Method for producing nickel oxide nanoparticles and nickel oxide nanoparticles produced using the same |
US11306005B2 (en) | 2017-06-30 | 2022-04-19 | Lg Chem, Ltd. | Method for preparing nickel oxide nanoparticles and nickel oxide nanoparticles produced by using the same |
CN112939098A (en) * | 2021-03-31 | 2021-06-11 | 景德镇陶瓷大学 | Process method for preparing magnetic nickel ferrite powder at low temperature in dry state |
CN112939098B (en) * | 2021-03-31 | 2024-03-29 | 景德镇陶瓷大学 | Process method for preparing magnetic nickel ferrite powder in dry state at low temperature |
CN113060766A (en) * | 2021-04-08 | 2021-07-02 | 成都理工大学 | Dispersed flaky magnesium ferrite spinel magnetic nano material and preparation method thereof |
CN113200572A (en) * | 2021-05-07 | 2021-08-03 | 景德镇陶瓷大学 | Process method for preparing cobalt ferrite powder at low temperature in dry state |
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