CN1718558A - Porous magnetic ferrite and its preparation method - Google Patents

Porous magnetic ferrite and its preparation method Download PDF

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CN1718558A
CN1718558A CN 200410062750 CN200410062750A CN1718558A CN 1718558 A CN1718558 A CN 1718558A CN 200410062750 CN200410062750 CN 200410062750 CN 200410062750 A CN200410062750 A CN 200410062750A CN 1718558 A CN1718558 A CN 1718558A
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magnetic ferrite
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CN1297511C (en
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段雪
李峰
杨巧珍
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Beijing University of Chemical Technology
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites

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Abstract

A porous magnetic ferrite MxMT(1-x) Fe2O4 or MMT(y)Fe(2-Y) O4 with large specific surface area and pore volume, low granularity and high magnetism is prepared through introducing MT to laminated hydrotalcite, high-temp calcining, and removing template agent MTO or MT2D3 by concentrated alkali solution.

Description

A kind of porous magnetic ferrite and preparation method thereof
Technical field:
The present invention relates to a kind of porous magnetic ferrite and preparation method thereof.
Technical background:
Porous material is because the homogeneity in its porousness and aperture, bigger specific surface area and high temperature resistant, weathering resistance and performance such as anticorrosive have potential application foreground in fields such as column material, high-strength light structured material, special cells material, advanced composite material at high-selectivity catalyst mutually with support of the catalyst, high-efficiency adsorbent, high efficient gas and liquid.Someone once proposed to carry out with this material the research of diffusion of material in the finite space and absorption, even as the embedded material of drug release, enzyme or proteinic carrier and be used for the aspects such as processing of radioactive waste.
Ferrite is a kind of novel nonmetal magnetic material, be widely used in high frequency or low frequency fields such as communication broadcasting, radar navigation, space travel, medical biotechnology, since carrying out systematic study and produce since nineteen forties, obtained development extremely rapidly and used widely.The composite oxides that ferrite is made up of iron and other one or more metals are MFe as the chemical molecular formula of spinel type ferrite 2O 4, wherein M is the ionic radius divalent-metal ion (Mn close with ferrous ion 2+, Zn 2+, Cu 2+, Ni 2+, Mg 2+, Co 2+Deng), therefore different along with alternative metals kind and quantity can be formed various dissimilar two component ferrites or many components ferrites.
At document 1:Junjie Liu, Feng Li, David G.Evans and Xue Duan, Chem.Comm.1 in 542 (2003), has introduced with the lamellar precursor legal system and has been equipped with ferrite MgFe 2O 4But the lamellar precursor method is again through high-temperature roasting, can obtain the ferrite that magnetic performance is good and size-grade distribution is little as firing precursor by preparing whole homogeneous, chemical constitution and structure modulation, active high simplification compound on microcosmic earlier.
Also there is document to report for work about porous ferrite research, at document J.B.da Silva and N.D.S.Mohallem, Journal of Magnetism and Magnetic Materials 226-230 in 1393 (2001), uses tetraethoxy (TEOS) to make SiO by sol-gel method 2The precursor of matrix is made ferritic precursor with the nitrate of Ni and Fe, and the Ni ferrite is dispersed in SiO 2Form ferrospinel NiFe in the matrix 2O 4With porousness SiO 2Mixture, its magnetic is better than the NiFe of coprecipitation method preparation 2O 4At document Janez Holc, Danjela Ku Cer, Marko Hrovat, Slavko Bemik and Drago Kolar, Solid State Ionics95 in 259 (1997), partly replaces calcium titanium type ferrite La with Al 0.8Sr 0.2FeO 3In Fe, the La of generation 0.8Sr 0.2Fe 1-XAl xO 3Have the permeability of increase and the particle size that reduces.But with the lamellar precursor legal system be equipped with big, the mesoporous and micropore of specific surface area and deposit, mean pore size is big, total pore volume is big porousness ferrospinel yet there are no report.
Summary of the invention:
The purpose of this invention is to provide a kind of porous magnetic ferrite, another object of the present invention provides the ferritic preparation method of this porousness.
Ferritic chemical general formula provided by the invention is:
M 2+ XM 2+ T(1-X)Fe 3+ 2O 4 (1)
Or M 2+M T 3+ (Y)Fe 3+ (2-Y)O 4(2)
Wherein the span of X is 0～1, the span 0～1.5 of Y;
M 2+For the ionic radius divalent-metal ion close, can be Mn with ferrous ion 2+, Zn 2+, Cu 2+, Ni 2+, Mg 2+Or Co 2+In one or more; M T 2+Be Zn 2+M T 3+Be ionic radius and Fe 3+Close trivalent metal ion, preferred Al 3+, Cr 3+Or Mn 3+One or more;
This ferritic mesoporous most probable aperture is 2.0～40nm, and the most probable aperture of micropore is 0.30nm～1.90nm, and mean pore size is 3～80nm, and total pore volume is 0.01～0.80cm 3/ g, specific surface area is 5～350m 2/ g, granularity is 5～150nm, specific saturation magnetization is 2～80emu/g.
Because chemical constitution and the structure of LDHs have Modulatory character and whole homogeneity on microcosmic, it itself is again the two-dimensional nano material, the material of this special construction and composition is the precursor material of synthetic good permeability and magnetic ferrite, therefore can introduce potential magnetic species and template M to its laminate by design T, prepare M 2+-M T K+-Fe 3+LDHs (k=2,3) compound obtains magnetic phase ferrospinel and the non magnetic M of intermediate oxide mutually by high-temperature roasting TO or M T2O 3, with alkali dissolution and remove M TO or M T2O 3, M TO or M T2O 3On magnetic ferrite, form a large amount of mesoporous and micropores when being removed, thereby obtain the single porous magnetic ferrite of whole microtexture.
Concrete preparation method is:
A. preparation contains divalent-metal ion M 2+, M T K+Ion and Fe 3+Mixing salt solution, wherein the volumetric molar concentration of each metal ion species is respectively M 2+: 0～0.25M, M T K+: 0.25～1.0M, Fe 3+: 0.15～0.5M; With sodium hydroxide and solubility inorganic sodium preparation mixed ammonium/alkali solutions, wherein naoh concentration is 1.0～3.0M again, and sodium salt concentration is 0～1.8M; Preparing above-mentioned two kinds of used solvents of mixing solutions is and passes through N 2Deionized water
M wherein 2+Be Mn 2+, Mg 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+Or Zn 2+In any one or multiple; M T K+Be the template ion, k=2 or 3; M T 2+(during k=2) is Zn 2+M T 3+(during k=3) is Al 3+, Cr 3+, Mn 3+In any one or multiple; Acid ion in the mixed salt solution is CO 3 2-, NO 3 -, Cl -, OH -, SO 4 2-, PO 4 3-, C 6H 6(COO -) 2In any one or multiple; The solubility inorganic sodium is any one in yellow soda ash, sodium sulfate, SODIUMNITRATE or the sodium-chlor;
B. at N 2The protection condition under, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution or drip alkaline solution simultaneously and salts solution in the container that fills small amount of deionized water, when the pH value in the system reaches 6～12, stop the dropping, at N 2Under the condition of protection, in 20～60 ℃ of water-baths, crystallization 5～25h after filtration, washing, drying, obtains M 2+-M T K+-Fe 3+LDHs stratum water talcum precursor;
Elder generation is with passing through N during washing 2The deionization frozen water wash to washings and show neutral, use 0～10 ℃ washing with alcohol 2～4 times again.
C. above-mentioned LDH is placed High Temperature Furnaces Heating Apparatus, be warming up to 300～1000 ℃ of roasting 2～10h, obtain M with the speed of 2～15 ℃/min 2+ XM T 2+ 1-XFe 2O 4/ M TO mixture or M 2+M T 3+ (X)Fe 3+ (2-X)O 4/ M T2O 3Mixture.
D. the mixture concentration that step C is obtained is that the alkaline solution of 5～15M is at room temperature handled 24-168h, then with deionized water wash to neutral to remove template M TO or M T2O 3, obtain porousness M 2+ XM T 2+ 1-XFe 2O 4Or M 2+M T 3+ (X)Fe 3+ (2-X)O 4Ferrospinel.Used alkaline solution is NaOH or KOH.
The ferrite sample that obtains carries out following sign:
With day island proper Tianjin XRD-6000 type X-ray diffractometer, at Cu, K αRay, λ=1.54 , tube voltage 40kV, tube current 30mA, 5 °/min of sweep velocity, sweep limit 3-90 ° characterizes the crystalline structure of sample down and calculates grain-size, and its mean particle size is 5～150nm as a result.
Carry out specific surface and aperture and pore distribution analysis with full-automatic specific surface of U.S. Quantachrome (Kang Ta) company and lacunarity analysis instrument AUTOSORB-1, recording its mesoporous most probable aperture is 2.0～40nm, the most probable aperture of micropore is 0.30nm～1.90nm, mean pore size is 3～80nm, and total pore volume is 0.005～0.90cm 3/ g, specific surface area is 5～350m 2/ g, granularity is 5～150nm;
With the specific saturation magnetization of JDM-13 type vibrating sample magnetometer working sample, with Ni fen-ting mark, maximum field is 15000Oe, and recording its specific saturation magnetization is 1～90emu/g.
The present invention has following unusual effect: 1. with the porousness ferrite of stratiform ferrite precursor methods preparation have porousness, granularity little, be uniformly dispersed, specific surface area is big and the good characteristics of magnetic performance; 2. this preparation method does not need raw material is carried out mix grinding technology, thereby can simplify production technique, shortens the production cycle, saves facility investment, saves production energy consumption significantly.
Embodiment:
Embodiment 1:
A. with Ni (NO 3) 2, Zn (NO 3) 2And Fe (NO 3) 3Add and pass through N 2Deionized water in prepare mixing salt solution, make GOLD FROM PLATING SOLUTION belong to respectively Ni of ionic concentration 2+: 0.05M, Zn 2+: 0.55M, Fe 3+: 0.2M; This mixing solutions is poured in the container; Preparation NaOH and NaCO 3Mixed ammonium/alkali solutions, make that NaOH concentration is 1.5M in the alkaline solution, NaCO 3Concentration is 0.8M.
B. mixed ammonium/alkali solutions slowly is added drop-wise in the container that fills mixing salt solution, when the pH value in the system reaches 8, stops dripping alkali liquid.In 40 ℃ of water-baths, crystallization 10h, suction filtration then with the frozen water washing by nitrogen, is used 0 ℃ washing with alcohol 2 times again, and drying obtains Ni 2+-Zn 2+-Fe 3+-CO 3 2-Type layered double hydroxide hydrotalcite (LDHs).
C. LDHs is put in the retort furnace, is warming up to 700 ℃ with the speed of 2 ℃/min, insulation 4h naturally cools to room temperature and obtains Ni XZn 1-XFe 2O 4The mixture of ferrite and ZnO,
D. the mixture that obtains is handled 96h with concentrated NaOH solution, remove excessive ZnO and obtain the porous magnetic ferrite.
Recording its specific saturation magnetization is 28emu/g, records its mesoporous most probable aperture and is respectively 2.96nm, 4.72nm, 31.58nm, and the most probable aperture of micropore is 0.58nm, and mean pore size is 24.42nm, and total pore volume is 0.14cm 3/ g, specific surface area is 23.42m 2/ g, granularity is 36nm.
Embodiment 2:
A. with NiSO 4, ZnSO 4And Fe 2(SO 4) 3Add and pass through N 2Deionized water in prepare mixing salt solution, make GOLD FROM PLATING SOLUTION belong to ionic concentration and be respectively Ni 2+: 0.06M, Zn 2+: 0.8M, Fe 3+: 0.2M; This mixing solutions is poured in the container; Preparation NaOH solution makes that NaOH concentration is 2.0M in the alkaline solution.
B. alkaline solution slowly is added drop-wise in the container that fills mixing salt solution, when the pH value in the system reaches 7.5, stops dripping alkali liquid.In 40 ℃ of water-baths, crystallization 10h, suction filtration then with the frozen water washing by nitrogen, is used 0 ℃ washing with alcohol 2 times again, and drying obtains Ni 2+-Zn 2+-Fe 3+-SO 4 2-Type layered double hydroxide hydrotalcite (LDHs).
C. LDHs is put in the retort furnace, is warming up to 900 ℃ with the speed of 10 ℃/min, roasting 7h naturally cools to room temperature and obtains Ni XZn 1-XFe 2O 4The mixture of ferrite and ZnO.
D. the mixture that obtains is handled 48h with concentrated NaOH solution, remove excessive ZnO and obtain the porous magnetic ferrite.
Record its specific saturation magnetization 65emu/g, record its mesoporous most probable aperture and be respectively and be 3.30nm, 9.30nm, the most probable aperture of micropore is 0.80nm, 1.18nm, 1.55nm, and mean pore size is 14.72nm, and total pore volume is 0.0326cm 3/ g, specific surface area is 9.04m 2/ g, granularity is 56nm.
Embodiment 3:
A. with CoSO 4, ZnSO 4And Fe 2(SO 4) 3Add and pass through N 2Deionized water in prepare mixing salt solution, make GOLD FROM PLATING SOLUTION belong to ionic concentration and be respectively Co 2+: 0.10M, Zn 2+: 0.7M, Fe 3+: 0.40M; This mixing solutions is poured in the container; Preparation NaOH solution makes that NaOH concentration is 2.4M in the alkaline solution.
B. alkaline solution slowly is added drop-wise in the container that fills mixing salt solution, when the pH value in the system reaches 7.0, stops dripping alkali liquid.In 50 ℃ of water-baths, crystallization 8h obtains Ni with embodiment 1 step B 2+-Zn 2+-Fe 3+-SO 4 2-Type layered double hydroxide hydrotalcite (LDHs).
C. LDHs is put in the retort furnace, is warming up to 700 ℃, insulation 6h with the speed of 15 ℃/min.Naturally cool to room temperature and obtain Co XZn 1-XFe 2O 4The mixture of ferrite and ZnO.
D. obtain the porous magnetic ferrite with embodiment 1 step D.
Record it for the paramagnetic iron oxysome, record its mesoporous most probable aperture and be respectively and be 2.41nm, 17.52nm, the most probable aperture of micropore is 0.72nm, 1.07nm, 1.64nm, and mean pore size is 65.12nm, and total pore volume is 0.287cm 3/ g, specific surface area is 43.61m 2/ g, granularity is 17nm.
Embodiment 4:
A. with MgSO 4, ZnSO 4And Fe 2(SO 4) 3Add and pass through N 2Deionized water in prepare mixing salt solution, make GOLD FROM PLATING SOLUTION belong to ionic concentration and be respectively Mg 2+: 0.05M, Zn 2+: 0.5M, Fe 3+: 0.20M; This mixing solutions is poured in the container; Preparation NaOH solution makes that NaOH concentration is 1.6M in the alkaline solution.
B. alkaline solution slowly is added drop-wise in the container that fills mixing salt solution, when the pH value in the system reaches 10.5, stops dripping alkali liquid.In 40 ℃ of water-baths, crystallization 20h obtains Ni with embodiment 1 step B 2+-Zn 2+-Fe 3+-SO 4 2-Type layered double hydroxide hydrotalcite (LDHs).
C. LDHs is put in the retort furnace, is warming up to 650 ℃, insulation 6h with the speed of 5 ℃/min.Naturally cool to room temperature and obtain Mg XZn 1-XFe 2O 4The mixture of ferrite and ZnO.
D. obtain the porous magnetic ferrite with embodiment 1 step D.
Record it for the paramagnetic iron oxysome, record its mesoporous most probable aperture and be respectively and be 2.13nm, 32.29nm, the most probable aperture of micropore is 0.60nm, 1.04nm, and mean pore size is 41.07nm, and total pore volume is 0.499cm 3/ g, specific surface area is 48.63m 2/ g, granularity is 18nm.
Embodiment 5
A. with ZnSO 4.7H 2O and FeSO 4.7H 2O adding passing through N 2Deionized water in prepare mixing salt solution, make GOLD FROM PLATING SOLUTION belong to ionic concentration and be respectively Zn 2+: 0.60M, Fe 3+: 0.25M; This mixing solutions is poured in the container; Preparation NaOH solution makes that NaOH concentration is 1.6M in the alkaline solution.
B. alkaline solution slowly is added drop-wise in the container that fills mixing salt solution, when the pH value in the system reaches 7.0, stops dripping alkali liquid.In 45 ℃ of water-baths, crystallization 20h obtains Zn with embodiment 1 step B 2+-Fe 3+-SO 4 2-Type layered double hydroxide hydrotalcite (LDHs).
C. LDHs is put in the retort furnace, is warming up to 500 ℃, insulation 5h with the speed of 10 ℃/min.Naturally cool to room temperature and obtain ZnFe 2O 4The mixture of ferrite and ZnO.
D. the mixture that obtains is handled 24h with concentrated NaOH solution, remove excessive ZnO and obtain the porous magnetic ferrite.
Record it and be the paramagnetic iron oxysome, recording its mesoporous most probable aperture is 5.50nm, and the most probable aperture of micropore is 0.84nm, 1.31nm, and mean pore size is 7.53nm, and total pore volume is 0.235cm 3/ g, specific surface area is 180.23m 2/ g, granularity is 6nm.

Claims (3)

1. porous magnetic ferrite, its chemical general formula is:
M 2+ XM 2+ T(1-X)Fe 3+ 2O 4 (1)
Or M 2+M T 3+ (Y)Fe 3+ (2-Y)O 4(2)
Wherein the span of X is 0～1, the span 0～1.5 of Y;
M 2+Be the ionic radius divalent-metal ion close with ferrous ion; M T 2+Be Zn 2+M T 3+Be ionic radius and Fe 3+Close trivalent metal ion;
This ferritic mesoporous most probable aperture is 2.0～40nm, and the most probable aperture of micropore is 0.30nm～1.90nm, and mean pore size is 3～80nm, and total pore volume is 0.01～0.80cm 3/ g, specific surface area is 5～350m 2/ g, granularity is 5～150nm, specific saturation magnetization is 2～80emu/g.
2. porous magnetic ferrite according to claim 1 is characterized in that M 2+Be Mn 2+, Zn 2+, Cu 2+, Ni 2+, Mg 2+Or Co 2+In one or more; M T 3+Be: Al 3+, Cr 3+, Mn 3+In a kind of, two or three.
1. the preparation method of a porous magnetic ferrite: concrete steps are as follows:
A. preparation contains divalent-metal ion M 2+, M T K+Ion and Fe 3+Mixing salt solution, wherein the volumetric molar concentration of each metal ion species is respectively M 2+: 0～0.25M, M T K+: 0.25～1.0M, Fe 3+: 0.15～0.5M; With sodium hydroxide and solubility inorganic sodium preparation mixed ammonium/alkali solutions, wherein naoh concentration is 1.0～3.0M again, and sodium salt concentration is 0～1.8M; Preparing above-mentioned two kinds of used solvents of mixing solutions is and passes through N 2Deionized water;
M wherein 2+Be Mn 2+, Mg 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+Or Zn 2+In any one or multiple; M T K+Be the template ion, k=2 or 3, M T 2+Be Zn 2+M T 3+Be Al 3+, Cr 3+, Mn 3+In a kind of, two or three; Acid ion in the mixed salt solution is CO 3 2-, NO 3 -, Cl -, OH -, SO 4 2-, PO 4 3-, C 6H 6(COO -) 2In any one or multiple; The solubility inorganic sodium is any one in yellow soda ash, sodium sulfate, SODIUMNITRATE or the sodium-chlor;
B. at N 2The protection condition under, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution or drip alkaline solution simultaneously and salts solution in the container that fills small amount of deionized water, when the pH value in the system reaches 6～12, stop the dropping, at N 2Under the condition of protection, in 20～60 ℃ of water-baths, crystallization 5～25h after filtration, washing, drying, obtains M 2+-M T K+-Fe 3+LDHs stratum water talcum precursor;
C. the stratum water talcum precursor with step B preparation places High Temperature Furnaces Heating Apparatus, is warming up to 300～1000 ℃ of roasting 2～10h with the speed of 2～15 ℃/min, obtains M 2+ XM T 2+ 1-XFe 2O 4/ MTO mixture or M 2+M T 3+ (X)Fe 3+ (2-X)O 4/ M T2O 3Mixture;
D. the mixture concentration that step C is obtained is that the alkaline solution of 5～15M is at room temperature handled 24-168h, then with deionized water wash to neutral to remove template M TO or M T2O 3, obtain porousness M 2+ XM T 2+ 1-XFe 2O 4Or M 2+M T 3+ (X)Fe 3+ (2-X)O 4Ferrospinel.
4. the preparation method of the described porous magnetic ferrite of claim 3, the washing process that it is characterized in that step B is earlier with passing through N 2The deionization frozen water wash to washings and show neutral, use 0～10 ℃ washing with alcohol 2～4 times again; The used alkaline solution of step D is NaOH or KOH.
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CN102430411A (en) * 2011-09-13 2012-05-02 浙江省地质矿产研究所 Hydrotalcite-like compound-spinel type ferrite composite material and preparation method thereof
CN102603278A (en) * 2012-03-07 2012-07-25 天通控股股份有限公司 Stress-resistant nickel zinc ferrite with initial permeability of 120, and preparation method of stress-resistant nickel zinc ferrite
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