CN1724382A - Homogeneous large grain size magnetic hydrotalcite and its preparation process - Google Patents
Homogeneous large grain size magnetic hydrotalcite and its preparation process Download PDFInfo
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- CN1724382A CN1724382A CNA2005100119967A CN200510011996A CN1724382A CN 1724382 A CN1724382 A CN 1724382A CN A2005100119967 A CNA2005100119967 A CN A2005100119967A CN 200510011996 A CN200510011996 A CN 200510011996A CN 1724382 A CN1724382 A CN 1724382A
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- magnetic
- grain size
- hydrotalcite
- large grain
- metal ion
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Abstract
A process for preparing high-uniformity and high-granularity magnetic hydro-talcite particles, which is composed of a magnetic core and a shell (carbonic acid radical-type hydrotalcite), includes such steps as co-depositing to prepare magnetic nano-cores, mixing with relative salt solution, and growing the carbonic acid radical-type hydrotalcite on the surface of each nano-core by urea method. Its advantage is high magnetic target performance.
Description
Technical field
The invention belongs to the hydrotalcite material technical field, a kind of homogeneous large grain size magnetic hydrotalcite and preparation method thereof particularly is provided.Can be applied to fields such as medical carrier, catalyzer or support of the catalyst and biosensor as a kind of base mateiral.
Background technology
(layered double hydroxide is a kind of anionic clay inorganic materials LDHs) to hydrotalcite, has laminate metallic element Modulatory character and interlayer anion interchangeability.Utilize the interchangeability of its interlayer anion, can be with between the organic molecule interposed layer.Change reaction conditionss such as temperature, crystallization time, can regulate and control the hydrotalcite particles size, make it all have unique advantage in preparation routine and aspects such as nanometer composite organic-inorganic material, biosensor.
People such as Makoto Ogawa synthesize the hydrotalcite with homogeneous large grain size at Langmuir the 18th phase 4240~4242 pages of reports in 2002 with Wyler's process, and its particle diameter is respectively 2.0,2.4 and 2.9 microns.People such as Zhang Hui and Duan Xue has reported synthetic captopril and the 5-aminosalicylic acid intercalated houghite with magnetic of coprecipitation method for 2525~2530 pages at Science Bulletin the 24th phase the 49th volume December in 2004, and its particle diameter is about 100nm.Duan Xue and Zhang Hui patent (application number: disclose 200410009903.2) magnetic hydrotalcite have as a kind of gastric antiacids intermediate good in and the performance of hydrochloric acid in gastric juice, its particle diameter is about 100nm.Still there are not relevant homogeneous large grain size (micron order) magnetic hydrotalcite material document and patent report at present both at home and abroad.
Summary of the invention:
The object of the present invention is to provide a kind of homogeneous large grain size magnetic hydrotalcite and preparation method thereof, it is a kind of material that outside magnetic core, coats carbonate type hydrotalcite, median size is about 3 microns, it can be applied to fields such as medical carrier, catalyzer or support of the catalyst and biosensor as a kind of base mateiral, in use can realize target setting control effect by the magneticstrength and the direction of control externally-applied magnetic field.
The chemical formula of the homogeneous large grain size magnetic hydrotalcite that the present invention is prepared is:
(N
2+)
1-x(M
3+)
x(OH)
2(CO
3 2-)
x/2·mH
2O/M’Fe
2O
4。(N wherein
2+)
1-x(M
3+)
x(OH)
2(CO
3 2-)
X/2MH
2O can be abbreviated as N-M-CO
3-LDH, M ' Fe
2O
4Be magnetic species, N-M-CO
3-LDH is for being coated on M ' Fe
2O
4Outer carbonate type hydrotalcite.Its quality percentage composition is:
M’Fe
2O
4:7%~55%,
N-M-CO
3-LDH:93%~45%;
Wherein N is divalent-metal ion Zn
2+Or Mg
2+, M is trivalent metal ion Al
3+, M ' is Co
2+, Mg
2+, Ba
2+, Zn
2+, Ni
2+Wherein any of divalent-metal ion, M and M ' can be the same or different; X=M
3+/ (N
2++ M
3+), 0<x<1; M is the crystallization water number, can be any rational number;
The preparation method of homogeneous large grain size magnetic hydrotalcite of the present invention is that the employing coprecipitation method prepares nano-scale magnetic nuclear earlier, with this magnetic core and corresponding salt solution mix, prepares the homogeneous large grain size hydrotalcite that contains magnetic core with Wyler's process.Concrete technology is:
A, nano-magnetic nuclear M ' Fe
2O
4Powder preparing
The soluble inorganic salt and two of M ', ferric soluble inorganic salt are mixed with mixing solutions, wherein (M '+Fe
2+)/Fe
3+Mol ratio is 1~5, M '/Fe
2+Mol ratio is 0.5~2.The volumetric molar concentration of M ' is 0.1~2.5M, Fe
3+Volumetric molar concentration be 0.2~5.0M; Use the NaOH alkaline solution, wherein the NaOH volumetric molar concentration is 0.1~5.0M; Under nitrogen protection alkali lye splashed in the salts solution to the pH value and equal 6~7,15~50 ℃ of crystallization are 4~48 hours in water-bath, reaction solution filtered, with taking off CO
2Deionized water wash is used absolute ethanol washing again, vacuum-drying, grinds to form powdery, obtains particle size range at the M ' of 200~800nm Fe through 800~1000 ℃ of high-temperature roastings
2O
4Powder.Obtain powder uniformly with the standard sieve screening.
B, homogeneous large grain size magnetic N-M-CO
3-LDH/M ' Fe
2O
4Preparation
With N (NO
3)
2, M (NO
3)
2Be dissolved in urea and be made into homogeneous mixture solotion, N in the deionized water
2+/ M
3+Mol ratio be 2~4, the volumetric molar concentration of divalent-metal ion is 10
-3~10
-1M, the volumetric molar concentration of trivalent metal ion is 10
-4~10
-1M, the volumetric molar concentration of urea is 5*10
-3~5*10
-2M; Press M ' Fe
2O
4With the mass ratio of divalence inorganic metal salt in the above-mentioned mixing salt solution be 1: 48~2.0, take by weighing corresponding M ' Fe
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; 60~180 ℃ of crystallization 24~180 hours, centrifugal, washing, 25~100 ℃ of dryings 6~72 hours.
Divalent iron salt can be among the above-mentioned steps a: FeCO
3, FeSO
4, FeCl
2Or Fe (NO
3)
2In any; Trivalent iron salt can be: Fe
2(CO
3)
3, Fe
2(SO
4)
3, FeCl
3, Fe (NO
3)
3In any; M ' salt is: M ' SO
4, M ' Cl
2, M ' (NO
3)
2In any, M ' is Co
2+, Mg
2+, Ba
2+, Zn
2+, Ni
2+Wherein any of divalent-metal ion.
Because the preparation homogeneous large grain size magnetic hydrotalcite adopts the Wyler's process reaction, the reaction solution degree of supersaturation is low, and urea decomposition is slow, and crystal is evenly grown, so the magnetic hydrotalcite that obtains is the even particle of micron-scale.At synthetic N-M-CO
3-LDH/M ' Fe
2O
4In the process, because a large amount of nucleus is examined M ' Fe at magnetic
2O
4Surface synchronous growth under identical crystallization condition has guaranteed the homogeneity of clad structure.The particle diameter of this homogeneous large grain size magnetic hydrotalcite material is 2~10 microns, its magnetic property index: specific saturation magnetization σ
xBe 2.0~32AM
2/ Kg, coercivity H is 0~120kA/m.Because this magnetic hydrotalcite material has magnetic, in use can realize the high dispersing and the target location of operation system magnetic hydrotalcite, disperse undesirable and shortcoming such as can't locate thereby solved in the past the ortho-water talc materials by control magneticstrength of externally-applied magnetic field and direction.
Advantage of the present invention is:
[1] prepared a kind of new homogeneous large grain size magnetic hydrotalcite, owing to have magnetic, can accurate localization and dispersion highly.
[2] by adjusting NM-CO
3-LDH/M ' Fe
2O
4Assembling condition, as changing N
2+The mol ratio of/M ' can obtain different magnetic hydrotalcites.
Description of drawings:
Fig. 1 is NiFe under embodiment 3 assembling conditions
2O
4X-ray powder diffraction figure.
Fig. 2 is MgAl-CO under embodiment 3 assembling conditions
3-LDH/NiFe
2O
4X-ray powder diffraction figure.
Fig. 3 is the MgAl-CO of embodiment 3 preparations
3-LDH/NiFe
2O
4SEM figure, Fig. 3 (a) be the whole pattern of magnetic hydrotalcite, Fig. 3 (b) is that a magnetic is examined a kind of existence form in this magnetic hydrotalcite.
Embodiment:
Embodiment 1
(1) magnetic core MgFe
2O
4The preparation of nano-powder
With magnesium/ferrous iron/ferric iron mol ratio is 2: 1: 1 ratio, takes by weighing 8.47g Mg (NO
3)
26H
2O and 6.666g Fe (NO
3)
39H
2O and 3.29g FeCl
24H
2O is dissolved in the 100ml ionized water and is made into mixing salt solution, takes by weighing 6.02g NaOH and 7.43g Na
2CO
3Be dissolved in the 100ml deionized water and be made into mixed ammonium/alkali solutions; Alkaline solution dropwise splashed in the salts solution to the pH value equal 6,50 ℃ of crystallization are 4 hours in water-bath, reaction solution filtered, with taking off CO
2Deionized water wash is used absolute ethanol washing again, vacuum-drying, grinds to form powdery, roasting 4 hours in 800 ℃, air atmosphere again, and 10 ℃/minute of temperature rise rates make magnetic nuclear MgFe
2O
4Obtain powder uniformly with the standard sieve screening.
(2) homogeneous large grain size magnetic MgAl-CO
3-LDH/MgFe
2O
4Preparation
With Mg (NO
3)
26H
2O/MgFe
2O
4Mol ratio is 17.1 for example.Take by weighing 1.2307g Mg (NO
3)
26H
2O, 0.4503g Al (NO
3)
39H
2O and 0.7270g urea are dissolved in the 400ml deionized water and are made into mixing salt solution, with the MgFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; In 60 ℃ of following thermostatic crystallization 180h, centrifugal, washing, 25 ℃ of dryings 72 hours promptly get homogeneous large grain size magnetic MgAl-CO
3-LDH/MgFe
2O
4
The grain-size that records this homogeneous large grain size magnetic hydrotalcite is in 2~10 micrometer ranges, and average grain size is 3.00 microns.The coercivity H value is 11kA/m, specific saturation magnetization б
xBe 10.32AM
2/ Kg.
Embodiment 2
(1) magnetic core NiFe
2O
4The preparation of nano-powder
With nickel/ferrous iron/ferric iron mol ratio is 2: 1: 1 ratio, takes by weighing 10.10g NiSO
46H
2O, 4.50g FeSO
47H
2O and 6.40g Fe
2(SO
4)
37H
2O is dissolved in the 150ml ionized water and is made into mixing salt solution, takes by weighing 8.00g NaOH and is dissolved in the 100ml deionized water and is made into mixed ammonium/alkali solutions; Under nitrogen protection alkali lye splashed in the salts solution to the pH value and equal 8,15 ℃ of crystallization 48h filter reaction solution in water-bath, with taking off CO
2Deionized water wash is used absolute ethanol washing again, vacuum-drying, grinds to form powdery, roasting 2 hours in 1000 ℃, air atmosphere again, and 10 ℃/minute of temperature rise rates make magnetic nuclear NiFe
2O
4Obtain powder uniformly with the standard sieve screening.
(2) homogeneous large grain size magnetic MgAl-CO
3-LDH/NiFe
2O
4Preparation
With Mg (NO
3)
26H
2O/NiFe
2O
4Mol ratio is 2.25 for example.Accurately take by weighing 1.5384gMg (NO
3)
26H
2O, 0.5627g Al (NO
3)
26H
2O, 0.9009g urea are dissolved in the 400ml deionized water and are made into mixing salt solution, with the NiFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; In 180 ℃ of following thermostatic crystallizations 24 hours, centrifugal, washing, 100 ℃ of dryings 6 hours promptly get homogeneous large grain size magnetic MgAl-CO
3-LDH/NiFe
2O
4
The grain-size that records this homogeneous large grain size magnetic hydrotalcite is in 2~10 micrometer ranges, and average grain size is 3.0 microns.The coercivity H value is 13kA/m, specific saturation magnetization б
xBe 31.14AM
2/ Kg.
Embodiment 3
(1) magnetic core NiFe
2O
4The preparation of nano-powder
With nickel/ferrous iron/ferric iron mol ratio is 0.5: 1: 1 ratio, takes by weighing 2.53g NiSO
46H
2O, 4.50g FeSO
47H
2O and 6.40g Fe
2(SO
4)
37H
2O is dissolved in the 150ml ionized water and is made into mixing salt solution, takes by weighing 8.00g NaOH and is dissolved in the 100ml deionized water and is made into mixed ammonium/alkali solutions; Under nitrogen protection alkali lye splashed in the salts solution to the pH value and equal 7,40 ℃ of crystallization are 16 hours in water-bath, reaction solution filtered, with taking off CO
2Deionized water wash is used absolute ethanol washing again, vacuum-drying, grinds to form powdery, roasting 2 hours in 900 ℃, air atmosphere again, and 10 ℃/minute of temperature rise rates make magnetic nuclear NiFe
2O
4Obtain than uniformed powder with the standard sieve screening.
(2) homogeneous large grain size magnetic MgAl-CO
3-LDH/NiFe
2O
4Preparation
With Mg (NO
3)
26H
2O/NiFe
2O
4Mol ratio is 48 for example.Take by weighing 1.2307g Mg (NO
3)
26H
2O, 0.4503g Al (NO
3)
39H
2O and 0.7270g urea are dissolved in the 400ml deionized water and are made into mixing salt solution, with the NiFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; In 100 ℃ of following thermostatic crystallizations 48 hours, centrifugal, washing, 60 ℃ of dryings 16 hours promptly get homogeneous large grain size magnetic MgAl-CO
3-LDH/NiFe
2O
4
The grain-size that records this homogeneous large grain size magnetic hydrotalcite is in 2~10 micrometer ranges, and average grain size is 3.0 microns.The coercivity H value is 21kA/m, specific saturation magnetization б
xBe 4.25AM
2/ Kg.
Claims (3)
1. homogeneous large grain size magnetic hydrotalcite, it is characterized in that: chemical formula is: (N
2+)
1-x(M
3+)
x(OH)
2(CO
3 2-)
X/2MH
2O/M ' Fe
2O
4(N wherein
2+)
1-x(M
3+)
x(OH)
2(CO
3 2-)
X/2MH
2O is abbreviated as N-M-CO
3-LDH; M ' Fe
2O
4Be magnetic species; N-M-CO
3-LDH is for being coated on M ' Fe
2O
4Outer carbonate type hydrotalcite; Each constituent mass percentage composition is: M ' Fe
2O
4: 7%~55%, N-M-CO
3-LDH:93%~45%; Wherein N is divalent-metal ion Zn
2+Or Mg
2+, M is trivalent metal ion Al
3+, M ' is Co
2+, Mg
2+, Ba
2+, Zn
2+, Ni
2+Wherein any of divalent-metal ion, M and M '; X=M
3+/ (N
2++ M
3+), 0<x<1; M is the crystallization water number.
2. a method for preparing the described homogeneous large grain size magnetic hydrotalcite of claim 1 adopts coprecipitation method to prepare nano-scale magnetic nuclear earlier, with this magnetic core and corresponding salt solution mix, prepares the homogeneous large grain size hydrotalcite that contains magnetic core with Wyler's process; Concrete technology is:
A, nano-magnetic nuclear M ' Fe
2O
4Powder preparing
The soluble inorganic salt and two of M ', ferric soluble inorganic salt are mixed with mixing solutions, wherein (M '+Fe
2+)/Fe
3+Mol ratio is 1~5, M '/Fe
2+Mol ratio is 0.5~2; The volumetric molar concentration of M ' is 0.1~2.5M, Fe
3+Volumetric molar concentration be 0.2~5.0M; Use the NaOH alkaline solution, wherein the NaOH volumetric molar concentration is 0.1~5.0M; Under nitrogen protection alkali lye splashed in the salts solution to the pH value and equal 6~7,15~50 ℃ of crystallization are 4~48 hours in water-bath, reaction solution filtered, with taking off CO
2Deionized water wash is used absolute ethanol washing again, vacuum-drying, grinds to form powdery, obtains particle size range at the M ' of 200~800nm Fe through 800~1000 ℃ of high-temperature roastings
2O
4Powder; Obtain powder uniformly with the standard sieve screening;
B, homogeneous large grain size magnetic N-M-CO
3-LDH/M ' Fe
2O
4Preparation
With N (NO
3)
2, M (NO
3)
2Be dissolved in urea and be made into homogeneous mixture solotion, N in the deionized water
2+/ M
3+Mol ratio be 2~4, the volumetric molar concentration of divalent-metal ion is 10
-3~10
-1M, the volumetric molar concentration of trivalent metal ion is 10
-4~10
-1M, the volumetric molar concentration of urea is 5*10
-3~5*10
-2M; Press M ' Fe
2O
4With the mass ratio of divalence inorganic metal salt in the above-mentioned mixing salt solution be 1: 48~2.0, take by weighing corresponding M ' Fe
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; 60~180 ℃ of crystallization 24~180 hours, centrifugal, washing, 25~100 ℃ of dryings 6~72 hours.
3. method according to claim 2 is characterized in that: divalent iron salt is among the above-mentioned steps a: FeCO
3, FeSO
4, FeCl
2Or Fe (NO
3)
2In any; Trivalent iron salt is: Fe
2(CO
3)
3, Fe
2(SO
4)
3, FeCl
3, Fe (NO
3)
3In any; M ' salt is: M ' SO
4, M ' Cl
2, M ' (NO
3)
2In any, M ' is Co
2+, Mg
2+, Ba
2+, Zn
2+, Ni
2+Wherein any of divalent-metal ion.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008083563A1 (en) * | 2007-01-12 | 2008-07-17 | Beijing University Of Chemical Technology | A microsphere of layered double hydroxide and method for preparing the same |
CN109225220A (en) * | 2018-08-28 | 2019-01-18 | 北京化工大学 | It a kind of calcined hydrotalcite catalyst with magnetic core, preparation and is reacted for Benzyl Side-Chain carbaldehyde alkylization |
CN110354314A (en) * | 2019-07-30 | 2019-10-22 | 东南大学 | A kind of magnetic enhancement is mutually modified medical composite material bone repairing support and manufacturing method |
CN110354313A (en) * | 2019-07-30 | 2019-10-22 | 东南大学 | A kind of magnetic enhancement phase modified composite material and preparation method thereof |
CN112195479A (en) * | 2020-09-28 | 2021-01-08 | 沈阳理工大学 | Method for catalyzing water electrolysis by using magnetic field-assisted defect transition metal layered hydroxide |
-
2005
- 2005-06-24 CN CN 200510011996 patent/CN1297482C/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008083563A1 (en) * | 2007-01-12 | 2008-07-17 | Beijing University Of Chemical Technology | A microsphere of layered double hydroxide and method for preparing the same |
CN109225220A (en) * | 2018-08-28 | 2019-01-18 | 北京化工大学 | It a kind of calcined hydrotalcite catalyst with magnetic core, preparation and is reacted for Benzyl Side-Chain carbaldehyde alkylization |
CN110354314A (en) * | 2019-07-30 | 2019-10-22 | 东南大学 | A kind of magnetic enhancement is mutually modified medical composite material bone repairing support and manufacturing method |
CN110354313A (en) * | 2019-07-30 | 2019-10-22 | 东南大学 | A kind of magnetic enhancement phase modified composite material and preparation method thereof |
CN110354314B (en) * | 2019-07-30 | 2021-11-12 | 东南大学 | Magnetic reinforcing phase modified medical composite bone repair support and manufacturing method thereof |
CN110354313B (en) * | 2019-07-30 | 2021-12-07 | 东南大学 | Magnetic reinforcing phase modified composite material and preparation method thereof |
CN112195479A (en) * | 2020-09-28 | 2021-01-08 | 沈阳理工大学 | Method for catalyzing water electrolysis by using magnetic field-assisted defect transition metal layered hydroxide |
CN112195479B (en) * | 2020-09-28 | 2022-03-18 | 沈阳理工大学 | Method for catalyzing water electrolysis by using magnetic field-assisted defect transition metal layered hydroxide |
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