CN102167290A - Method for synthesizing hydrotalcite like compound nano particles by room temperature solid phase method - Google Patents
Method for synthesizing hydrotalcite like compound nano particles by room temperature solid phase method Download PDFInfo
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- CN102167290A CN102167290A CN 201110006908 CN201110006908A CN102167290A CN 102167290 A CN102167290 A CN 102167290A CN 201110006908 CN201110006908 CN 201110006908 CN 201110006908 A CN201110006908 A CN 201110006908A CN 102167290 A CN102167290 A CN 102167290A
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- ldh
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Abstract
The invention discloses a method for synthesizing hydrotalcite like compound nano particles by a room temperature solid phase method. The method comprises the following steps of: adding a mixture of solid M<2+> and M<3+> metal salt, alkali and carbonate which is ground until the mixture has certain fineness in advance in to a mortar according to certain proportion at room temperature, grinding at uniform speed until the mixture is dried, and performing centrifugal washing by using distilled water for 3 to 4 times to obtain nano M(II)/M(III)-LDH precursors; dispersing the obtained precursors in secondary distilled water, and peptizing at the temperature of between 60 and 100 DEG C to obtain M(II)/M(III)-LDH size; and performing vacuum drying on the M(II)/M(III)-LDH size to obtain M(II)/M(III)-LDH nano particles. Solid-phase reaction is performed at room temperature, crystallization is performed under normal pressure, the method is easy to operate, and various hydrotalcite like compound nano particles with high dispersibility can be synthesized.
Description
Technical field
The present invention relates to a kind of synthetic method of hydrotalcite-based compound, especially be particularly related to a kind of method of indoor temperature solid phase method synthesis hydrotalcite-like material nanoparticle.
Background technology
Layered double hydroxide LDHs(Layered Double Hydroxides) claims houghite (Hydrotalcite-like Compounds again, HTlcs) or mixed metal hydroxides (Mixed Metal Hydroxides, MMHs), be that a kind of interlayer has commutative anionic lamellar compound, its composition can be expressed as with chemical general formula: [M
2+ 1-xM
3+ x(OH)
2]
X+A
N- X/nMH
2O.M wherein
2+And M
3+Be respectively divalence and trivalent metal cation, be positioned at the octahedral interstices on the main body laminate, x is M
3+The mark of amount, i.e. x=M
3+/ (M
2++ M
3+); A
N-Be interlayer anion,
mBe interlayer crystal water number.Typical LDH compound is Mg-Al-LDH-CO
3On the synusia of houghite owing to trivalent metal ion isomorphous substitution part divalent-metal ion has the residue positive charge, this electric charge that is produced by crystalline structure itself and ambient conditions are (as the pH of dispersion medium, dielectric medium etc.) irrelevant, so be called permanent positive charge.For keeping electric neutrality, in passage, exist negatively charged ion with the balance lamella with the residue positive charge.Negatively charged ion in the passage can exchange, and relevant with ambient conditions (pH value, ionogen etc.), thereby houghite is also sometimes referred to as anionic clay.Layered double hydroxide LDHs has the electrical properties of uniqueness and the concern that wide prospect in industrial application obtains academia and industry member because of it.
Hydrotalcite-based compound is because its rich choice of products, Halogen low toxicity, easily characteristic such as preparation and particular structure and electrical property is just becoming the emphasis of functional material exploitation, they have widely in various fields such as catalyzer, support of the catalyst, sterilant, sewage-treating agent, electrorheological conditioning agent, medicine, medical carriers uses, and along with nano materials research deeply and the exploitation of novel process, the expansion of hydrotalcite-based compound preparation of industrialization and Application Areas will progressively realize.In fact, houghite family has formed the very potential mineral compound of class family.
The most frequently used synthetic method of hydrotalcite is exactly a coprecipitation method, promptly with the mixing solutions of solubility divalence that constitutes the hydrotalcite layer and trivalent metal cation co-precipitation takes place under the effect of alkali at a certain temperature and prepare, primary process comprises steps such as precipitation, crystallization, washing.Other houghite synthetic methods are a lot, but method in common is all carried out in solution at present, are mixing solutions and alkali mixing formation slurries, again in autoclave the crystallization of elder generation with metallic cation as hydrothermal method.Obtain the good hydrotalcite sample of degree of crystallinity, need the pH value and the crystallization aftertreatment of suitable ratio of components, strict control solution, settling step gained slurries place autoclave, hydro-thermal static crystallization under comparatively high temps, better than crystallization gained hydrotalcite crystalline form under normal temperature, normal pressure, crystal grain is bigger.Problems such as the houghite particle morphology that the aforesaid method ubiquity is synthesized is inhomogeneous, agglomeration serious, solvent treatment trouble, these problems have seriously hindered the industrial application of houghite.
Summary of the invention
The object of the present invention is to provide a kind of method of indoor temperature solid phase method synthesis hydrotalcite-like material nanoparticle, described method adopts indoor temperature solid phase method synthesis hydrotalcite-like material compound, can overcome problems such as the resulting houghite product of existing synthetic method crystalline form is inhomogeneous, agglomeration is serious, synthesize good dispersity, uniform acrylic/hydrotalcite-like nano particle, expand the industrial application of houghite greatly.
The present invention adopts following technical scheme: a kind of method of indoor temperature solid phase method synthesis hydrotalcite-like material nanoparticle may further comprise the steps:
1) under the room temperature, in advance respectively with solid M
2+And M
3+Metal-salt, alkali and carbonate are ground to certain fineness, take by weighing M by a certain percentage
2+And M
3+Metal-salt is an amount of, adds to fill in the mortar of alkali and carbonate mixture, at the uniform velocity is ground to the mixture drying, uses distilled water centrifuge washing 3 ~ 4 times, makes nanometer M
(II)/ M
(III)-LDH precursor;
2) the resulting precursor of step 1) is scattered in the redistilled water, puts into baking oven, 60 ~ 100 ℃ of following peptizations get M
(II)/ M
(III)-LDH slurries;
3) M
(II)/ M
(III)The vacuum-drying of-LDH slurries promptly gets M
(II)/ M
(III)-LDH nanoparticle.
Described divalent metal M
2+Comprise Mg
2+, Zn
2+, Ni
2+, Cu
2+Or Co
2+, trivalent metal cation M
3+Comprise Al
3+, Fe
3+Or Cr
3+M
2+Metal-salt and M
3+The amount of substance of metal-salt is than being 2:1 ~ 4:1.
Described metal-salt can adopt nitrate, vitriol or muriate, preferably nitrate.
Described alkali can adopt sodium hydroxide or potassium hydroxide etc.
Described carbonate can adopt yellow soda ash or salt of wormwood etc.
In described alkali and the carbonate mixture, alkali is 16:1 with the amount ratio of carbonate material.
Described M
3+Metal-salt is 1:9 with the amount of substance ratio of alkali.
Step 2) in, the peptization time of precursor is 16 ~ 20h.
All reaction process of the inventive method all are room temperature reactions, compare with traditional high temperature solid state reaction, have saved a large amount of energy.Resulting acrylic/hydrotalcite-like nano particle is through X-ray diffraction analysis, the bright LDH nanoparticle of XRD figure stave degree of crystallinity height, and crystal formation is full.TEM figure shows the houghite even particle size that makes, and is hexagonal plate, regular shape.Its size-grade distribution meets normal distribution, and the sample monodispersity is good.
The inventive method is at room temperature carried out solid state reaction, and crystallization under the normal pressure is simple to operate, can synthesize the acrylic/hydrotalcite-like nano particle of various favorable dispersities.Specifically, the inventive method has the following advantages:
1, use solid phase method, operating procedure is simple, does not need solvent and auxiliary reagent, and the operation of equipment expense is low, pollutes and lacks, and saves the energy.Not using solvent in the building-up process, thereby can avoid the agglomeration that occurs in liquid phase is synthetic, is a kind of method of simple possible of synthesizing the LDH nanoparticle of good dispersity;
2, synthesis condition gentleness, the particle morphology rule, monodispersity is good;
3, the preparation method is reliable, good reproducibility;
4, owing to do not use any solvent in the preparation process, particle surface is cleaner.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited by claim.
Description of drawings
Fig. 1 Mg
3-Al-CO
3The XRD figure of-LDH powder;
Fig. 2 Mg
3-Al-CO
3The TEM figure of-LDH nanoparticle;
Fig. 3 Mg
3-Al-CO
3The particle size distribution figure of-LDH nanoparticle;
Fig. 4 Mg
2-Al-CO
3The TEM figure of-LDH nanoparticle;
Fig. 5 Mg
2-Al-CO
3The particle size distribution figure of-LDH nanoparticle;
Fig. 6 Ni
3-Al-CO
3The XRD figure of-LDH powder;
Fig. 7 Ni
3-Al-CO
3The TEM figure of-LDH nanoparticle;
Fig. 8 Mg
3-Fe-CO
3The TEM figure of-LDH nanoparticle;
Fig. 9 Zn
3-Al-CO
3The TEM figure of-LDH nanoparticle.
Embodiment
Adopt the synthetic Mg of the inventive method
3-Al-CO
3-LDH nanoparticle may further comprise the steps:
(1) under the room temperature, at first respectively to Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O, Na
2CO
3Grind 2min in advance with NaOH, take by weighing 0.7692g Mg (NO again
3)
26H
2O and 0.3751g Al (NO
3)
39H
2The O(amount of substance is than being 3:1), be added to and fill 0.0596g Na
2CO
3With (Na in the mortar of 0.36g NaOH mixture
2CO
3Be 1:16 with NaOH amount of substance ratio), manually at the uniform velocity grind 30～100min, to the mixture drying.With distilled water centrifuge washing 3 ~ 4 times, promptly get nanometer LDH precursor.
(2) precursor is scattered in the 20ml redistilled water, puts into baking oven, 80 ℃ of following peptization 20h have just obtained the Mg of regular shape, favorable dispersity
3-Al-CO
3-LDH slurries.
(3) Mg
3-Al-CO
3The vacuum-drying of-LDH slurries promptly gets Mg
3-Al-CO
3-LDH nano material.
Resulting Mg
3-Al-CO
3The XRD figure of-LDH nanoparticle spectrum as shown in Figure 1, Fig. 1 shows: (003), (006) peak height and sharp-pointed illustrates the Mg that obtains
3-Al-CO
3-LDH nanoparticle degree of crystallinity height, crystal formation is full.
TEM schemes as shown in Figure 2, and Fig. 2 shows the houghite even particle size that makes, and is hexagonal plate, regular shape.According to the particle size distribution figure (see figure 3) as can be known, fine with indoor temperature solid phase method synthetic sample monodispersity, meet normal distribution.
According to the synthetic Mg of the method identical with embodiment 1
2-Al-CO
3-LDH nanoparticle changes Mg (NO
3)
26H
2O and Al (NO
3)
39H
2The amount of substance of O is than being 2:1, and other conditions remain unchanged, the synthetic Mg that obtains
2-Al-CO
3-LDH nanoparticle.
Mg
2-Al-CO
3The TEM figure of-LDH nanoparticle and particle size distribution figure such as Fig. 4, shown in Figure 5 of nanoparticle, the result shows the Mg that obtains
2-Al-CO
3-LDH nano particle still keeps good dispersiveness and regular appearance.
According to the synthetic Mg of the method identical with embodiment 1
4-Al-CO
3-LDH nanoparticle changes Mg (NO
3)
26H
2O and Al (NO
3)
39H
2The amount of substance of O is than being 4:1, and other conditions remain unchanged, the synthetic Mg that obtains
4-Al-CO
3-LDH nanoparticle.
Embodiment 4
Adopt the synthetic Ni of the inventive method
3-Al-CO
3-LDH nanoparticle may further comprise the steps:
(1) under the room temperature, at first respectively to Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O, Na
2CO
3Grind 2min in advance with NaOH, take by weighing 0.8724g Ni (NO again
3)
26H
2O and 0.3751g Al (NO
3)
39H
2The O(amount of substance is than being 3:1), be added to and fill 0.0596g Na
2CO
3With (Na in the mortar of 0.36g NaOH mixture
2CO
3Be 1:16 with NaOH amount of substance ratio), manually at the uniform velocity grind 30～100min, to the mixture drying.With distilled water centrifuge washing 3 ~ 4 times, promptly get nanometer LDH precursor.
(2) precursor is scattered in the 20ml redistilled water, puts into baking oven, 80 ℃ of following peptization 20h have just obtained the Ni of regular shape, favorable dispersity
3-Al-CO
3-LDH slurries.
(3) Ni
3-Al-CO
3The vacuum-drying of-LDH slurries promptly gets Ni
3-Al-CO
3-LDH nano material.
By the XRD figure (see figure 6), resulting as can be known Ni
3-Al-CO
3-LDH nanoparticle crystal formation is full, and favorable dispersity, and its TEM figure sees Fig. 7.
Embodiment 5
According to the synthetic Mg of the method identical with embodiment 1
3-Fe-CO
3-LDH nanoparticle, used metal-salt are Mg (NO
3)
26H
2O and Fe (NO
3)
39H
2O, wherein Mg (NO
3)
26H
2O and Fe (NO
3)
39H
2The amount of substance of O is than being 3:1, and other conditions remain unchanged, the synthetic Mg that obtains
3-Fe-CO
3-LDH nanoparticle.Mg
3-Fe-CO
3The TEM of-LDH nanoparticle schemes as shown in Figure 8, and the result shows the Mg that obtains
3-Fe-CO
3-LDH nano particle still keeps good dispersiveness and regular appearance.
Embodiment 6
According to the synthetic Zn of the method identical with embodiment 1
3-Al-CO
3-LDH nanoparticle, used metal-salt are Zn (NO
3)
26H
2O and Al (NO
3)
39H
2O, wherein Zn (NO
3)
26H
2O and Al (NO
3)
39H
2The amount of substance of O is than being 3:1, and other conditions remain unchanged, the synthetic Zn that obtains
3-Al-CO
3-LDH nanoparticle.Zn
3-Al-CO
3The TEM of-LDH nanoparticle schemes as shown in Figure 9, and the result shows the Zn that obtains
3-Al-CO
3-LDH nano particle still keeps good dispersiveness and regular appearance.
Claims (8)
1. the method for an indoor temperature solid phase method synthesis hydrotalcite-like material nanoparticle may further comprise the steps:
1) under the room temperature, in advance respectively with solid M
2+And M
3+Metal-salt, alkali and carbonate are ground to certain fineness, take by weighing M by a certain percentage
2+And M
3+Metal-salt is an amount of, adds to fill in the mortar of alkali and carbonate mixture, at the uniform velocity is ground to the mixture drying, uses distilled water centrifuge washing 3 ~ 4 times, makes nanometer M
(II)/ M
(III)-LDH precursor;
2) the resulting precursor of step 1) is scattered in the redistilled water, puts into baking oven, 60 ~ 100 ℃ of following peptizations get M
(II)/ M
(III)-LDH slurries;
3) M
(II)/ M
(III)The vacuum-drying of-LDH slurries promptly gets M
(II)/ M
(III)-LDH nanoparticle.
2. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: described divalent metal M
2+Be Mg
2+, Zn
2+, Ni
2+, Cu
2+Or Co
2+, trivalent metal cation M
3+Be Al
3+, Fe
3+Or Cr
3+
3. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: described M
2+Metal-salt and M
3+The amount of substance of metal-salt is than being 2:1 ~ 4:1.
4. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: described metal-salt adopts nitrate, vitriol or muriate.
5. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: described alkali adopts sodium hydroxide or potassium hydroxide.
6. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: in described alkali and the carbonate mixture, alkali is 16:1 with the amount ratio of carbonate material.
7. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: described M
3+Metal-salt is 1:9 with the amount of substance ratio of alkali.
8. the method for synthesis hydrotalcite-like material nanoparticle according to claim 1 is characterized in that: step 2) in, the peptization time of precursor is 16 ~ 20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641507A (en) * | 2012-05-15 | 2012-08-22 | 山东炳坤腾泰陶瓷科技有限公司 | Preparation method for methotrexate/layered double hydroxide nanocomposite |
| CN107513240A (en) * | 2017-09-26 | 2017-12-26 | 山东农业大学 | A kind of houghite based high molecular polymer heat preserving master batch and preparation method thereof |
| CN107824798A (en) * | 2017-09-18 | 2018-03-23 | 山东炳坤腾泰陶瓷科技股份有限公司 | The preparation method of the sandwich core-shell nano materials of Au@LDH MTX |
| CN111448286A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Layered double hydroxide for oil-based drilling fluids |
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| US20070022916A1 (en) * | 2005-08-01 | 2007-02-01 | Laila Raki | Controlled release of chemical admixtures |
| CN101746734A (en) * | 2008-12-01 | 2010-06-23 | 中国科学院过程工程研究所 | Hydrotalcite preparation method |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070022916A1 (en) * | 2005-08-01 | 2007-02-01 | Laila Raki | Controlled release of chemical admixtures |
| CN101746734A (en) * | 2008-12-01 | 2010-06-23 | 中国科学院过程工程研究所 | Hydrotalcite preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 《人工晶体学报》 20101031 于洪波等 机械力化学法合成Mg-Al类水滑石研究 1292-1296，1307 1-8 第39卷, 第5期 * |
| 《材料导报》 20090131 杜宝中等 室温固相法合成纳米Mg-Al－CO3 层状双金属氢氧化物 77-79 1-8 第23卷, 第1期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641507A (en) * | 2012-05-15 | 2012-08-22 | 山东炳坤腾泰陶瓷科技有限公司 | Preparation method for methotrexate/layered double hydroxide nanocomposite |
| CN102641507B (en) * | 2012-05-15 | 2013-05-15 | 山东炳坤腾泰陶瓷科技有限公司 | Preparation method for methotrexate/layered double hydroxide nanocomposite |
| CN111448286A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Layered double hydroxide for oil-based drilling fluids |
| CN107824798A (en) * | 2017-09-18 | 2018-03-23 | 山东炳坤腾泰陶瓷科技股份有限公司 | The preparation method of the sandwich core-shell nano materials of Au@LDH MTX |
| CN107513240A (en) * | 2017-09-26 | 2017-12-26 | 山东农业大学 | A kind of houghite based high molecular polymer heat preserving master batch and preparation method thereof |
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Application publication date: 20110831 |