CN102976417A - Preparation method and application of layered double-metal hydroxides containing transition metal - Google Patents
Preparation method and application of layered double-metal hydroxides containing transition metal Download PDFInfo
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- CN102976417A CN102976417A CN2012104303146A CN201210430314A CN102976417A CN 102976417 A CN102976417 A CN 102976417A CN 2012104303146 A CN2012104303146 A CN 2012104303146A CN 201210430314 A CN201210430314 A CN 201210430314A CN 102976417 A CN102976417 A CN 102976417A
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Abstract
The invention relates to a preparation method and application of layered double-metal hydroxides (LDHs) containing a transition metal. The preparation method comprises the following steps: dissolving a soluble divalent metal salt and a soluble trivalent metal salt in water to obtain a solution A; dissolving a soluble alkali in water to obtain an alkaline solution B; slowly adding the solution A and the alkaline solution B into a reaction bottle drop by drop at the same time for mixing and carrying out violent stirring; and subjecting mixed suspension to repeated centrifugation and flushing until the suspension is neutral and then to drying and grinding so as to obtain target products, i.e., transition metal LDHs, which can be used as an active catalyst for oxidation of the persistent refractory organic matter nitrobenzene in water. According to the invention, structural characteristics and properties of LDHs and chemical activity of transition metal hydroxides are combined, so the target products present excellent catalysis performance; the LDHs are used as a carrier, the transition metal is introduced and used as an important component of a laminate, activity of the transition metal can be fully utilized, so more catalytic active sites are provided, a catalysis effect is greatly improved, and the LDHs and the transition metal can be recycled.
Description
Technical field
The invention belongs to the technical field of layered double hydroxide (LDHs) material preparation, be specifically related to a kind of preparation method who contains the layered double hydroxide of transition metal, and as active catalyst and the application thereof of oxidation biodegradable organic compounds oil of mirbane in the water treatment.
Background technology
Layered double hydroxide (LDHs) claim again hydrotalcite-type compound or anionic clay, its structure and brucite (Mg (OH)
2) laminate structure is similar.This material is comprised of the laminate that is parallel to each other, and is positioned at the divalent metal M on the laminate
IICan be by the close trivalent metal cation M of ionic radius in certain proportional range
IIIIsomorphous substitution is so that laminate band permanent positive charge; Interlayer has tradable negatively charged ion to keep charge balance.The chemical constitution of LDHs has following general formula: [M
II 1-xM
III x(OH)
2]
X+[A
N- X/nMH
2O], M wherein
IIAnd M
IIIBe respectively divalence and trivalent metal cation, be positioned on the main body laminate; A
N-Be interlayer anion; X is M
3+/ (M
2++ M
3+) molar ratio; M is the number of middle water molecule.Because LDHs has the restorability of Modulatory character, structure of special laminate chemical constitution, interlayer anion kind and quantity, grain size distribution and soda acid bi-functional etc. and is paid attention to widely in absorption, catalysis, environment, medicine, electrochemistry, photochemistry, agricultural chemicals, nano material, military project material, filed of functional, is the novel inorganic functional materials that a class has wide application prospect.
Transition metal is owing to exist different oxidation state, thereby possesses unique physics, chemical property, is widely used in the fields such as electromagnetism, photoelectricity and catalysis.Studies show that the oxide catalyst of transition metal oxide, particularly Cu, Mn, Cr, Co and Ni has very high catalytic activity.For LDHs, that people's most study is Mg up to now
3Al-CO
3-LDHs, and less for the LDHs bibliographical information that contains transition metal, the domestic LDHs bibliographical information that transient metal Mn not yet occurs containing.
Summary of the invention
The invention provides a kind of simple to operate, preparation method and application thereof of layered double hydroxide that regulation and control contain transition metal LDHs easily, purpose is that the basic physical and chemical performance of LDHs and the peculiar property of transition metal are combined, and is applied in the water treatment hardly degraded organic substance be carried out catalyzed oxidation as catalyzer.
The preparation method of the layered double hydroxide that contains transition metal that the present invention proposes, utilize the constant pH coprecipitation method, reaction solution pH is kept under certain condition, will consist of metal ion mixing salt solution and the mixed ammonium/alkali solutions generation co-precipitation of LDHs, concrete steps are as follows:
(1) with solubility divalent metal salt M
IIWith solubility trivalent metal salt M
IIISolution obtains mixed salt solution A in deionized water; It is Co that described divalent metal salt adopts divalent-metal ion
2+, trivalent metal salt adopts trivalent metal ion Mn
3+Or Al
3+, and make mixing salt solution Atom ratio equal (2 ~ 4): 1;
(2) water soluble alkali is dissolved in the deionized water, obtains mixed alkali liquor B;
(3) mixed salt solution A and mixed alkali liquor B are slowly splashed in the glass reactor simultaneously, regulate flow velocity, vigorous stirring keeps reacting liquid pH value constant, this reaction suspension crystallization under constant temperature; Crystallization temperature is controlled at 25 ~ 60 ℃, and crystallization time is 2.0 ~ 6.0 h;
(4) reaction suspension that step (3) is made is after centrifugation, and to neutral, oven dry is ground, and makes target product with deionized water wash.
Among the present invention, described in the step (1) in solubility divalent metal salt or the solubility trivalent metal salt negatively charged ion be NO
3-Or Cl
-Deng being easy to exchanged ion.
Among the present invention, water soluble alkali is Na described in the step (2)
2CO
3With the NaOH mixed solution, and OH in the mixed alkali liquor
- :CO
3 2-Mol ratio be (4 ~ 8)
:1.
Among the present invention, the pH value remains alkalescence 10～11 in the step (3), and is relevant with the trivalent metal ion kind with selected divalent-metal ion.
Among the present invention, there are important impact crystallization temperature, time on the crystalline structure of material, and need strictly control: crystallization temperature is controlled at 25 ~ 60 ℃, crystallization time 2.0 ~ 6.0 h.
The layered double hydroxide that contains transition metal of gained of the present invention is applied to the nitrobenzene oxidation reaction as catalyzer.
The present invention has following advantage: adopt the constant pH coprecipitation method that transition metal is introduced layered double hydroxide, the method is simple to operate, regulation and control are convenient, can be effectively in conjunction with the property of layered double hydroxide and transition metal, thereby provide more catalytic active center, significantly improve the catalytic activity of material, and easily realize the recycle of material.
Description of drawings
Fig. 1 is the powder X-ray RD diffracting spectrum of the layered double hydroxide of embodiment 1-3 preparation.Wherein a is the XRD diffracting spectrum of Co4Al2-LDH among the embodiment 1, and b is the XRD diffracting spectrum of Co4MnAl-LDH among the embodiment 2, and c is the XRD diffracting spectrum of Co4Mn2-LDH among the embodiment 3.
Fig. 2 is the TEM photo of the layered double hydroxide of embodiment 1-3 preparation.Wherein a is the TEM photo of Co4Al2-LDH among the embodiment 1, and b is the TEM photo of Co4MnAl-LDH among the embodiment 2, and c is the TEM photo of Co4Mn2-LDH among the embodiment 3.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:The preparation of Co4Al2-LDH
Co (the NO of preparation proper ratio
3)
2And Al (NO
3)
3Mixing solutions 250 ml, so that atoms metal equals 2 than Co/Al, total concentration of metal ions equals 1.0 mol/L; Compound concentration is that 0.5 mol/L and NaOH concentration are mixed alkali liquor 500 ml of 3.0 mol/L; Metal salt solution and mixed alkali liquor are slowly splashed into glass reactor simultaneously carry out coprecipitation reaction, vigorous stirring, reacting solution pH value maintains 10.0; Glass reactor is placed 25 ℃ of waters bath with thermostatic control, continue violent magnetic agitation 2.0 h; Suspension is carried out repeatedly centrifugation, and it is approaching neutral to pH repeatedly to wash product with deionized water; Product is dried under 60 ° of C conditions, mill, obtain target product Co4Al2-LDH.
Embodiment 2:The preparation of Co4MnAl-LDH
Co (the NO of preparation proper ratio
3)
2, Mn (NO
3)
2And Al (NO
3)
3Mixing solutions 250 ml, so that atoms metal equals 2 than Co/ (Mn+Al), total concentration of metal ions equals 1.0 mol/L; Compound concentration is that 0.5 mol/L and NaOH concentration are mixed alkali liquor 500 ml of 3.0 mol/L; Metal salt solution and mixed alkali liquor are slowly splashed into glass reactor simultaneously carry out coprecipitation reaction, vigorous stirring, reacting solution pH value maintains 10.0; Glass reactor is placed 25 ℃ of waters bath with thermostatic control, continue violent magnetic agitation 2.0 h; Suspension is carried out repeatedly centrifugation, and it is approaching neutral to pH repeatedly to wash product with deionized water; Product is dried under 60 ° of C conditions, mill, obtain target product Co4MnAl-LDH.
Embodiment 3:The preparation of Co4Mn2-LDH
Co (the NO of preparation proper ratio
3)
2And Mn (NO
3)
2Mixing solutions 250 ml, so that atoms metal equals 2 than Co/Mn, total concentration of metal ions equals 1.0 mol/L; Compound concentration is that 0.5 mol/L and NaOH concentration are mixed alkali liquor 500 ml of 3.0 mol/L; Metal salt solution and mixed alkali liquor are slowly splashed into glass reactor simultaneously carry out coprecipitation reaction, vigorous stirring, reacting solution pH value maintains 10.0; Glass reactor is placed 25 ℃ of waters bath with thermostatic control, continue violent magnetic agitation 2.0 h; Suspension is carried out repeatedly centrifugation, and it is approaching neutral to pH repeatedly to wash product with deionized water; Product is dried under 60 ° of C conditions, mill, obtain target product Co4Mn2-LDH.
X-ray powder diffraction (XRD) and TEM test result show that material is nanoplatelet, and have the constitutional features of layered double hydroxide.
Embodiment 4:The application of LDHs catalyzed oxidation organic pollutants
Material can be applicable in hydrogen peroxide and the ozone oxidation system.Ozone oxidation system: Co4Al2-LDH, Co4MnAl-LDH and Co4Mn2-LDH dosage: 0.5 g/L; Ozone dosage: 1.0 ~ 1.5mg/L, choosing oil of mirbane is Typical Organic Pollutants, nitrobenzene degradation efficient reaches respectively 39.8%, 47.2% and 59.5%, and ozone oxidation p-nitrophenyl degradation rate only is 13.2 % separately.In the hydrogen peroxide oxidation system: Co4Al2-LDH, Co4MnAl-LDH and Co4Mn2-LDH dosage: 1.0 g/L; Hydrogen peroxide dosage: 400 ~ 800mg/L, choosing oil of mirbane is Typical Organic Pollutants, wherein the Co4Al2-LDH degradation efficiency is best, reaches 64.8 %, and hydrogen peroxide oxidation p-nitrophenyl degradation rate only is 22.2 % separately.The nitrobenzene oxidation degraded product has 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and phenol, and product ion has formate, acetate moiety, nitrate radical and nitrite anions.
Claims (5)
1. preparation method who contains the layered double hydroxide of transition metal, utilize the constant pH coprecipitation method, it is characterized in that making reaction solution pH to keep under certain condition, will consist of metal ion mixing salt solution and the mixed ammonium/alkali solutions generation co-precipitation of LDHs, concrete steps are as follows:
With solubility divalent metal salt M
IIWith solubility trivalent metal salt M
IIISolution obtains mixed salt solution A in deionized water; It is Co that described divalent metal salt adopts divalent-metal ion
2+, trivalent metal salt adopts trivalent metal ion Mn
3+Or Al
3+, and make in the mixing salt solution
Atomic ratio equals (2 ~ 4)
:1;
Water soluble alkali is dissolved in the deionized water, obtains mixed alkali liquor B;
Mixed salt solution A and mixed alkali liquor B are slowly splashed in the glass reactor simultaneously, regulate flow velocity, vigorous stirring keeps reacting liquid pH value constant, this reaction suspension crystallization under constant temperature; Crystallization temperature is controlled at 25 ~ 60 ℃, and crystallization time is 2.0 ~ 6.0 h;
The reaction suspension that step (3) is made is after centrifugation, and to neutral, oven dry is ground, and makes target product with deionized water wash.
2. preparation method according to claim 1 is characterized in that negatively charged ion is NO in solubility divalent metal salt described in the step (1) or the solubility trivalent metal salt
3-Or Cl
-
3. preparation method according to claim 1 is characterized in that water soluble alkali is Na described in the step (2)
2CO
3With the NaOH mixed solution, and OH in the mixed alkali liquor
- :CO
3 2-Mol ratio be (4 ~ 8)
:1.
4. preparation method according to claim 1 is characterized in that the pH value is 10～11 in the step (3), and is relevant with the trivalent metal ion kind with selected divalent-metal ion.
One kind as claimed in claim 1 the transition metal stratiform double-metal hydroxide that obtains of preparation method as the application of catalyzer in the oxidation oil of mirbane process.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098201A (en) * | 2015-07-08 | 2015-11-25 | 青岛大学 | Preparation method of platinum/layered bimetal oxide methanol fuel cell catalyst |
| CN111974400A (en) * | 2020-07-31 | 2020-11-24 | 浙江天地环保科技股份有限公司 | Composite nano material based on layered double hydroxides and preparation and application thereof |
| CN112221515A (en) * | 2020-11-16 | 2021-01-15 | 常州大学 | Mn (III) -containing hydrotalcite-like catalyst, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616495A (en) * | 2003-11-13 | 2005-05-18 | 北京化工大学 | Preparing nano sheet type polymer using LDHs as template and its preparing method |
| CN101177466A (en) * | 2007-10-30 | 2008-05-14 | 中山大学 | Method for in-situ preparation of polyethylene-LDHs nano composite material by organic modified LDHs loaded acenaphthenequinonediimine nickel catalyst |
-
2012
- 2012-11-01 CN CN2012104303146A patent/CN102976417A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616495A (en) * | 2003-11-13 | 2005-05-18 | 北京化工大学 | Preparing nano sheet type polymer using LDHs as template and its preparing method |
| CN101177466A (en) * | 2007-10-30 | 2008-05-14 | 中山大学 | Method for in-situ preparation of polyethylene-LDHs nano composite material by organic modified LDHs loaded acenaphthenequinonediimine nickel catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 隋铭皓等: "Co-Mn-Al层状双氢氧化物催化臭氧氧化水中有机污染物的活性", 《催化学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098201A (en) * | 2015-07-08 | 2015-11-25 | 青岛大学 | Preparation method of platinum/layered bimetal oxide methanol fuel cell catalyst |
| CN105098201B (en) * | 2015-07-08 | 2016-05-04 | 青岛大学 | A kind of platinum/layered bi-metal oxide methanol fuel cell catalyst preparation method |
| CN111974400A (en) * | 2020-07-31 | 2020-11-24 | 浙江天地环保科技股份有限公司 | Composite nano material based on layered double hydroxides and preparation and application thereof |
| CN112221515A (en) * | 2020-11-16 | 2021-01-15 | 常州大学 | Mn (III) -containing hydrotalcite-like catalyst, preparation method and application thereof |
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Application publication date: 20130320 |