CN101279858A - Preparation of rare-earth oxide macroporous material - Google Patents
Preparation of rare-earth oxide macroporous material Download PDFInfo
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- CN101279858A CN101279858A CNA2008100520265A CN200810052026A CN101279858A CN 101279858 A CN101279858 A CN 101279858A CN A2008100520265 A CNA2008100520265 A CN A2008100520265A CN 200810052026 A CN200810052026 A CN 200810052026A CN 101279858 A CN101279858 A CN 101279858A
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Abstract
The invention is a process for preparing a rare earth oxide macroporous material, which takes rare-earth salts or rare earth oxides as sources of metal ions and an L-asparagine as an organic ligand, and adopts the method of hydro-thermal synthesis to prepare a macropore rare earth coordination polymer precursor {Ln[(Asp)m(Asn)n]}p. Wherein, the Ln is La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er and a plurality of mixtures thereof; and the Asp is an aspartic acid and the Asn is an asparagine. The obtained macropore rare earth coordination polymer is calcined in air, then the corresponding rare earth oxide macroporous material can be obtained. The rare earth oxide macroporous material prepared by the process of the invention has high yield and the macropore aperture is between 1 and 100 mu m. The process of preparation has advantages of environment protection, simplicity, low cost and easy mass production. The obtained material has good application prospect in fields such as catalysis, optics and chromatogram.
Description
Technical field
The invention belongs to the preparation method of the preparation field of porous material, particularly a kind of rare-earth oxide macroporous material.
Background technology
Large pore material (aperture＞50nm) comprise the macropore metal oxide, silicon-dioxide, macropore carbon material and superpolymer, in heterogeneous catalysis, separate organizational project, transmitter, fields such as electrode materials and chromatogram have important use (C.F.Blanford, H.Yan, R.C.Schroden, M.A1-Daous, A.Stein, Adv.Mater.2001,13,401; G.T.Chandrappa, N.Steunou, J.Livage, Nature 2002,416, and 702; D.Walsh, L.Arcelli, T.Ikoma, J.Tanaka, S.Mann, Nature Mater.2003,2,386).Generally speaking, large pore material can make by hard template and soft template method.Easy gas Bubbling method can prepare macropore foam materials (G.T.Chandrappa, N.Steunou, J.Livage, Nature 2002,416,702) by the process of collosol and gel.There is bibliographical information to pass through, can obtains the oxide material (E.S.Toberer, T.D.Schladt, R.Seshadri, J.Am.Chem.Soc.2006,128,1462) of macropore the phase selectivity elimination in the two-phase mixture.Chinese patent CN1339329 adopts the chemical enlargement agent to be prepared into the macroporous silicon dioxide carrier that mean pore size is 30～600nm through high-temperature roasting reaming method.
Amino acid is obtaining effective application aspect the growth of control mineral crystal, and simultaneously as a kind of environmental friendliness, lower-cost good bridgingligand has obtained important use in the rare-earth transition metal ligand polymer is synthetic.
With amino acid as part, utilize the hydrothermal synthesis method of no template obtained macropore rare earth coordination polymer presoma Ln[(Asp)
m(Asn)
n]
p, the macropore rare earth coordination polymer presoma roasting in air with gained promptly obtains rare-earth oxide macroporous material.The preparation method of this rare-earth oxide macroporous material proposition that still belongs to the first time, simple, environmentally friendly.The rare-earth oxide macroporous material of gained is in heterogeneous catalysis, and there is important use in fields such as optics.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of rare-earth oxide macroporous material, technology of the present invention is simple, good reproducibility, productive rate height.The synthesis condition gentleness, environmentally friendly, cost is low.
The preparation method of rare-earth oxide macroporous material of the present invention is metal ion source with rare-earth salts or rare earth oxide, with altheine as organic ligand, adopt hydro-thermal synthetic method prepare macropore rare earth coordination polymer presoma Ln[(Asp)
m(Asn)
n]
pLn=La wherein, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er and multiple mixing wherein; Asp is an aspartic acid, and Asn is a l-asparagine.Macropore rare earth coordination polymer roasting in air with obtaining promptly obtains corresponding rare-earth oxide macroporous material.
The step that the preparation method of rare-earth oxide macroporous material of the present invention comprises:
Approach A: with rare-earth salts as metal ion source
1) altheine with 6 mmoles is dissolved in 24 ml waters under the condition of 40-45 ℃ of heating.
2) under brute force stirs, the rare-earth salts of 0.5 mmole is joined in the aqueous solution of above-mentioned altheine, make that the pH value of solution is 3.0～5.0.
3) with 2) in gained solution move in 30 milliliters of reactors and seal, at 120-160 ℃ of reaction 12-120h down, after water and the raw spirit washing, 60 ℃ of dryings obtain macropore rare earth coordination polymer presoma.
4) resulting macropore rare earth coordination polymer presoma is promptly obtained corresponding rare-earth oxide macroporous material at 360 ℃ of-720 ℃ of roasting 1-5h.
Approach A) step 2 described in) middle-weight rare earths salt is rare earth nitrate, one or both mixing in the rare earth chloride.Rare earth element is one or more mixing in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, the erbium.
Approach B: with rare earth oxide as metal ion source
1) 0.25 mmole rare earth oxide is dissolved under the condition of 40-45 ℃ of heating in the 5-7 milliliter salpeter solution.
2) under agitation with 1) in solution mix with altheine solution.Add an amount of sodium hydroxide solution and water in gained solution, make that the solution final volume is 24 milliliters, the pH value is 3.0～5.0.
3) with step 3) among the A
4) with step 4) among the A
Approach B) the step 1) middle-weight rare earths oxide compound described in is one or more mixing in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, dysprosium oxide, the Erbium trioxide, and salpeter solution is with 0.5-2 milliliter 3 mol nitric acid and 4.5-5 ml water mixing gained.
Approach B) altheine solution is for to be dissolved in gained in the 13-15 ml water with 6 mmole altheines described step 2), and oxygen sodium oxide concentration is 2 mol.
The rare-earth oxide macroporous material productive rate height of the inventive method preparation, aperture, macropore hole is 1～100 μ m, these good character can be applicable to support of the catalyst, chromatogram, fields such as optics.
The rare-earth oxide macroporous material of the inventive method preparation has extensively adjustable composition (lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, lanthanum cerium, lanthanum europium etc.), and this is very favourable to its application.
The inventive method adopts cheaply amino acid as organic ligand, adopts the hydrothermal synthesis method of no template, and is environmentally friendly, simple, the productive rate height, and cost is low, is easy to scale operation
Description of drawings
The cerium dioxide large pore material sem photograph of Fig. 1 embodiment of the invention 1: (a, b) cerium dioxide large pore material scanning electron microscope picture.
The cerium dioxide large pore material XRD figure of Fig. 2 embodiment of the invention 1.
The europiumsesquioxide large pore material sem photograph of Fig. 3 embodiment of the invention 2: (a, b) europiumsesquioxide large pore material scanning electron microscope picture.
The europiumsesquioxide large pore material XRD figure of Fig. 4 embodiment of the invention 2.
Embodiment
Further describe feature of the present invention below by example, but the present invention is not limited to following example.
Embodiment 1
(1) altheine with 6 mmoles is dissolved in 24 ml waters under the condition of 45 ℃ of heating;
(2) under brute force stirs, seven water Cerium II Chlorides of 0.5 mmole are joined in the aqueous solution of above-mentioned altheine, make that the pH value of solution is 4.0;
(3) with 2) in gained solution move in 30 milliliters of reactors and seal, at 160 ℃ of reaction 12h down, after water and the raw spirit washing, 60 ℃ of dryings obtain the cerium coordination polymer macropore material;
(4) resulting cerium coordination polymer macropore material is promptly obtained corresponding cerium dioxide large pore material at 360 ℃ of roasting 1h, macropore diameter 5～20 μ m.
Embodiment 2
(1) 0.25 mmole europiumsesquioxide is dissolved in (1 milliliter of 3 mol nitric acid+4 ml water) in 5 milliliters of salpeter solutions under the condition of 45 ℃ of heating.
(2) under agitation with 1) in solution mix with altheine solution (the 6mmol altheine is dissolved in 15mL water).0.4 milliliter of 2 mol sodium hydroxide solution of adding and 3.6 ml waters make that the solution final volume is 24 milliliters in gained solution, and the pH value is 3.0.
(3) with step (3) among the embodiment 1, obtain the europium coordination polymer macropore material;
(4) resulting europium coordination polymer macropore material is promptly obtained corresponding europiumsesquioxide large pore material at 720 ℃ of roasting 2h, macropore diameter 1～100 μ m.
Claims (4)
1, a kind of preparation method of rare-earth oxide macroporous material is characterized in that the step that comprises:
Approach A: with rare-earth salts as metal ion source
1) altheine with 6 mmoles is dissolved in 24 ml waters under the condition of 40-45 ℃ of heating.
2) under brute force stirs, the rare-earth salts of 0.5 mmole is joined in the aqueous solution of above-mentioned altheine, make that the pH value of solution is 3.0～5.0.
3) with 2) in gained solution move in 30 milliliters of reactors and seal, at 120-160 ℃ of reaction 12-120h down, after water and the raw spirit washing, 60 ℃ of dryings obtain macropore rare earth coordination polymer presoma.
4) resulting macropore rare earth coordination polymer presoma is promptly obtained corresponding rare-earth oxide macroporous material at 360 ℃ of-720 ℃ of roasting 1-5h.
Approach A) step 2 described in) middle-weight rare earths salt is rare earth nitrate, one or both mixing in the rare earth chloride.Rare earth element is one or more mixing in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, the erbium.
Approach B: with rare earth oxide as metal ion source
1) 0.25 mmole rare earth oxide is dissolved under the condition of 40-45 ℃ of heating in the 5-7 milliliter salpeter solution.
2) under agitation with 1) in solution mix with altheine solution.Add an amount of sodium hydroxide solution and water in gained solution, make that the solution final volume is 24 milliliters, the pH value is 3.0～5.0.
3) with step 3) among the A
4) with step 4) among the A
Approach B) the step 1) middle-weight rare earths oxide compound described in is one or more mixing in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, dysprosium oxide, the Erbium trioxide, and salpeter solution is with 0.5-2 milliliter 3 mol nitric acid and 4.5-5 ml water mixing gained.
Approach B) altheine solution is for to be dissolved in gained in the 13-15 ml water with 6 mmole altheines described step 2), and naoh concentration is 2 mol.
2, the method for claim 1 is characterized in that the described step 1) of approach A, and in the described step 1) of approach B, amino acid ligand is an altheine;
3, the method for claim 1 is characterized in that the described step 2 of approach A) in metal ion source be rare-earth salts, the metal ion source is rare earth oxide in the described step 1) of approach B.
4, the method for claim 1 is characterized in that the described step 3) of approach A, in the described step 3) of approach B, the presoma of rare-earth oxide macroporous material be the macropore rare earth coordination polymer Ln[(Asp)
m(Asn)
n]
p
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241696A (en) * | 2011-04-02 | 2011-11-16 | 太原科技大学化学与生物工程学院 | Preparation method of rare earth coordination polymer crystal |
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN114870827A (en) * | 2022-05-13 | 2022-08-09 | 南开大学 | Preparation method of cerium lanthanum composite oxide carrier, platinum-loaded catalyst and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202006C (en) * | 2003-01-30 | 2005-05-18 | 复旦大学 | Kinds of materials with multiple constituents of big bores oxide media and its preparing method |
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2008
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241696A (en) * | 2011-04-02 | 2011-11-16 | 太原科技大学化学与生物工程学院 | Preparation method of rare earth coordination polymer crystal |
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103058724B (en) * | 2012-09-22 | 2014-12-03 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN114870827A (en) * | 2022-05-13 | 2022-08-09 | 南开大学 | Preparation method of cerium lanthanum composite oxide carrier, platinum-loaded catalyst and application thereof |
| CN114870827B (en) * | 2022-05-13 | 2023-06-16 | 南开大学 | Preparation method of cerium-lanthanum composite oxide carrier, platinum-loaded catalyst and application thereof |
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