CN1308077C - Preparation of metal complex aluminium phosphate molecular sieve composite material - Google Patents
Preparation of metal complex aluminium phosphate molecular sieve composite material Download PDFInfo
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- CN1308077C CN1308077C CNB2004100645385A CN200410064538A CN1308077C CN 1308077 C CN1308077 C CN 1308077C CN B2004100645385 A CNB2004100645385 A CN B2004100645385A CN 200410064538 A CN200410064538 A CN 200410064538A CN 1308077 C CN1308077 C CN 1308077C
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- molecular sieve
- phosphate molecular
- aluminium phosphate
- composite material
- metal complex
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Abstract
The present invention relates to a method for preparing composite material of metal complex molecular sieves, which belongs to the physicochemical field. The present invention is characterized in that an aluminum phosphate molecular sieve is taken as a main body, metal ions are led into the aluminum phosphate molecular sieve with an immersion method or an isomorphous replacement method, and the metal ions are matched with ligand which can diffuse and enter an opening of the selected main body under certain conditions, so the metal complexes are fixed in the aluminum phosphate molecular sieve. The preparing method is simple and practical, and has widespread applicability for preparing the composite material of metal complex aluminum phosphate molecular sieves in different structures. In addition, the present invention can control preparing conditions, and can prepare novel composite material in which isomorphous replacement metal and the metal complexes coexist. The prepared composite material has different performance.
Description
One, technical field
The preparation method of metal complex aluminium phosphate molecular sieve composite material of the present invention belongs to the physical chemistry field, specifically exactly the metal complex fixed sealing is loaded on the preparation method in the aluminium phosphate molecular sieve matrix.
Two, background technology
In the present disclosed report, the relevant preparation method that metal complex is fixed in the molecular sieve matrix has three kinds usually, that is: free ligand method, template agent synthetic method and zeolite synthetic method [(1) K.J.Baulkus Jr., A.K.Khanmamedova, K.M.Dixon and F.Bedioui, Appl.Catal.143 (1996) 159, (2) P.P.Knops-Gerrits, D.D.Vos, F.Thibault-Starzys and P.A.Jacobs, Nature, 369 (1994) 5431; (3) C.R.Jacob, S.P.Varky, and P.Ratnasamy, Microporous andMesoporous Materials, 22 (1998) 465; (4) B.Z.Zhan and X.Y.Li, Chem.Commun., 349 (1998)].Used material of main part is mainly X, y-type zeolite, is that the research report of material of main part is less for the molecular sieve that adopts different pore passage structures and skeleton to form.For metal compounding material molecular sieve composite material, its physico-chemical property depends on metal complex, material of main part and preparation method.The electronics of material of main part and geometry environment produce very big influence to the character of packaged complex.Aluminum phosphate series molecular sieve is a series of novel molecular sieves of the eighties by the exploitation of U.S. Union Carbide Corp, be different from general Si-Al molecular sieve, its skeleton is made up of phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, the surface is electroneutral, does not have ion-exchange performance [(1) US patent No.4310440 (1982), (2) O.V.Kikhtyanin, E.A.Paukshtis, K.G.Ioneand V.M.Mastikhin, J.Catal., 126 (1990) 1].The special architectural feature of aluminium phosphate molecular sieve makes it need adopt the preparation method who is different from main body X commonly used, y-type zeolite when fixing the encapsulation metal complex, be in particular in the following aspects, at first aluminium phosphate molecular sieve is not owing to have ion-exchange performance, thereby can not adopt free ligand method and template agent method, by ion-exchange metallic is introduced in the aluminium phosphate molecular sieve; Secondly, aluminium phosphate molecular sieve synthetic all is to synthesize by hydro-thermal to prepare in the presence of the organic formwork agent molecule, template agent in the synthetic product needs high-temperature roasting to remove, thereby can not adopt the zeolite synthetic method that metal complex is fixed or is packaged in the phosphate aluminium molecular sieve.Report seldom about the research of fixing metal complex aluminium phosphate molecular sieve composite material at present.Man-Hyoung Ryoo and Hakze Chan once reported and by dipping metal complex be packaged among the VPI-5 of macropore Co (Saloph) complex, and utilize the structural instability of VPI-5, but be APO 150 ℃ of thaumatropies promptly
4This characteristic of-8 is packaged in Co (Saloph) AlPO of aperture
4In-8 [M.Ryoo and H.Chon, Micropporous Materials, 10 (1997) 35].Though above-mentioned preparation method can successfully be packaged in Co (Saloph) in the aluminium phosphate molecular sieve, this method does not possess general applicability.In a word, current do not have as yet to preparing the preparation method that metal complex aluminium phosphate molecular sieve composite material is simple, feasible, have general applicability.
Three, summary of the invention
The objective of the invention is to propose a kind of the metal complex fixed sealing is loaded on the technical scheme of the preparation metal complex aluminium phosphate molecular sieve composite material in the aluminium phosphate molecular sieve matrix, for advanced composite material (ACM) provides a method simple possible, that generally use.
The preparation of metal complex aluminium phosphate molecular sieve composite material of the present invention, it is characterized in that based on aluminium phosphate molecular sieve, with water-soluble slaine is the central ion precursors, metal ion is introduced in the aluminium phosphate molecular sieve, cooperate under certain condition with the part that can diffuse into selected main body aperture again, metal complex is immobilized in aluminium phosphate molecular sieve, in engagement process used amount of ligand be theoretical amount of calculation 1.5-3.5 doubly, condition of no solvent needs down to carry out under vacuum, or at N
2, carry out in the self-generated pressure still under the inert gas shielding, cooperate temperature to be higher than 20-90 ℃ of selected part fusing point, the cooperation time was greater than 15 hours; having under the solvent condition; according to the character of selected part, under room temperature or in the self-generated pressure still, under less than 120 ℃, cooperate, the cooperation time is greater than 15h.The preparation of above-mentioned metal complex aluminium phosphate molecular sieve composite material is characterized in that metal ion introduced and adopts infusion process in the aluminium phosphate molecular sieve, and the slaine that is adopted can be nitrate, acetate or chlorate.Tenor is less than 3wt.% when introducing metal ion, and aluminium phosphate molecular sieve comprises AlPO
4-5, AlPO
4-37 and AlPO
4-18 grades have the molecular sieve of big port size.The preparation of above-mentioned metal complex aluminium phosphate molecular sieve composite material, it is characterized in that metal ion introduced and adopt isomorphous substitution method in the aluminium phosphate molecular sieve, M transition metal ions in the synthesized gel rubber/P phosphorus (mol ratio) is less than 0.2, metal ion is Fe, Co and Mn, the slaine that is adopted can be nitrate, acetate or chlorate.The preparation of above-mentioned metal complex aluminium phosphate molecular sieve composite material, it is characterized in that, part is can be by diffusing into selected aluminium phosphate molecular sieve aperture, can cooperate with selected metal, and the metal complex that cooperates the back to be generated can not be from the material of employing aluminium phosphate molecular sieve aperture escape.
Can be applicable to optics, catalysis, aspects such as adsorbing separation by the prepared metal complex aluminium phosphate molecular sieve of this method.At the MAlPO that adopts the isomorphous to replace
4When-n is predecessor, can prepare isomorphous substituted metal and metal complex with being stored in a kind of advanced composite material (ACM) by the control preparation condition, prepared composite has different physical and chemical performances.This preparation method is simple, and the metal complex aluminium phosphate molecular sieve composite material for preparing different structure is had general applicability.
Four, description of drawings
Fig. 1: the DRS spectrogram of sample
A:Mnsalen/AlPO
4-5 (infusion process is introduced Mn, 140 ℃ of cooperations of vacuum)
B:Fesalen/AlPO
4-5 (isomorphous replaces introducing Fe, 140 ℃ of cooperations in the self-generated pressure still)
C:Mnsalen/AlPO
4-5 (isomorphous replaces introducing Mn, 140 ℃ of cooperations in the self-generated pressure still)
D:Cosalen/AlPO
4-5 (isomorphous replaces introducing Co, 140 ℃ of cooperations in the self-generated pressure still)
Fig. 2: the FTIR spectrogram of sample
A:Mnsalen/AlPO
4-5 (infusion process is introduced Mn, 140 ℃ of cooperations of vacuum)
B:Fesalen/AlPO
4-5 (isomorphous replaces introducing Fe, 140 ℃ of cooperations in the self-generated pressure still)
C:Mnsalen/AlPO
4-5 (isomorphous replaces introducing Mn, 140 ℃ of cooperations in the self-generated pressure still)
D:Cosalen/AlPO
4-5 (isomorphous replaces introducing Co, 140 ℃ of cooperations in the self-generated pressure still)
Five, the specific embodiment
Embodiment 1: with 2g AlPO
4-5 place and are dissolved with 0.1g cobalt nitrate (Co (NO
3)
26H
2O) go in the 20mL aqueous solution, stirred 2 hours under the room temperature, and then remove aqueous solvent under vacuum heating conditions, the gained sample obtains Co/AlPO in 90 ℃ of following freeze-day with constant temperature
4-5.
Embodiment 2: with 2g AlPO
4-5 place and are dissolved with 0.08g frerrous chloride (FeCl
26H
2O) go in the 20mL aqueous solution, stirred 2 hours under the room temperature, and then remove aqueous solvent under vacuum heating conditions, the gained sample obtains Fe/AlPO in 90 ℃ of following freeze-day with constant temperature
4-5.
Embodiment 3: with 2g AlPO
4-5 place and are dissolved with 0.09g manganese acetate (Mn (CH
3COO)
24H
2O) go in the 20mL aqueous solution, stirred 2 hours under the room temperature, and then remove aqueous solvent under vacuum heating conditions, the gained sample obtains Mn/AlPO in 90 ℃ of following freeze-day with constant temperature
4-5.
Embodiment 4: 5g is visitd aluminium stone (Al
2O
3Content is 72.4%) be dissolved in the 26.8mL water, stirring at room 1 hour, and then with the inferior cobalt (Co (CH of 0.87g acetic acid
3COO)
24H
2O) mix with 8.18g (85%) phosphoric acid solution, this mixture is dropwise added under 0 ℃ visit in the mixture of aluminium stone and water, ageing is 2 hours under room temperature, and then under stirring condition the 5.6g triethylamine is dropwise added in the above-mentioned made mixture.Stir after 1 hour, this mixture is sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, in 200 ℃ of following crystallization 48 hours, the gained solid product was through washing, dry also in 550 ℃ of following roastings after 10 hours CoAlPO
4-5.
Embodiment 5: 5g is visitd aluminium stone (Al
2O
3Content is 72.4%) be dissolved in the 26.8mL water, stirring at room 1 hour, and then with 0.87g manganese acetate (Mn (CH
3COO)
24H
2O) mix with 8.18g (85%) phosphoric acid solution, this mixture is dropwise added under 0 ℃ visit in the mixture of aluminium stone and water, ageing is 2 hours under room temperature, and then under stirring condition the 5.6g triethylamine is dropwise added in the above-mentioned made mixture.Stir after 1 hour, this mixture is sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, in 200 ℃ of following crystallization 48 hours, the gained solid product was through washing, dry also after 550 ℃ of following roasting l0 hours MnAlPO
4-5.
Embodiment 6: 5g is visitd aluminium stone (Al
2O
3Content is 72.4%) be dissolved in the 26.8mL water, stirring at room 1 hour, and then with 1.7g (FeCl
26H
2O) mix with 8.18g (85%) phosphoric acid solution, this mixture is dropwise added under 0 ℃ visit in the mixture of aluminium stone and water, ageing is 2 hours under room temperature, and then under stirring condition the 5.6g triethylamine is dropwise added in the above-mentioned made mixture.Stir after 1 hour, this mixture is sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, in 200 ℃ of following crystallization 48 hours, the gained solid product was through washing, dry also in 550 ℃ of following roastings after 10 hours FeAlPO
4-5.
Embodiment 7: get Fe (the II)/AlPO that adopts the preparation of method described in the example 2
4-5 (Fe 1.0wt%) 2g places the 20ml ethanolic solution that is dissolved with the 0.3g o-phenanthroline, stirs to cooperate in 24 hours under room temperature, and the gained solid product must be fixed with the AlPO of Fephen after the drying till the ethanol extracting is colourless to extract
4-5 composites.
Embodiment 8: get the CoAlPO that adopts the preparation of method described in the example l
4-5 (Co, 1.0wt%) 2g and the abundant ground and mixed of 0.41gSalen part are even, and then place the vial that has vacuum cock, cooperate 24 hours down for 140 ℃ in vacuum, the gained sample must be fixed with the AlPO of CoSalen after the drying till the abundant extracting of acetone is colourless to extract
4-5 composites.
Embodiment 9: the Mn/AlPO that will adopt the preparation of method described in the example 3
4-5 (Mn, 1.0wt%) 2g and the abundant ground and mixed of 0.41gSalen part are even, and then place through N
2Displacement has in the self-generated pressure still of polytetrafluoroethylene (PTFE) pad, cooperates 24 hours down in 140 ℃, and the gained sample must be fixed with the AlPO of MnCoSalen after the drying till the abundant extracting of acetone is colourless to extract
4-5 composites.The FTIR figure and the diffuse reflection ultraviolet spectrogram of sample are seen accompanying drawing 1 and accompanying drawing 2 respectively.
Embodiment 10: get the CoAlPO that adopts the preparation of method described in the example 4
4-5 (Co/P=0.04, mol) 2g and 0.63gSalen and 10ml acetone fully mix, and then place the self-generated pressure still that is lined with the polytetrafluoroethylene (PTFE) pad, cooperate 24 hours down in 90 ℃, the gained sample must be fixed with the AlPO of CoSalen after the drying till the abundant extracting of acetone is colourless to extract
4-5 composites.
Embodiment 11: get the Mn/AlPO that adopts the preparation of method described in the example 3
4-5 adopt the Mn/AlPO of preparation
4-5 (Mn, 1.0wt%) 2g and the abundant ground and mixed of 0.2g second bipyridine body are even, and then place the vial that has vacuum cock, cooperate 24 hours down for 120 ℃ in vacuum, the gained sample must be fixed with the AlPO of Mnbipy after the drying till the abundant extracting of ethanol is colourless to extract
4-5 composites.
Embodiment 12: get the CoAlPO that adopts the preparation of method described in the example 4
4-5 (Co/P=0.04, mol) 2g and the abundant ground and mixed of 0.63gSalen part are even, and then place through N
2Displacement has in the self-generated pressure still of polytetrafluoroethylene (PTFE) pad, down cooperates 24 hours in 140 ℃, the gained sample till the abundant extracting of acetone is colourless to extract, the dried AlPO that is fixed with CoSalen
4-5 composites.The FTIR figure and the diffuse reflection ultraviolet spectrogram of sample are seen accompanying drawing 1 and accompanying drawing 2 respectively.
Embodiment 13: get the MnAlPO that adopts the preparation of method described in the example 5
4-5 (Mn/P=0.04, mol) 2g and the abundant ground and mixed of 0.63gSalen part are even, and then place through N
2Displacement has in the self-generated pressure still of polytetrafluoroethylene (PTFE) pad, down cooperates 24 hours in 140 ℃, the gained sample till the abundant extracting of acetone is colourless to extract, the dried AlPO that is fixed with MnSalen
4-5 composites.The FTIR figure and the diffuse reflection ultraviolet spectrogram of sample are seen accompanying drawing 1 and accompanying drawing 2 respectively
Embodiment 14: get the FeAlPO that adopts the preparation of method described in the example 6
4-5 (Fe/P=0.1, mol) 2g and the abundant ground and mixed of 0.98gSalen part are even, and then place through N
2Displacement has in the self-generated pressure still of polytetrafluoroethylene (PTFE) pad, down cooperates 24 hours in 140 ℃, the gained sample till the abundant extracting of acetone is colourless to extract, the dried AlPO that is fixed with FeSalen
4-5 composites.The FTIR figure and the diffuse reflection ultraviolet spectrogram of sample are seen accompanying drawing 1 and accompanying drawing 2 respectively.
Claims (3)
1. the preparation of metal complex aluminium phosphate molecular sieve composite material, it is characterized in that based on aluminium phosphate molecular sieve, with water-soluble slaine is the central ion precursors, metal ion is introduced in the aluminium phosphate molecular sieve, again with the part that can diffuse into selected main body aperture under the condition of no solvent or having under the solvent condition and cooperate, metal complex is immobilized in aluminium phosphate molecular sieve, part is can be by diffusing into selected aluminium phosphate molecular sieve aperture, can cooperate with selected metal, and the material that the metal complex that cooperates the back to be generated can not be escaped from employing aluminium phosphate molecular sieve aperture, in engagement process used amount of ligand be theoretical amount of calculation 1.5-3.5 doubly, condition of no solvent needs down to carry out under vacuum, or at N
2, carry out in the self-generated pressure still under the inert gas shielding; cooperate temperature to be higher than 20-90 ℃ of selected part fusing point; the cooperation time was greater than 15 hours; having under the solvent condition; character according to selected part; cooperate under less than 120 ℃ under room temperature or in the self-generated pressure still, the cooperation time, described metal was cobalt, iron or manganese greater than 15h.
2. according to the preparation of the described metal complex aluminium phosphate molecular sieve composite material of claim 1, it is characterized in that metal ion introduced and adopt infusion process in the aluminium phosphate molecular sieve, the slaine that is adopted is nitrate, acetate or chlorate, tenor is less than 3wt.% when introducing metal ion, and aluminium phosphate molecular sieve comprises AlPO
4-5, AlPO
4-37 and AlPO
4-18.
3. according to the preparation of the described metal complex aluminium phosphate molecular sieve composite material of claim 1, it is characterized in that metal ion introduced and adopt isomorphous substitution method in the aluminium phosphate molecular sieve, the mol ratio of metal ion/phosphorus is less than 0.2 in the synthesized gel rubber, and the slaine that is adopted is nitrate, acetate or chlorate.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167942A (en) * | 1990-11-21 | 1992-12-01 | Board Of Regents, The University Of Texas System | Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167942A (en) * | 1990-11-21 | 1992-12-01 | Board Of Regents, The University Of Texas System | Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes |
Non-Patent Citations (6)
| Title |
|---|
| Cr-AlPO4-5的合成及其对苯直接氧化制苯酚反应的催化性能 任永利等，催化学报，第25卷第9期 2004 * |
| Cr-AlPO4-5的合成及其对苯直接氧化制苯酚反应的催化性能 任永利等，催化学报，第25卷第9期 2004;Fephen/Y复合材料的制备、表征及其催化性能 范彬彬等，催化学报，第21卷第1期 2000;沸石分子筛的表面改性技术进展 王绪绪等，无机化学学报，第18卷第6期 2002;浸滞溶剂对Fe/AlPO4-5催化剂性能的影响 马静红等，催化学报，第15卷第3期 1994;磷酸铝系列分子筛合成及应用进展 苏建明等，齐鲁石油化工，第30卷第4期 2002 * |
| Fephen/Y复合材料的制备、表征及其催化性能 范彬彬等，催化学报，第21卷第1期 2000 * |
| 沸石分子筛的表面改性技术进展 王绪绪等，无机化学学报，第18卷第6期 2002 * |
| 浸滞溶剂对Fe/AlPO4-5催化剂性能的影响 马静红等，催化学报，第15卷第3期 1994 * |
| 磷酸铝系列分子筛合成及应用进展 苏建明等，齐鲁石油化工，第30卷第4期 2002 * |
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