CN1272402A - Preparation of metal compounding material molecular sieve composite material - Google Patents
Preparation of metal compounding material molecular sieve composite material Download PDFInfo
- Publication number
- CN1272402A CN1272402A CN 00117838 CN00117838A CN1272402A CN 1272402 A CN1272402 A CN 1272402A CN 00117838 CN00117838 CN 00117838 CN 00117838 A CN00117838 A CN 00117838A CN 1272402 A CN1272402 A CN 1272402A
- Authority
- CN
- China
- Prior art keywords
- mcm
- molecular sieve
- metal complex
- preparation
- predecessor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A preparation of metal complex molecular sieve composite material, belonging to the field of physical chemistry, is characterized by using ML/MCM-41 as raw material, adopting the recrystallization process and fixing the metal complex in the molecular sieve matrix. Said invented method is simple and easy to implement, can be used for preparing molecular sieve composite material with high load of metal complex.
Description
The preparation method of metal compounding material molecular sieve composite material of the present invention belongs to the physical chemistry field, specifically is exactly a kind of new preparation method who metal complex fixed sealing of different nature is loaded in the molecular sieve matrix.
In the disclosed at present report, about the preparation method who metal complex is fixed in the molecular sieve matrix has three kinds usually: 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)], these methods all are by different modes, the three-dimensional restriction of the special space that utilizes host molecule sieve aperture road structure to be had realizes fixing the object metal complex.Common selected material of main part is X, y-type zeolite, owing to be subjected to the restriction of less port size of selected material of main part and vestibule volume, adopts the metal complex that said method can not be bigger with molecular dimension to be fixed in the vestibule of molecular sieve effectively; Simultaneously small apertures size and vestibule volume also are unfavorable for effective diffusion of reactant and product in the macromolecular reaction.In order to overcome above-mentioned deficiency, have the novel M41S series mesopore material that the aperture is big, pore size distribution evenly reaches Large ratio surface and be used as material of main part.Though M41S series mesopore material has bigger port size and vestibule volume, but its special pore passage structure and surface nature, make metal complex fixedly being different from general micro porous molecular sieve thereon, if metal complex will be anchored on securely on the M41S series mesopore material, need functionalized processing is carried out on its surface, just can make and produce certain bonding action [(5) C.J.Liu between its surface and some metal complex, S.G.Li, W.Q.Pang and C.M.Che, Chem.Commun. (1997) 65; (6) P.Sutra, D.Bruner, Chem.Commun., (1996) 2485; A.Bleloch, B.F.G.Johnson, S.V.Ley, A.J.Price, D.S.Shephard and A.W.Thomas, Chem.Commun., (1999) 1907], not only made the unusual very complicated of preparation process like this, and the character of complex proposed certain requirement that incompatibility has thereon fixing of various metal complexs of different nature; The pore passage structure of M41S is difficult to metal complex is applied space steric effect simultaneously.
The objective of the invention is to propose a profit metal complex can be fixed in preparation method in the molecular sieve matrix effectively, it can be effectively applied in the heterogeneous catalytic reaction.
The preparation of metal compounding material molecular sieve composite material of the present invention is characterized in that it being a kind of preparation method that metal complex can be fixed on effectively in the molecular sieve matrix.This method is the MCM-41 (ML/MCM-41 that metal complex is arranged with load, M is a transition metal, and L is an organic ligand) be predecessor, utilize crystallization technology again, make it change ML/ (MCM-41)/Y under certain condition into, metal complex is fixed in the molecular sieve matrix.The preparation method of the predecessor of ML/MCM-41 of the present invention is as follows:
Example 1: the ML/MCM-41 with the preparation of direct crystallization method is a predecessor
Concrete preparation method is as follows: with ML (M=Fe, Co, Cr, Cu, Mn; L=o-phenanthroline (phenanthroline, be abbreviated as: phen), 8-hydroxy-quinoline (8-quinolinol, be abbreviated as Qx), salicylic acid (Salicylic acid, be abbreviated as: SA), second bipyridine (2,2 '-bipyridyl is abbreviated as: the bipy) special alkali (Schifi-bases of Schiff, be abbreviated as: salen), phthalocyanine (phthalocyanine, be abbreviated as: Pc), porphyrin (porphyrin) mixes according to a certain percentage with the reactant mixture of MCM-41, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, after treating that crystallization is finished, the gained solid is fully washed with deionized water, to remove surfactant as much as possible, sample after will washing then obtains ML/MCM-41 in 90 ℃ of following freeze-day with constant temperature.
Example 1.1 is as follows: earlier with 6.08g CTAB and 85ml water glass solution ([SiO
2]=1.30M, [OH
-]=0.75M) mixes, subsequently with the sodium aluminate solution ([Al of 11.8ml
2O
3]=0.047M, [OH
-]=0.17M) slowly adds, and uses the H of 8.7ml again
2SO
4(3.77M) solution is regulated the pH value of above-mentioned prepared gel, at last again with Fe (phen)
3Cl
2Complex compound adds, after itself and reactant mixture fully mixed, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, after treating that crystallization is finished, the gained solid is fully washed with deionized water, and the sample after will washing then obtains the Fephen/MCM-41 predecessor in 90 ℃ of following freeze-day with constant temperature.
Example 1.2 is as follows: earlier with 6.08g CTAB and 85ml water glass solution ([SiO
2]=1.30M, [OH
-]=0.75M) mixes, subsequently with the sodium aluminate solution ([Al of 11.8ml
2O
3]=0.047M, [OH
-]=0.17M) slowly adds, and uses the H of 8.7ml again
2SO
4(3.77M) solution is regulated the pH value of above-mentioned prepared gel, again the sulfonated phthalocyanine cobalt complex is added at last, after itself and reactant mixture fully mixed, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, treat that crystallization is finished after, the gained solid is fully washed with deionized water, sample after will washing then obtains sulfonated phthalocyanine cobalt network/MCM-41 predecessor in 90 ℃ of following freeze-day with constant temperature.
Example 2: the ML/MCM-41 with immersion process for preparing is a predecessor
Concrete preparation method is as follows: will mix with certain density metal ethanolic solution by a certain percentage through 550 ℃ of baked MCM-41 mesopore materials, and under stirring condition, be evaporated to dried in 50 ℃ of left and right sides scopes.Example is as follows: 2g is placed 1.2g Fe (phen) through 550 ℃ of baked MCM-41
3Cl
2The 20ml ethanolic solution in, under stirring condition, in 50 ℃ of left and right sides scopes, be evaporated to dried, the Fephen/MCM-41 predecessor.Example 3: the ML/MCM-41 with the hetero-atom molecular-sieve preparation is a predecessor
Concrete preparation method is as follows: M-MCM-41 (the described method of preparation process reference literature) and the organic ligand of certain M/Si are carried out getting the ML/MCM-41 predecessor after the complexing.Example is as follows: 1.2g is crossed Fe-MCM-41 (Si/Fe=100) through 550 ℃ of roastings, place 10ml to contain the ethanolic solution of 1.0g o-phenanthroline, complexing is 24 hours under room temperature, after filtration, dried Fephen/MCM-41 predecessor.
Be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in adopting the resulting ML/MCM-41 predecessor of distinct methods and waterglass, sodium metaaluminate and directed agents fully to mix to be enclosed within, under specified criteria, synthesize ratio range: (5-10) SiO
2: Al
2O
3: (1.5-3.0) Na
2O: (0-0.4) ML: (350-920) H
2O.Main feature of the present invention is simple, can be fixed in effectively in the molecular sieve matrix having positive electricity, negative electricity and neutral metal complex, having widened the range of choice to metal complex greatly, is a kind of preparation method with broad applicability of preparation metal compounding material molecular sieve composite material.Can prepare the composite that is fixed with the high content gold metal complex by the content of modulation metal complex in the MCM mesopore material, this is that the at present existing preparation method of employing institute is inaccessiable.By M-MCM-41 being carried out crystallization and crystal formation conversion processing, can obviously improve M-MCM-41 metal component leakage in catalytic reaction.In addition, this method is not subjected to the restriction of metal complex molecular dimension yet.Realize that preferred example of the present invention is as follows:
1. at first with 1.78ml water glass solution ([SiO
2]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO
2: Al
2O
3: 16Na
2O: 320H
2O) mix, then with 0.89ml sodium aluminate solution ([Al
2O
3]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared FephenL/MCM-41 predecessor 1.0g of infusion process last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 2 days under 363K, the Fephen sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is Y type (seeing accompanying drawing 1).The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.
2. at first with 1.78ml water glass solution ([SiO
2]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO
2: Al
2O
3: 16Na
2O: 320H
2O) mix, then with 0.89ml sodium aluminate solution ([Al
2O
3]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared sulfonated phthalocyanine cobalt/MCM-41 predecessor 1.0g of direct crystallization method last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, products therefrom is fixed the sample of sulfonated phthalocyanine cobalt after washing, ethanol extracting, crystalline phase is the Y type.
3. at first with 1.78ml water glass solution ([SiO
2]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO
2: Al
2O
3: 16Na
2O: 320H
2O) mix, then with 0.89ml sodium aluminate solution ([Al
2O
3]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared FeSA/MCM-41 predecessor 1.0g of infusion process last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 2 days under 363K, the FeSA sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is the Y type.The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.
4. at first with 1.78ml water glass solution ([SiO
2]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO
2: Al
2O
3: 16Na
2O: 320H
2O) mix, then with 0.89ml sodium aluminate solution ([Al
2O
3]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, add at last prepared FeQx/MCM-41 predecessor 1.0g again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, the FeQx sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is the Y type.The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.
5. at first with 1.78ml water glass solution ([SiO
2]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO
2: Al
2O
3: 16Na
2O: 320H
2O) mix, then with 0.89ml sodium aluminate solution ([Al
2O
3]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared CrQx/MCM-41 predecessor 1.0g of hetero-atom molecular-sieve complexometry last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, the CrQx sample that products therefrom is fixed after washing, ethanol extracting, product are the Y type mutually.
Metal compounding material molecular sieve composite material by this method preparation not only has very high heat endurance, chemical stability and shape selective catalysis performance etc., but also can replace to come the surface property of modulation zeolite by the isomorphous of ion-exchange or backbone element, making it be applicable to different reaction requirements, is a kind of novel heterogeneousization of homogeneous reaction catalyst.This method is not limited by assembled metal complex size and the existence form in synthetic system, has extensive applicability.
Claims (5)
1. the preparation method of metal compounding material molecular sieve composite material, it is characterized in that with ML/MCM-41 being predecessor, adopt crystallization method again, change ML/MCM-41 into ML/ (MCM-41)/Y, metal complex is fixed in the molecular sieve matrix, its preparation process is for after fully mixing ML/MCM-41, sodium metaaluminate, directed agents and sodium hydrate aqueous solution in proportion, be sealed in the reactor, in room temperature to 90 ℃ following crystallization 1-10 days, products therefrom after filtration, washing, organic solvent extracting and dry back be standby.
2. according to the described preparation method of claim 1, M41S comprises the M-M41S series material that hetero atom replaces, and M is a transition metal.
3. according to the described preparation method of claim 1, it is characterized in that with ML/MCM-41 being predecessor, methods such as the ML/MCM-41 predecessor can be synthetic by original position, dipping and the complexing of metallic M41S series mesopore material obtain, the predecessor that is adopted can be any mesopore series material that load has metal complex, and its silica alumina ratio (mole) can be selected between infinite-30.
4. according to the described preparation method of claim 1, the metal complex that will have different electrical properties is fixed in the molecular sieve matrix.
5. according to the described preparation method of claim 1, be fixed in metal complex size in the molecular sieve matrix greater than the vestibule size of micro porous molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001178385A CN1136991C (en) | 2000-05-24 | 2000-05-24 | Preparation of metal compounding material molecular sieve composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001178385A CN1136991C (en) | 2000-05-24 | 2000-05-24 | Preparation of metal compounding material molecular sieve composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272402A true CN1272402A (en) | 2000-11-08 |
| CN1136991C CN1136991C (en) | 2004-02-04 |
Family
ID=4587077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001178385A Expired - Fee Related CN1136991C (en) | 2000-05-24 | 2000-05-24 | Preparation of metal compounding material molecular sieve composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1136991C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005051843A1 (en) * | 2003-11-28 | 2005-06-09 | Shanghai Jahwa United Co., Ltd. | Molecular sieves based nano-composite uv-resistant material, preparation process and use thereof |
| CN100424012C (en) * | 2005-12-30 | 2008-10-08 | 中国科学院大连化学物理研究所 | Method for preparing middle-aperture material using silicon oxide as main body |
| US7528201B2 (en) | 2004-12-22 | 2009-05-05 | Exxonmobil Chemical Patents Inc. | Synthesis of silicoaluminophosphate molecular sieves |
| CN101940950A (en) * | 2010-06-29 | 2011-01-12 | 大连理工大学 | Catalyst for hydroxylation reaction of phenol and preparation method thereof |
| CN102513144A (en) * | 2011-12-14 | 2012-06-27 | 常州大学 | Preparation method of shape-selective catalyst used for p-dialkyl benzene synthesis process |
| CN112310500A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院过程工程研究所 | Method for separating aluminum element from waste lithium iron phosphate material |
-
2000
- 2000-05-24 CN CNB001178385A patent/CN1136991C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005051843A1 (en) * | 2003-11-28 | 2005-06-09 | Shanghai Jahwa United Co., Ltd. | Molecular sieves based nano-composite uv-resistant material, preparation process and use thereof |
| JP2007512216A (en) * | 2003-11-28 | 2007-05-17 | 上海家化朕合股▲フェン▼有限公司 | Molecular sieve mainly composed of UV-resistant nanocomposites, preparation method thereof, and utilization method thereof |
| US7528201B2 (en) | 2004-12-22 | 2009-05-05 | Exxonmobil Chemical Patents Inc. | Synthesis of silicoaluminophosphate molecular sieves |
| CN100424012C (en) * | 2005-12-30 | 2008-10-08 | 中国科学院大连化学物理研究所 | Method for preparing middle-aperture material using silicon oxide as main body |
| CN101940950A (en) * | 2010-06-29 | 2011-01-12 | 大连理工大学 | Catalyst for hydroxylation reaction of phenol and preparation method thereof |
| CN101940950B (en) * | 2010-06-29 | 2013-05-08 | 大连理工大学 | Catalyst for hydroxylation reaction of phenol and preparation method thereof |
| CN102513144A (en) * | 2011-12-14 | 2012-06-27 | 常州大学 | Preparation method of shape-selective catalyst used for p-dialkyl benzene synthesis process |
| CN112310500A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院过程工程研究所 | Method for separating aluminum element from waste lithium iron phosphate material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1136991C (en) | 2004-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Forster et al. | Hybrid inorganic–organic solids: an emerging class of nanoporous catalysts | |
| CN104959044B (en) | Method for synthesizing metal organic framework film | |
| Zhu et al. | Metal hydrogen-bonded organic frameworks: structure and performance | |
| CN108070089A (en) | A kind of preparation method of the zirconium-based metallic organic framework material rich in zirconium ion | |
| CN106967219B (en) | Cadmium metal organic framework material based on 3,3 ', 5, 5' -biphenyltetracarboxylic acid and preparation method and application thereof | |
| CN102616795A (en) | Method for preparing pure silicon-based mesoporous silica nanoparticles | |
| CN108129670A (en) | A kind of preparation method of gradient porous metal organic framework ZIF-8 | |
| CN102295298A (en) | Method for synthesizing mesoporous silica molecular sieve | |
| CN101837988A (en) | Method for preparing iron modified SBA-15 mesoporous molecular sieve | |
| CN109400869A (en) | Multi-styrene phenol polyoxyethylene ether sulfate dispersing agent and the preparation method and application thereof | |
| CN103170161B (en) | Preparation method of organic-inorganic hybridized monolithic column | |
| CN1136991C (en) | Preparation of metal compounding material molecular sieve composite material | |
| CN106925244A (en) | A kind of preparation method of mercury ion adsorbent | |
| CN106694050A (en) | Preparation method of visible-light-induced photocatalyst with core-shell structure | |
| CN108554455A (en) | A kind of water oxidation catalyst and preparation method thereof immobilized with metal-organic framework material | |
| Wang et al. | A Series of Organic–Inorganic Hybrid Zinc Phosphites Containing Extra-Large Channels | |
| CN101721977B (en) | Palladium loaded chelate resin and preparation method thereof | |
| CN103212444A (en) | Synthesis method of organic-inorganic hybrid porous solid material with quadruple catalysis and adsorption functions | |
| CN108722488B (en) | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof | |
| Olkhovyk et al. | Polymer-templated mesoporous organosilicas with two types of multifunctional organic groups | |
| CN104607150B (en) | Multi-ion adsorption material prepared by inorganic ion doping and large-steric-hindrance organic modification | |
| CN1380250A (en) | Double mesopore molecular sieve and its preparation method | |
| CN109939726A (en) | A kind of preparation and application of the catalyst of the molecular sieve of MTT containing hetero atom | |
| CN114887662A (en) | Metal organic framework material-molecular sieve composite material and preparation method and application thereof | |
| CN111097386B (en) | Two-dimensional layered water-stable dye adsorbent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |