CN104338556A - Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material - Google Patents
Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material Download PDFInfo
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- CN104338556A CN104338556A CN201310317051.2A CN201310317051A CN104338556A CN 104338556 A CN104338556 A CN 104338556A CN 201310317051 A CN201310317051 A CN 201310317051A CN 104338556 A CN104338556 A CN 104338556A
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Abstract
The invention discloses a method for directly synthesizing a mesoporous material coated heteropolyacid functionalized MOF material, and relates to a method for a mesoporous material coated polyacid modified metal organic framework material, wherein a mesoporous molecular sieve, phosphorus molybdenum heteropoly acid, tetramethylammonium hydroxide, 1,3,5-trimesic acid, and Cu(NO3)2.3H2O are adopted as raw materials, a hydrothermal synthesis method is adopted, and water is adopted as a solvent to carry out one step synthesis at a temperature of 90-230 DEG C to obtain the target material. The catalysis material synthesized by the method is applied in the benzene hydroxylation reaction, wherein the good stability performance of the material is presented under the mild reaction conditions.
Description
Technical field
The present invention relates to a kind of with mesoporous SBA-15, phosphato-molybdic heteropolyacid, TMAH, 1,3,5-trimesic acid, Cu (NO
3)
23H
2o is raw material, by the method for Hydrothermal Synthesis, under the reaction temperature of 90 DEG C-230 DEG C, uses water as solvent, the method for one-step synthesis target material.
Background technology
Heteropoly acid (POMs) is a class multi-metal oxygen cluster compound that early stage, transition metal was formed, its structure can regulate and control in the level of molecule or atom, has the wide application sent out in fields such as catalysis, electrochemistry, photochemistry, bioscience and material science.Heteropoly acid is the homogeneous catalysis material that a class is excellent, and difficulty or ease are separated from liquid phase reaction medium.Therefore, scholars pay close attention to always and do with the heterogeneous chemical industry of heteropoly acid.The technology such as reaction-controlled phase-transfer and reaction induced self-separation and a series of carrier are if zeolite, silica gel, silica, periodic mesoporous silicon materials, material with carbon element, diazo resin etc. are all in the heterogeneous chemical industry work of heteropoly acid.
Metal-organic framework materials (MOF) is the promising hydridization crystalline material of a class, is made up of organic ligand and node metal.Metal-organic framework materials has high aperture and large specific area, simultaneously, its configuration and composition can well regulate and control, therefore, this kind of material has a wide range of applications at numerous areas such as gas storage, gas separaion, gas absorption, insoluble drug release, heterogeneous linear optical research, magnetic property researchs.In recent years, by covalent bond or electrostatic interaction, researcher is had successfully heteropoly acid to be coated on metal-organic framework materials.But because such material is unstable in the liquid phase, many research is only around the catalytic property of the aspect such as hydrolysis, esterification, gaseous oxidation of such clad material, and for liquid phase oxidation reaction, such material report is less.The present invention uses mesoporous material, carry out coated to the metal-organic framework materials of heteropoly acid functional modification, and this material is used in the reaction of the benzene direct oxidation phenol carried out in liquid phase, in the oxidation environment that this is harsher, this material can circulate repeatedly, and significant change does not occur for its structure and catalytic performance.
The metal-organic framework materials using the coated heteropoly acid of mesoporous material to modify there is no bibliographical information.
Summary of the invention
The object of the invention is the method for the metal-organic framework materials that the coated heteropoly acid of exploitation one class mesoporous material is modified.
The preparation method of the metal-organic framework materials that the coated heteropoly acid of mesoporous material provided by the invention is modified, with mesoporous SBA-15, Cu (NO
3)
23H
2o, 1,3,5-trimesic acid, TMAH are raw material, by the method for Hydrothermal Synthesis, under the reaction temperature of 90 DEG C-230 DEG C, use water as solvent, the method for the metal-organic framework materials that the coated heteropoly acid of one-step synthesis mesoporous material is modified.
Being suitable for mesopore molecular sieve of the present invention is the silica-based molecular sieve such as M41S, SBA, HMS, MSU and Al
2o
3, WO
3, ZrO
2deng metal oxide.Cationic part has 1,3,5-trimesic acid, EDTA, sulfosalicylic acid, Isosorbide-5-Nitrae-terephthalic acid (TPA), 4-toluene sulfonic acide, 2, the nitrogenous class of the form such as dipicolimic acid 2,4-HBA or carboxylic acids part, these raw materials can commercially be bought.
In the present invention, the metal of metal-organic framework materials and the organic backbone mol ratio of metal-organic framework materials between 1:40-40:1, and preferably between 1:5-5:1.
Being applicable to reaction medium of the present invention is the aqueous solution.
Be suitable for reaction temperature of the present invention between 90 DEG C-230 DEG C, and preferably between 110 DEG C-190 DEG C.
The preparation method of the vanadium base catalysis material of catalysis benzene hydroxylation phenol of the present invention, uses common mesopore molecular sieve, phosphomolybdic acid, TMAH, 1,3,5-trimesic acid, Cu (NO
3)
23H
2o is raw material, and reaction condition is gentle, and reaction yield is high, simple synthetic method.
Accompanying drawing explanation
Fig. 1
embodiment 1the infrared spectrum of resulting materials: SBA-15 use 1 expression, the metal-organic framework materials of the heteropoly acid modification that SBA-15 is coated uses 2 to represent, metal-organic framework materials use 3 expression that SBA-15 is coated, and metal-organic framework materials use 4 represents.As can be seen from the figure, target material 2 is containing laying respectively at 951,868,798cm
-1ν
as(Mo-O
t), ν
as(Mo-O
b-Mo) and ν
as(Mo-O
c-Mo) vibration absorption peak, and be positioned at 1071,1055cm
-1ν (P O) vibration absorption peak.Characteristic peak, the characteristic peak of SBA-15 and the characteristic peak of metallic organic framework of target compound 2 simultaneously containing polyacid.
Fig. 2
embodiment 1transmission electron microscope (TEM) figure: the SBA-15 clad metal organic framework material of resulting materials uses 1 to represent, the metal-organic framework materials target material that the coated heteropoly acid of SBA-15 is modified uses 2 to represent.TEM shows, and have obvious filler in target material duct, shown Electronic Speculum figure has identical pore passage structure with the Electronic Speculum figure of standard SBA-15, can judge from TEM, and it is inner that target material is coated on SBA-15 duct.
Fig. 3
embodiment 1the XRD powder diffraction of resulting materials: SBA-15 mesoporous material uses 1 to represent, metal-organic framework materials use 2 expression that SBA-15 is coated, the metallic organic framework target material of the heteropoly acid modification that SBA-15 is coated uses 3 to represent, metal-organic framework materials uses 4 to represent.XRD powder data shows, the SBA-15 target material of the metallic organic framework that the SBA-15 of coated metallic organic framework and coated heteropoly acid are modified all demonstrates SBA-15 and the common characteristic peak of metal-organic framework materials, illustrate that the ordered structure of skeleton is not subject to the impact of coated polyacid, SBA-15 can carry out coated to the metal-organic framework materials that metallic organic framework and heteropoly acid are modified.
Fig. 4
embodiment 1the N of resulting materials
2absorption: SBA-15 mesoporous material uses 1 expression, metal-organic framework materials use 2 expression that SBA-15 is coated, metal-organic framework materials uses 3 to represent, metallic organic framework target material use 4 expression of the heteropoly acid modification that SBA-15 is coated.N
2adsorpting data shows, and the SBA-15 target material of the metallic organic framework that the SBA-15 of coated metallic organic framework and coated heteropoly acid are modified all demonstrates the less N of SBA-15
2adsorbance, to illustrate in duct that the metal-organic framework materials really modified by metallic organic framework or coated heteropoly acid is filled.
Fig. 5
embodiment 1the N of resulting materials
2the pore-size distribution of absorption: SBA-15 mesoporous material uses 1 expression, metal-organic framework materials use 2 expression that SBA-15 is coated, metal-organic framework materials uses 3 to represent, metallic organic framework target material use 4 expression of the heteropoly acid modification that SBA-15 is coated.N
2adsorpting data shows, and the SBA-15 target material of the metallic organic framework that the SBA-15 of coated metallic organic framework and coated heteropoly acid are modified all demonstrates the less N of SBA-15
2adsorbance, to illustrate in duct that the metal-organic framework materials really modified by metallic organic framework or coated heteropoly acid is filled.
Detailed description of the invention
Following embodiment will describe more comprehensively to the present invention.
In example, material is obtained by washing, drying, and productive rate calculates based on Mo.
embodiment 1
By 0.180g SBA-15,0.1062g H
4pMo
11vO
4019H
2o (0.05mmol), 0.240gCu (NO
3)
23H
2o (1mmol), 0.105g1,3,5-trimesic acid (0.5mmol), 0.09g TMAH (1mmol) is dissolved in 10mL deionized water, uses 2M NaOH to regulate pH2.5.Be transferred to by this solution in 23mL autoclave, temperature programming 5 DEG C/h, rise to 160 DEG C and keep 48h, after slow cooling to room temperature, target material is that lenticular is separated out from reactant liquor.Washed by resulting materials, use XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 35%.
The catalysis material obtained is used to react for benzene hydroxylation, by 0.025mmol catalyst, 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g ascorbic acid, 2MPa O
2add in 50mL autoclave and react, magnetic agitation, reaction temperature is 80 DEG C, and keep 4h, obtaining phenol yield is 7.5%.
embodiment 2
By 0.20g SBA-15,0.2123g H
4pMo
11vO
4019H
2o (0.1mmol), 0.120gCu (NO
3)
23H
2o (0.5mmol), 0.105g1,3,5-trimesic acid (0.5mmol), 0.045g TMAH (0.5mmol) is dissolved in 10mL deionized water, uses 2M NaOH to regulate pH7.8.Be transferred to by this solution in 23mL autoclave, temperature programming 50 DEG C/h, rise to 120 DEG C and keep 72h, after slow cooling to room temperature, target material is that lenticular is separated out from reactant liquor.Washed by resulting materials, use XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 25%.
The catalysis material obtained is used to react for benzene hydroxylation, by 0.10g catalyst, 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g ascorbic acid, 2MPa O
2add in 50mL autoclave and react, magnetic agitation, reaction temperature is 80 DEG C, and keep 20min, obtaining phenol yield is 5.8%.
embodiment 3
By 0.16g SBA-15,0.2123g H
4pMo
11vO
4019H
2o (0.1mmol), 0.240gCu (NO
3)
23H
2o (1mmol), 0.105g1,3,5-trimesic acid (0.5mmol), 0.18g TMAH (2mmol) is dissolved in 10mL deionized water, uses 2M NaOH to regulate pH4.8.Be transferred to by this solution in 46mL autoclave, temperature programming 20 DEG C/h, rise to 240 DEG C and keep 16h, after slow cooling to room temperature, target material is that lenticular is separated out from reactant liquor.Washed by resulting materials, use XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 42%.
The catalysis material obtained is used to react for benzene hydroxylation, by 0.20g catalyst, 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g ascorbic acid, 2MPa O
2add in 50mL autoclave and react, magnetic agitation, reaction temperature is 80 DEG C, and keep 40min, obtaining phenol yield is 6.2%.
embodiment 4-10
Be similar to embodiment 1, be with its difference: the organic backbone of metal-organic framework materials, polyoxoanion mass concentration, reaction temperature, crystallization time, the following result (table one) after reaction terminates:
Table one
embodiment 11-15
Be similar to embodiment 1, be with its difference: the mol ratio adopting the organic backbone of the organic backbone of different metal organic framework material, heteropoly acid mass concentration, heteropoly acid and metal-organic framework materials, obtain following result (table two):
Table two
The catalysis material that the inventive method is synthesized is applied to benzene hydroxylation reaction, presents the good stability of this material at the reaction condition of gentleness.
Claims (10)
1. the method for direct synthesize meso-porous material coated heteropoly acid functionalization MOF material, it is characterized in that: take water as solvent, use mesopore molecular sieve, heteropoly acid, TMAH, the metallic compound of metal-organic framework materials is provided, the organic framework compounds of metal-organic framework materials is raw material, the metal-organic framework materials modified by the coated polyacid of the method one-step synthesis target mesoporous material of Hydrothermal Synthesis; Described reaction temperature is between 90 DEG C-230 DEG C.
2. method according to claim 1, is characterized in that: reaction medium is water, and filling rate is in a kettle. between 30%-90%.
3. method according to claim 1, is characterized in that: meso-porous molecular sieve material used is the silica-based molecular sieve such as M41S, SBA, HMS, MSU and Al
2o
3, WO
3, ZrO
2deng one or two or more kinds in the mesoporous material of metal oxide.
4. method according to claim 1, is characterized in that: the heteropoly acid of heteropolyacid anions that provides used is one in a kind of in titanium, cadmium, vanadium, chromium, iron, manganese, cobalt, zinc, nickel, cerium, copper, platinum, silver, gold, palladium, rhodium, ruthenium, iridium etc. or two kinds of metal-doped phosphorus heteropoly tungstic acids, phosphato-molybdic heteropolyacid, arsenic heteropoly tungstic acid, As-Mo heteropoly acid, silicotungstic heteropolyacid, silicon-molybdenum heteropoly acid, germanium heteropoly tungstic acid, germanomolybdate; Wherein, the doping of doping metals is 1-12 times of phosphorus, silicon, germanium or arsenic hetero atom quantity.
5. method according to claim 1, it is characterized in that: the organic framework compounds of described metal-organic framework materials is EDTA, 1,3,5-trimesic acid, 1,4-terephthalic acid (TPA), sulfosalicylic acid, 4-toluene sulfonic acide, 4-HBA, 2, one or two or more kinds in dipicolimic acid 2; The metallic compound of metal-organic framework materials is provided to be one or two or more kinds in the nitrate of one or two or more kinds, chloride or sulfate in molybdenum, vanadium, tungsten, iron, copper, nickel, manganese, cobalt metal.
6. method according to claim 1 or 5, is characterized in that: provide the organic framework compounds mol ratio of metal in the metallic compound of metal-organic framework materials and metal-organic framework materials between 1:40-40:1.
7. the method according to claim 1,2,3,4 or 5, is characterized in that: when reaction starts, and the temperature of reaction system is warming up to from room temperature start program reacts temperature required, heating rate 3 DEG C/h-45 DEG C/h.
8. the method according to claim 1,2,3,4,5 or 6, is characterized in that:
The metal in the metallic compound of metal-organic framework materials and heteropolyacid anions mol ratio is provided to be between 30:1-1:60;
TMAH and heteropolyacid anions mol ratio are between 1:4-12:1;
Mesopore molecular sieve consumption is for add according to mass ratio with polyacid, and molecular sieve and polyacid mass ratio are 1:3-3:3.
9. the method according to claim 1,2 or 8, it is characterized in that: in reaction system, the heteropoly acid providing heteropolyacid anions, the metallic compound providing metal-organic framework materials, the organic framework compounds of metal-organic framework materials, TMAH, four kinds of reaction mass total mass concentrations are between 1%-75%.
10. method according to claim 1, is characterized in that: when reaction starts front, uses NaOH or KOH regulation system pH1-10; After reaction terminates, reclaim product by washing, yield is 25%-90%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1130427A2 (en) * | 2000-03-04 | 2001-09-05 | Lucent Technologies Inc. | Decoupling of transverse spatial modes in microstructure optical fibers |
| CN103191786A (en) * | 2013-04-23 | 2013-07-10 | 浙江师范大学 | Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst |
-
2013
- 2013-07-25 CN CN201310317051.2A patent/CN104338556A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1130427A2 (en) * | 2000-03-04 | 2001-09-05 | Lucent Technologies Inc. | Decoupling of transverse spatial modes in microstructure optical fibers |
| CN103191786A (en) * | 2013-04-23 | 2013-07-10 | 浙江师范大学 | Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CHUN-YAN SUN等: ""Highly Stable Crystalline Catalysts Based on a Microporous Metal-Organic Framework and Polyoxometalates"", 《J. AM. CHEM. SOC.》, vol. 131, no. 5, 15 January 2009 (2009-01-15) * |
| 杨华等: ""介孔SBA-15 包覆的多酸功能化MOF 材料合成及催化"", 《中国化学会第五届全国多酸化学学术研讨会论文摘要集》, 15 July 2013 (2013-07-15), pages 37 * |
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| CN112871190B (en) * | 2021-01-13 | 2021-08-20 | 泰州九润环保科技有限公司 | Chromium-based metal organic framework solid acid catalyst for synthesizing hydroquinone monomethyl ether and preparation method and application thereof |
| CN113533317A (en) * | 2021-07-08 | 2021-10-22 | 吉林大学 | Iron-based metal organic framework material of heteropoly acid and application of iron-based metal organic framework material in xanthine detection |
| CN113533317B (en) * | 2021-07-08 | 2022-12-02 | 吉林大学 | Heteropoly iron-based metal organic framework material and application thereof in xanthine detection |
| CN117427696A (en) * | 2023-12-21 | 2024-01-23 | 烟台大学 | Supported heteropolyacid salt catalyst, preparation method and application thereof |
| CN117427696B (en) * | 2023-12-21 | 2024-02-23 | 烟台大学 | Supported heteropolyacid salt catalyst, preparation method and application thereof |
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Application publication date: 20150211 |