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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
metal
organic framework
material
acid
framework materials
Prior art date
Application number
CN201310317051.2A
Other languages
Chinese (zh)
Inventor
高爽
杨华
王连月
李军
吕迎
Original Assignee
中国科学院大连化学物理研究所
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Priority to CN201310317051.2A priority Critical patent/CN104338556A/en
Publication of CN104338556A publication Critical patent/CN104338556A/en

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

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

The method of direct synthesize meso-porous material coated heteropoly acid functionalization MOF material

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%.
CN201310317051.2A 2013-07-25 2013-07-25 Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material CN104338556A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310317051.2A CN104338556A (en) 2013-07-25 2013-07-25 Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310317051.2A CN104338556A (en) 2013-07-25 2013-07-25 Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material

Publications (1)

Publication Number Publication Date
CN104338556A true CN104338556A (en) 2015-02-11

Family

ID=52495502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310317051.2A CN104338556A (en) 2013-07-25 2013-07-25 Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material

Country Status (1)

Country Link
CN (1) CN104338556A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105154063A (en) * 2015-07-22 2015-12-16 北京理工大学 Indium-based metal organic framework wrapped functional positive ion Ru(bpy)32+ fluorescent material and preparation method therefor
CN105646899A (en) * 2016-01-20 2016-06-08 辽宁大学 Metal organic anion framework based on InIII and preparation method and application thereof
CN105713208A (en) * 2016-04-15 2016-06-29 中国科学院上海高等研究院 CuZn bi-metal organic framework material and preparing method thereof
CN105772093A (en) * 2016-04-05 2016-07-20 哈尔滨理工大学 Encapsulated [VW12]4-cluster metal organic nanotube micropore crystalline state material, and preparation method and application thereof
CN106268964A (en) * 2015-05-12 2017-01-04 北京化工大学 A kind of base supported multifunction catalyst of polyacid and preparation method thereof
CN106622384A (en) * 2016-12-06 2017-05-10 北京林业大学 Preparation method and application of non-sulphurized hydrodeoxygenation catalyst
CN106622151A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Composite containing metal-organic framework material and preparation method and application thereof
CN106622142A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Metal organic skeleton material Cu3(BTC)2, and preparation method and application thereof
CN106622139A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Metal organic framework material and preparation method and application thereof
CN106669831A (en) * 2016-12-06 2017-05-17 北京林业大学 Preparation method and application of dual-functional hydrodeoxygenation catalyst
CN107597190A (en) * 2017-08-14 2018-01-19 湖北大学 A kind of preparation method and applications of zeolite molecular sieve grain surface assembling metal organic framework film
CN107694611A (en) * 2017-09-29 2018-02-16 中国石油大学(华东) A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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), XP009140592, DOI: doi:10.1021/ja807357r *
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 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268964A (en) * 2015-05-12 2017-01-04 北京化工大学 A kind of base supported multifunction catalyst of polyacid and preparation method thereof
CN105154063A (en) * 2015-07-22 2015-12-16 北京理工大学 Indium-based metal organic framework wrapped functional positive ion Ru(bpy)32+ fluorescent material and preparation method therefor
CN106622139A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Metal organic framework material and preparation method and application thereof
CN106622142B (en) * 2015-11-03 2019-05-17 中国石油化工股份有限公司 A kind of metal-organic framework materials Cu3(BTC)2And its preparation method and application
CN106622139B (en) * 2015-11-03 2019-05-21 中国石油化工股份有限公司 A kind of metal-organic framework materials and the preparation method and application thereof
CN106622151B (en) * 2015-11-03 2019-04-12 中国石油化工股份有限公司 Composite material and preparation method and application containing metal-organic framework materials
CN106622151A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Composite containing metal-organic framework material and preparation method and application thereof
CN106622142A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Metal organic skeleton material Cu3(BTC)2, and preparation method and application thereof
CN105646899B (en) * 2016-01-20 2019-01-01 辽宁大学 One kind being based on InⅢMetal organic anion skeleton and its preparation method and application
CN105646899A (en) * 2016-01-20 2016-06-08 辽宁大学 Metal organic anion framework based on InIII and preparation method and application thereof
CN105772093A (en) * 2016-04-05 2016-07-20 哈尔滨理工大学 Encapsulated [VW12]4-cluster metal organic nanotube micropore crystalline state material, and preparation method and application thereof
CN105772093B (en) * 2016-04-05 2018-03-16 哈尔滨理工大学 Nang Bao [VW12]4‑Metal organic nanotube microporous crystalline material of cluster and its preparation method and application
CN105713208A (en) * 2016-04-15 2016-06-29 中国科学院上海高等研究院 CuZn bi-metal organic framework material and preparing method thereof
CN106669831A (en) * 2016-12-06 2017-05-17 北京林业大学 Preparation method and application of dual-functional hydrodeoxygenation catalyst
CN106622384A (en) * 2016-12-06 2017-05-10 北京林业大学 Preparation method and application of non-sulphurized hydrodeoxygenation catalyst
CN107597190A (en) * 2017-08-14 2018-01-19 湖北大学 A kind of preparation method and applications of zeolite molecular sieve grain surface assembling metal organic framework film
CN107597190B (en) * 2017-08-14 2019-12-06 湖北大学 preparation method and application of zeolite molecular sieve crystal grain surface assembled metal organic framework film
CN107694611A (en) * 2017-09-29 2018-02-16 中国石油大学(华东) A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst

Similar Documents

Publication Publication Date Title
Tran et al. Expanding applications of metal− organic frameworks: zeolite imidazolate framework ZIF-8 as an efficient heterogeneous catalyst for the knoevenagel reaction
Nishimura et al. Characterization, synthesis and catalysis of hydrotalcite-related materials for highly efficient materials transformations
Sarmah et al. Green and sustainable tandem catalytic approach for fine-chemicals synthesis using octahedral MnO2 molecular sieve: Catalytic activity versus method of catalyst synthesis
Antonelli et al. Synthesis and characterization of hexagonally packed mesoporous tantalum oxide molecular sieves
Bromberg et al. Chromium (III) terephthalate metal organic framework (MIL-101): HF-free synthesis, structure, polyoxometalate composites, and catalytic properties
Wang et al. Hydrothermal synthesis and characterization of a novel one-dimensional titanium glycolate complex single crystal: Ti (OCH2CH2O) 2
Ciesla et al. Highly ordered porous zirconias from surfactant-controlled syntheses: zirconium oxide− sulfate and zirconium oxo phosphate
Zhou et al. Recent advances in polyoxometalate-based heterogeneous catalytic materials for liquid-phase organic transformations
Raja et al. Constraining asymmetric organometallic catalysts within mesoporous supports boosts their enantioselectivity
Jia et al. Small-sized HZSM-5 zeolite as highly active catalyst for gas phase dehydration of glycerol to acrolein
Brégeault et al. From polyoxometalates to polyoxoperoxometalates and back again; potential applications
Prior et al. Chiral direction and interconnection of helical three-connected networks in metal-organic frameworks
Bhaumik et al. Mesoporous titanium phosphate molecular sieves with ion-exchange capacity
Hoang et al. Ultrafast and continuous synthesis of unaccommodating inorganic nanomaterials in droplet-and ionic liquid-assisted microfluidic system
Morey et al. Pseudotetrahedral O3/2V O Centers Immobilized on the Walls of a Mesoporous, Cubic MCM-48 Support: Preparation, Characterization, and Reactivity toward Water As Investigated by 51V NMR and UV− Vis Spectroscopies
CN1330416C (en) Modification method of titanium silicone molecular sieve and its application
Lu et al. Surfactant media to grow new crystalline cobalt 1, 3, 5-benzenetricarboxylate metal–organic frameworks
Kuruppathparambil et al. A room temperature synthesizable and environmental friendly heterogeneous ZIF-67 catalyst for the solvent less and co-catalyst free synthesis of cyclic carbonates
Suzuki et al. Strategic design and refinement of Lewis acid–base catalysis by rare-earth-metal-containing polyoxometalates
Thomas et al. Molecular sieve catalysts for the regioselective and shape-selective oxyfunctionalization of alkanes in air
Tanabe et al. Modular, Active, and Robust Lewis Acid Catalysts Supported on a Metal− Organic Framework
Das et al. Synthesis, characterization, and biofuel application of mesoporous zirconium oxophosphates
Liu et al. Ionothermal synthesis of zirconium phosphates and their catalytic behavior in the selective oxidation of cyclohexane
Karimi et al. A highly efficient and recyclable silica-based scandium (III) interphase catalyst for cyanosilylation of carbonyl compounds
Luca et al. Study of the structure and mechanism of formation through self-assembly of mesostructured vanadium oxide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150211