CN106669841A - Phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with mesoporous structure and preparation method - Google Patents
Phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with mesoporous structure and preparation method Download PDFInfo
- Publication number
- CN106669841A CN106669841A CN201510749153.0A CN201510749153A CN106669841A CN 106669841 A CN106669841 A CN 106669841A CN 201510749153 A CN201510749153 A CN 201510749153A CN 106669841 A CN106669841 A CN 106669841A
- Authority
- CN
- China
- Prior art keywords
- acid
- composite material
- pmo
- sulfonic acid
- solid matter
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with a mesoporous structure and a preparation method, which belong to the chemical field. The phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material has the following chemical composition: H3PW12O40/SO3H-C3H6-Si(OH)3-m(SiO)m-(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n, i.e. pr-SO3H-PMO/H3PW12O40. The product disclosed by the invention adopts Keggin-structure polyacid (H3PW12O40) as an active component, bridged organic silane reagent (1,2-bis(triethoxysilyl)ethane-BTSE) as an organosilicon precursor, nonionic surfactant (P123, M=5800) as a structure-directing agent and 3-mercaptopropyl-trimethoxysilane (MPTMS) as a silanizing reagent, and a one-step hydrolysis-cocondensation-integrated hydrothermal treatment technique is adopted to design and prepare the phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with the mesoporous structure. The process of preparing the composite material pr-SO3H-PMO/H3PW12O40 is simple, the reaction specificity is good, the conversion rate is high when the composite material is used for catalyzing para-diphenylmethanol and Alpha-nitro ketene dithioacetal to carry out C-C coupling reaction, the purity of the product is high, the purity of the product is high, and the reaction process is clean.
Description
Technical field
The invention belongs to chemical field, be related to it is a kind of with meso-hole structure based on phosphotungstic acid and organic silicon composite and preparation method of sulfonic acid funtionalized。
Background technology
The liquid acids such as sulfuric acid are widely used in Chemical Manufacture as traditional acid catalyst, and the sulfuric acid that 15,000,000 tons are had more than every year is consumed.These liquid acid catalysts must be removed from reaction system in order to obtain pure product, this process consumes the substantial amounts of energy, and produces large amount of sewage, causes serious energy waste and environmental pollution.And liquid acid has serious corrosiveness to production equipment, improves cost of equipment maintenance, the service life of production equipment is shortened, be problem demanding prompt solution in industrial production.The chemical engineering process of " green " is advocated and the liquid acid catalyst that not can be recycled is substituted using the solid acid of reusable edible.Therefore, solid acid catalyst has obtained scientists and has more and more paid close attention to.Sulfonic acid group is often used as solid acid catalyst activity functional group because it can efficiently provide proton, and in the research of many polyelectrolyte films it is verified it solid has good compatibility with polymer etc..
Since 20 century 70s, polyoxometallate is increasingly favored in petrochemical industry and catalyst preparation field as catalyst by catalyst operation person.Heteropoly acid is not only a kind of very strong pure Bronsted acid of acid strength, or the acid catalysis and redox " difunctional " property catalyst of a class excellent performance.Therefore, heteropoly acid is used as catalysis activity is high, selective good, free of contamination environmental type solid acid catalyst, with advantageous advantage and wide application prospect.But pure polyacid as catalyst have the shortcomings that little specific surface area, etching apparatus, pollute environment, be soluble in polar solvent, catalysis activity can not give full play to and can not recycling, greatly limit heteropoly acid popularization and application in the industrial production.Therefore modified and heterogeneousization for studying heteropoly acid is needed, to solving the problems, such as that polyacid is not easily recycled as homogeneous catalyst.
At present, people mostly using by way of sulfonic acid group or heteropoly acid are individually supported on silica pore material support improving its specific surface area, heat endurance, catalysis activity and its reusability etc., so as to realize the heterogeneous acid catalysis of sulfonic group or polyacid and redox function.But, the surface of inorganic silicon dioxide composite has the hydroxyl of high concentration, with stronger hydrophily, the easy strong adsorption of hydrophily product is in the surface and duct of silica in catalytic reaction, cause catalyst serious inactivation during recycling, also, mostly using rear grafting or infusion process, operating process is complicated, and experimental period is long.
Result of study shows that changing the type of the organic group species and carrier being embedded in hole wall affects to a great extent the catalytic performance of material.Find through research, material hole wall be internally embedded or channel surfaces introduce organic group after, while meso-hole structure is kept, parent/the hydrophobicity at duct interface can be improved again, be conducive to improving the hydrothermal stability of mesoporous material, even with the species and introduction volume that change organic group the regulation and control of its interfacial property are carried out.Therefore, the order mesoporous organosilicon composite catalyst that design is prepared simultaneously containing catalytic active component sulfonic group and polyacid is significant.Preparation process can ensure that organic silicon composite has the pore passage structure similar to PMO carriers, and, compared with parent multi-acid salt, its BET specific surface area is expected to significantly improve, and the diffusion rate of reactant or product is higher, the accesibility in duct is preferably and resistance to mass tranfer is less, so as to the catalysis activity for causing it higher.Therefore, we using an one-step hydrolysis cocondensation with reference to hydrothermal technology design be prepared for it is a kind of with meso-hole structure based on phosphotungstic acid and organic silicon composite and preparation method of sulfonic acid funtionalized, synthesispr-SO3H-PMO/H3PW12O40Composite.
The content of the invention
The technical problem to be solved in the present invention be using an one-step hydrolysis cocondensation with reference to hydrothermal technology design be prepared for it is a kind of with meso-hole structure based on phosphotungstic acid and organic silicon composite of sulfonic acid funtionalized.
Product of the present invention adopts structure with Keggin polyacid(H3PW12O40)As active component;Bridging organosilane reagents(Double (triethoxy silicon substrate) ethane-BTSE of 1,2-)For organosilane precursor;Nonionic surfactant(P123, M=5800)As structure directing agent;3- mercaptopropyl-trimethoxy silane(MPTMS)For silylating reagent, using an one-step hydrolysis cocondensation with reference to hydrothermal technology design be prepared for it is a kind of with meso-hole structure based on phosphotungstic acid and organic silicon composite of sulfonic acid funtionalized.
The present invention has following chemical composition with meso-hole structure based on organic silicon composite of phosphotungstic acid and sulfonic acid funtionalized:H3PW12O40/SO3H-C3H6-Si(OH)3-m(SiO)m-(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n, i.e.,:pr-SO3H-PMO/H3PW12O40。
With meso-hole structure based on phosphotungstic acid and the preparation method of organic silicon composite of sulfonic acid funtionalized, completed by following steps and condition:
(1)The 1.0 g P123 for weighing are dissolved in the 30 mL watery hydrochloric acid that concentration is 0.5 mol/L, in being placed on the magnetic stirring apparatus with heating, 40 DEG C is then heated the solution to, and are stirred continuously until that all dissolving obtains the settled solution containing structure directing agent to P123;
(2)Weigh 3.0 g KCl to pour into the settled solution described in step 1, be added dropwise over 1.8 mL BTSE after 30 min thereto again, 0.39 mL is added dropwise respectively after 45 min(3- mercaptopropyis)- trimethoxy silane(MPTMS)With the H of 3.6 mL2O2.Now, mixed liquor has gelatin phenomenon to produce, and increases stirring dynamics, promotes the gel to be formed to stir;
(3)After 1 h, by H3PW12O40(0.2 g、0.4 g、0.6 g、0.8 g)Dissolving fills respective amount distilled water(2.5 mL、5.0 mL、7.5 mL、10 mL)Another small beaker in, subsequently with glue head dropper by H3PW12O40
The aqueous solution is dropwise added drop-wise in the gel described in step 2;Continue heating stirring under the conditions of 40 DEG C, make gel be gradually converted into colloidal sol;
(4)After 24 h, the colloidal sol described in step 3 is poured into 100 mL teflon-lined reactors, the h of hydro-thermal reaction 24 under the conditions of 100 DEG C.Pour beaker after cooling into and be put into 80 DEG C of h of drying 10 in vacuum drying chamber, obtain white solid matter;
(5)By the solid matter described in dried step 4 at 80 DEG C with 80 mL absolute ethyl alcohol reflux extractions, to accelerate extraction process, the dense HCl of 0.5 mL are added every time, solid matter in centrifugation liquid mixed above, this step is in triplicate, 7 h every time, thoroughly to remove the structure directing agent P123 in solid matter;
(6)The solid matter for removing structure directing agent is placed in vacuum drying chamber into 80 DEG C to be dried overnight, white powdery solids composite is obtained, final product is usedpr-SO3H-PMO/H3PW12O40- x represents that x represents H3PW12O40Loading.
After testing, obtainpr-SO3H-PMO/H3PW12O40H in-x3PW12O40Content be the wt% of x=9.35,11.69,20.67,23.14, its result obtains by ICP-AES,pr-SO3H-PMO/H3PW12O40For ordered mesopore structure, average pore size is in 4.82-5.33 nm.
pr-SO3H-PMO/H3PW12O40Catalytic effect is evaluated --- tested as probe with the carbon carbon coupling reaction carried out to benzhydrol and α-nitro dithio keteal.
Experiment base stock used:To benzhydrol, α-nitro dithio keteal, acetonitrile and normal octane.Testing composite used ispr-SO3H-PMO/H3PW12O40-x(x=9.35、11.69、20.67、23.14 wt%), have rated different H3PW12O40The catalysis activity of load capacity composite.
Composite is placed on into 110 DEG C of 2 h of vacuum drying in vacuum drying chamber before catalysis test.
pr-SO3H-PMO/H3PW12O40It is catalyzed the Jing rows in 25 mL, the two mouthfuls of round-bottomed flasks with condenser pipe of the carbon carbon coupling reaction to benzhydrol and α-nitro dithio keteal.By 100 mg catalyst, 182 mg(1 mmol)To benzhydrol, 198 mg(1.2 mmol)α-nitro dithio keteal and 0.172 mL(1 mmol)Normal octane(Make internal standard)In being added sequentially to round-bottomed flask, in being placed in the magnetic stirring apparatus with heating, flow back 12 h under the conditions of 70 DEG C.The difference H of table 13PW12O40Load capacitypr-SO3H-PMO/H3PW12O40The conversion ratio and yield and the selectivity of coupled product to benzhydrol and α-nitro dithio keteal reaction of catalysis.
Table 1
The target product of acquisition, is analyzed, analysis condition with gas chromatograph Agilent GC6890:Chromatographic column Agilent 19091N-133
HP-INNOWAX Polyethylene Glycol, fid detector, injector temperature is 250 DEG C, and detector temperature is 280 DEG C, and gas-chromatography carries out qualitative to benzhydrol, and benzhydrol conversion ratio is analyzed, and gas phase data analysing method adopts normalization method.
The result of analytical table 1 is visible, compositepr-SO3H-PMO/H3PW12O40The reaction specificity that catalysis carries out carbon carbon coupling to benzhydrol and α-nitro dithio keteal is good, high conversion rate, course of reaction cleaning, is suitable to industrialization promotion;Additionally,pr-SO3H-PMO/H3PW12O40H in -23.14 composites3PW12O40Load capacity nearly reach saturation, its catalytic reaction yield also has no and significantly improves, it is contemplated that financial cost problem, and we are final to determine and usepr-SO3H-PMO/H3PW12O40- 20.67 is dreamboat composite.
Description of the drawings
Fig. 1 be the present invention with meso-hole structure based on phosphotungstic acid and organic silicon composite of sulfonic acid funtionalizedpr-SO3H-PMO/H3PW12O40- 20.67 scheme perpendicular to the TEM of pore passage structure.By figure it can be found that composite has obvious two-dimentional six side(p6mm)Ordered mesopore structure, it is mesoporous to be evenly distributed and in ordered arrangement.
Specific embodiment:
(1)The 1.0 g P123 for weighing are dissolved in the 30 mL watery hydrochloric acid that concentration is 0.5 mol/L, in being placed on the magnetic stirring apparatus with heating, 40 DEG C is then heated the solution to, and are stirred continuously until that all dissolving obtains the settled solution containing structure directing agent to P123;
(2)Weigh 3.0 g KCl to pour into the settled solution described in step 1, be added dropwise over 1.8 mL BTSE after 30 min thereto again, 0.39 mL is added dropwise respectively after 45 min(3- mercaptopropyis)- trimethoxy silane(MPTMS)With the H of 3.6 mL2O2.Now, mixed liquor has gelatin phenomenon to produce, and increases stirring dynamics, promotes the gel to be formed to stir;
(3)After 1 h, by 0.6 g H3PW12O40Dissolving is filled in another small beaker of the mL of respective amount distilled water 7.5, subsequently uses glue head dropper by H3PW12O40
The aqueous solution is dropwise added drop-wise in the gel described in step 2;Continue heating stirring under the conditions of 40 DEG C, make gel be gradually converted into colloidal sol;
(4)After 24 h, the sol solution described in step 3 is poured into 100 mL teflon-lined reactors, the h of hydro-thermal reaction 24 under the conditions of 100 DEG C.Pour beaker after cooling into and be put into 80 DEG C of h of drying 10 in vacuum drying chamber, obtain white solid matter;
(5)By the solid matter described in dried step 4 at 80 DEG C with 80 mL absolute ethyl alcohol reflux extractions, to accelerate extraction process, the dense HCl of 0.5 mL are added every time, solid matter in centrifugation liquid mixed above, this step is in triplicate, 7 h every time, thoroughly to remove the structure directing agent P123 in solid matter;
(6)The solid matter for removing structure directing agent is placed in vacuum drying chamber into 80 DEG C to be dried overnight, white powdery solids composite is obtained, final product is usedpr-SO3H-PMO/H3PW12O40- 20.67 represent.
Claims (2)
1. it is a kind of with meso-hole structure based on phosphotungstic acid and organic silicon composite of sulfonic acid funtionalized, it is characterised in that with following chemical composition:H3PW12O40/SO3H-C3H6-Si(OH)3-m(SiO)m-(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n, i.e.,:pr-SO3H-PMO/H3PW12O40;WhereinprExpression-CH2CH2CH2- group, PMO is organosilicon.
2. according to claims 1 with meso-hole structure based on phosphotungstic acid and the preparation method of organic silicon composite of sulfonic acid funtionalized, completed by following steps and condition:
(1)The 1.0 g P123 for weighing are dissolved in the 30 mL watery hydrochloric acid that concentration is 0.5 mol/L, in being placed on the magnetic stirring apparatus with heating, 40 DEG C is then heated the solution to, and are stirred continuously until that all dissolving obtains the settled solution containing structure directing agent to P123;
(2)Weigh 3.0 g KCl to pour into the settled solution described in step 1, be added dropwise over 1.8 after 30 min thereto again
ML BTSE, are added dropwise respectively 0.39 mL after 45 min(3- mercaptopropyis)- trimethoxy silane(MPTMS)With the H of 3.6 mL2O2, now, mixed liquor has gelatin phenomenon to produce, and increases stirring dynamics, promotes the gel to be formed to stir;
(3)After 1 h, by H3PW12O40(0.2 g、0.4 g、0.6 g、0.8 g)Dissolving fills respective amount distilled water(2.5 mL、5.0 mL、7.5 mL、10 mL)Another small beaker in, subsequently with glue head dropper by H3PW12O40The aqueous solution is dropwise added drop-wise in the gel described in step 2;Continue heating stirring under the conditions of 40 DEG C, make gel be gradually converted into colloidal sol;
(4)After 24 h, the colloidal sol described in step 3 is poured into 100 mL teflon-lined reactors, the h of hydro-thermal reaction 24 under the conditions of 100 DEG C;Pour beaker after cooling into and be put into 80 DEG C of h of drying 10 in vacuum drying chamber, obtain white solid matter;
(5)By the solid matter described in dried step 4 at 80 DEG C with 80 mL absolute ethyl alcohol reflux extractions, to accelerate extraction process, the dense HCl of 0.5 mL are added every time, solid matter in centrifugation liquid mixed above, this step is in triplicate, 7 h every time, thoroughly to remove the structure directing agent P123 in solid matter;
(6)The solid matter for removing structure directing agent is placed in vacuum drying chamber into 80 DEG C to be dried overnight, white powdery solids composite is obtained, final product is usedpr-SO3H-PMO/H3PW12O40- x represents that x represents H3PW12O40Loading(x=9.35、11.69、20.67、23.14 wt%), its result obtains by ICP-AES.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510749153.0A CN106669841B (en) | 2015-11-06 | 2015-11-06 | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510749153.0A CN106669841B (en) | 2015-11-06 | 2015-11-06 | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106669841A true CN106669841A (en) | 2017-05-17 |
CN106669841B CN106669841B (en) | 2019-07-23 |
Family
ID=58858229
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510749153.0A Active CN106669841B (en) | 2015-11-06 | 2015-11-06 | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106669841B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107376965A (en) * | 2017-07-19 | 2017-11-24 | 江苏大学 | A kind of preparation method and applications of the magnetic mesoporous earth silicon material of phosphato-molybdic heteropolyacid support type |
CN110369003A (en) * | 2019-07-25 | 2019-10-25 | 长春工业大学 | A kind of phosphotungstic acid titanium silicon composite and preparation method thereof with meso-hole structure |
CN111804335A (en) * | 2020-07-09 | 2020-10-23 | 长春工业大学 | Phosphotungstic acid and propylsulfonic acid functionalized silicon oxide composite material in non-hydrochloric acid system and preparation method thereof |
CN111825579A (en) * | 2020-07-23 | 2020-10-27 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol ester |
CN111847517A (en) * | 2020-07-09 | 2020-10-30 | 长春工业大学 | Ordered mesoporous carbon composite material directly introduced with tungsten trioxide by hard template method and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6841499B1 (en) * | 1999-10-08 | 2005-01-11 | Chirotech Technology Limited | Supported ferrocene-based catalysts for selective aldehyde hydrogenation |
CN1886196A (en) * | 2003-09-30 | 2006-12-27 | 通用电气公司 | Functionalized zeolite compositions and methods for their preparation and use |
JP2007099746A (en) * | 2005-09-06 | 2007-04-19 | Ube Ind Ltd | Method for producing phenol and cycloalkanone |
CN102218347A (en) * | 2011-04-19 | 2011-10-19 | 东北师范大学 | Polyoxometalates-based organic-inorganic hybrid catalyst with core-shell structure and preparation method thereof |
-
2015
- 2015-11-06 CN CN201510749153.0A patent/CN106669841B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6841499B1 (en) * | 1999-10-08 | 2005-01-11 | Chirotech Technology Limited | Supported ferrocene-based catalysts for selective aldehyde hydrogenation |
CN1886196A (en) * | 2003-09-30 | 2006-12-27 | 通用电气公司 | Functionalized zeolite compositions and methods for their preparation and use |
JP2007099746A (en) * | 2005-09-06 | 2007-04-19 | Ube Ind Ltd | Method for producing phenol and cycloalkanone |
CN102218347A (en) * | 2011-04-19 | 2011-10-19 | 东北师范大学 | Polyoxometalates-based organic-inorganic hybrid catalyst with core-shell structure and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
DEUK JU KIM ET AL: "Properties of SPAES/Phosphotungsticacid/Sulfonated Silica Composite Membranes Prepared by the In situ and Sol-Gel Process", 《MACROMOL. RES.》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107376965A (en) * | 2017-07-19 | 2017-11-24 | 江苏大学 | A kind of preparation method and applications of the magnetic mesoporous earth silicon material of phosphato-molybdic heteropolyacid support type |
CN107376965B (en) * | 2017-07-19 | 2019-12-31 | 江苏大学 | Preparation method and application of phosphomolybdic heteropoly acid loaded magnetic mesoporous silica material |
CN110369003A (en) * | 2019-07-25 | 2019-10-25 | 长春工业大学 | A kind of phosphotungstic acid titanium silicon composite and preparation method thereof with meso-hole structure |
CN110369003B (en) * | 2019-07-25 | 2022-02-01 | 长春工业大学 | Titanium-silicon phosphotungstate composite material with mesoporous structure and preparation method thereof |
CN111804335A (en) * | 2020-07-09 | 2020-10-23 | 长春工业大学 | Phosphotungstic acid and propylsulfonic acid functionalized silicon oxide composite material in non-hydrochloric acid system and preparation method thereof |
CN111847517A (en) * | 2020-07-09 | 2020-10-30 | 长春工业大学 | Ordered mesoporous carbon composite material directly introduced with tungsten trioxide by hard template method and preparation method thereof |
CN111825579A (en) * | 2020-07-23 | 2020-10-27 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol ester |
Also Published As
Publication number | Publication date |
---|---|
CN106669841B (en) | 2019-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106669841A (en) | Phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with mesoporous structure and preparation method | |
CN108816287B (en) | Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof | |
CN110252407B (en) | Method for preparing core-shell structure catalyst by carboxyl functionalized ionic liquid | |
CN105772077A (en) | Magnetic attapulgite supported ionic liquid catalyst and preparation method thereof | |
CN101829551A (en) | Silica gel fixed phase of mixed model as well as preparation method and application thereof | |
CN105665018B (en) | The preparation method and application of composite solid catalyst for production of superstrong | |
CN105854942A (en) | Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction | |
CN105665014A (en) | Supported hydrosilylation platinum catalyst and preparation method thereof | |
CN107188849A (en) | Mesoporous ionic liquid heteropolyacid salt catalyst reacted for benzene hydroxylation and its preparation method and application | |
CN103638988B (en) | Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material | |
CN107774246A (en) | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core | |
CN106191023B (en) | A kind of chitosan/micro- mesic molecule sieves immobilization laccase preparation method, a kind of biodegrading process of phenol wastewater | |
CN102218347B (en) | Polyoxometalates-based organic-inorganic hybrid catalyst with core-shell structure and preparation method thereof | |
CN105521823A (en) | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor | |
CN111375431A (en) | Solid acid catalyst, preparation method thereof and application thereof in esterification ester exchange reaction | |
Teng et al. | Hollow Mesoporous Organic Polymeric Nanospheres (HMOPNs)‐Supported Carbene Rovis Catalyst: Mesopore and Morphology‐Dependent Catalytic Performances in Asymmetric Organocascade | |
Lie et al. | Molecularly imprinted mesoporous silica: Potential of the materials, synthesis and application in the active compound separation from natural product | |
CN105642130A (en) | Ionic liquid modified mesoporous molecular sieve/polymer composite film and preparation and application thereof | |
CN107335472A (en) | A kind of magnetic iron oxide heteropolyacid catalyst and its synthetic method | |
CN104888766A (en) | Hydrogenation deoxidation catalyst and preparation method thereof | |
CN106669830A (en) | Organosilicon-carried phosphotungstic acid composite material with mesoporous structure, preparation method thereof and method for preparing coupled product with same | |
Bakhtiari et al. | Design of an acidic sulfonated mesoporous carbon catalyst for the synthesis of butyl levulinate from levulinic acid | |
CN104525183B (en) | A kind of mesoporous catalyst loading chromio and its preparation method and application | |
CN104383942B (en) | A kind of CTiO of nucleocapsid structure2Solid acid catalyst and preparation method thereof | |
CN102247875A (en) | Preparation method of heteropoly acid / alumina mesoporous composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |