CN109289912A - A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof - Google Patents
A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109289912A CN109289912A CN201811112068.3A CN201811112068A CN109289912A CN 109289912 A CN109289912 A CN 109289912A CN 201811112068 A CN201811112068 A CN 201811112068A CN 109289912 A CN109289912 A CN 109289912A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solid base
- trimethylammonium bromide
- base catalyst
- cetyl trimethylammonium
- 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.)
- Pending
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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
This application discloses a kind of three-dimensional short-bore road mesoporous solid base catalyst and preparation method thereof, which is added ammonium hydroxide after its dissolution, stirs, obtain clear transparent solutions the following steps are included: being dissolved in water cetyl trimethylammonium bromide;Clear transparent solutions are heated under stiring, ethyl bridged silane and amido bridged silane are then sequentially added into this solution, then continue to stir by this solution, is cooled to and stands overnight;Obtained solution is filtered, obtains white solid after removing template agent removing cetyl trimethylammonium bromide.Catalyst of the invention not only has three-dimensional cage structure, but also duct is shorter, is conducive to the absorption and diffusion of reaction species, to be conducive to the raising of catalytic activity.
Description
Technical field
The application belongs to chemical technology field, specifically, be related to a kind of three-dimensional short-bore road mesoporous solid base catalyst and
Preparation method and application.
Background technique
The alkali that Henle reaction can be used as catalyst has potassium hydroxide, potassium carbonate, sodium bicarbonate, sodium alkoxide, amine, calcium hydroxide
Deng;Henry reaction refers to the condensation reaction synthesis of nitroparaffins and aldehydes or ketones, is formation carbon-carbon bond in Synthetic Organic Chemistry
One of most important reaction, in general, fatty aldehyde reacts under secondary amine catalysis with nitroparaffins generates nitro vinyl compound.Nitre
Base vinyl compound is widely used in organic synthesis, and it also has preferable sterilization and antitumor isoreactivity.The reaction is logical
Common potassium hydroxide, potassium carbonate, sodium bicarbonate, sodium alkoxide, amine, calcium hydroxide etc. are catalyst.Most of catalyst one used
Aspect has stronger alkalinity, has certain corrosivity to reaction vessel;The separation of another aspect catalyst difficulty, hardly possible repeat to make
With, therefore not only pollute the environment, and increase manufacturing cost.
Mesoporous silicon material with biggish specific surface area and regular orderly structure due to being widely used catalytic field.?
It has been reported that confirmation, not only can solve catalyst in organic synthesis using ordered mesoporous silicon material as the carrier of catalyst
Difficult separation problem, and resulting catalyst may be reused repeatedly.The mesoporous organosilicon material of caged three-dimensional open-framework, one
Aspect has the hole of adjustable inlet port, than the suction that the mesoporous silicon material of traditional two-dimensional channel is more advantageous to organic reaction substrate
Echo mass transfer;Organic group in another aspect skeleton enhances the hydrophobicity of catalyst, improves organic matter and catalyst activity
Central contact chance, to improve catalytic efficiency.The three-dimensional ordered mesoporous organosilicon (PMO) in short-bore road not only has above excellent
Point, and due to its shorter duct, reaction absorption and mass transfer velocity are improved, to further increase the catalytic of catalyst
Energy.
Have been reported that phenyl bridging organosilicon is copolymerized long duct three-dimensional order obtained in surfactant P123 effect at present
Mesoporous organosilicon is applied to catalysis, and the short-bore road being prepared by the effect of P123, the organic silica polycondensate of vinyl bridging
Two-dimentional organosilicon applied catalysis, this solid catalyst two-dimensional structure longer or short due to resulting 3 D pore canal, is unfavorable for
The mass transfer of reactant molecule, activity are also subject to certain restrictions.
Summary of the invention
In view of this, this application provides a kind of three-dimensional short-bore road mesoporous solid base catalyst and preparation method thereof with answer
With.
In order to solve the above-mentioned technical problem, this application discloses a kind of preparations of three-dimensional short-bore road mesoporous solid base catalyst
Method, comprising the following steps:
Cetyl trimethylammonium bromide is dissolved in water by step 1, ammonium hydroxide is added after its dissolution, and stir, is obtained
Clear transparent solutions;
Step 2 under stiring heats clear transparent solutions, then sequentially added into this solution ethyl bridged silane and
Then this solution is continued to stir by amido bridged silane, be cooled to and stand overnight;
Step 3, the solution obtained to step 2 processing filter, and remove template agent removing cetyl trimethylammonium bromide
(CTAB) white solid is obtained after, and three-dimensional short-bore road mesoporous solid base catalyst is prepared.
Optionally, the molar ratio of the cetyl trimethylammonium bromide and water is 1:8.87-1:9.85.
Optionally, the Molar of ammonium hydroxide and cetyl trimethylammonium bromide ratio (ml/mmol) is 12:1-11.3:1.
Optionally, the mixing time in the step 1 is 12-18min, and whipping temp is 20-30 DEG C.
Optionally, ethyl bridged silane is (triethoxysilyl) ethane of 1,2- bis- or 1, (the trimethoxy first of 2- bis-
Silylation) ethane;Amido bridged silane is bis- [3- (triethoxysilane) propyl] amine or bis- [3- (trimethoxy silane) third
Base] amine.
Optionally, the molar ratio (mmol/mmol) of ethyl bridged silane and cetyl trimethylammonium bromide is 1.30:1-
1.54:1;The molar ratio (mmol/mmol) of amido bridged silane and cetyl trimethylammonium bromide is 1:1.56-1:2.92.
Optionally, the temperature after the heating in the step 2 is 53-60 DEG C, and heating rate is 1-3 DEG C/min;It is described
Step 2 in whipping temp be 53-60 DEG C, mixing time 7-9h;Temperature after cooling is 20-30 DEG C in step 2.
The invention also discloses a kind of three-dimensional short-bore road mesoporous solid base catalysts that above-mentioned preparation method is prepared.
Optionally, specific surface area 850-110m2/ g, aperture 2.5-3.5nm, duct are 200~350nm.
The invention also discloses a kind of above-mentioned three-dimensional short-bore road mesoporous solid base catalysts in aqueous medium Knoevenagel
Application in reaction.
Compared with prior art, the application can be obtained including following technical effect:
1) organic base secondary amine catalyst is immobilized on the order mesoporous organosilicon material in three-dimensional short-bore road using copolymerization method by the present invention
On material, using mesoporous material bigger serface, orderly regular three-D pore structure, short duct and hydrophobicity the features such as, one
Coming into full contact with for catalytic active site high degree of dispersion, substrate and activated centre may be implemented in aspect, on the other hand, by covalent bond with
The catalytic active center that carrier is connected is not easy to be lost from carrier, is able to achieve recycling for catalyst, finally realizes organic
React greenization.
2) compared with the three-dimensional long order mesoporous solid base in duct, since solid base catalyst provided by the invention has three-dimensional
Cage structure, is conducive to the absorption and diffusion of reaction species, to be conducive to the raising of catalytic activity.
3) compared with two-dimentional short-bore road catalyst, catalyst hydrophobicity organic group rich in provided by the present invention
Group, improves organic reactant in the absorption of catalyst surface, is conducive to the raising of catalytic activity.
4) present invention prepares the three-dimensional ordered mesoporous solid base in short-bore road under alkaline condition, and is prepared under acid condition
Sequence mesoporous solid base catalyst is compared, and this method does not need to be handled with saturated sodium carbonate, this not only reduces the use of chemical reagent,
And becoming preparation method simply, production cost is greatly reduced.
Certainly, any product for implementing the application must be not necessarily required to reach all the above technical effect simultaneously.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 is the N of the embodiment of the present application 1 gained three-dimensional short-bore road solid base catalyst2Adsorption-desorption isothermal figure;
The longitudinal axis is to absorb volume, and horizontal axis is relative pressure;
Fig. 2 is the small angle XRD diagram of the three-dimensional short-bore of the embodiment of the present application 1 road solid base catalyst;
Fig. 3 is that the SEM figure (a) of the embodiment of the present application 1 gained three-dimensional short-bore road solid base catalyst and TEM scheme (b) and TEM
Scheme (c);
Fig. 4 is the relational graph for applying number and yield of three-dimensional short-bore road solid base catalyst obtained by the application;The longitudinal axis is
Yield, horizontal axis are to repeat to apply number.
Specific embodiment
Presently filed embodiment is described in detail below in conjunction with accompanying drawings and embodiments, how the application is applied whereby
Technological means solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The invention discloses a kind of preparation methods of three-dimensional short-bore road mesoporous solid base catalyst, comprising the following steps:
Cetyl trimethylammonium bromide (CTAB) is dissolved in water by step 1, wherein cetyl trimethyl bromination
The molar ratio (mmol/mol) of ammonium and water is 1:8.87-1:9.85, ammonium hydroxide is added after its dissolution, wherein ammonium hydroxide and hexadecane
The Molar ratio (ml/mmol) of base trimethylammonium bromide is 12:1-11.3:1, stirs 12-18min at 20-30 DEG C, obtains
Clear transparent solutions;
Clear transparent solutions are heated to 53-60 DEG C under stiring by step 2, and heating rate is 1-3 DEG C/min, then to
Ethyl bridged silane and amido bridged silane are sequentially added in this solution, wherein ethyl bridged silane and cetyl trimethyl
The molar ratio (mmol/mmol) of ammonium bromide is 1.30:1-1.54:1;Amido bridged silane and cetyl trimethylammonium bromide
Molar ratio (mmol/mmol) is 1:1.56-1:2.92;Ethyl bridged silane be (triethoxysilyl) ethane of 1,2- bis- or
1,2- bis- (trimethoxysilyl) ethane;Amido bridged silane is bis- [3- (triethoxysilane) propyl] amine or bis- [3-
(trimethoxy silane) propyl] amine;Then this solution is continued to be cooled to 20-30 DEG C after stirring 7-9h at 53-60 DEG C
And it stands overnight;
Step 3, the solution obtained to step 2 processing filter, and remove template agent removing cetyl trimethylammonium bromide
(CTAB) white solid is obtained after, as three-dimensional short-bore road mesoporous solid base catalyst.
In above-mentioned preparation method, CTAB is template, and ammonium hydroxide provides alkalinity, and ethyl bridging organosilicon provides catalyst
Skeleton, amido bridged silane improves catalyst base catalysis active sites.That is, CTAB first is in alkalescent ammonia spirit
In hydrolyze to form micella, then organosilicon its surface carry out self assembly, finally by extracting process removal surfactant be
Obtain the three-dimensional ordered mesoporous solid base catalyst in short-bore road.The power and temperature of alkalinity will affect the formation of micella, to influence
Catalyst structure.The amount ranges of CTAB and ammonium hydroxide are extremely important, this determines micelle forma-tion speed and shape, if alkalinity is too strong
It may cannot get three-dimensional structure;The dosage of another organosilan and CTAB ratio range are also extremely important, if organic
Silane dosage is too big or too small, all hardly results in ordered mesopore structure.
Embodiment 1
1.4mmol cetyl trimethylammonium bromide (CTAB) is dissolved in 13mol water first, is added after its dissolution
The ammonium hydroxide of 16.8ml stirs 15min at 25 DEG C, obtains clear transparent solutions.This solution 53 DEG C are heated under stiring (to rise
Warm rate is 2 DEG C/min) sequentially add in backward this solution (triethoxysilyl) ethane of 2.16mmol1,2- bis- and
Then bis- [3- (triethoxysilane) propyl] amine of 0.48mmol continue this solution to be cooled to after stirring 7h at 53 DEG C
It 25 DEG C and stands overnight.White solid finally is obtained after filtering, going template agent removing CTAB, three-dimensional short-bore road is prepared and is situated between
Hole solid base catalyst.
As shown in Figure 1, the nitrogen Adsorption and desorption isotherms of sample belong to I type Adsorption and desorption isotherms, show that sample has
There is meso-hole structure;As shown in Fig. 2, sample has ordered mesopore structure.Wherein in 2 θ=1.7,1.9,2.1 diffraction maximums occurred,
It corresponds respectively to [200] of sample, [210], [211] face, and the diffraction maximum occurred in 2 θ=3.0,3.1,3.3 corresponds respectively to
[320] of sample, [321], [400] face, these results confirm sample long-range order three-dimensional structure (pm3n) pore structure.This
Apply for that SEM figure and the TEM figure of embodiment 1 gained three-dimensional short-bore road solid base catalyst are as shown in Figure 3;It can from SEM figure
Gained catalyst near-spherical out, it can be seen that the duct of sample is shorter, Fig. 3 c further confirms the ratio table of gained catalyst
Area is 850-110m2/ g, aperture 2.5-3.5nm, duct are about 200~350nm.As shown in figure 4, the catalyst repeats to make
After 6 times, catalytic activity is not substantially reduced, and is used to the 6th time, efficiency of pcr product remains to reach 88%.
Embodiment 2
1.5mmol cetyl trimethylammonium bromide (CTAB) is dissolved in 13.3mol water first, is added after its dissolution
The ammonium hydroxide for entering 17ml stirs 15min at 20 DEG C, obtains clear transparent solutions.This solution 53 DEG C are heated under stiring (to rise
Warm rate is 2 DEG C/min) sequentially add in backward this solution (triethoxysilyl) ethane of 1.95mmol1,2- bis- and
Then bis- [3- (trimethoxy silane) propyl] amine of 0.96mmol continue this solution to be cooled to after stirring 8h at 56 DEG C
It 20 DEG C and stands overnight.White solid finally is obtained after filtering, going template agent removing CTAB, three-dimensional short-bore road is prepared and is situated between
Hole solid base catalyst.
Embodiment 3
1.3mmol cetyl trimethylammonium bromide (CTAB) is dissolved in 12.8mol water first, is added after its dissolution
The ammonium hydroxide for entering 15.0ml stirs 15min at 30 DEG C, obtains clear transparent solutions.This solution is heated to 53 DEG C under stiring
Sequentially added in (heating rate be 2 DEG C/min) this backward solution (trimethoxysilyl) ethane of 2.0mmol1,2- bis- and
With bis- [3- (triethoxysilane) propyl] amine of 0.72mmol, then this solution is continued at 58 DEG C stir 7.5h after its is cold
But it to 30 DEG C and stands overnight.White solid finally is obtained after filtering, going template agent removing CTAB, three-dimensional short-bore is prepared
Road mesoporous solid base catalyst.
Comparative example 1
NH-MSN-2D-S comes from document: Journal of Molecular Catalysis A:Chemical 363-
364 (2012) 387-397. indicate the order mesoporous solid base catalyst in two-dimentional short-bore road, and the skeleton of catalyst is mainly titanium dioxide
Silicon.
Application of 4 catalyst of embodiment in aqueous medium Knoevenagel reaction
1.0mmol benzaldehyde, 1.2mmol ethyl cyanoacetate, 3.0ml deionized water, internal standard compound is being added just in reaction flask
The tetradecane and catalyst (the amount 0.040mmol containing N), react 4h at 40 DEG C.After reaction, it is extracted with ethyl acetate out anti-
The organic matter in system is answered, to its quantitative analysis in gas-chromatography, experimental result is shown in Table 1.
Catalytic performance of 1 different catalysts of table in aqueous medium Knoevenagel reaction
Serial number | Catalyst | Conversion ratio (%) |
Embodiment 1 | NH-PMO(Et)-3D-S | 98 |
Embodiment 2 | NH-PMO(Et)-3D-S | 96 |
Embodiment 3 | NH-PMO(Et)-3D-S | 97 |
Comparative example 1 | NH-MSN-2D-S | 90 |
Wherein, NH-PMO (Et) -3D-S is the catalyst of 1-3 of embodiment of the present invention method preparation.
As used some vocabulary in the specification and claims to censure special component or method.Art technology
Personnel are, it is to be appreciated that different regions may call the same ingredient with different nouns.This specification and claims are not
In such a way that the difference of title is as ingredient is distinguished.As the "comprising" mentioned by throughout the specification and claims is
One open language, therefore should be construed to " including but not limited to "." substantially " refer within the acceptable error range, this field
Technical staff can solve the technical problem within a certain error range, basically reach the technical effect.Specification is subsequent
It is described as implementing the better embodiment of the application, so the description is for the purpose of the rule for illustrating the application, not
To limit scope of the present application.The protection scope of the application is as defined by the appended claims.
It should also be noted that, the terms "include", "comprise" or its any other variant are intended to nonexcludability
Include, so that commodity or system including a series of elements not only include those elements, but also including not clear
The other element listed, or further include for this commodity or the intrinsic element of system.In the feelings not limited more
Under condition, the element that is limited by sentence "including a ...", it is not excluded that in the commodity or system for including the element also
There are other identical elements.
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification
And environment, and can be carried out within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then it all should be in the appended power of invention
In the protection scope that benefit requires.
Claims (10)
1. a kind of preparation method of three-dimensional short-bore road mesoporous solid base catalyst, which comprises the following steps:
Cetyl trimethylammonium bromide is dissolved in water by step 1, ammonium hydroxide is added after its dissolution, and stir, is clarified
Clear solution;
Step 2 under stiring heats clear transparent solutions, and ethyl bridged silane and amino are then sequentially added into this solution
Then this solution is continued to stir by bridged silane, be cooled to and stand overnight;
Step 3, the solution obtained to step 2 processing filter, and remove template agent removing cetyl trimethylammonium bromide (CTAB)
After obtain white solid, three-dimensional short-bore road mesoporous solid base catalyst is prepared.
2. preparation method according to claim 1, which is characterized in that the cetyl trimethylammonium bromide and water
Molar ratio is 1:8.87-1:9.85.
3. preparation method according to claim 1, which is characterized in that the volume of ammonium hydroxide and cetyl trimethylammonium bromide
Molar ratio (ml/mmol) is 12:1-11.3:1.
4. preparation method according to claim 1, which is characterized in that the mixing time in the step 1 is 12-
18min, whipping temp are 20-30 DEG C.
5. preparation method according to claim 1, which is characterized in that ethyl bridged silane is (the triethoxy first of 1,2- bis-
Silylation) ethane or 1,2- bis- (trimethoxysilyl) ethane;Amido bridged silane is bis- [3- (triethoxysilane) third
Base] amine or bis- [3- (trimethoxy silane) propyl] amine.
6. preparation method according to claim 1, which is characterized in that ethyl bridged silane and cetyl trimethyl bromination
The molar ratio (mmol/mmol) of ammonium is 1.30:1-1.54:1;Mole of amido bridged silane and cetyl trimethylammonium bromide
It is 1:1.56-1:2.92 than (mmol/mmol).
7. preparation method according to claim 1, which is characterized in that the temperature after heating in the step 2 is 53-
60 DEG C, heating rate is 1-3 DEG C/min;Whipping temp in the step 2 is 53-60 DEG C, mixing time 7-9h;Step
Temperature after cooling is 20-30 DEG C in 2.
8. the three-dimensional short-bore road mesoporous solid alkali that preparation method described in any claim is prepared in claim 1-7 is urged
Agent.
9. three-dimensional short-bore road according to claim 8 mesoporous solid base catalyst, which is characterized in that its specific surface area is
850-110m2/ g, aperture 2.5-3.5nm, duct are 200~350nm.
10. three-dimensional short-bore road mesoporous solid base catalyst according to any one of claims 8 answering in aqueous medium Knoevenagel reaction
With.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811112068.3A CN109289912A (en) | 2018-09-25 | 2018-09-25 | A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811112068.3A CN109289912A (en) | 2018-09-25 | 2018-09-25 | A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109289912A true CN109289912A (en) | 2019-02-01 |
Family
ID=65163909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811112068.3A Pending CN109289912A (en) | 2018-09-25 | 2018-09-25 | A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109289912A (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101069847A (en) * | 2007-05-25 | 2007-11-14 | 上海师范大学 | Mesoporous-structure metal nickel catalyst and its preparing method and use |
CN101791573A (en) * | 2010-02-26 | 2010-08-04 | 上海师范大学 | Diamine-bridged ordered mesoporous organic base heterogeneous catalyst, and preparation method and applications thereof |
CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
CN104445214A (en) * | 2014-11-03 | 2015-03-25 | 东华大学 | Mesoporous silica nano hollow sphere and preparation method thereof |
CN104624233A (en) * | 2015-02-06 | 2015-05-20 | 淮阴师范学院 | Ethylenediamine functionalized three-dimensional ordered mesopore organosilicone immobilized Pd(II) catalyst |
-
2018
- 2018-09-25 CN CN201811112068.3A patent/CN109289912A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101069847A (en) * | 2007-05-25 | 2007-11-14 | 上海师范大学 | Mesoporous-structure metal nickel catalyst and its preparing method and use |
CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
CN101791573A (en) * | 2010-02-26 | 2010-08-04 | 上海师范大学 | Diamine-bridged ordered mesoporous organic base heterogeneous catalyst, and preparation method and applications thereof |
CN104445214A (en) * | 2014-11-03 | 2015-03-25 | 东华大学 | Mesoporous silica nano hollow sphere and preparation method thereof |
CN104624233A (en) * | 2015-02-06 | 2015-05-20 | 淮阴师范学院 | Ethylenediamine functionalized three-dimensional ordered mesopore organosilicone immobilized Pd(II) catalyst |
Non-Patent Citations (1)
Title |
---|
BUYUAN GUAN ET AL.: "Highly ordered periodic mesoporous organosilica nanoparticles with controllable pore structures", 《NANOSCALE》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20080175783A1 (en) | Amino-Functionalized Mesoporous Silica | |
CN106622326B (en) | A kind of hud typed carbon nitride material and preparation method thereof | |
Dencic et al. | From a review of noble metal versus enzyme catalysts for glucose oxidation under conventional conditions towards a process design analysis for continuous-flow operation | |
CN111085265B (en) | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof | |
CN104307514B (en) | A kind of titania/silica compound spherical shell parcel nano catalyst and preparation method thereof | |
CN101264453A (en) | Titanium-silicon molecular sieve/tripolite composite catalyst and preparation | |
CN106495105A (en) | A kind of method of synthesis nanometer selenium material | |
CN104098106A (en) | One-step synthesizing method for hollow type multilevel-hole Fe-Silicalite-1 | |
CN107185594A (en) | A kind of preparation method of Ni Zn K Ru/MOF catalyst | |
CN103055938B (en) | Preparation method of acid-base bifunctional graphene-based nano heterogeneous catalyst | |
CN102295524A (en) | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane | |
CN104030312B (en) | A kind of synthetic method of titanium-silicon molecular sieve TS-1 | |
CN104725169A (en) | Method for performing alkoxylation reaction in microreactor | |
CN103787360B (en) | A kind of preparation method of whole process TS-1 mesoporous titanium-silicon molecular screen | |
CN109289912A (en) | A kind of three-dimensional short-bore road mesoporous solid base catalyst and the preparation method and application thereof | |
CN107497473B (en) | Preparation method of Y molecular sieve catalyst with cordierite as carrier | |
CN106362739A (en) | Nano-gold catalyst supported on mesoporous carbon-silicon dioxide composite body and preparation method thereof | |
CN101343629A (en) | Improved process for polyvinyl alcohol aluminum salt immobilization microorganism | |
CN108187739A (en) | A kind of currant bread Shi Jin-silica nanometer catalyst and its preparation and application | |
CN104711299A (en) | Method for preparing adrenaline | |
CN1768940A (en) | Hydrotalcite like structurization catalyst with mica as matrix and preparation method | |
CN114560982B (en) | Two-dimensional covalent organic framework material based on tripyridine trioxymethylene, and preparation method and application thereof | |
CN110560107A (en) | Ni-MoS2/RGO/Ti3C2Method for preparing composite material | |
CN101823001B (en) | Preparation method of amido bridged regular mesoporous organic base heterogeneous catalyst | |
CN102174033A (en) | New method for preparing 1,3-dioxolane by catalytic condensation |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190201 |
|
RJ01 | Rejection of invention patent application after publication |