CN110368986A - A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction - Google Patents
A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction Download PDFInfo
- Publication number
- CN110368986A CN110368986A CN201910649762.7A CN201910649762A CN110368986A CN 110368986 A CN110368986 A CN 110368986A CN 201910649762 A CN201910649762 A CN 201910649762A CN 110368986 A CN110368986 A CN 110368986A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- pickering lotion
- knoevenagel
- pickering
- 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
- B01J31/0272—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
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of Pickering lotion catalyst system for Knoevenagel reaction.For Pickering lotion using having amphiphilic catalyst amino-functionalization graphene oxide, benzaldehyde and aqueous solvent to be formed by simple ultrasound and after being vigorously stirred, amino-functionalization graphene oxide is that aminopropyl trimethoxysilane (APTMS) is immobilized to made from the surface of GO.The formation of Pickering lotion can effectively increase the contact surface of catalyst and reactant, when the emulsion system to be used to be catalyzed the Knoevenagel condensation reaction of benzaldehyde and malononitrile, amino-functionalization graphene oxide catalyst can obtain higher catalytic activity in a mild condition.The lotion catalyst system preparation method is simple, preparation process is environmental-friendly and preparation cost is low, at the same catalyst be reused many times after can still prepare stable Pickering emulsion system, have good recycling.
Description
Technical field
The present invention relates to Knoevenagel condensation catalyst and its preparation technical field, in particular to one kind is used for
The preparation method of the Pickering lotion catalyst system of Knoevenagel reaction.Background technique
Knoevenagel condensation reaction is industrial synthesis α, one of important reaction of beta-unsaturated carbonyl compound, the product
It is that one kind has valuable intermediate very much in medicine, cosmetics and chemical pesticide industry.Although traditional homogeneous catalyst
Higher yield can be obtained by being catalyzed the reaction, but the catalyst exists and is difficult to separate and recycle asking for difficulty with product
Topic, therefore the preparation of heterogeneous catalysis is paid attention to use.Preparing the common carrier material of heterogeneous catalysis includes
Polymer, molecular sieve, silica gel etc., these carrier materials but have swellability, hydrothermal stability difference and are easy to burst apart
The disadvantages of.Graphene oxide (GO) is a kind of novel two-dimentional carbon material, with production cost is low, thermal stability is high, mass transfer resistance
The advantages that power is small, large specific surface area, therefore can be using GO as the ideal carrier of immobilized organic amine.
Most of Knoevenagel condensation reaction carries out in organic solvent, and organic solvent itself it is toxic and
Certain pollution can be caused to environment.Water has the advantages that environmental-friendly, cheap and easy to get as a kind of green solvent.However water is not
It is dissolved in benzaldehyde and its derivative, therefore using water as solvent when is unfavorable for the stable progress of Knoevenagel condensation reaction.Have
Part researcher reports the method using water as solvent catalysis Knoevenagel condensation reaction, but when being catalyzed the reaction
There is catalyst amounts it is big, reaction condition is relatively harsh the disadvantages of.
Amino-functionalization graphene oxide is a kind of modification derivant of GO, due to surface oxygen-containing functional group rich in,
This makes it effectively facilitate the formation of Pickering lotion with superior amphipathic characteristic.Pickering lotion
The contact surface of catalyst and reactant (such as benzaldehyde) can be effectively increased so as to further increase urging for catalyst by being formed
Change activity, therefore the purpose of efficient catalytic Knoevenagel condensation reaction in water phase may be implemented using this short-cut method.
Summary of the invention
Present invention research technical problems to be solved are to have used for conventional catalyst Knoevenagel condensation reaction to ring
The disagreeableness organic solvent in border and the disadvantages of catalyst amount is big, reaction condition is relatively harsh when using water as solvent, provides
A kind of environmentally protective, the easy Pickering lotion easily prepared is for efficient catalytic Knoevenagel condensation reaction in water phase
Method.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction, wherein being catalyzed the reaction
Pickering lotion is prepared into immiscible benzaldehyde and water using with amphiphilic amino-functionalization graphene oxide
It arrives.Specific step is as follows for this method:
It weighs a certain amount of amino-functionalization graphene oxide catalyst to be added in 50 mL round-bottomed flasks, add a certain amount of
Water and 1.5 mL benzaldehydes, then ultrasonic (180 W, 60 Hz) handle 5 min, mechanical with 800 rpm revolving speeds after ultrasonic
Pickering lotion can be prepared by stirring 5 min.
Amino-functionalization graphene oxide catalyst of the present invention is prepared in accordance with the following methods:
In ice-water bath, 2 g crystalline flake graphites, 1 g sodium nitrate are uniformly mixed with the concentrated sulfuric acid of 50 mL, 9 are slowly added in stirring
g KMnO4, 2 DEG C or less 1 h of sustained response are kept, transfer them to 35 DEG C of 4 h of water-bath, then 100 mL are slowly added dropwise and go
Ionized water can obviously observe mixture by brown stain at glassy yellow after temperature rises to 98 DEG C the reaction was continued 1 h.Then add
Enter the H that 20 mL mass fractions are 30%2O2Solution processing.Above-mentioned solution is filtered, is washed twice with 5% HCl solution, then spend
Ionized water is sufficiently washed to neutrality, and finally filter cake is put into baking oven and is sufficiently drying to obtain graphite oxide for 80 DEG C.Weigh 0.2 g
Graphite oxide is added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyl trimethoxysilanes is then added dropwise, then
Ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution in N2Under atmosphere protection with
Then 100 DEG C of 24 h of return stirring are filtered and are washed repeatedly with dehydrated alcohol, finally dry 12 h can be obtained at 80 DEG C
Amino-functionalization graphene oxide catalyst.
It is found after research, utilizes amino-functionalization graphene oxide catalyst in benzaldehyde and water phase into mistake under certain condition
Ultrasound and the Pickering emulsion droplet size for finding to be formed after high-speed stirred are smaller, while even droplet distribution is intensive, will
Higher catalytic activity is achieved when the emulsion system is for being catalyzed the Knoevenagel condensation reaction of benzaldehyde and malononitrile.
Amino-functionalization graphene oxide catalyst can still prepare stable Pickering lotion after being repeated as many times,
The emulsion droplet size that catalyst is prepared after reusing three times is distinguished less compared with more for the first time with densely distributed degree, and
Higher catalytic activity is similarly achieved when being used to be catalyzed reaction for the emulsion system, benzaldehyde conversion ratio slightly reduces, because
This Pickering emulsion system has shown preferable recycling.
The present invention can be effective using the Pickering lotion that the superior amphipathic characteristic of amino-functionalization graphite oxide is prepared
Ground increases the contact surface of catalyst and reactant, therefore catalysis Knoevenagel condensation reaction can greatly improve in water phase
Pickering lotion is used for catalysis Knoevenagel condensation reaction in water phase and still belonged to the first time by catalytic activity.
The present invention is existing when can effectively solve tradition using green solvent water as solvent using organic solvent as solvent
The problem of pollution environment, while reduction catalytic amount, optimization can be effectively achieved instead using the catalysis reaction of Pickering lotion
Answer the purpose of condition.This research method is not only environmentally protective, easy to operate, also prepares lotion for more amphipathic nature materials and is used for
Efficient catalytic reaction provides possibility, has high application value.
Specific embodiment:
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate to be used,
And it is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1:
It weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyls three is then added dropwise
Methoxy silane, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution
In N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed repeatedly with dehydrated alcohol, finally at 80 DEG C
Dry 12 h can be obtained amino-functionalization graphene oxide.20 mg amino-functionalization graphene oxides are weighed again is added to 50 mL circle
In the flask of bottom, 3 mL water and 1.5 mL benzaldehydes are subsequently added into, subsequent 5 min of ultrasound (180 W, 60 Hz), after ultrasonic
Pickering emulsion system can be prepared with 800 rpm revolving speed mechanical stirring, 5 min, is denoted as Emulsion 1.
Embodiment 2:
It weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyls three is then added dropwise
Methoxy silane, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution
In N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed repeatedly with dehydrated alcohol, finally at 80 DEG C
Dry 12 h can be obtained amino-functionalization graphene oxide.20 mg amino-functionalization graphene oxides are weighed again is added to 50 mL circle
In the flask of bottom, 4 mL water and 1.5 mL benzaldehydes are subsequently added into, which is handled without ultrasound and high-speed stirred, it should
System is denoted as Emulsion 2.
Embodiment 3:
It weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyls three is then added dropwise
Methoxy silane, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution
In N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed repeatedly with dehydrated alcohol, finally at 80 DEG C
Dry 12 h can be obtained amino-functionalization graphene oxide.20 mg amino-functionalization graphene oxides are weighed again is added to 50 mL circle
In the flask of bottom, 4 mL water and 1.5 mL benzaldehydes are subsequently added into, subsequent 5 min of ultrasound (180 W, 60 Hz), after ultrasonic
Pickering emulsion system can be prepared with 800 rpm revolving speed mechanical stirring, 5 min, is denoted as Emulsion 3.
Embodiment 4:
It weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyls three is then added dropwise
Methoxy silane, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution
In N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed repeatedly with dehydrated alcohol, finally at 80 DEG C
Dry 12 h can be obtained amino-functionalization graphene oxide.20 mg amino-functionalization graphene oxides are weighed again is added to 50 mL circle
In the flask of bottom, 5 mL water and 1.5 mL benzaldehydes are subsequently added into, subsequent 5 min of ultrasound (180 W, 60 Hz), after ultrasonic
Pickering emulsion system can be prepared with 800 rpm revolving speed mechanical stirring, 5 min, is denoted as Emulsion 4.
Embodiment 5:
It weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, 2 g aminopropyls three is then added dropwise
Methoxy silane, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.Secondly by this bottle of solution
In N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed repeatedly with dehydrated alcohol, finally at 80 DEG C
Dry 12 h can be obtained amino-functionalization graphene oxide.15 mg amino-functionalization graphene oxides are weighed again is added to 50 mL circle
In the flask of bottom, 4 mL water and 1.5 mL benzaldehydes are subsequently added into, subsequent 5 min of ultrasound (180 W, 60 Hz), after ultrasonic
Pickering emulsion system can be prepared with 800 rpm revolving speed mechanical stirring, 5 min, is denoted as Emulsion 5.
1 ~ Emulsion of catalyst system Emulsion 5 that Examples 1 to 5 is obtained is for benzaldehyde and malononitrile
In Knoevenagel condensation reaction, reaction equation is as follows:
Reaction condition are as follows: under normal pressure, will be separately added into 1 ~ Emulsion of catalyst system Emulsion obtained above 5
0.99 g malononitrile, 0.3 mL n-dodecane stir 1 h under 50 DEG C of oil baths as internal standard compound.To be cooled to room after reaction
Temperature, after Filtration of catalyst, with chloroform extraction filtrate.Supernatant is centrifuged, in SP-6890 type gas phase color
It is analyzed on spectrometer (GC) using fid detector and FFAP capillary column and (calculates conversion ratio and selection using internal standard dodecane
The data of property).By filter from reaction mixture recycle amine functions graphene oxide catalyst, and handle by washing with water with
It reuses.
Concrete outcome is as shown in table 1.
The catalytic activity of 1 catalyst system of table
| Catalyst system | Benzaldehyde conversion ratio (%) | Benzyl subunit malononitrile selectivity (%) |
| Emulsion 1 | 87.0 | >99.5 |
| Emulsion 2 | 83.1 | >99.5 |
| Emulsion 3 | 96.1 | >99.5 |
| Emulsion 4 | 86.8 | >99.5 |
| Emulsion 5 | 82.9 | >99.5 |
As it can be seen from table 1 Pickering lotion catalyst system of the invention is applied in Knoevenagel reaction, lotion
System shows higher catalytic activity.
The amino-functionalization graphene oxide catalyst in reaction solution is recycled using the method for filtering, repeats to make after drying
With reuse result of the catalyst system Emulsion 3 in the Knoevenagel condensation reaction of benzaldehyde and malononitrile is such as
Shown in table 2.
The repetition experimental result of 2 catalyst system of table
| Cycle-index | Benzaldehyde conversion ratio (%) | Benzyl subunit malononitrile selectivity (%) |
| 1 | 96.1 | >99.5 |
| 2 | 94.2 | >99.5 |
| 3 | 92.4 | >99.5 |
From table 2 it can be seen that benzaldehyde conversion still with higher later is recycled three times in the Pickering emulsion system
Rate, selectivity of product tend towards stability, and are positively retained at 99.5% or more, prepare after reusing this illustrates catalyst
Pickering lotion catalyst system still catalytic activity with higher.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (6)
1. a kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction, it is characterised in that utilize
The amphipathic of amino-functionalization graphene oxide has prepared stable Pickering lotion in benzaldehyde and aqueous solvent, and will
The emulsion system is for being catalyzed Knoevenagel condensation reaction.
2. a kind of preparation side of the Pickering lotion catalyst system for Knoevenagel reaction according to claim 1
Method, it is characterised in that this method carried out as steps described below:
(1) it weighs 0.2 g graphite oxide to be added in the round-bottomed flask equipped with 100 mL DMSO, it is organic that 2 g is then added dropwise
Amine, then ultrasound three times (180 W, 60 Hz), 30 min, 5 min of midfeather every time.
3. secondly by this bottle of solution in N2With 100 DEG C of 24 h of return stirring under atmosphere protection, then filters and washed with dehydrated alcohol
It washs repeatedly, finally dry 12 h at 80 DEG C, can be obtained amino-functionalization graphene oxide catalyst；
(2) step (1) obtained solid catalyst is dispersed in 4 mL water, 1.5 mL benzaldehydes is then added, then mix this
It closes object and is ultrasonically treated (180 W, 60 Hz) and high speed machine stirring, Pickering lotion can be prepared；
(3) 0.99 g malononitrile is added in the Pickering lotion that step (2) is prepared, while 0.3 mL positive 12 is added
Alkane then carries out Knoevenagel condensation reaction as internal standard compound.
4. a kind of preparation side of Pickering lotion catalyst system for Knoevenagel reaction as claimed in claim 2
Method, it is characterised in that organic amine described in step (1) is aminopropyl trimethoxysilane.
5. a kind of preparation side of Pickering lotion catalyst system for Knoevenagel reaction as claimed in claim 2
Method, it is characterised in that Pickering lotion preparation condition described in step (2) are as follows: catalytic amount be 20 mg, 5 min of ultrasound,
800 rpm mechanical stirring, 5 min.
6. a kind of preparation side of Pickering lotion catalyst system for Knoevenagel reaction as claimed in claim 2
Method, it is characterised in that Knoevenagel condensation reaction condition described in step (3): 50 DEG C of reaction temperature, 1 h of reaction time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910649762.7A CN110368986A (en) | 2019-07-18 | 2019-07-18 | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910649762.7A CN110368986A (en) | 2019-07-18 | 2019-07-18 | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110368986A true CN110368986A (en) | 2019-10-25 |
Family
ID=68253951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910649762.7A Pending CN110368986A (en) | 2019-07-18 | 2019-07-18 | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110368986A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195528A (en) * | 2020-03-09 | 2020-05-26 | 常州大学 | Preparation method of bifunctional Pickering emulsion catalyst |
| CN111704146A (en) * | 2020-06-09 | 2020-09-25 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN112657553A (en) * | 2020-12-16 | 2021-04-16 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
| CN112705261A (en) * | 2021-02-01 | 2021-04-27 | 福州大学 | Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055938A (en) * | 2012-12-27 | 2013-04-24 | 上海师范大学 | An acid-base bifunctional graphene-based nano heterogeneous catalyst and a preparation method thereof |
| CN104084230A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of solid catalyst for Knoevenagel reaction |
| CN104368384A (en) * | 2014-09-29 | 2015-02-25 | 常州大学 | Preparation method of organic diamine-modified graphene oxide solid catalyst |
-
2019
- 2019-07-18 CN CN201910649762.7A patent/CN110368986A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055938A (en) * | 2012-12-27 | 2013-04-24 | 上海师范大学 | An acid-base bifunctional graphene-based nano heterogeneous catalyst and a preparation method thereof |
| CN104084230A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of solid catalyst for Knoevenagel reaction |
| CN104368384A (en) * | 2014-09-29 | 2015-02-25 | 常州大学 | Preparation method of organic diamine-modified graphene oxide solid catalyst |
Non-Patent Citations (3)
| Title |
|---|
| YANMEI ZHANG: "Interface-Active Metal Organic Frameworks for Knoevenagel Condensations in Water", 《CATALYSTS》 * |
| 丁顺民: "3-氨基丙基三乙氧基硅烷嫁接氧化石墨烯催化Knoevenagel缩合反应及硅氢加成铂催化剂的研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
| 卫林峰: "氧化石墨烯和石墨烯量子点的两亲性调控及其在Pickering 乳液聚合中的应用", 《化学进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195528A (en) * | 2020-03-09 | 2020-05-26 | 常州大学 | Preparation method of bifunctional Pickering emulsion catalyst |
| CN111704146A (en) * | 2020-06-09 | 2020-09-25 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN111704146B (en) * | 2020-06-09 | 2021-12-31 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN112657553A (en) * | 2020-12-16 | 2021-04-16 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
| CN112657553B (en) * | 2020-12-16 | 2023-08-29 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
| CN112705261A (en) * | 2021-02-01 | 2021-04-27 | 福州大学 | Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110368986A (en) | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction | |
| CN102274750B (en) | Mesoporous molecular sieve supported solid acid catalyst used for santene essential-oil isomerous esterification reaction | |
| Krumlinde et al. | Asymmetric synthesis of bicyclic diol derivatives through metal and enzyme catalysis: application to the formal synthesis of sertraline | |
| Safari et al. | Sulfonated starch nanoparticles: An effective, heterogeneous and bio-based catalyst for synthesis of 14-aryl-14-H-dibenzo [a, j] xanthenes | |
| EP2805935B1 (en) | Green process for producing 3-methyl-3-pentene-2-one | |
| Aoyama et al. | Silica gel-supported polyphosphoric acid (PPA/SiO2) as an efficient and reusable catalyst for conversion of carbonyl compounds into oxathioacetals and dithioacetals | |
| CN106669841B (en) | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure | |
| CN106632073A (en) | Synthesis method of 3,4-dihydropyrimidin-2-ketone compounds catalyzed by ionic liquid at room temperature | |
| Arai et al. | A dendrimer-supported heterobimetallic asymmetric catalyst | |
| CN104248950A (en) | Palladium/carbon nanotube catalyst and preparation and application thereof | |
| CN108067304A (en) | A kind of mesoporous function hybrid material and preparation method and application | |
| EP2706051B1 (en) | Method for oxidating cyclohexane | |
| CN102989499B (en) | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method | |
| CN109608408A (en) | The preparation method of Paeonol Schiff link 1,2,3- triazole compound with anti-tumor activity | |
| CN106905121A (en) | A kind of preparation method of benzaldehyde | |
| CN111195528A (en) | Preparation method of bifunctional Pickering emulsion catalyst | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN101786016B (en) | Preparation method and application method of novel immobilized Lewis acid catalyst | |
| CN104624242B (en) | A kind of biodiesel synthesis acidic ion liquid immobilized AlCl_3 catalyst and preparation method thereof | |
| CN107694610B (en) | A kind of phase transfer catalyst and preparation method thereof for cyclohexanol synthesizing cyclohexanone | |
| CN114716631B (en) | Pyrrolidinyl covalent organic framework material and preparation method and application thereof | |
| CN110152661A (en) | A kind of nitrobenzene compounds hydrogenation synthesis amino benzenes compounds nanometer Au-CeO2(cube) catalyst | |
| Yadav et al. | [Bmim] BF4 ionic liquid: A novel and recyclable reaction media for the synthesis of homoallylic amines | |
| Salavati et al. | Preparation, characterization and heterogeneous catalytic activity of heteropolyanion/polyaniline nanocomposite | |
| CN108424373A (en) | A kind of method that primary amine oxidative coupling prepares imine compound |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191025 |