CN107983410B - Preparation method of graphene/MOFs crystal composite pore catalyst - Google Patents
Preparation method of graphene/MOFs crystal composite pore catalyst Download PDFInfo
- Publication number
- CN107983410B CN107983410B CN201711155086.5A CN201711155086A CN107983410B CN 107983410 B CN107983410 B CN 107983410B CN 201711155086 A CN201711155086 A CN 201711155086A CN 107983410 B CN107983410 B CN 107983410B
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite pore
- lewis acid
- crystal composite
- catalyst
- 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.)
- Active
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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
Abstract
The invention provides a preparation method of a graphene/MOFs crystal composite pore catalyst, which comprises the following steps: dispersing reduced graphene oxide in a solvent to obtain a graphene dispersion liquid, adding a Lewis acid metallocene catalyst and a 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution; adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution, carrying out microwave treatment, adding potassium tert-butoxide to adjust the pH value to be alkalescent, heating and stirring for reaction, and cooling to room temperature to obtain a crude crystal; and crushing and grinding the crude crystal, adding an organic solvent to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the graphene/MOFs crystal composite pore catalyst. The catalyst prepared by the invention utilizes the Lewis acid metallocene catalyst to uniformly disperse graphene in MOFs, and removes the Lewis acid metallocene catalyst by using an organic solvent to obtain the composite pore type catalyst.
Description
Technical Field
The invention belongs to the field of pharmaceutical chemistry, and particularly relates to a preparation method of a graphene/MOFs crystal composite pore catalyst.
Background
In organic synthesis reactions, it has been desired to find a cheap, environmentally friendly and highly catalytic catalyst for organic synthesis reactions to replace the commonly used toxic or expensive transition metal catalysts. Lewis acids are a class of substances that can accept an electron pair and are a class of substances having a vacant orbital in their structure. Because lewis acid has the advantages of good catalytic activity, short reaction time, proper dosage, less possibility of causing side reaction and equipment corrosion, cost saving and the like, lewis acid is more and more emphasized by people as a catalyst or promoted organic synthesis reaction, and is widely used in the production fields of food, daily necessities, medicines and the like. The Lewis acid can directly act with a substrate to form a target product, can also be complexed with the substrate to activate the substrate, and reacts with other reagents to form the target product, and can realize the dissociation.
Chinese patent CN 105174243B discloses a method for preparing a graphitized multi-stage porous carbon sphere, which comprises subjecting polystyrene microspheres and halogenated hydrocarbons to friedel-crafts alkylation reaction under the catalysis of anhydrous chlorinated railway lewis acid catalyst to obtain a suspension, adding toluene, acetone, ethanol or tetrahydrofuran organic solvent to separate out the dissolved lewis acid catalyst, separating and drying to obtain porous polystyrene microspheres loaded with lewis acid catalyst, carbonizing the porous polystyrene microspheres loaded with lewis acid catalyst under inert or protective atmosphere, dissolving in acidic solution, separating, and drying to obtain the graphitized multi-stage porous carbon sphere, wherein the graphitized multi-stage porous carbon sphere prepared by the method can be used in the fields of super capacitors, battery negative electrode materials, dye battery catalyst carriers, and the like. Chinese patent CN 105400157B discloses a method for improving the dispersibility of graphene in a polymer matrix, which comprises mixing polyolefin, aromatic polyester, aliphatic polyester, polyamide resin, polystyrene, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyformaldehyde or polyvinylidene chloride polymer material, graphene, aluminum trichloride, ferric trichloride, boron trifluoride or trifluoromethanesulfonic acid Lewis acid catalyst, melting and blending the mixture above the melting point of the polymer material and below the thermal decomposition temperature to obtain the polymer/graphene/Lewis acid catalyst composite material, and finally, melting and blending the polymer/graphene composite material master batch and pure polymer again at the temperature of above the melting point and below the thermal decomposition temperature to obtain the polymer/graphene composite material. The preparation method utilizes the Lewis acid catalyst to improve the dispersibility of the graphene in the polymer matrix and reduce the defects caused by the existence of the aggregates, and the method does not need the surface functionalization of the graphene, is simple and environment-friendly. The prior art shows that the Lewis acid catalyst has an outstanding effect in the preparation process of the graphene composite material, so that the dispersity of the graphene and the coordination polymer can be obviously improved, and the catalytic performance of the graphene and the coordination polymer is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a graphene/MOFs crystal composite pore catalyst. The catalyst fully combines graphene and MOFs, has good porosity, improves the catalytic activity of the catalyst, and improves the application field of the graphene/MOFs crystal composite pore catalyst in the preparation of medical intermediates.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a graphene/MOFs crystal composite pore catalyst comprises the following steps:
(1) dispersing reduced graphene oxide in a solvent to obtain a graphene dispersion liquid, adding a Lewis acid metallocene catalyst and a 2-benzenesulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution;
(2) adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution, carrying out microwave treatment, adding potassium tert-butoxide to adjust the pH value to be alkalescent, heating and stirring for reaction, and cooling to room temperature to obtain a crude crystal;
(3) and crushing and grinding the crude crystal, adding an organic solvent to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the graphene/MOFs crystal composite pore catalyst.
Preferably, in the step (1), the mass ratio of the template material, the graphene and the lewis acid metallocene catalyst in the base solution is 100:8-16: 0.5-2.
Preferably, in the step (1), the lewis acid metallocene catalyst is composed of a transition metal element or a rare earth metal element and cyclopentadiene or cyclopentadiene derivatives.
Preferably, in the step (1), the transition metal element in the lewis acid metallocene catalyst is titanium, zirconium or antimony.
Preferably, in the step (2), the microwave treatment is performed under 50-100W for 5-15 min.
Preferably, in the step (2), the mass ratio of the 2-benzenesulfonylpyridine to the dimethylimidazole-methylenebenzene in the base solution is 6.5-8: 5-6.
Preferably, in the step (2), the temperature for heating and stirring the reaction is 170-180 ℃ and the time is 24-36 h.
As a preferred mode of the above technical solution, in the step (2), the pH value of the weak base is 8.5-10.
Preferably, in the step (3), the organic solvent is ethanol.
Preferably, in the step (3), the particle size of the graphene/MOFs crystal composite pore catalyst is micron-sized.
Compared with the prior art, the invention has the following beneficial effects:
the graphene/MOFs crystal composite pore catalyst prepared by the invention mainly comprises graphene and MOFs coordination polymer, in order to improve the dispersion performance of the graphene and the MOFs coordination polymer, a Lewis acid metallocene catalyst is added into the preparation process of the graphene and the MOFs coordination polymer, a substrate solution prepared by mixing the graphene, the Lewis acid metallocene catalyst and a 2-diphenylsulfonyl pyridine template material is reacted with a dimethyl imidazole-methylene benzene ligand, the graphene can be uniformly dispersed in the MOFs, and then the Lewis acid metallocene catalyst is removed by using an organic solvent ethanol, so that the composite pore catalyst is obtained. The catalyst fully combines graphene and MOFs, has good porosity, improves the catalytic activity of the catalyst, and improves the application field of the graphene/MOFs crystal composite pore catalyst in the preparation of medical intermediates.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of a template material to graphene to a Lewis acid metallocene catalyst of 100:8:0.5 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst consisting of titanium and cyclopentadiene and the 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene of 6.5:5 in the substrate solution, carrying out microwave treatment for 5min under the power of 50W, adding potassium tert-butoxide to adjust the pH to 8.5, heating and stirring at 170 ℃ for reaction for 24h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Example 2:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of the template material to the graphene to the Lewis acid metallocene catalyst of 100:16:2 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst consisting of zirconium and cyclopentadiene derivatives and the 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 8:6 of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene in the substrate solution, carrying out microwave treatment for 15min under the power of 100W, adding potassium tert-butoxide to adjust the pH to 10, heating and stirring at 180 ℃ for reaction for 36h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Example 3:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of the template material to the graphene to the Lewis acid metallocene catalyst of 100:10:1.5 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst consisting of antimony and cyclopentadiene and the 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 7:5 of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene in the substrate solution, carrying out microwave treatment for 10min under the power of 60W, adding potassium tert-butoxide to adjust the pH to 9, heating and stirring at 175 ℃ for reaction for 26h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Example 4:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of a template material to graphene to a Lewis acid metallocene catalyst of 100:12:1 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst consisting of titanium and cyclopentadiene and the 2-diphenylsulfonylpyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 7.5:5.5 of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene in the substrate solution, carrying out microwave treatment for 10min under the power of 80W, adding potassium tert-butoxide to adjust the pH to 9.5, heating and stirring at 175 ℃ for reaction for 30h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Example 5:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of a template material to graphene to a Lewis acid metallocene catalyst of 100:12:0.9 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst consisting of titanium and cyclopentadiene and the 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 7:6 of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene in the substrate solution, carrying out microwave treatment for 12min under the power of 65W, adding potassium tert-butoxide to adjust the pH to 9.5, heating and stirring at 170 ℃ for reaction for 36h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Example 6:
(1) dispersing reduced graphene oxide in a solvent according to the mass ratio of the template material to the graphene to the Lewis acid metallocene catalyst of 100:14:1 to obtain a graphene dispersion liquid, adding the Lewis acid metallocene catalyst containing zirconium and cyclopentadiene and the 2-diphenylsulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution.
(2) Adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution according to the mass ratio of 7.5:5.5 of 2-diphenylsulfonyl pyridine to dimethyl imidazole-methylene benzene in the substrate solution, carrying out microwave treatment for 12min under the power of 85W, adding potassium tert-butoxide to adjust the pH to 9, heating and stirring at 180 ℃ for reaction for 24h, and cooling to room temperature to obtain a crude crystal.
(3) And crushing and grinding the crude crystal, adding an organic solvent ethanol to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the micron-sized graphene/MOFs crystal composite pore catalyst.
Through detection, the results of particle size, porosity and yield of the graphene/MOFs crystal composite pore catalysts prepared in examples 1 to 6 are as follows:
as can be seen from the above table, the particle size of the graphene/MOFs crystal composite pore catalyst prepared by the present invention is micron-sized, pores exist, and the yield of the preparation method of the catalyst is high.
The graphene/MOFs crystal composite pore catalyst prepared in the embodiments 1-6 is used in the hydrogenation catalytic reaction of a medical intermediate, and has good catalytic effect and good reuse effect.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A preparation method of a graphene/MOFs crystal composite pore catalyst is characterized by comprising the following steps:
(1) dispersing reduced graphene oxide in a solvent to obtain a graphene dispersion liquid, adding a Lewis acid metallocene catalyst and a 2-benzenesulfonyl pyridine template material into the graphene dispersion liquid, and uniformly mixing to obtain a substrate solution;
(2) adding a DMF (dimethyl formamide) solution of a dimethyl imidazole-methylene benzene ligand into a substrate solution, carrying out microwave treatment, adding potassium tert-butoxide to adjust the pH value to be alkalescent, heating and stirring for reaction, and cooling to room temperature to obtain a crude crystal;
(3) crushing and grinding the crude crystal, adding an organic solvent to separate out the dissolved Lewis acid metallocene catalyst, separating and drying to obtain the graphene/MOFs crystal composite pore catalyst; wherein the Lewis acid metallocene catalyst consists of titanium, zirconium or antimony or rare earth metal elements and cyclopentadiene or cyclopentadiene derivatives.
2. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the template material, the graphene and the Lewis acid metallocene catalyst in the substrate solution is 100:8-16: 0.5-2.
3. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the microwave treatment is carried out under the condition of 50-100W for 5-15 min.
4. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the 2-benzenesulfonylpyridine to the dimethylimidazole-methylenebenzene in the substrate solution is 6.5-8: 5-6.
5. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the temperature for heating and stirring reaction is 170-180 ℃, and the time is 24-36 h.
6. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the pH value of the alkalescence is 8.5-10.
7. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (3), the organic solvent is ethanol.
8. The method for preparing the graphene/MOFs crystal composite pore catalyst according to claim 1, wherein the method comprises the following steps: in the step (3), the particle size of the graphene/MOFs crystal composite pore catalyst is micron-sized.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711155086.5A CN107983410B (en) | 2017-11-20 | 2017-11-20 | Preparation method of graphene/MOFs crystal composite pore catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711155086.5A CN107983410B (en) | 2017-11-20 | 2017-11-20 | Preparation method of graphene/MOFs crystal composite pore catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107983410A CN107983410A (en) | 2018-05-04 |
CN107983410B true CN107983410B (en) | 2020-09-04 |
Family
ID=62030985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711155086.5A Active CN107983410B (en) | 2017-11-20 | 2017-11-20 | Preparation method of graphene/MOFs crystal composite pore catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107983410B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114471467B (en) * | 2020-10-23 | 2024-01-26 | 中国石油化工股份有限公司 | Truncated polyhedral MOFs@rGO material and preparation method and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6897273B2 (en) * | 2000-12-04 | 2005-05-24 | Univation Technologies, Llc | Catalyst composition, method of polymerization and polymer therefrom |
WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
CN104448309B (en) * | 2015-01-04 | 2017-02-01 | 苏州大学 | Hybridization catalyst for curing cyanate ester and preparing method thereof |
CN104448822B (en) * | 2015-01-04 | 2017-02-22 | 苏州大学 | Modified cyanate ester resin and preparation method thereof |
CN106752105A (en) * | 2016-12-16 | 2017-05-31 | 安徽北马科技有限公司 | A kind of span of coated by titanium dioxide carrys out polyimide modified pearl filler |
-
2017
- 2017-11-20 CN CN201711155086.5A patent/CN107983410B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN107983410A (en) | 2018-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | 3D macropore carbon-vacancy g-C3N4 constructed using polymethylmethacrylate spheres for enhanced photocatalytic H2 evolution and CO2 reduction | |
Chen et al. | Preparation of Pt and PtRu nanoparticles supported on carbon nanotubes by microwave-assisted heating polyol process | |
CN107029668B (en) | A kind of honeycomb type molecular sieve-active carbon compound adsorbent, preparation method and applications | |
CN102631913B (en) | Preparation method of graphene supported cerium oxide nano cubit compound | |
Di et al. | Bi4O5Br2 ultrasmall nanosheets in situ strong coupling to MWCNT and improved photocatalytic activity for tetracycline hydrochloride degradation | |
CN106902842A (en) | A kind of preparation and application for deriving load type palladium catalyst of the carbon-based material as carrier with MOFs | |
CN104016328B (en) | A kind of preparation method of nitrogenous carbon nanotube | |
CN108160073A (en) | A kind of porous carbon materials for loading ruthenium nano particle and its preparation method and application | |
Wang et al. | Novel CNT/PbBiO2Br hybrid materials with enhanced broad spectrum photocatalytic activity toward ciprofloxacin (CIP) degradation | |
CN111115631B (en) | High-mechanical-strength coffee-grounds-based molded porous carbon material and preparation method thereof | |
Zhang et al. | Selective oxidation of glycerol over nitrogen-doped carbon nanotubes supported platinum catalyst in base-free solution | |
CN107252685A (en) | A kind of hydroxyl aminated compounds functional magnetic graphene oxide catalysis material and its preparation method and application | |
CN103433071B (en) | IPN supported palladium nanocatalyst and Synthesis and applications thereof | |
CN106732559A (en) | A kind of palladium catalyst of cherry stone carbon load and preparation method and application | |
CN101327451B (en) | Uses of planar polymerized phthalocyanine or porphyrin transition metal complexes | |
CN107983410B (en) | Preparation method of graphene/MOFs crystal composite pore catalyst | |
Ning et al. | A 3D/0D cobalt-embedded nitrogen-doped porous carbon/supramolecular porphyrin magnetic-separation photocatalyst with highly efficient pollutant degradation and water oxidation performance | |
CN104752074A (en) | Molybdenum oxide/carbon sphere composite material preparation method | |
Wei et al. | Microplasma electrochemistry (MIPEC) strategy for accelerating the synthesis of metal organic frameworks at room temperature | |
Jin et al. | Covalent organic framework‐supported Pd nanoparticles: An efficient and reusable heterogeneous catalyst for Suzuki–Miyaura coupling reactions | |
Almaradhi et al. | Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction | |
Liang et al. | Preparation of Mo-based catalyst appreciated from agricultural waste for efficient high-value conversion of 1-hexene | |
CN104815657A (en) | Preparation method of catalyst for producing catechol and hydroquinone through hydroxylation of phenol | |
Yang et al. | Fabricating transfer channel and charge trap in carbon nitride ultrathin nanosheet for enhanced photocatalytic hydrogen evolution | |
Chen et al. | Research progress in the application of metal organic frameworks and its complex in microbial fuel cells: Present status, opportunities, future directions and prospects |
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 |