CN108525675A - It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination - Google Patents
It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination Download PDFInfo
- Publication number
- CN108525675A CN108525675A CN201810305385.0A CN201810305385A CN108525675A CN 108525675 A CN108525675 A CN 108525675A CN 201810305385 A CN201810305385 A CN 201810305385A CN 108525675 A CN108525675 A CN 108525675A
- Authority
- CN
- China
- Prior art keywords
- palladium
- cobalt
- mofs
- catalyst
- magnetic carbon
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 32
- 239000010941 cobalt Substances 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 238000005576 amination reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 235000008429 bread Nutrition 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000013461 design Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- -1 primary amine compound Chemical class 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000006268 reductive amination reaction Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application are prepared for being catalyzed reduction amination.The Co-MOFs porous materials that the present invention is prepared using solvent-thermal process method is carriers, palladium is uniformly loaded in Co-MOFs materials duct by Double solvent method, the persursor material of Pd (II)/compound Co-MOFs is obtained, then by the presoma of Pd (II)/compound Co-MOFs in N2/H2Reducing atmosphere under heat-treat be made magnetic carbon/palladium-cobalt multiple elements design multiplex catalyst.The catalyst of the present invention is capable of the pairing synthetic reaction of efficient catalysis of carbonyl chemical combination object and ammonia, prepares aminated compounds, and stability is good and high catalytic efficiency, recyclable to be repeatedly used to be catalyzed efficiently synthesizing for primary amine.
Description
Technical field
The invention belongs to materialogy technical fields, are related to a kind of catalyst, specifically a kind of for being catalyzed reduction amine
Change prepares magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application.
Background technology
Aminated compounds has as common building block in fine chemistry industry, pharmaceutical chemistry and materials science field extensive
Application.As important industrial chemicals, aminated compounds can be used for synthetic resin and plastics, textile, disinfection and washing are used
Product etc..Important research direction, wherein carbonyl compound in the reaction always methodology of organic synthesis of the new structure C-N keys of development
The reductive amination process of object is the common method for preparing aminated compounds.In general, the reductive amination process one that ammonia participates in
As need to carry out under the action of the noble metal catalysts such as Ru, Ir, Pt, Pd, reaction while generating primary amine often along with it
Its side reaction occurs, thus the catalyst for developing other cheap metals realizes that highly selective reduction amination process causes related neck
The close attention of domain researcher.
Metal-organic framework materials (Metal-Organic Frameworks, abbreviation MOFs) are more as a kind of novel nano
Porous materials are connected by coordinate bond with organic ligand by metal ion or cluster unit, one kind that self assembly is constructed
There is the porous material of periodic network structure.Since it is in optics, ion exchange, gas storage and heterogeneous catalysis etc. exhibition
The tempting application prospect that reveals and the concern for receiving numerous chemists and material scholar.
Co catalysts and its preparation side of a kind of hydrogenation deoxidation are disclosed in Chinese patent application CN201610060837.4
Method.The method cobalt salt is mixed with biological material after in NH3Atmosphere under calcine, obtain a kind of monometallic catalyst of cobalt.It should
Method is applicable in biological material, and catalyst substrate spectrum applicatory is wider.However material is in NH3Lower high temperature pyrolysis, to sky
The pollution of gas is larger, while the catalyst prepared is not magnetic, it is difficult to realize that separation recycles, so it is unfavorable for extensive work
Industry metaplasia is produced.A kind of nitrogen-doped carbon material load cobalt catalyst and profit are disclosed in Chinese patent application CN201610963798.9
The method for preparing primary amine compound with its catalytic hydrogenating reduction amination.Method synthesis is simple, and cost is relatively low, but does not have equally
It is magnetic, it is more difficult to recycling.
Above two material is all monometallic type catalyst, and catalytic performance need further to be promoted.Meanwhile it is obtained
Catalyst it is nonmagnetic, be not readily separated and cycling and reutilization.
Invention content
For the above-mentioned prior art the problem of, the present invention provides one kind preparing aminated compounds for being catalyzed reduction amination
Magnetic carbon/palladium-cobalt multiplex catalyst, preparation method and application.The present invention can solve in the prior art obtained by it is big
Majority catalysis is all monometallic homogeneous catalyst, and does not all have magnetism substantially, is difficult separation in actual industrial production
The technical issues of recycling again.The method yield of aminated compounds is prepared using above-mentioned catalyst to catalyzing hydrogenating and reducing amination
Height, side reaction is few, pollution-free, is suitble to industrial production.
The method that the present invention first uses solvent heat prepares Co-MOFs materials, and Co-MOFs porous structure materials are as load
Material of main part；Then palladium is uniformly loaded to by solution dipping method in Co-MOFs materials duct, obtain Pd (II)/
Persursor material compound Co-MOFs；Finally by thermal reduction by the presoma of Pd (II)/compound Co-MOFs in N2/H2It is mixed
It closes in atmosphere, heat-treat the catalyst that corresponding carbon/palladium-cobalt multiple elements design is made at a temperature of 400~700 DEG C.The skill of the present invention
Art scheme is specifically described as follows.
The present invention, which provides, a kind of to be prepared magnetic carbon/palladium-cobalt multiple elements design of aminated compounds for being catalyzed reduction amination and urges
The preparation method of agent, includes the following steps：
1) 2,5-Dihydroxyterephthalic acid and cobalt acetate are dissolved into the in the mixed solvent of tetrahydrofuran and water, ultrasound is shaken
It swings to being completely dissolved；Then it is reacted 3~5 days at a temperature of 100~140 DEG C, after reaction, is filtered, washed, dries, obtain
To Co-MOFs materials；Wherein：The molar ratio of 2,5- dihydric para-phthalic acids and cobalt acetate is 1:2~1:4；
2) it is 1 in mass ratio:10~1:20, polyethylene glycol and Co-MOFs materials are mixed, leaching is added after mixing thereto
The ethyl alcohol of sample size is not crossed, and is ground, until polyethylene glycol and Co-MOFs materials are uniformly mixed, it is dry, obtain surface packet
Cover the Co-MOFs materials of polyethylene glycol；
3) aqueous solution of palladium is added dropwise to the hexane solution that surface coats the Co-MOFs materials of polyethylene glycol
In, continue 4~8h of mixing after adding so that divalent palladium ion is adequately adsorbed onto in the duct of Co-MOFs materials, finally
Washing, vacuum drying, obtain the presoma of Pd (II)/compound Co-MOFs；Wherein：Palladium and surface coat polyethylene glycol
The mass ratio of Co-MOFs materials is 1:50~1:100；
4) by presoma N compound Pd (II)/Co-MOFs2/H2Mixed gas atmosphere under calcine, with stove after calcining
It is cooling, obtain magnetic carbon/palladium-cobalt multiplex catalyst that aminated compounds is prepared for being catalyzed reduction amination.
It is 1 by the molar ratio of 2,5-Dihydroxyterephthalic acid and cobalt acetate in step 1) in the present invention:2~1:4；Instead
It is 100~120 DEG C to answer temperature, and the reaction time is 3~5 days.
In the present invention, in step 1), the volume ratio of in the mixed solvent, tetrahydrofuran and water is 1:1~1:2.
In the present invention, in step 1), washed with water and tetrahydrofuran；It is dry to use vacuum drying mode, vacuum drying temperature
Degree is 80-100 DEG C.
In the present invention, in step 3), in acetic acid aqueous palladium, the mass volume ratio of palladium and water is 3:1~1:10mg/
ml；Surface coats in the hexane solution of the Co-MOFs materials of polyethylene glycol, and surface coats the Co-MOFs materials of polyethylene glycol
With the mass volume ratio 1 of n-hexane:5~1:20g/mL.
In the present invention, in step 4), N2/H2Mixed gas in, H2Mass fraction be 2~4%.
In the present invention, in step 4), calcination temperature is 400~700 DEG C, calcination time 4-6h.
The present invention also provides prepare aminated compounds for being catalyzed reduction amination made from a kind of above-mentioned preparation method
Magnetic carbon/palladium-cobalt multiplex catalyst.
The present invention further provides magnetic carbon/palladium-cobalt multiple elements designs that aminated compounds is prepared for being catalyzed reduction amination
The application of catalyst, application process are as follows：
In the organic solvent of tetrahydrofuran or n-butanol, carbonyls and magnetic carbon/palladium-cobalt multiple elements design is added
The rate of charge of catalyst, magnetic carbon/palladium-cobalt multiplex catalyst amount and carbonyls is 5~10mg:1mmol leads to respectively
Enter ammonia and hydrogen, volume ratio is about 1：4~1:6, in the item that reaction temperature is 70~120 DEG C, reaction pressure is 1~5MPa
It is reacted 2~10.0 hours under part, obtains corresponding aminated compounds.
Compared to the prior art, the beneficial effects of the present invention are：
1, in the present invention, using MOFs materials as template, precious metal ion is passed through into liquid impregnation first by Double solvent method
Technology is adsorbed onto in MOFs materials duct, and then is heat-treated technique by high temperature and prepared the stable carbon-based composite wood of nanoporous
Material.Simultaneously because the extra specific surface area of the nano-scale and ordered arrangement and material in MOFs materials duct, may be implemented metal
The polymolecularity of catalytic active component in the porous material is prepared cost-effective to improve the catalytic activity of noble metal member
Effective catalyst.The design of polynary based composites can not only reduce the dosage of expensive noble metal simultaneously, and due to double
Synergistic effect between metal can further improve the catalytic performance of material.
2, the present invention can control the content of porous material Technique of Nano Pd by controlling the impregnation increment of palladium, in addition can lead to
The thermal reduction temperature for spending the control later stage, regulates and controls the morphology and size of Technique of Nano Pd and nanometer cobalt particle fraction under porous carbon coating, from
And realize the control of composite material hierarchical porous structure, improve the catalytic performance of material.The catalyst is in catalytic hydrogenating reduction simultaneously
Amination prepares high catalytic efficiency and high circulation during benzylamine compound.The present invention can efficiently be catalyzed benzaldehyde in ammonia
Reaction prepares benzylamine in the presence of gas, and conversion ratio reaches as high as 100%, still up to 97% after recycling 10 times.Such catalyst
It is easy to magnetic recovery with preferable magnetism, can be widely used in terms of heterogeneous catalysis.
Description of the drawings
Fig. 1 is carbon/palladium-cobalt multiple elements design material under porous carbon coating prepared by the Examples 1 and 2 under different reduction temperatures
The X-ray powder diffraction figure of material.
Fig. 2 is the scanning electron microscope (SEM) photograph of carbon/palladium-cobalt multi-element composite material under the porous carbon coating of embodiment 2.
Specific implementation mode
Further detailed complete explanation is done to the present invention with reference to specific embodiment.Such as without spy in following instance
Very illustrate to be conventional method, involved all drugs are all from commercial sources in example.Content as described below is to this
The technical solution of invention is further described, but the present invention is not limited to the following embodiments.
Embodiment 1
(1) solvent-thermal process of Co-MOFs materials
A. by 2,5- dihydric para-phthalic acids H2DOBDC, cobalt acetate Co (CH3COO)2It is 1 in molar ratio:2 are claimed
Amount.
B. by H2DOBDC and Co (CH3COO)2It is distributed to the mixed solution (volume ratio 1 of tetrahydrofuran/water:2) in, surpass
Sound wave shock is to being completely dissolved.
C. the reaction solution obtained by b is transferred to solvent than in the reaction kettle for 1/3, being reacted 3 days at 110 DEG C, crystalline substance is made
State nano material.
D. c obtained crystalline material tetrahydrofurans and water are washed 3 times repeatedly, be dried in vacuo at 90 DEG C to get
Co-MOFs materials.
(2) cladding of the surface dispersant of Co-MOFs materials
A. surface capping agents polyethylene glycol and Co-MOFs materials are weighed, and the two is mixed, wherein the quality of polyethylene glycol
Score is 5%.
B. the ethyl alcohol for submerging sample size is added in mixture obtained in above-mentioned a, and is ground, until material is mixed
Uniform, drying is closed, the Co-MOFs materials of surface cladding polyethylene glycol are obtained.
(3) the Double solvent method self assembly of palladium (II) ion
A. it weighs 10mg palladiums to be dispersed in 20ml water, stirring is allowed to be completely dissolved.
B., the Co-MOFs materials 1g that surface obtained in (2) is coated to polyethylene glycol is dispersed in 10mL n-hexanes, simultaneously
The aqueous solution of palladium is added dropwise during being stirred continuously, gained mixed liquor is then stirred into 6~12h so that forerunner
Palladium (II) ion of body can be substantially filled in the duct of Co-MOFs materials.
C. mixed liquor in b filtered, be dried in vacuo at 70 DEG C, obtain the compound presoma materials of Pd (II)/Co-MOFs
Material.
(4) in the N that flow velocity is 30mL/min2/H2Mixed gas (wherein H2Mass percent is about heat 3%) under atmosphere
Pd (II)/Co-MOFs presomas in (2) are restored, 400 DEG C of calcination temperature is controlled, the time is 3 hours, and magnetic is obtained after furnace cooling
The heterogeneous catalysis of carbon/palladium-cobalt multiple elements design of property.
Fig. 1 discloses the X-ray powder diffraction figure of 1 gained sample of embodiment, and as seen from Figure 1, sample presents orderly
Porous structure, porous carbon are coated with the mixed phase of the cobalt simple substance and cobaltosic oxide that are thermally cracked to produce, simultaneously because the palladium of load
Content is relatively low, so the diffraction maximum of palladium is not detected from powder diffraction spectrum.
Embodiment 2
(1) solvent-thermal process of Co-MOFs materials
A. by H2DOBDC and Co (CH3COO)2, it is in molar ratio 1:3 are weighed.
B. by H2DOBDC and Co (CH3COO)2It is distributed to the mixed solution (volume ratio 1 of tetrahydrofuran/water:2) in, surpass
Sound wave shock is to being completely dissolved.
C. the reaction solution obtained by b is transferred to solvent than in the reaction kettle for 1/3, reaction 5 days is heated at 120 DEG C.
D. c obtained crystalline material tetrahydrofurans and water are washed 3 times repeatedly, be dried in vacuo at 90 DEG C to get
Co-MOFs materials.
(2) cladding of the surface dispersant of Co-MOFs materials
A. surface capping agents polyethylene glycol and Co-MOFs materials are weighed, and the two is mixed, wherein the quality of polyethylene glycol
Score is 10%.
B. the ethyl alcohol for submerging sample size is added in mixture obtained in above-mentioned a, and is ground, until poly- second two
Alcohol and Co-MOFs materials are uniformly mixed, dry, obtain the Co-MOFs materials of surface cladding polyethylene glycol.
(3) the Double solvent method self assembly of palladium (II) ion
A. it weighs 15mg palladiums to be dispersed in 30ml water, stirring is allowed to be completely dissolved.
B., 1 gram of the Co-MOFs materials that surface obtained in (2) is coated to polyethylene glycol are dispersed in 10mL n-hexanes, together
When the aqueous solution of palladium is added dropwise during being stirred continuously, gained mixed liquor is then stirred into 6~12h so that preceding
Driving palladium (II) ion of body can be substantially filled in the duct of Co-MOFs materials.
C. mixed liquor in b filtered, be dried in vacuo at 70 DEG C, obtain the compound presoma materials of Pd (II)/Co-MOFs
Material.
(4) in the N that flow velocity is 30mL/min2/H2Mixed gas (wherein H2Mass percent is about heat 3%) under atmosphere
Pd (II)/Co-MOFs presomas in (2) are restored, 600 DEG C of calcination temperature is controlled, the time is 4 hours, and magnetic is obtained after furnace cooling
The heterogeneous catalysis of carbon/palladium-cobalt multiple elements design of property nucleocapsid.
Fig. 1 discloses the X-ray powder diffraction figure of 2 gained sample of embodiment, and as seen from Figure 1, sample presents orderly
Porous structure, porous carbon is coated with cobalt simple substance phase, and since palladium content is relatively low, the diffraction maximum of palladium is not detected from powder diffraction.
Compared with embodiment 1, the diffraction peak intensity of carbon reduces in composite material, shows that its content is reduced, but cobalt ions is pyrolyzed at high temperature
It is completely converted into the cobalt simple substance of catalytic activity, improves catalytic efficiency.
Fig. 2 is the scanning electron microscope (SEM) photograph of carbon/palladium-cobalt multi-element composite material under the porous carbon coating of embodiment 2, such as Fig. 2 institutes
Show, cobalt simple substance and palladium even particulate dispersion are coated by porous carbon materials, form multi-element composite material.
Application Example 1
In the stainless steel autoclave of 10mL, be added magnetic carbon described in 0.5mmol benzaldehydes plus examples detailed above 2/
Palladium-cobalt heterogeneous catalyst 5mg (about 10wt%), is added 3ml n-butanols and does reaction dissolvent, each lead into NH3And H2Gas,
Wherein NH3Make reaction gas, and H2Make reducing atmosphere gas, pressure control is controlled in 30 atmospheric pressure, temperature in 100 DEG C or so items
It is reacted 8 hours under part, corresponding benzylamine is made, yield is close to 100%.It is above-mentioned after reaction, catalyst can be by simple
Magnetic absorption realize separation, carrying out washing treatment, carry out the catalyst recycling experiment of next one, specific reaction step is same
On.It recycles 10 times or more, catalytic conversion efficiency is held essentially constant, and still reaches 97% or more.
Under similar reaction condition, we have investigated reduction amine of the catalyst to the benzaldehyde containing different substituents
Change catalytic efficiency, shown in reaction equation formula (1)：
Experimental result is as shown in table 1, and for the reductive amination process of different benzaldehydes, which all has high
Catalytic efficiency, when contraposition is the substituent group of electron-withdrawing group, catalytic efficiency slightly reduces, but still reaches 90% or more, table
The bright catalysis material has fabulous catalytic performance to such reaction.
Table 1
| R | Yield |
| H | 100% |
| OCH3 | 100% |
| CH3 | 100% |
| CN | 99% |
| Cl | 97% |
| CF3 | 93% |
Above description is only main feature of the present invention and central scope, and the various change based on the present invention belongs to the present invention
Protective scope of the claims.
Claims (7)
1. a kind of preparation side preparing magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds for being catalyzed reduction amination
Method, which is characterized in that include the following steps：
1) by 2,5- dihydric para-phthalic acids H2DOBDC and cobalt acetate Co (CH3COO)2·4H2O is dissolved into tetrahydrofuran and water
In the mixed solvent, sonic oscillation is to being completely dissolved；Then it is reacted under the conditions of solvent heat, after reaction, be filtered, washed,
It is dry, obtain Co-MOFs materials；
2) it is 1 in mass ratio:10~1:20, polyethylene glycol and Co-MOFs materials are mixed, is added and submerged thereto after mixing
The ethyl alcohol of sample size, and be ground, until polyethylene glycol and Co-MOFs materials are uniformly mixed, and it is dry, it is poly- to obtain surface cladding
The Co-MOFs materials of ethylene glycol；
3) aqueous solution of palladium is added dropwise in the hexane solution for the Co-MOFs materials that surface coats polyethylene glycol,
Continue 4~8h of mixing after adding so that divalent palladium ion is adequately adsorbed onto in the duct of Co-MOFs materials, is finally washed
It washs, be dried in vacuo, obtain the presoma of Pd (II)/compound Co-MOFs；Wherein：The Co- of palladium and surface cladding polyethylene glycol
The mass ratio of MOFs materials is 1:50~1:100；
4) by the presoma of Pd (II)/compound Co-MOFs in N2/H2Mixed gas atmosphere under calcine, with furnace cooling after calcining
But, obtain preparing magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds for being catalyzed reduction amination.
2. preparation method according to claim 1, which is characterized in that in step 1), 2,5-Dihydroxyterephthalic acid and
The molar ratio of cobalt acetate is 1:2~1:4；The tetrahydrofuran of in the mixed solvent and the volume ratio of water are 1:1~1:2；Reaction temperature
It is 100~120 DEG C；Reaction time is 3~5 days.
3. preparation method according to claim 1, which is characterized in that in step 2), surface coats the Co- of polyethylene glycol
In the hexane solution of MOFs materials, the mass volume ratio of Co-MOFs materials and n-hexane that bread covers polyethylene glycol is 1:5~
1:20g/mL。
4. preparation method according to claim 1, which is characterized in that in step 3), in acetic acid aqueous palladium, palladium and
The mass volume ratio of water is 3:1~1:10mg/ml.
5. preparation method according to claim 1, which is characterized in that in step 4), N2/H2Mixed gas in, H2Matter
It is 2~4% to measure score, and calcination temperature is 400~700 DEG C, and calcination time is 4~6h.
6. preparing amine chemical combination for being catalyzed reduction amination made from a kind of preparation method according to one of claim 1-5
Magnetic carbon/palladium-cobalt multiplex catalyst of object.
7. it is a kind of it is according to claim 6 for be catalyzed reduction amination prepare aminated compounds magnetic carbon/palladium-cobalt it is polynary
The application of composite catalyst, which is characterized in that application process is as follows：
In organic solvent, carbonyls is added and magnetic carbon/palladium-cobalt multiplex catalyst, magnetic carbon/palladium-cobalt is polynary
The rate of charge of composite catalyzing dosage and carbonyls is 5~10mg:1mmol each leads into ammonia and hydrogen, and volume ratio is about
It is 1：4~1:6, it reacts 2~10.0 hours, obtains under conditions of reaction temperature is 70~120 DEG C, reaction pressure is 1~5MPa
To corresponding aminated compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810305385.0A CN108525675A (en) | 2018-04-08 | 2018-04-08 | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810305385.0A CN108525675A (en) | 2018-04-08 | 2018-04-08 | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108525675A true CN108525675A (en) | 2018-09-14 |
Family
ID=63482850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810305385.0A Pending CN108525675A (en) | 2018-04-08 | 2018-04-08 | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108525675A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180498A (en) * | 2018-09-20 | 2019-01-11 | 大连理工大学 | A kind of preparation method replacing Armeen |
| CN109622037A (en) * | 2018-12-07 | 2019-04-16 | 辽宁大学 | A kind of Pd@Co4(tpt)2(btb) composite material and preparation method and application |
| CN111111689A (en) * | 2019-12-26 | 2020-05-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN113634271A (en) * | 2021-07-16 | 2021-11-12 | 华南理工大学 | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781571A (en) * | 2009-12-03 | 2012-11-14 | 巴斯夫欧洲公司 | Catalyst and method for producing an amine |
| CN105228742A (en) * | 2013-05-20 | 2016-01-06 | 乐天化学株式会社 | For the catalyst and uses thereof of reductive amination process |
| CN106034401A (en) * | 2013-09-04 | 2016-10-19 | 塔明克公司 | Improved process for the reductive amination and selective hydrogenation of substrates containing a selected halogen |
| CN106552661A (en) * | 2016-10-28 | 2017-04-05 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and the method for preparing aminated compoundss using its catalytic hydrogenating reduction amination |
| CN106669737A (en) * | 2017-01-04 | 2017-05-17 | 上海应用技术大学 | Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure |
| CN107189074A (en) * | 2017-05-26 | 2017-09-22 | 西安电子科技大学 | The surface-functionalized method of modifying of metal-organic framework materials based on liposome membrane |
-
2018
- 2018-04-08 CN CN201810305385.0A patent/CN108525675A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781571A (en) * | 2009-12-03 | 2012-11-14 | 巴斯夫欧洲公司 | Catalyst and method for producing an amine |
| CN105228742A (en) * | 2013-05-20 | 2016-01-06 | 乐天化学株式会社 | For the catalyst and uses thereof of reductive amination process |
| CN106034401A (en) * | 2013-09-04 | 2016-10-19 | 塔明克公司 | Improved process for the reductive amination and selective hydrogenation of substrates containing a selected halogen |
| CN106552661A (en) * | 2016-10-28 | 2017-04-05 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and the method for preparing aminated compoundss using its catalytic hydrogenating reduction amination |
| CN106669737A (en) * | 2017-01-04 | 2017-05-17 | 上海应用技术大学 | Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure |
| CN107189074A (en) * | 2017-05-26 | 2017-09-22 | 西安电子科技大学 | The surface-functionalized method of modifying of metal-organic framework materials based on liposome membrane |
Non-Patent Citations (3)
| Title |
|---|
| ZHANG JIAN-YONG ET AL: "Structural diversity and catalytic properties of five Co-2(COO)(4) cluster-based coordination polymers modified with R-isophthalic acid (R = H, NO2, CH3, OH and Bu-t)", 《CRYSTENGCOMM》 * |
| 李信林: "由MOFs合成的介孔碳材料负载贵金属催化剂的制备及其在选择性氢化反应中的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 潘梅 等: "配位超分子自组装", 《化学进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180498A (en) * | 2018-09-20 | 2019-01-11 | 大连理工大学 | A kind of preparation method replacing Armeen |
| CN109622037A (en) * | 2018-12-07 | 2019-04-16 | 辽宁大学 | A kind of Pd@Co4(tpt)2(btb) composite material and preparation method and application |
| CN109622037B (en) * | 2018-12-07 | 2022-04-05 | 辽宁大学 | Pd @ Co4(tpt)2(btb) composite material, and preparation method and application thereof |
| CN111111689A (en) * | 2019-12-26 | 2020-05-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN111111689B (en) * | 2019-12-26 | 2022-07-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN113634271A (en) * | 2021-07-16 | 2021-11-12 | 华南理工大学 | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108525675A (en) | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination | |
| CN103949286B (en) | A kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage | |
| CN104525264B (en) | Ammonobase organic framework material, its preparation method and application comprising active metal component | |
| US9499402B2 (en) | Method for preparing a supported ruthenium catalyst | |
| CN112387295B (en) | Nitrogen-doped carbon-loaded ruthenium monatomic catalyst as well as preparation method and application thereof | |
| CN108393092A (en) | Preparation method of catalyst for nitrile compounds Hydrogenation secondary amine and products thereof and application | |
| CN105457653B (en) | A kind of surface strengthened palladium-based catalyst and preparation method thereof for low-concentration methane catalysis burning | |
| CN108404987B (en) | Method for improving catalytic efficiency of nanoparticle @ MOFs material | |
| CN108689786B (en) | Method for synthesizing imine and amine compounds by hydrogen reduction coupling | |
| CN110404573A (en) | A kind of preparation method and application of extra small palladium-base alloy material | |
| CN106179446B (en) | The method of cobalt/nitrating porous carbon composite and its preparation method and catalysis silane oxidation | |
| CN112495444A (en) | TiO22Preparation method and application of @ HKUST-1 composite photocatalyst | |
| CN104069882A (en) | Preparation method of nanocrystalline metal catalyst loaded with carbon and nitrogen materials | |
| CN107308976A (en) | A kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application | |
| CN107754851A (en) | A kind of monatomic iridium catalyst and its preparation and application | |
| CN104258874A (en) | Catalyst for use in one-step preparation of imine through selective hydrogenation coupling of cyanophenyl and preparation method and application | |
| CN106669737B (en) | A kind of carbon/palladium-cobalt heterogeneous catalyst preparation method of magnetic core-shell structure | |
| CN112076748A (en) | Dehydrogenation catalyst | |
| CN109046328A (en) | A kind of photo-thermal catalytic hydrogenation catalyst and its preparation and the application in 3,4- dichloronitrobenzene selective hydrogenation | |
| CN113522294B (en) | Ni-based catalyst, preparation method thereof and application thereof in reductive amination | |
| CN116809072B (en) | Cobalt monoatomic heterogeneous catalyst synthesized by microwave method and application thereof | |
| CN107694595B (en) | A kind of preparation method of oxygen doping boron nitride catalyst carrier | |
| CN109046442A (en) | The molecular sieve carried platinum iron double metal catalyst of multi-stage porous and its preparation and application | |
| CN111318296B (en) | Preparation method and application of supported cobalt/carbon nanotube material derived from zeolite imidazole framework material | |
| CN109158114A (en) | A kind of method that one-step method prepares CdS@C composite photo-catalyst |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180914 |