CN115845892A - N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof - Google Patents
N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof Download PDFInfo
- Publication number
- CN115845892A CN115845892A CN202210734489.XA CN202210734489A CN115845892A CN 115845892 A CN115845892 A CN 115845892A CN 202210734489 A CN202210734489 A CN 202210734489A CN 115845892 A CN115845892 A CN 115845892A
- Authority
- CN
- China
- Prior art keywords
- zinc
- carbon material
- doped carbon
- material loaded
- preparation
- 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
- 239000011701 zinc Substances 0.000 title claims abstract description 60
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 58
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 56
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000007126 N-alkylation reaction Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- -1 amine compound Chemical class 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 125000004429 atom Chemical group 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000013170 zeolitic imidazolate framework-5 Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000012840 feeding operation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a N and S co-doped carbon material loaded zinc monoatomic atom and a preparation method and application thereof, wherein the preparation method of the N and S co-doped carbon material loaded zinc monoatomic atom comprises the following steps: mixing 2-methylimidazole, aniline, ammonia water and thiourea, and dispersing in a solvent to obtain a first mixture; mixing a zinc nitrate aqueous solution with the first mixture, performing ball milling dispersion to obtain a second mixture, washing, drying to obtain a precursor, and calcining under an inert atmosphere to obtain the zinc nitrate aqueous solution; controlling the feeding molar ratio of 2-methylimidazole, aniline, thiourea and zinc nitrate to be 2-6: 0.5-1.5: 1, and controlling the feeding molar ratio of ammonia to zinc nitrate in the ammonia water to be 2.5-12: 1; the N and S co-doped carbon material loaded zinc monoatomic atom shows excellent activity in an N-alkylation reaction of arylamine and alcohol, can be used as a catalyst to synthesize an amine compound with high efficiency, low cost and milder reaction conditions, and is high in stability and recoverable.
Description
Technical Field
The invention relates to the technical field of organic synthesis and monatomic catalysts, in particular to a N and S co-doped carbon material loaded zinc monatomic, and a preparation method and application thereof.
Background
The amine compound is a central compound in the chemical field, and has wide application in the aspects of agricultural chemicals, medicines, catalytic ligands, dyes and bioactive compounds. The alcohol is used as an alkylating reagent and reacts with the amine by a hydrogen strategy to only generate water as a byproduct, so that the method is environment-friendly for preparing the amine compound.
In this context, catalytic systems such as Ru, ir, pd, etc. were first applied (ACS Catal6 2613,3,6, 565-511) (Green Chem62617,19, 3142-3161) (Journal of Colloid and Interface Science 2622,666, 1346-1361), and then the hydrogen borrowing ability of metals such as Fe, co, mn, mo, W, etc. was also explored (Org 6 Lett 2616,17, 1656-1659) (Org 6 Chem. Front6,2619,6, 562-567) (Org 6 Lett6 2619,21, 3142-3147) (CaACS Catal6 2621,11, 16377-16352). However, these methods have some disadvantages, such as low atom utilization; noble metal catalysts such as Ru, ir, pd and the like are expensive and cannot be used on a large scale, or 1-3 equivalent of alkali is often required to be added into a reaction system, and the reaction conditions are harsh; homogeneous catalyst systems are not conducive to product separation and do not allow for catalyst recovery.
In recent years, the zinc catalytic system constructs C-C and C-N bonds to enter the field of researchers. In 2626, mannathan et al reported that zinc nitrate hexahydrate catalyzes the N-alkylation of alcohols and amines, and demonstrated Zn catalytic activity in the N-alkylation for the first time (Adv 6 Synth6Catal62626,362, 4469-44). However, the catalytic system conditions are severe (146 ℃,36 h), and the homogeneous catalyst cannot be recycled.
Disclosure of Invention
The invention aims to overcome one or more defects of the prior art and provide a novel preparation method of N and S co-doped carbon material loaded zinc monoatomic atoms.
The invention also provides a N and S co-doped carbon material prepared by the method for loading the zinc monoatomic atom.
The invention also provides application of the N and S co-doped carbon material loaded with the zinc monoatomic atom in catalyzing amine and alcohol amination reaction by hydrogen.
In order to achieve the purpose, the invention adopts a technical scheme that:
a preparation method of N and S co-doped carbon material loaded with zinc monoatomic atoms comprises the following steps:
mixing 2-methylimidazole, aniline, ammonia water and thiourea, and dispersing in a solvent to obtain a first mixture;
mixing a zinc nitrate aqueous solution with the first mixture, performing ball milling dispersion to obtain a second mixture, washing, and drying to obtain a precursor;
calcining the precursor in an inert atmosphere to obtain the N and S co-doped carbon material loaded with zinc monoatomic atoms;
wherein the feeding molar weight ratio of the 2-methylimidazole, the aniline, the thiourea and the zinc nitrate is controlled to be 2-6: 666-166: 1, and the feeding molar weight ratio of the ammonia in the ammonia water and the zinc nitrate is 266-12: 1.
According to some preferred and specific aspects of the present invention, the feeding molar ratio of the 2-methylimidazole, the aniline, the thiourea and the zinc nitrate is controlled to be 3-6: 665-162: 1.
According to a specific aspect of the present invention, the ammonia water may be an analytical reagent with a concentration of about 26 wt. 6% to 25 wt. 6%, and the amount of the ammonia water relative to the amount of the zinc nitrate is: 662-665mL/mmol.
According to some preferred aspects of the present invention, the 2-methylimidazole, aniline, aqueous ammonia, and thiourea are mixed and ball milled prior to mixing and dispersing the 2-methylimidazole, aniline, aqueous ammonia, and thiourea in the solvent. In some embodiments of the invention, zirconia may be used as the milling balls during the ball milling process to facilitate a uniform mixture.
According to some preferred aspects of the present invention, the solvent is selected from organic solvents that can dissolve each component, and specifically may be a combination of one or more selected from methanol, ethanol, and propanol.
According to some preferred aspects of the invention, the washing is centrifugal washing with deionized water, and the drying is performed by vacuum drying. In some embodiments of the invention, the vacuum drying is carried out at 76-96 ℃.
According to some preferred aspects of the invention, the inert atmosphere is a nitrogen atmosphere and/or an argon atmosphere.
According to some particular aspects of the invention, an aqueous solution of zinc nitrate may be obtained by dissolving zinc nitrate hexahydrate in deionized water.
According to some specific aspects of the present invention, the ball milling dispersion prior to obtaining the second mixture may be performed in the following manner: the rotating speed is 366-666rpm, and the ball milling is carried out for 1-6 hours; wherein, the process is repeated after the ball milling is finished after the ball milling is suspended for 2 to 16min every 26 to 46min of rotation.
According to some preferred aspects of the invention, the calcination temperature of the calcination is 566-1666 ℃. Further, the calcination temperature of the calcination is 566-966 ℃.
According to some preferred aspects of the invention, the calcination is carried out for a calcination time of from 1 to 6 hours. Further, the calcination time of the calcination is 1-6h.
According to some preferred aspects of the present invention, the temperature increase rate for increasing the temperature from room temperature to the calcination temperature is controlled to be 3 to 5 ℃/min.
The invention provides another technical scheme that: the N and S co-doped carbon material prepared by the preparation method is loaded with zinc monoatomic atoms.
According to the invention, the loading capacity of zinc in the N and S co-doped carbon material loaded zinc monoatomic atoms is 2 wt6-6 wt% in terms of weight percentage. Further, the loading amount of zinc in the N and S co-doped carbon material loaded zinc single atom is 266 wt% to 466 wt% 6 wt%.
The invention provides another technical scheme that: the N and S co-doped carbon material loaded with zinc monatomic is used as a catalyst in the hydrogen-borrowing N-alkylation reaction of aromatic amine and alcohol.
According to some preferred and specific aspects of the present invention, aromatic amines are reacted with alcohols in the presence of a base, in a solvent, under an inert atmosphere, at 116-136 ℃ and under the single atom catalysis of zinc supported by N, S co-doped carbon materials to generate corresponding amine compounds.
According to some preferred aspects of the present invention, in the N-alkylation reaction by hydrogen, the reaction temperature of the reaction is from 116 to 126 ℃.
According to the invention, in the N-alkylation reaction by means of hydrogen, the reaction time is 6 to 26 hours.
According to the invention, the N and S co-doped carbon material loaded zinc monoatomic atoms are recycled after the reaction is finished, the recycling frequency can reach 5 times or more, and the catalytic activity is not obviously attenuated.
According to some preferred aspects of the present invention, in the N-alkylation reaction by hydrogen, the solvent may be toluene, ethylbenzene, or the like.
According to some preferred aspects of the present invention, in the N-alkylation reaction by hydrogen, the base may be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or the like.
According to some preferred aspects of the present invention, the aromatic amine, alcohol, base, and zinc are used in a molar ratio of 1:166-266:661-666:66661-661. Further, in the hydrogen N-alkylation reaction, the molar ratio of the aromatic amine to the alcohol to the alkali to the zinc is 1:165-262:6616-6646:66663-6666.
According to a specific aspect of the invention, in the N-alkylation reaction by hydrogen, the dosage ratio of the N and S co-doped carbon material loaded with the zinc single atom to the aromatic amine is 16-26mg/mmol.
According to some preferred and specific aspects of the present invention, in the N-alkylation reaction by hydrogen, the aromatic amine may be one or more selected from the following structures:
in the formula (1), R 1 Is selected from H and C 1-6 Alkyl, halogen, aryl or C 1-6 Alkoxy, a may be 6,1, 2, 3, 4 or 6, b may be 1, 2, 3, 4, 6, 7, 5, 9 or 16, X is CH or N;
in the formula (2), R 2 Is selected from H, C 1-6 Alkyl, halogen, aryl or C 1-6 Alkoxy, c may be 1, 2, 3 or 4, Y is CH or N.
Further, the aromatic amine may be
Further preferably, C 1-6 The alkyl group may be substituted or unsubstituted as follows: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, hexyl, and the like; halogen may be fluorine, chlorine or bromine; the aryl group may be a substituted or unsubstituted phenyl group; c 1-6 The alkoxy group may be a substituted or unsubstituted group as follows: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy and the like.
In the N-alkylation by hydrogen according to the present invention, the alcohol is not particularly limited, and may be an aliphatic alcohol, an aromatic alcohol, etc., and may be, for example, a substituted or unsubstituted C 1-16 Alkyl alcohols, substituted or unsubstituted α -phenyl alkyl alcohols, hydroxy substituted heterocycles, enol-containing compounds, and the like. Wherein, the heterocyclic ring can be a 3-16 membered heterocyclic ring, and the hetero atom of the heterocyclic ring can be one or more of oxygen, sulfur and nitrogen.
In the present invention<xnotran> , , , , , , , , , , , , </xnotran>
/>
Etc.; wherein A is CH or N, B is S or O, M is CH or N, d, i are independently 1, 2, 3, 4, 6, 7, 5, 9 or 16, e, g are independently 6,1, 2, 3, 4, 6 or 6.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
through continuous experiments, researches show that the specific compound combination is adopted for doping N and S, so that the electronic structure of a Zn center is effectively improved, and the reaction can be completed mildly in a short time; the specific surface area and pore volume of the catalyst are increased by a unique in-situ doping carbonization mode, so that the adsorption of reactants is facilitated, and the catalytic efficiency is increased; the N and S co-doped carbon material loaded zinc monatomic catalyst has excellent catalytic performance for the hydrogen-borrowing N-alkylation reaction of amine and alcohol, is high in yield, economic and environment-friendly, and avoids the use of a noble metal catalyst; meanwhile, the substrate has wide application range, can react with straight-chain alcohol, and can recycle the catalyst after the reaction is finished.
Drawings
Fig. 1 is an XRD pattern of the N and S co-doped carbon material loaded zinc monoatomic precursor prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the N and S co-doped carbon material loaded with a zinc monoatomic precursor prepared in example 1 of the present invention.
Fig. 3 is an XRD pattern of zinc monoatomic supported by the N and S co-doped carbon material prepared in example 1 of the present invention.
Fig. 4 is a TEM image of the N and S co-doped carbon material loaded with zinc monoatomic atoms prepared in example 1 of the present invention.
FIG. 5 is a HAADF-STEM-EDS diagram of a N and S co-doped carbon material loaded with a zinc monoatomic atom prepared in example 1 of the present invention;
fig. 6 is a diagram of XANES and EXAFS of zinc monoatomic-supported N, S co-doped carbon material prepared in example 1 of the present invention.
Detailed Description
The above scheme is further explained by combining with specific embodiments; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not noted are generally those in routine experiments.
The following examples are not specifically illustrated and all starting materials are either commercially available or prepared by conventional methods known in the art.
Example 1
The embodiment provides a preparation method of N and S co-doped carbon material loaded with zinc monoatomic atoms, which comprises the following steps:
And step 3, pouring the liquid B into the liquid A, and performing ball milling for three hours at the rotating speed of 466rpm to obtain viscous white liquid. The sample was centrifugally washed with deionized water and dried in vacuo at 56 ℃ to obtain precursor ZIF-5-AA @ S (XRD pattern and SEM pattern are shown in FIGS. 1 and 2, respectively).
The XRD, TEM, HAADF-STEM-EDS, XANES and EXAFS diagrams are shown in FIG. 3, FIG. 4, FIG. 6 and FIG. 6, respectively, wherein:
FIG. 1: according to the XRD spectrum result of ZIF-5-AA @ S, the prepared precursor material has a complete ZIF-5 structure.
FIG. 2: SEM images according to ZIF-5-AA @ S show that the precursor is microspherical in size of about 266 nm.
FIG. 3: in CNS @ Zn 1 The XRD pattern of AA has two broad peaks at 24 ° and 43 °, which are respectively assigned to the (662) and (161) crystal planes of the graphitic carbon material. No zinc species were detected, not including the presence of large crystalline zinc particles. Only the diffraction peak of graphitic carbon was detected and no peak of Zn atom was observed, indicating that zinc may be present as a single atom in the catalyst.
FIG. 4: no highly crystalline Zn species was observed in TEM, consistent with XRD results.
FIG. 6: in the HAADF-STEM-EDS diagram, a large number of bright spots marked with circles represent isolated zinc atoms. EDX elemental mapping images showed uniformly distributed N, O, S and Zn signals, indicating that Zn, N and S have been successfully doped into carbon matrices.
FIG. 6: according to XANES and EXAFS results, zinc is present in the material in a monoatomic form, with 3 to 4 nitrogens, 1 sulfur being present outside the first shell.
Example 2
The preparation steps of the catalyst are basically the same as those in example 1, except that in the preparation method described in example 1, the dosage of aniline is adjusted from 24mmol to 21mmol, and the N and S co-doped carbon material loaded with zinc monoatomic atoms is prepared.
Example 3
The preparation procedure of the catalyst is basically the same as that in example 1, except that in the preparation method described in example 1, the amount of ammonia water is adjusted from 3ml to 2.5ml, so as to prepare the N and S co-doped carbon material loaded with zinc monatomic.
Example 4
This example provides a process for the preparation of aromatic amines by the hydrogen N-alkylation reaction of an alcohol, specifically:
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 16mg of CNS @ Zn prepared in example 1 1 AA was placed in a 26ml sealed tube under nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction is finished, the sealed tube is cooled toThe catalyst and solution were centrifuged at room temperature and the solution was analyzed by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS) to give a 96% yield of 3 a.
The reaction process is schematically shown as follows:
comparative example 1
The procedure for preparing the catalyst was substantially the same as in example 1, except that in the preparation method described in example 1, aniline was not added, the precursor name was ZIF-5-Am @ S, and CNS @ Zn was obtained by calcination 1 -Am。
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 1695g of CNS @ Zn 1 Am was placed in a 26ml sealed tube under nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction, the sealed tube was cooled to room temperature, and the catalyst and the solution were separated by centrifugation. The solution was analyzed by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS) and the 3a yield was 6%.
Comparative example 2
The procedure for preparing the catalyst was substantially the same as in example 1, except that in the preparation method described in example 1, thiourea was not added, the name of the precursor was ZIF-5, and CN @ Zn was obtained by calcination 1 。
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 1695g of CN @ Zn 1 The mixture was placed in a 26ml sealed tube and protected with nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction, the sealed tube was cooled to room temperature, and the catalyst and the solution were separated by centrifugation. The solution was analyzed by Gas Chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) and the 3a yield was 34%.
Comparative example 3
The procedure for the preparation of the catalyst is essentially the same as in example 1, except that in the preparation described in example 1, thiourea is replaced by an equimolar amount of triphenylphosphine, the precursor name is ZIF-5@ P, and CNP @ Zn is obtained by calcination 1 。
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 1695g of CNP @ Zn 1 The mixture was placed in a 26ml sealed tube under nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction is finished, sealingThe tube is sealed and cooled to room temperature, and the catalyst and the solution are centrifugally separated. The solution was analyzed by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS) to give a 62% yield of 3 a.
Comparative example 4
The preparation of the catalyst is essentially the same as example 1, except that in the preparation method described in example 1, ammonia is not added, the name of the precursor is ZIF-5-an @ S, and CNS-2@ Zn is obtained by calcining 1 -An。
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 1695g of CNS @ Zn 1 An is placed in a 26ml sealed tube and protected by nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction, the sealed tube was cooled to room temperature, and the catalyst and the solution were separated by centrifugation. The solution was analyzed by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS) and the 3a yield was 6%.
Comparative example 5
The procedure for the preparation of the catalyst was essentially the same as in example 1, except that in the preparation described in example 1, the amount of 2-methylimidazole was adjusted from 24mmol to 4mmol, the precursor name was ZIF-5-AA-2@ S, and the catalyst was calcined to obtain CNS-2@ Zn 1 -AA。
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 16mg of CNS-2@ Zn 1 AA was placed in a 26ml sealed tube under nitrogen. Heating to 126 ℃, and reacting for 12h. After the reaction, the sealed tube was cooled to room temperature, and the catalyst and the solution were separated by centrifugation. The solution was analyzed by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS) and the 3a yield was 16%.
Examples 5 to 18
These examples provide the preparation of aromatic amines and alcohols by the N-alkylation reaction with hydrogen, essentially as in example 4, with only one or 2 of the starting aromatic amines and alcohols being varied, as shown in Table 1.
TABLE 1
In the table, -Ph is phenyl and-OMe is methoxy.
Example 19:
this example provides the preparation of an aromatic amine by hydrogen N-alkylation with an alcohol as in example 4, except that: the catalyst adopts the N and S co-doped carbon material prepared in example 2 to load zinc monoatomic atoms, and the yield of 3a is 55%.
Example 20:
this example provides the preparation of an aromatic amine by hydrogen N-alkylation with an alcohol as in example 4, except that: the catalyst adopts the N and S co-doped carbon material prepared in example 3 to load zinc monoatomic atoms, and the yield of 3a is 59%.
Example 21: catalyst reuse Activity test
1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 16mg of CNS @ Zn prepared in example 1 1 AA was placed in a 26ml sealed tube under nitrogen. Heated to 126 ℃ and reacted for 12h. After the reaction is completed, the sealed tube is cooled to room temperature, and the catalyst and the solution are separated by centrifugation. The catalyst was washed with a small amount of water and ethyl acetate, transferred to a 26mL sealed tube, and 1mmol of aniline, 2mmol of benzyl alcohol, 663mmol of KOH, 2mL of toluene and 1695g of CNS @ Zn were added 1 And (4) heating to 126 ℃ under the protection of nitrogen, and reacting for 12 hours. And after the reaction is finished, cooling the sealed tube to room temperature, and repeating the catalyst recovery and the material feeding operation. The yields of the target product 3a in the reactions in which the catalyst was used fresh and applied 1-5 times, as analyzed by Gas Chromatography (GC) and gas chromatography-mass spectrometry (GC-MS), respectively, were as follows: 96%,96%,59%,96%,59%,96%,59%, 59%. The activity of the catalyst is not obviously reduced.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A preparation method of N and S co-doped carbon material loaded with zinc monoatomic atoms is characterized by comprising the following steps:
mixing 2-methylimidazole, aniline, ammonia water and thiourea, and dispersing in a solvent to obtain a first mixture;
mixing a zinc nitrate aqueous solution with the first mixture, performing ball milling dispersion to obtain a second mixture, washing, and drying to obtain a precursor;
calcining the precursor in an inert atmosphere to obtain the N and S co-doped carbon material loaded with zinc monoatomic atoms;
wherein the feeding molar weight ratio of the 2-methylimidazole, the aniline, the thiourea and the zinc nitrate is controlled to be 2-6: 0.5-1.5: 1, and the feeding molar weight ratio of the ammonia in the ammonia water and the zinc nitrate is controlled to be 2.5-12: 1.
2. The method for preparing the N and S co-doped carbon material loaded with the zinc monoatomic atom according to claim 1, wherein the feeding molar weight ratio of the 2-methylimidazole, the aniline, the thiourea and the zinc nitrate is controlled to be 3-5: 0.8-1.2: 1.
3. The preparation method of the N and S co-doped carbon material loaded with the zinc monoatomic atom according to claim 1, wherein 2-methylimidazole, aniline, ammonia water and thiourea are mixed and ball-milled before being dispersed in the solvent; and/or the solvent is one or more selected from methanol, ethanol and propanol.
4. The preparation method of the N and S co-doped carbon material loaded zinc monoatomic atom according to claim 1, wherein the washing is centrifugal washing with deionized water, and the drying is performed in a vacuum drying manner; and/or the inert atmosphere is a nitrogen atmosphere and/or an argon atmosphere.
5. The preparation method of the N and S co-doped carbon material loaded with the zinc monoatomic atom according to claim 1, wherein the calcining temperature is 800-1000 ℃, and the calcining time is 1-5h.
6. The method for preparing N and S co-doped carbon material loaded with zinc monoatomic atoms according to claim 5, wherein the temperature rise rate from room temperature to the calcination temperature is controlled to be 3-8 ℃/min.
7. The N and S co-doped carbon material prepared by the preparation method of any one of claims 1-6 carries zinc monoatomic atoms.
8. The N and S co-doped carbon material loaded zinc monoatomic atom according to claim 7, wherein the loading amount of zinc in the N and S co-doped carbon material loaded zinc monoatomic atom is 2-5 wt.%.
9. The use of the N and S co-doped carbon material loaded with zinc monatomic as defined in claim 7 or 8 as a catalyst in a hydrogen-borrowing N-alkylation reaction of aromatic amine and alcohol.
10. The application of claim 9, wherein aromatic amine and alcohol react in the presence of alkali, in a solvent, under an inert atmosphere, at 110-130 ℃ and under catalysis of a nitrogen and sulfur co-doped carbon material loaded zinc monatomic to generate a corresponding amine compound, the reaction time is 5-20h, and the nitrogen and sulfur co-doped carbon material loaded zinc monatomic is recycled after the reaction is finished.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210734489.XA CN115845892A (en) | 2022-06-27 | 2022-06-27 | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210734489.XA CN115845892A (en) | 2022-06-27 | 2022-06-27 | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115845892A true CN115845892A (en) | 2023-03-28 |
Family
ID=85660196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210734489.XA Pending CN115845892A (en) | 2022-06-27 | 2022-06-27 | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845892A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058805A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院福建物质结构研究所 | Method for synthesizing amine and imine |
| CN111203273A (en) * | 2020-01-13 | 2020-05-29 | 辽宁大学 | Super-hydrophobic metal organic framework composite material based on porous polymer PDVB-vim and preparation method and application thereof |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
| CN111477889A (en) * | 2020-06-02 | 2020-07-31 | 浙江大学 | Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof |
| CN111584889A (en) * | 2020-05-29 | 2020-08-25 | 深圳大学 | Zinc-containing monatomic catalyst and preparation method and application thereof |
| CN111715203A (en) * | 2019-03-19 | 2020-09-29 | 南开大学 | Preparation method of novel carbon-based material loaded zinc monoatomic catalyst |
| CN112495417A (en) * | 2020-12-04 | 2021-03-16 | 江苏丽源医药有限公司 | Iron monatomic catalyst and preparation method and application thereof |
-
2022
- 2022-06-27 CN CN202210734489.XA patent/CN115845892A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058805A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院福建物质结构研究所 | Method for synthesizing amine and imine |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
| CN111715203A (en) * | 2019-03-19 | 2020-09-29 | 南开大学 | Preparation method of novel carbon-based material loaded zinc monoatomic catalyst |
| CN111203273A (en) * | 2020-01-13 | 2020-05-29 | 辽宁大学 | Super-hydrophobic metal organic framework composite material based on porous polymer PDVB-vim and preparation method and application thereof |
| CN111584889A (en) * | 2020-05-29 | 2020-08-25 | 深圳大学 | Zinc-containing monatomic catalyst and preparation method and application thereof |
| CN111477889A (en) * | 2020-06-02 | 2020-07-31 | 浙江大学 | Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof |
| CN112495417A (en) * | 2020-12-04 | 2021-03-16 | 江苏丽源医药有限公司 | Iron monatomic catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| VELAYUDHAM SANKAR等: "Zinc-Catalyzed N-Alkylation of Aromatic Amines with Alcohols:A Ligand-Free Approach", 《ADV. SYNTH. CATAL.》, vol. 362, pages 4409 - 4414 * |
| 单洪滨: "ZIFs衍生碳材料负载廉价金属催化剂的制备及其在合成芳香胺中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 1 - 59 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112495417B (en) | Iron single-atom catalyst and preparation method and application thereof | |
| EP1941946A1 (en) | Carbonitrides as catalysts | |
| Wang et al. | Atomic zinc dispersed on graphene synthesized for active CO 2 fixation to cyclic carbonates | |
| CN102698811A (en) | Solid basic catalyst, preparation method of solid basic catalyst and application of solid basic catalyst in ester exchange reaction | |
| CN115646501B (en) | Cobalt monoatomic catalyst synthesized by molten salt method and application thereof | |
| CN115845892A (en) | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof | |
| WO2023193343A1 (en) | Catalyst for synthesizing dimethyl carbonate by means of methanol oxidative carbonylation and preparation method for and application of catalyst | |
| CN113198520A (en) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method | |
| CN113713839A (en) | Boron nitride loaded metal ruthenium catalyst, preparation method and application in imine preparation | |
| CN105967981B (en) | A kind of method that solid base catalyst [Smim] X/SBA 15 catalyzes and synthesizes propylene glycol monomethyl ether | |
| CN113333021A (en) | Porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction | |
| CN106316866B (en) | A kind of preparation method of N- methyl aminated compounds | |
| CN109603874B (en) | Copper-doped nitrogen-modified carbon material, application and reaction method for oxidizing and coupling aromatic amine into symmetric/asymmetric azobenzene | |
| CN112827510B (en) | Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof | |
| CN107954879B (en) | Application of carbon-loaded ruthenium nano material in preparation of N-alkyl aromatic amine compound | |
| CN108043442B (en) | Carbon-supported ruthenium nano material, preparation method thereof and application of carbon-supported ruthenium nano material in catalyzing reaction of alcohol and aromatic diamine | |
| CN107602354A (en) | A kind of method of synthesizing propanediol butyl ether | |
| CN108043441B (en) | Application of carbon-supported ruthenium nano material in catalyzing reaction of aromatic amine and aromatic methanol | |
| CN112375041B (en) | Preparation method of 2-substituted benzimidazole compound | |
| CN113019453B (en) | Catalyst for synthesizing diphenyl carbonate, preparation method and application | |
| Naeimi et al. | Nanocrystalline magnesium oxide as a solid base catalyst promoted one pot synthesis of gem-dichloroaziridine derivatives under thermal conditions | |
| US20230321641A1 (en) | Catalyst for oxidative carbonylation of methanol to synthesize dimethyl carbonate, and preparation method and applications thereof | |
| CN115155640B (en) | Molybdenum catalyst, catalytic composition and application thereof in preparation of amine compounds | |
| JP6650840B2 (en) | Method for producing MgO-supported catalyst | |
| CN113731469B (en) | Solid catalyst for catalytic oxidation esterification reaction, and preparation method and application thereof |
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 |