CN113856726A - High-efficiency low-cost heterogeneous catalyst suitable for preparation of beta-nitroalcohol - Google Patents
High-efficiency low-cost heterogeneous catalyst suitable for preparation of beta-nitroalcohol Download PDFInfo
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- CN113856726A CN113856726A CN202111259018.XA CN202111259018A CN113856726A CN 113856726 A CN113856726 A CN 113856726A CN 202111259018 A CN202111259018 A CN 202111259018A CN 113856726 A CN113856726 A CN 113856726A
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 38
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical compound OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 8
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 8
- -1 etc.) Chemical compound 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 238000006842 Henry reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 4
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 4
- 101001072091 Homo sapiens ProSAAS Proteins 0.000 description 4
- 102100036366 ProSAAS Human genes 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- GAOZFHWIKYMRGU-UHFFFAOYSA-N 1,4,7,10-tetrazacyclododecan-1-amine Chemical compound NN1CCNCCNCCNCC1 GAOZFHWIKYMRGU-UHFFFAOYSA-N 0.000 description 2
- 229910015183 FeNx Inorganic materials 0.000 description 2
- 229910005849 NiNx Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KOTBJOXPSFOFPU-UHFFFAOYSA-N ethane-1,2-diamine;nickel Chemical compound [Ni].NCCN KOTBJOXPSFOFPU-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 description 1
- 238000011925 1,2-addition Methods 0.000 description 1
- 229910016547 CuNx Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229960004203 carnitine Drugs 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QDYBCIWLGJMJGO-UHFFFAOYSA-N dinitromethanone Chemical compound [O-][N+](=O)C(=O)[N+]([O-])=O QDYBCIWLGJMJGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to preparation of a novel monatomic dispersed heterogeneous catalyst and application thereof in catalytic synthesis, belongs to the field of materials and catalytic science, and discloses preparation of the monatomic dispersed heterogeneous catalyst prepared by a surface fixation method and application thereof in beta-nitroalcohol synthesis. Compared with the traditional method for synthesizing beta-nitroalcohol through Henry reaction, the heterogeneous catalyst disclosed by the invention is simple in method, mild in condition, high in reaction atom economy, high in raw material conversion rate, good in product regioselectivity, and easy to separate, recover and recycle after the reaction is finished. Meanwhile, the catalyst is simple in preparation method, cheap and easily available in raw materials, easy for mass preparation and good in application prospect.
Description
The technical field is as follows:
the invention relates to preparation of a heterogeneous catalyst and application of the heterogeneous catalyst in Henry reaction, belonging to the field of materials and catalysis science.
Background art:
the nitroalkane performs a 1, 2-addition reaction to the carbonyl group of an aldehyde or ketone to produce a β -nitroalcohol compound, known as the henry reaction. The nitroalcohol product can be converted into compounds with various purposes, such as aminoalcohol by reduction, alcohol by denitration, nitroolefin by dehydration, nitroketone by oxidation, and the like, and is an organic intermediate for synthesizing various natural products and important compounds of medicines. However, the existing method for synthesizing the beta-nitroalcohol compound has a plurality of defects, strong alkali is generally needed to promote the reaction to be carried out and the reaction is reversible, the generated beta-nitroalcohol compound can be further dehydrated into nitroolefin under the condition, and other side reactions such as a carnitine zaro reaction and the like can also be carried out, so that the synthesis yield of the beta-nitroalcohol is low, and the production cost is greatly increased. When the substrate is multi-carbon nitroalkane such as nitroethane, various cis-trans isomeric products also exist in the reaction product. The use of other homogeneous metal catalysts can result in heavy metal residues in the beta-nitroalcohol product, which can seriously affect the product quality and have low efficiency. Therefore, the development of highly efficient, highly selective heterogeneous catalysts is an important solution for the realization of economical industrial production of β -nitroalcohols. In recent years, due to the characteristics of excellent catalytic activity and selectivity, high atom utilization rate, easy separation and the like, the monatomic dispersed heterogeneous catalyst is widely concerned, so that the development of the monatomic dispersed heterogeneous catalyst with high efficiency and low cost is the key for realizing the economic and high-efficiency production of the beta-nitroalcohol, and meanwhile, the heterogeneous catalyst can also enable the product to have special regioselectivity, which is a problem to be solved in the large-scale preparation of the compounds at present.
The invention content is as follows:
aiming at the problems existing in the catalytic preparation of the beta-nitroalcohol at present, the invention aims to provide a high-efficiency low-cost monatomic dispersed heterogeneous catalyst, which can improve the conversion efficiency and the regioselectivity of the reaction for preparing the beta-nitroalcohol, simultaneously can quickly and efficiently separate a product from the catalyst and reduce the cost for separating and purifying the product.
Furthermore, the invention discloses the application of the monoatomic dispersion heterogeneous catalyst synthesized by the surface immobilization method in catalyzing the Henry reaction for the first time, and the catalyst has good reactivity and selectivity, high regioselectivity and convenient recovery. Has great application value in the industrial preparation of beta-nitroalcohol.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a method for preparing beta-nitroalcohol by catalyzing with a monatomic dispersed heterogeneous catalyst prepared by a surface immobilization method for the first time, wherein the monatomic dispersed heterogeneous catalyst is added into a mixed solution of aromatic aldehyde ketone and nitroalkane, and the catalytic reaction can be carried out at room temperature to generate the beta-nitroalcohol, so that high conversion efficiency and high regioselectivity can be realized. After the reaction, the catalyst in the reaction system can be effectively removed by filtering. After the catalyst is recycled for multiple times, the catalytic performance of the catalyst can still be maintained.
Further, the preparation method of the monoatomic dispersion heterogeneous catalyst in the invention comprises the step of preparing the pre-organized MNxOyThe complex precursor is loaded on the surface of the substrate material in a homogeneous solution system. The high temperature treatment at 200-400 ℃ causes the bonding of carbon bonds and the reconstruction reaction of MNxOyThe complex precursor is fixed on the surface of the substrate material to form the heterogeneous catalyst with the monoatomic dispersion.
Further, MN fixed on the surface of the monoatomic dispersion heterogeneous catalyst used in the present inventionxOyThe metal atom in the precursor of the structural complex can be Mn, Fe, Cu, Co, Ni, Ru, Rh, Pd and the like, and the ligand is a bidentate or polydentate ligand containing coordination sites such as amino, imine, phenolic hydroxyl, nitrogen-containing aromatic ring and the like. A complex precursor of a single metal atom or a complex precursor of a plurality of metal atoms may be added to the surface of the substrate.
Furthermore, the substrate material used in the invention is a frame structure material (such as MOF, COF and the like) or a two-dimensional lamellar material with a large specific surface area, and is a pure organic or organic-inorganic hybrid material, and in a homogeneous solution system, precursor molecules can be uniformly dispersed on the surface of the substrate material to form monomolecular dispersion.
Further, the monoatomic dispersion heterogeneous catalyst used in the present invention is prepared by dispersing MN on the surfacexOyThe precursor is heated to the substrate at the temperature of 200-400 ℃ for bonding preparation, and MN with different proportions is added on the surface of the substratexOyThe precursor can obtain catalysts with different surface active species concentrations.
Further, the content of the metal atom in the monoatomic dispersed heterogeneous catalyst for catalyzing the preparation of β -nitroalcohol used in the present invention is 2 to 20 mol%, preferably 5 to 15 mol%.
Furthermore, the monoatomic dispersion heterogeneous catalyst used in the invention is convenient to recover and can be recycled.
Furthermore, the substrate suitable for preparing the beta-nitroalcohol in the invention is various aromatic aldehydes or ketones, the aromatic ring can be provided with different numbers of various different substituents and the like, the aromatic ring can be a benzene ring, a pyridine ring, a pyrimidine ring, pyridazine, pyrazine, imidazole, quinoline and the like, and the reaction conversion rates of different reaction substrates are different.
Further, examples of nitroalkanes suitable for use in the present invention for the preparation of β -nitroalcohols include nitromethane, nitroethane, and other linear nitroalkanes, with varying conversion rates corresponding to the reaction.
Further, the solvent used in the henry reaction of the present invention may be a mixture of one or more solvents selected from alcohols (other alcohols such as methanol, ethanol, and isopropyl alcohol), N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide, dimethylsulfoxide, tetrahydrofuran, and diethyl ether.
Furthermore, the reaction temperature range of the preparation of the beta-nitroalcohol is 20-150 ℃, and the reaction time is 2-100 h.
The monoatomic dispersion heterogeneous catalyst prepared by the surface immobilization method has the advantages of low raw material cost, easy mass preparation and high yield. When the catalyst is used for preparing beta-nitroalcohol in a catalytic mode, the reaction condition is mild, the reaction conversion rate is high, the regioselectivity is good, the catalyst is easy to recover and can be recycled, the catalytic performance of the catalyst is not obviously reduced after the catalyst is used for 10 times, the economic benefit is good, and the catalyst has a good application prospect in large-scale preparation of beta-nitroalcohol.
Description of the drawings:
FIG. 1 shows FeN according to example 2 of the present inventionxXRD schematic of a monoatomic Dispersion heterogeneous catalyst (Fe-SAC)
FIG. 2 shows FeN according to example 2 of the present inventionxHAADF-STEM images of monoatomic dispersion heterogeneous catalysts
The specific implementation scheme is as follows:
in order to make the present invention clearer and clearer, the present invention is described in further detail below. The described embodiments are only a part of the embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without inventive labor based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1: surface fixed NiNxPreparation of the monoatomic dispersion heterogeneous catalyst
500mg of cobalt nitrate hexahydrate, 35mg of nickel ethylenediamine and 1000mg of surfactant SAAS were added into a 1000ml reaction flask, respectively, and 200ml of deionized water was added. After the reactants were completely dispersed and dissolved, 200ml of dichloromethane was added, and the mixed solution was vigorously stirred for 10min to form a uniform emulsion. Subsequently, 300mg of dimethylimidazole was dissolved in 30ml of dichloromethane and slowly added dropwise to the emulsion system. The mixed solution is stirred vigorously for 12 hours at room temperature. After the reaction is finished, removing the water layer through a separating funnel, and drying the organic layer through a vacuum rotary evaporator and an oven.
And placing the sample obtained after the post-treatment in a muffle furnace for calcining. The calcination procedure was: the temperature rise rate is 5 ℃ per minute, and when the temperature rises to 350 ℃, the temperature is kept for 1 h. And finally, naturally cooling to room temperature to obtain a gray foamy powder material, fully grinding the gray foamy powder material, and using the gray foamy powder material for subsequent experiments.
Example 2: surface fixed FeNxPreparation of the monoatomic dispersion heterogeneous catalyst
500mg of cobalt nitrate hexahydrate, 35mg of 1, 4, 7, 10-tetraazacyclododecylamine coordinated iron and 1000mg of surfactant SAAS are respectively added into a 1000ml reaction bottle, and 200ml of deionized water is added. After the reactants were completely dispersed and dissolved, 200ml of dichloromethane was added, and the mixed solution was vigorously stirred for 10min to form a uniform emulsion. Subsequently, 300mg of dimethylimidazole was dissolved in 30ml of dichloromethane and slowly added dropwise to the emulsion system. The mixed solution is stirred vigorously for 12 hours at room temperature. After the reaction is finished, removing the water layer through a separating funnel, and drying the organic layer through a vacuum rotary evaporator and an oven.
And placing the sample obtained after the post-treatment in a muffle furnace for calcining. The calcination procedure was: the temperature rise rate is 5 ℃ per minute, and when the temperature rises to 350 ℃, the temperature is kept for 1 h. And finally, naturally cooling to room temperature to obtain a gray foamy powder material, fully grinding the gray foamy powder material, and using the gray foamy powder material for subsequent experiments.
Example 3: surface fixed FeNx/NiNxPreparation of the monoatomic dispersion heterogeneous catalyst
500mg of cobalt nitrate hexahydrate, 17.5mg of 1, 4, 7, 10-tetraazacyclododecylamine coordinated iron, 17.5mg of nickel ethylenediamine and 1000mg of surfactant SAAS are respectively added into a 1000ml reaction bottle, and 200ml of deionized water is added. After the reactants were completely dispersed and dissolved, 200ml of dichloromethane was added, and the mixed solution was vigorously stirred for 10min to form a uniform emulsion. Subsequently, 300mg of dimethylimidazole was dissolved in 30ml of dichloromethane and slowly added dropwise to the emulsion system. The mixed solution is stirred vigorously for 12 hours at room temperature. After the reaction is finished, removing the water layer through a separating funnel, and drying the organic layer through a vacuum rotary evaporator and an oven.
And placing the sample obtained after the post-treatment in a muffle furnace for calcining. The calcination procedure was: the temperature rise rate is 5 ℃ per minute, and when the temperature rises to 350 ℃, the temperature is kept for 1 h. And finally, naturally cooling to room temperature to obtain a gray foamy powder material, fully grinding the gray foamy powder material, and using the gray foamy powder material for subsequent experiments.
Example 4: surface fixed CuNxPreparation of the monoatomic dispersion heterogeneous catalyst
500mg of cobalt nitrate hexahydrate, 35mg of copper ethylenediamine, 1000mg of surfactant SAAS were added to a 1000ml reaction flask, respectively, and 200ml of deionized water was added thereto. After the reactants were completely dispersed and dissolved, 200ml of dichloromethane was added, and the mixed solution was vigorously stirred for 10min to form a uniform emulsion. Subsequently, 300mg of dimethylimidazole was dissolved in 30ml of dichloromethane and slowly added dropwise to the emulsion system. The mixed solution is stirred vigorously for 12 hours at room temperature. After the reaction is finished, removing the water layer through a separating funnel, and drying the organic layer through a vacuum rotary evaporator and an oven.
And placing the sample obtained after the post-treatment in a muffle furnace for calcining. The calcination procedure was: the temperature rise rate is 5 ℃ per minute, and when the temperature rises to 350 ℃, the temperature is kept for 1 h. And finally, naturally cooling to room temperature to obtain a gray foamy powder material, fully grinding the gray foamy powder material, and using the gray foamy powder material for subsequent experiments.
Example 5:
2ml of methanol, 0.1ml of benzaldehyde, 0.5ml of nitromethane and 50mg of the Ni monatomic dispersed heterogeneous catalyst prepared in example 1 were respectively added into a 20ml autoclave, the mixed solution was ultrasonically treated, the air in the autoclave was evacuated by a vacuum pump, and the reaction was carried out at room temperature with stirring for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 98 percent
Example 6:
2ml of N, N-dimethylformamide, 0.1ml of benzaldehyde, 0.5ml of nitromethane and 50mg of the Ni monoatomic dispersion heterogeneous catalyst prepared in example 1 were respectively added to a 20ml autoclave, the mixed solution was subjected to ultrasonic treatment, air in the autoclave was evacuated by a vacuum pump, and the mixture was stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 95 percent
Example 7:
2ml of methanol, 150mg of p-nitrobenzaldehyde, 0.5ml of nitromethane and 50mg of the Fe monatomic dispersed heterogeneous catalyst prepared in example 2 were respectively added into a 20ml autoclave, the mixed solution was ultrasonically treated, the air in the autoclave was evacuated by a vacuum pump, and the mixture was stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 99 percent
Example 8:
2ml of methanol, 150mg of p-nitrobenzaldehyde, 0.5ml of nitromethane and 50mg of the Cu monatomic dispersed heterogeneous catalyst prepared in example 4 were respectively added into a 20ml autoclave, the mixed solution was ultrasonically treated, the air in the autoclave was evacuated by a vacuum pump, and the mixture was stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 94 percent
Example 9:
2ml of methanol, 0.12ml of p-methoxybenzaldehyde, 0.5ml of nitromethane and 50mg of the Ni monoatomic dispersion heterogeneous catalyst prepared in example 1 were respectively charged into a 20ml autoclave, the mixed solution was ultrasonically treated, and the air in the autoclave was evacuated by a vacuum pump and stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 92 percent
Example 10:
2ml of methanol, 150mg of p-nitrobenzaldehyde, 0.5ml of nitromethane and 50mg of the Fe/Ni monoatomic dispersion heterogeneous catalyst prepared in example 3 were respectively added into a 20ml autoclave, the mixed solution was ultrasonically treated, air in the autoclave was evacuated by a vacuum pump, and the mixture was stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The instrument shows that the conversion rate of the obtained reaction is 99 percent
Example 11:
2ml of methanol, 150mg of p-nitrobenzaldehyde, 0.5ml of nitroethane and 50mg of the Ni monatomic dispersed heterogeneous catalyst prepared in example 1 were respectively added into a 20ml autoclave, the mixed solution was ultrasonically treated, the air in the autoclave was evacuated by a vacuum pump, and the mixture was stirred at room temperature for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The conversion rate of the obtained reaction is 99% through instrument characterization, and the cis-trans isomerization selectivity of the product reaches 15: 1.
example 12:
2ml of methanol, 0.1ml of benzaldehyde, 0.5ml of nitroethane and 50mg of the Ni monatomic dispersed heterogeneous catalyst prepared in example 1 were respectively added to a 20ml autoclave, the mixed solution was ultrasonically treated, the air in the autoclave was evacuated by a vacuum pump, and the reaction was carried out at room temperature with stirring for 72 hours. In the post-treatment, ethyl acetate is added into the mixed solution, then the mixed solution is simply filtered by using filter paper to obtain a product, the solvent is removed by using a vacuum rotary evaporator at the temperature of 50 ℃, and the product is placed in an oven for overnight. A yellow liquid was obtained. The conversion rate of the obtained reaction is 97% through instrument characterization, and the cis-trans isomerization selectivity of the product reaches 15: 1.
Claims (5)
1. a high-efficiency low-cost monatomic dispersed heterogeneous catalyst suitable for preparing beta-nitroalcohol is characterized in that MN is prepared by utilizing a surface fixation methodxOyThe complex precursor is loaded on the surface of the substrate material in a homogeneous solution system through reaction at 200-400-High-temperature treatment at the temperature of DEG C generates carbon bond bonding and reconstruction reaction, thereby leading MN to bexOyFixing the precursor on the surface of a base material; MN (Mobile node)xOyThe precursor can form active catalytic sites with scattered monoatomic atoms after being fixed, can be used for catalyzing the reaction of preparing beta-nitroalcohol from aromatic aldehyde or ketone and nitroalkane without other additives under mild reaction conditions, has high catalytic reaction activity and selectivity, is easy to separate reaction products from the catalyst, and can be recycled.
2. The heterogeneous catalyst of claim 1 prepared by surface immobilization of MNxOyWhen the precursor of the complex is structured, the metal atoms in the precursor can be Mn, Fe, Cu, Co, Ni, Ru, Rh, Pd and the like, and the ligand is a bidentate or polydentate ligand containing coordination sites such as amino, imine, phenolic hydroxyl, nitrogen-containing aromatic ring and the like; the single metal atom complex precursor or the multiple metal atom complex precursor can be added on the surface of the substrate to prepare the catalyst of single metal or multiple metal sites, and the substrate material is a framework structure material (such as MOF, COF and the like) or a two-dimensional lamellar material with large specific surface area, and is a pure organic or organic-inorganic hybrid material.
3. As described in claim 2, the monoatomic dispersion catalyst suitable for preparing beta-nitroalcohol has precursor metal atoms preferably Fe, Cu, Co, Ni, etc., loading amount preferably 5-15 mol%, and high temperature treatment temperature preferably 280-360 ℃.
4. The method as claimed in claim 1, wherein the catalyst catalyzes β -nitroalcohol production reaction, the substrates are various aromatic aldehydes or ketones and nitroalkanes, the aromatic aldehydes or ketones can have different numbers of various substituents, the aromatic rings can be benzene rings, pyridine rings, pyrimidine rings, pyridazine, pyrazine, imidazole, quinoline, etc., and the nitroalkanes can be nitromethane, nitroethane and other linear nitroalkanes.
5. As described in claim 1, the solvent used in the reaction for preparing β -nitroalcohol in the present invention may be any one or more of alcohol (other alcohols such as methanol, ethanol, isopropanol, etc.), N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide, dimethylsulfoxide, tetrahydrofuran, and diethyl ether; the reaction temperature is 20-150 ℃, preferably 40-80 ℃; the reaction time is 2-100 h.
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