CN111871462A - Iron-cobalt organic catalyst, preparation method thereof and CO conversion method thereof2Use of benzazepine for the synthesis of benzazepine - Google Patents
Iron-cobalt organic catalyst, preparation method thereof and CO conversion method thereof2Use of benzazepine for the synthesis of benzazepine Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 18
- DQFQCHIDRBIESA-UHFFFAOYSA-N 1-benzazepine Chemical compound N1C=CC=CC2=CC=CC=C12 DQFQCHIDRBIESA-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000005406 washing Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000013032 photocatalytic reaction Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910017061 Fe Co Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- -1 o-aminobenzonitrile compound Chemical class 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000005431 greenhouse gas Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000007788 liquid Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SLIBXRZCKZOXQV-UHFFFAOYSA-N O1CCCC1.NC1=C(C#N)C=CC=C1 Chemical compound O1CCCC1.NC1=C(C#N)C=CC=C1 SLIBXRZCKZOXQV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention relates to the field of catalysts and aims at CO2The invention provides an iron-cobalt organic catalyst which is a microsphere with the diameter of 200-400nm and has layered crystals on the surface. The space formed between the catalyst particles increases the contact area of the reactants with the catalyst. Also provides a preparation method of the iron-cobalt organic catalyst, which comprises the steps of adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol, stirring for dissolving, and then sequentially adding FeCl3And Co (NO)3)2•6H2O stirring, 1Reacting at 50-200 deg.c for 10-20 hr, washing and drying. The preparation method is simple and has high repeatability. Also provides an iron-cobalt organic catalyst for converting CO2The application of the benzo-azacyclo is mild in reaction condition, and can effectively fix greenhouse gases to generate a drug intermediate with additional value.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an iron-cobalt organic catalyst, a preparation method thereof and CO conversion by using the iron-cobalt organic catalyst2Application of synthesizing benzazepine.
Background
CO2Is a greenhouse gas with large amount, no toxicity and stability in nature. With the global industrial development and the dramatic increase of population, CO is generated every year2The discharge amount is suddenly increased, and the ecological environment is destroyed. Thus, CO is converted2Efficient conversion of green to other compounds has been a very hot topic of research. At present, a large amount of CO exists2Is physically sealed on the seabed, can store a large amount of greenhouse gases in a short time, has a plurality of disadvantages, is a great hidden danger of the ecological environment, and can not fundamentally solve the problem of CO2Excessive discharge problems. It can also be stored or reacted into C1 compound such as methanol, formic acid, etc. by chemical method due to CO2The chemical potential energy is low and the activation is difficult, so that the finding of a green and environment-friendly catalyst for high-efficiency catalytic reaction is a difficult problem in the field. At present, with CO2The photocatalytic reaction as a raw material is mostly carried out under relatively severe conditions. Some of them need to be catalyzed at high temperature and high pressure, some are added with expensive rare earth metal elements, and some are added with photosensitizer. For example, chinese patent publication No. CN105749914B discloses a symmetric bifunctional photocatalyst and a dual-chamber photoreactor, belonging to the technical field of comprehensive utilization of carbon dioxide, wherein the symmetric bifunctional photocatalyst comprises dual-sided TiO2And depositing a graphene intermediate electron transport layer on the nanotube array substrate, and depositing narrow-gap semiconductor nanoparticles as a photosensitizer. The symmetrical photocatalyst provided by the invention has the advantages that the photoresponse of the three-way composite photocatalyst is expanded to a visible light region through the introduction of the electron transport layer and the photosensitizer component, meanwhile, the effective separation of a photoproduction electron-hole pair is promoted, and the photocatalytic reduction of CO by the composite photocatalyst is enhanced2OfForce; after the double-sided symmetrical ternary composite catalyst is matched with a double-chamber photoreactor, photocatalytic water oxidation and CO are carried out2The reduction reactions are respectively carried out in independent areas, so that the occurrence of reverse reactions is reduced, and the photocatalytic CO is further improved2The reduction efficiency is high, but the preparation of the photosensitizer is complicated and has requirements on a reactor. Therefore, a simple and efficient new carbon fixation way needs to be found.
Disclosure of Invention
In order to solve the technical problems, the invention provides an iron-cobalt organic catalyst, a preparation method thereof and CO conversion thereof2The application of synthesizing benzoazacyclo, uses hydrothermal method to synthesize a novel homogeneous phase photocatalyst, its preparation method is simple, its repeatability is high, said catalyst can make photocatalytic reaction under the moderate condition of normal temp. and normal pressure, and can effectively fix CO2And converting it into a more valuable pharmaceutical intermediate.
In order to achieve the purpose, the invention adopts the following technical scheme: an iron-cobalt organic catalyst, wherein the catalyst is microspheres with the diameter of 200-400nm, and layered crystals are arranged on the surfaces of the microspheres. The microsphere has perfect surface crystallization and regular lattice structure. The microsphere has uniform particle size. Some of the spaces formed between the catalyst particles increase the contact area of the reactants with the catalyst, facilitating the reaction.
The invention also provides a preparation method of the iron-cobalt organic catalyst, which comprises the following steps: adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol, stirring and dissolving, and adding FeCl3Stirring for 5-15 min, and adding Co (NO)3)2·6H2Stirring for 5-15 min with FeCl3And Co (NO)3)2·6H2The amount of O is 1-10 times of that of aromatic acid, the reaction is carried out for 10-20 hours at the temperature of 150-200 ℃, and the product is washed and dried in vacuum to obtain the iron-cobalt organic catalyst. The invention prepares the iron-cobalt organic catalyst with the surface having the lamellar crystal without a template agent, realizes the control of the product appearance, and has simple preparation method and high repeatability.
Preferably, the volume ratio of DMF to absolute ethyl alcohol in the mixed solvent is 1 (0.1-10).
Preferably, the washing is carried out by alternately washing with anhydrous ethanol and DMF, and the amount of washing liquid used is 5-10ml per mol of product, and the washing is carried out until the product quality is unchanged. DMF has good solubility to organic solvent, aromatic acid also has good solubility in ethanol, and the alternate washing of the DMF and the aromatic acid can effectively remove redundant aromatic acid and cobalt nitrate in the product and improve the purity of the catalyst. The washing sequence or times of DMF and ethanol is not limited, as long as the washing is ensured to be as complete as possible, the washing effect of a small amount of washing for many times is better than that of a large amount of washing for many times, and the effect of washing until the weight is not changed can be achieved by washing for 4-5 times in total.
Preferably, the vacuum drying is carried out at 80-100 deg.C for 5-10 hr. The vacuum drying can reduce the boiling point of the solvent, enhance the volatilization effect of the solvent at the same temperature, ensure the complete volatilization of the organic solvent in the product and shorten the drying time. Drying at 80-100 deg.c for 5-10 hr to volatilize residual organic solvent and ensure complete volatilization of the organic solvent and no damage to the layered crystal on the surface of the catalyst.
The invention also provides a method for converting CO by using the iron-cobalt organic catalyst2The application of synthesizing benzazepine is characterized by that under the condition of normal pressure, in 5-20mL portion of 0.05-1mmol/L tetrahydrofuran solution of o-aminobenzonitrile compound 1-10mg of described iron-cobalt organic catalyst is added, and continuously adding CO2The gas is subjected to photocatalytic reaction under a sunlight simulator to synthesize the benzoazacyclo. The general formula of the o-aminobenzonitrile compound is as follows:
the catalyst has the mesoporous property and the sea urchin-shaped surface structure, so that the catalyst has large specific surface area and can convert CO2More effective contact areas and active sites can be provided in the reaction of synthesizing the benzazepine, which is beneficial to CO2The adsorption of gas and high catalytic activity. The invention can be carried out under normal pressure, the temperature is not high, the reaction can be carried out at room temperature, the reaction condition is mild, the greenhouse gas can be effectively fixed, and the additive value is generatedA pharmaceutical intermediate.
Preferably, the reaction temperature is 20 to 80 ℃. The organic Fe-Co catalyst of the present invention may be used in converting CO at normal temperature2The benzazepine is synthesized, and the conversion rate can be improved by properly increasing the temperature.
Compared with the prior art, the iron-cobalt organic catalyst has simple preparation method and high repeatability; the catalyst has lamellar crystals on the surface and large surface area, and can effectively fix greenhouse gases under mild conditions when being used for photocatalytic reaction to generate a drug intermediate with added value.
Drawings
FIG. 1 is an SEM image of an Fe-Co organic catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of an iron-cobalt organic catalyst comprises the following steps: adding 0.1mmol of terephthalic acid into 50mL of mixed solvent of DMF and absolute ethanol with the volume ratio of 1:0.1, stirring for dissolving, and adding 1mmol of FeCl3Stirred for 10 minutes, then 10mmolCo (NO) was added3)2·6H2And O is stirred for 10 minutes and reacts for 15 hours at the temperature of 200 ℃, the product is washed alternately by absolute ethyl alcohol and DMF for 4 times, the mass is not reduced any more, the using amount of the washing liquid for each mole of the product is 8ml, the product is put into a vacuum drying oven to be dried, and the iron-cobalt organic catalyst is obtained after the product is dried for 5 hours at the temperature of 100 ℃.
The SEM image of the iron-cobalt organic catalyst is shown in figure 1, the catalyst is microspheres with the diameter of 200-400nm, and layered crystals are arranged on the surfaces of the microspheres.
The iron-cobalt organic catalyst is applied to converting CO2Synthesis of a benzazepine ring: at 80 ℃ and under normal pressure, at 5mL of 0.05mmol/L of o-ring1mg of the iron-cobalt organic catalyst is added to the tetrahydrofuran solution of the aminobenzonitrile, and CO is continuously blown in2And (3) carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 86%.
Example 2
A preparation method of an iron-cobalt organic catalyst comprises the following steps: adding 0.5mmol of 1,4,5, 8-naphthalene tetracarboxylic acid into 50mL of mixed solvent of DMF and absolute ethyl alcohol with the volume ratio of 1:10, stirring and dissolving, and adding 5mmol of FeCl3Stirred for 15 minutes, then 5mmolCo (NO) was added3)2·6H2And stirring the mixture for 5 minutes, reacting for 10 hours at 150 ℃, alternately washing the product for 5 times by using absolute ethyl alcohol and DMF (dimethyl formamide), wherein the mass of the product is not reduced any more, the using amount of the washing liquid is 10ml of mixed liquid used for each mole of the product, drying the product in a vacuum drying oven, and drying for 10 hours at 80 ℃ to obtain the iron-cobalt organic catalyst.
The iron-cobalt organic catalyst is microspheres with the diameter of 300-400nm, and layered crystals are arranged on the surfaces of the microspheres.
The iron-cobalt organic catalyst is applied to converting CO2Synthesis of a benzazepine ring: at 20 ℃ and normal pressure, adding 5mg of the iron-cobalt organic catalyst into 10mL of 1mmol/L tetrahydrofuran solution of o-aminobenzonitrile, and continuously blowing CO2And (3) carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 53%.
Example 3
A preparation method of an iron-cobalt organic catalyst comprises the following steps: adding 1mmol of 2, 5-dipicolinic acid into 50mL of mixed solvent of DMF and absolute ethanol with the volume ratio of 1:5, stirring for dissolving, and adding 10mmol of FeCl3Stirred for 5 minutes and then 1mmol Co (NO) was added3)2·6H2And stirring the mixture for 5 minutes, reacting for 20 hours at 180 ℃, alternately washing the product for 4 times by using absolute ethyl alcohol and DMF (dimethyl formamide), wherein the mass of the product is not reduced any more, the using amount of the washing liquid is 5ml of mixed liquid used for each mole of the product, drying the product in a vacuum drying oven, and drying for 8 hours at 90 ℃ to obtain the iron-cobalt organic catalyst.
The iron-cobalt organic catalyst is microspheres with the diameter of 200-400nm, and layered crystals are arranged on the surfaces of the microspheres.
The iron-cobalt organic catalyst is applied to converting CO2Synthesis of a benzazepine ring: at 40 ℃ and normal pressure, adding 10mg of the iron-cobalt organic catalyst into 20mL of 0.1mmol/L o-aminobenzonitrile tetrahydrofuran solution, and continuously blowing CO2And (3) carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 77%.
The iron-cobalt organic catalyst prepared by the invention can perform photocatalytic reaction under mild conditions of normal temperature and normal pressure, and effectively fix CO2And the compound is converted into a more valuable drug intermediate with high yield.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. An iron-cobalt organic catalyst is characterized in that the catalyst is microspheres with the diameter of 200-400nm, and layered crystals are arranged on the surfaces of the microspheres.
2. A method for preparing an iron-cobalt organic catalyst according to claim 1, comprising the steps of: adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol, stirring and dissolving, and adding FeCl3Stirring for 5-15 min, and adding Co (NO)3)2•6H2Stirring for 5-15 min with FeCl3And Co (NO)3)2•6H2The amount of O is 1-10 times of that of aromatic acid, the reaction is carried out for 10-20 hours at the temperature of 150-And after washing, carrying out vacuum drying to obtain the iron-cobalt organic catalyst.
3. The method for preparing Fe-Co organic catalyst according to claim 2, wherein the volume ratio of DMF and absolute ethanol in the mixed solvent is 1 (0.1-10).
4. The method for preparing Fe-Co organic catalyst according to claim 2 or 3, wherein the washing is performed by alternately washing with absolute ethanol and DMF, and the amount of washing solution used is 5-10ml per mole of product, and the washing is performed until the product quality is unchanged.
5. The method for preparing an iron-cobalt organic catalyst according to claim 2 or 3, wherein the drying under vacuum is carried out at 80-100 ℃ for 5-10 hours.
6. The Fe-Co organic catalyst of claim 1 for CO conversion2The application of synthesizing benzazepine is characterized by that under the condition of normal pressure, in the 5-20mL of 0.05-1mmol/L tetrahydrofuran solution of o-aminobenzonitrile compound 1-10mg of the described iron-cobalt organic catalyst is added, and continuously the CO is blown2The gas is subjected to photocatalytic reaction under a sunlight simulator to synthesize the benzoazacyclo.
7. The organic Fe-Co catalyst of claim 6 for CO conversion2The application of the benzoazacyclo is characterized in that the reaction temperature is 20-80 ℃.
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| CN114345413A (en) * | 2021-04-19 | 2022-04-15 | 杭州师范大学 | Aromatic acid coordinated iron-cobalt nitrogen fixation catalyst and preparation method and application thereof |
Citations (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114345413A (en) * | 2021-04-19 | 2022-04-15 | 杭州师范大学 | Aromatic acid coordinated iron-cobalt nitrogen fixation catalyst and preparation method and application thereof |
| CN114345413B (en) * | 2021-04-19 | 2024-06-04 | 杭州师范大学 | Aromatic acid coordinated iron-cobalt nitrogen fixation catalyst and preparation method and application thereof |
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