CN115888683A - Zinc monoatomic catalyst, preparation method thereof and application thereof in catalytic preparation of N-formyl compound - Google Patents
Zinc monoatomic catalyst, preparation method thereof and application thereof in catalytic preparation of N-formyl compound Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 46
- 239000011701 zinc Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- -1 amine compound Chemical class 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 9
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000001237 Raman spectrum Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 claims 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 34
- 238000006170 formylation reaction Methods 0.000 abstract description 18
- 239000001569 carbon dioxide Substances 0.000 abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 239000005431 greenhouse gas Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002471 indium Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 239000007848 Bronsted acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a zinc monoatomic catalyst, a preparation method thereof and application thereof in preparing N-formyl compounds under the atmosphere of normal temperature (30 ℃) and normal pressure carbon dioxide in a catalytic manner, wherein metal monoatomic contains Zn monoatomic, and a carrier for loading the metal monoatomic is indium oxide. The zinc monatomic catalytic material can realize the high-efficiency catalysis of the N-formylation reaction of the green chemical reagent carbon dioxide to the amine compound in a mild system with room temperature and normal pressure atmosphere, compared with the prior art, the invention has the advantages of mild reaction condition, convenient operation and simple process,the raw materials are cheap and easy to obtain, the catalyst has excellent performance of converting amine compounds into N-formyl compounds with higher added value, and efficiently activates and catalyzes greenhouse gas carbon dioxide (CO) 2 ) Participate in the reaction to realize CO 2 And (5) resource utilization.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a zinc monatomic catalyst, a preparation method thereof and a method for catalyzing CO at normal temperature and normal pressure 2 And the application of amine compounds in preparing N-formyl compounds.
Background
The N-formylation reaction of amine can prepare chemicals with high added values, can be widely applied to chemical solvents, chemical intermediates, medicaments, agricultural chemicals, dyes and the like, and has important application value in industrial production and life. In the traditional N-formylation reaction, carboxylic acid and derivatives thereof, formic acid, carbon monoxide and the like are generally adopted as N-formylation reagents, and the catalyst has high cost and has the prominent problems of harsh reaction conditions, toxic and flammable reagents, more byproducts, complex subsequent separation and purification, easy corrosion of equipment and the like. The greenhouse gas carbon dioxide can be used as a safe, stable, cheap and easily-obtained N-formylation reagent, but the N-formylation reagent has stable chemical properties and is difficult to activate, and the N-formylation reagent usually needs to participate in the reaction under harsh conditions of high temperature, high pressure and the like.
Therefore, the novel high-efficiency catalyst is developed to be used for the N-formylation reaction of carbon dioxide to amine compounds, the requirement of green and safe chemical process is met, and the method has important scientific research and industrial significance. Tadashi Ema et al reported that N-methylaniline was efficiently converted to N-methylformanilide at low temperature and pressure using a macrocyclic polynuclear zinc-nickel containing complex as a homogeneous catalyst in Angew. Chem. Int. Ed.2019,58, 9984-9988; however, the homogeneous catalysts have complex reaction systems, high cost in the separation and purification process and difficult recycling, so that the application of the homogeneous catalysts in industrial production is limited. Furthermore, chen Chen et al reported a platinum monatomic catalyst supported on MXenes in J.Am.chem.Soc.2019,141,4086-4093 for the efficient conversion of aniline to N-phenylformamide at high temperatures and pressures; however, the catalyst uses noble metal Pt, the noble metal resource is scarce, the preparation process of the catalyst is complicated, the hydrofluoric acid generated in situ has corrosiveness, and the high catalytic reaction temperature (140 ℃) is needed to realize the higher yield of the N-phenylformamide, so that the large-scale application of the N-phenylformamide in industrial production is difficult to realize due to high production cost and high equipment requirement.
Disclosure of Invention
It is an object of the present invention to provide such a catalytic synthesis technique for the preparation of N-formyl compounds which involves the use of CO 2 Realizing N-formylation reaction of amine compounds. In order to realize the purpose of the invention, the following technical scheme is adopted:
one aspect of the present invention relates to a zinc monoatomic catalyst having a metal monoatomic atom containing a zinc monoatomic atom and a carrier supporting the metal monoatomic atom, the carrier being indium oxide. The preparation method of the monatomic catalytic material is simple, stable in structure and high in catalytic activity. The N-formylation reaction catalyzed by the catalytic material prepared by the invention has simple operation and process, does not need expensive noble metal, can convert amine compounds into N-formylation compounds with higher added value, has mild reaction condition (preferably room temperature), and efficiently utilizes greenhouse gas CO 2 And the air pollution is reduced.
In a preferred embodiment of the invention, the catalytic Fourier transform infrared spectrum is in the range of 700 to 2800cm -1 With broad peaks in between. The existence of the broad peak indicates that the catalyst has metal active sites and rich oxygen defects, so that more kinds of active sites are provided for the catalyst, different reactant molecules in a multi-site concerted catalysis reaction system can be realized, namely the catalyst is used for N-formylation reaction in which multiple molecules participate, and the catalysis yield is improved.
In a preferred embodiment of the present invention, the Raman spectrum of the catalyst is 327. + -.2 cm -1 、387±2cm -1 、415±2cm -1 、561±2cm -1 、595±2cm -1 Has a characteristic peak at least one, two or all of them. The existence of the characteristic peak indicates that the disorder degree of the surface lattice arrangement of the catalyst is higher, so that the catalytic activity is further improved.
Another aspect of the present invention relates to a process for preparing the above catalyst, characterized in that it comprises the steps of:
a. respectively dispersing transition metal salt and organic amine micromolecules in deionized water, sequentially adding the transition metal salt and the organic amine micromolecules into preheated deionized water, heating, stirring, cooling, centrifugally washing, and drying the obtained precipitate;
b. b, performing high-temperature calcination on the precipitate obtained in the step a, wherein the high-temperature calcination is performed in a hydrogen-argon atmosphere, air and nitrogen at the temperature of 200-400 ℃; among them, the preferred embodiment is carried out in a hydrogen argon atmosphere at 200 to 400 ℃.
c. And d, dispersing the product obtained in the step b in an organic solvent, dropwise adding the aqueous dispersion of the metal zinc salt, stirring for a certain time, and centrifugally washing and drying to obtain the zinc monoatomic catalyst.
In a preferred embodiment of the present invention, the transition metal salt in step a is a metal indium salt, including but not limited to indium chloride, indium nitrate, and the like.
In a preferred embodiment of the present invention, the organic amine small molecule in step a includes, but is not limited to, hexamethylenetetramine, ethylenediamine, etc.
In a preferred embodiment of the present invention, the metal zinc salt in step c includes, but is not limited to, zinc chloride, zinc nitrate, and the like.
In a preferred embodiment of the present invention, the specific reaction conditions of step a are: respectively adding 2-10mmol of metal indium salt and organic amine micromolecules into 10-100mL of deionized water, sequentially adding into 100-200mL of deionized water preheated to 50-100 ℃, heating and stirring for 1-4h, cooling, washing and centrifuging, and drying the obtained precipitate.
In a preferred embodiment of the present invention, the specific reaction conditions of step c are: dispersing the product calcined in the step b in an alcohol solution (including but not limited to methanol, ethanol and isopropanol), dropwise adding 1-20mL of 0.01-1M zinc ion aqueous dispersion, soaking for 5-12h, washing and centrifuging, and drying the obtained product.
Another object of the present invention is to provide the use of the above catalyst for the catalytic preparation of N-formyl compounds, the catalytic substrate being CO 2 And amine compounds. Prepared by the inventionThe catalyst can catalyze CO efficiently at normal temperature 2 The method for N-formylation of amine compounds has the advantages of simple reaction system, easy control, easily obtained and abundant raw materials, low cost, and adoption of safe, stable, cheap and easily obtained N-formylation reagent CO 2 The method is a preparation method which accords with green chemistry and atom economy and has industrial synthesis value.
In a preferred embodiment of the present invention, the amount of the catalyst used in the catalytic reaction is 1% to 500% of the amount of the amine compound, the reaction temperature is 20 to 40 ℃ (preferably room temperature), the reaction pressure is normal pressure, and the reaction time is 5 to 24 hours.
In a preferred embodiment of the present invention, the amine compound used in the catalytic reaction includes, but is not limited to, amine molecules with different steric hindrance, electron-donating group, and electron-deficient group functional groups, such as aniline, morpholine, cyclohexylamine, N-methylaniline, p-chloroaniline, p-methoxyaniline, and the like.
The invention has the following beneficial results: the invention constructs the load type zinc monatomic catalytic material with the solid hindered Lewis acid-base pair by combining the chemical liquid phase preparation and the high-temperature calcination modification method, and promotes the catalysis of CO by regulating the appearance, the surface structure and the electronic state of the catalyst 2 Activity in N-formylation of an amine compound. Compared with the prior art, the preparation method of the monatomic catalytic material is simple, stable in structure, high in catalytic activity and free of precious metals. The N-formylation reaction catalyzed by the catalytic material prepared by the invention has simple operation and process, can convert amine compounds into N-formylation compounds with higher added values, has mild reaction conditions, and efficiently utilizes greenhouse gas CO 2 The method has the advantages of reduction of atmospheric pollution, cheap and easily-obtained raw materials, small damage to production equipment and low cost, is a preparation method which accords with green chemistry and atom economy and has industrial synthesis value, obtains good technical effect, and provides a new idea for the design and preparation of novel transition metal single-atom catalytic materials.
Drawings
FIG. 1: transmission electron microscopy images of the Zn/In-H-2 catalytic material prepared In example 1.
FIG. 2 is a schematic diagram: the high resolution transmission electron micrograph of the spherical aberration corrected Zn/In-H-2 catalytic material prepared In example 1 and the atomic intensity profile of the designated area are shown with Zn atoms In the yellow circle.
FIG. 3: transmission electron microscopy images of the Zn/In-A-2 catalytic material prepared In example 2.
FIG. 4: transmission electron microscopy images of the Zn/In-N-2 catalytic material prepared In example 3.
FIG. 5: transmission electron microscopy of the Zn/In-H-4 catalytic material prepared In comparative example 1.
FIG. 6: pyridine infrared spectra of the Zn/In-H-2 catalytic material prepared In example 1 at different desorption temperatures. In the figure, the characteristic peak of pyridine adsorbed on a Lewis acid site is indicated in an L area, and the characteristic peak of pyridine adsorbed on a Bronsted acid site is indicated in a B area. The catalyst is proved to have abundant catalytic active sites.
FIG. 7: the raman spectra of the Zn/In-H-2 prepared In example 1 and the Zn/In-a-2 catalytic material prepared In example 2. From the figure, raman peaks, 308cm, were observed on both Zn/In-H-2 and Zn/In-A-2 -1 、366cm -1 、497cm -1 And 630cm -1 In derived from body centered cubic 2 O 3 And (5) structure. Besides the above spectral peaks, zn/In-H-2 has a characteristic Raman peak at 327cm -1 、387cm -1 、415cm -1 、561cm -1 、595cm -1 That is, it indicates that the surface lattice arrangement of Zn/In-H-2 is more disordered. Illustrating that the two materials obtained by different preparation methods have a difference in surface lattice structure.
FIG. 8: fourier transform infrared spectra of Zn/In-H-2 prepared In example 1 and Zn/In-A-2 catalytic material prepared In example 2. As can be seen from comparison of the graphs, the surface of Zn/In-A-2 has a lower hydroxyl group content and has a thickness of 700 to 2800cm -1 Broad peak, indicating that the product has rich oxygen defects, which is mutually verified with the peak result of Raman spectrum. Illustrating that the two materials obtained by different preparation methods have a difference in the content of surface functional groups, thereby resulting in the generation of catalytic activity thereofA difference.
Detailed Description
Example 1
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Putting the dried precipitate In a tube furnace, heating to 200-400 ℃ In the atmosphere of hydrogen-argon mixed gas, and calcining for 2-5h to obtain In 2 O 3-x (OH) y -H 2 -T 1 (x, y represent non-stoichiometric ratios) noted In-H-2;
c. and c, dispersing 130mg of the product In-H-2 obtained In the step b into 10mL of methanol, adding 10mL of 0.01-1M zinc chloride aqueous dispersion, stirring for 10H, washing, centrifuging and drying to obtain a catalytic material Zn/SAs In 2 O 3-x (OH) y -H 2 -T 1 And is marked as Zn/In-H-2.
Example 2
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Putting the dried precipitate into a muffle furnace, heating to 200-400 ℃, and calcining for 2-5h to obtain In 2 O 3-x (OH) y -Air-T 1 In-A-2;
c. and c, dispersing 130mg of the product In-A-2 obtained In the step b into 10mL of methanol, adding 10mL of 0.01-1M zinc chloride aqueous dispersion, stirring for 10h, washing, centrifuging and drying to obtain a catalytic material Zn/SAs In 2 O 3-x (OH) y -Air-T 1 And is marked as Zn/In-A-2.
Example 3
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Placing the dried precipitate in a tube furnace, heating to 200-400 deg.C in nitrogen atmosphere, and calcining for 2-5 ℃h, in is obtained 2 O 3-x (OH) y -N 2 -T 1 In-N-2;
c. and c, dispersing 130mg of the product In-N-2 obtained In the step b into 10mL of methanol, adding 10mL of 0.01-1M zinc chloride aqueous dispersion, stirring for 10h, washing, centrifuging and drying to obtain a catalytic material Zn/SAs In 2 O 3-x (OH) y -N 2 -T 1 And is marked as Zn/In-N-2.
Comparative example 1
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Transferring the dried precipitate into a tube furnace, heating to 450-600 ℃ In the atmosphere of hydrogen-argon mixed gas, and calcining for 2-5h to obtain In 2 O 3-x (OH) y -H 2 -T 2 Is marked as In-H-4;
c. and c, dispersing 130mg of the product In-H-4 obtained In the step b into 10mL of methanol, dropwise adding 10mL of 0.01-1M zinc chloride aqueous dispersion, stirring for 10H, washing, centrifuging and drying to obtain a catalytic material Zn/SAs In 2 O 3-x (OH) y -H 2 -T 2 And is marked as Zn/In-H-4.
Comparative example 2
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Putting the dried precipitate into a tube furnace, heating to 200-400 ℃ In the atmosphere of hydrogen-argon mixed gas, and calcining for 2-5h to obtain In 2 O 3-x (OH) y -H 2 -T 1 And is marked as In-H-2.
c. And c, taking 130mg of the product In-H-2 obtained In the step b, dispersing the product In-H-2 In 10mL of methanol, adding 10mL of 0.01-1M copper chloride aqueous dispersion, stirring for 10 hours, washing, centrifuging and drying to obtain the catalytic material Cu/SAs In 2 O 3-x (OH) y -H 2 -T 1 And is marked as Cu/In-H-2.
Comparative example 3
a. Respectively adding 4mmol of indium chloride and hexamethylenetetramine into 20mL of deionized water, then adding into 160mL of deionized water at 50-100 ℃, heating and stirring for 1-4h, and washing and centrifuging to obtain a precipitate.
b. Putting the dried precipitate into a tube furnace, heating to 200-400 ℃ In the atmosphere of hydrogen-argon mixed gas, and calcining for 2-5h to obtain In 2 O 3-x (OH) y -H 2 -T 1 And is marked as In-H-2.
c. And c, dispersing 130mg of the product In-H-2 obtained In the step b into 10mL of methanol, adding 10mL of 0.1M manganese chloride aqueous dispersion, stirring for 10H, washing, centrifuging and drying to obtain a catalytic material Mn/SAs In 2 O 3-x (OH) y -H 2 -T 1 And is marked as Mn/In-H-2.
Example 4
Putting 100mg of Zn/In-H-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main tube port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of the N-phenylformamide to be 99% by gas chromatography.
Example 5
Putting 100mg of Zn/In-A-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main pipe port, sealing the system, reacting for 8 hours under magnetic stirring at 30 ℃, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifuging to separate the catalyst and a supernatant, and calculating the yield of N-phenylformamide to be 37% through gas chromatography.
Example 6
Putting 100mg of Zn/In-N-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main tube port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of N-phenylformamide to 47% by gas chromatography.
Comparative example 4
Putting 100mg of Zn/In-H-4 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main tube port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of the N-phenylformamide to be 16% by gas chromatography.
Comparative example 5
Putting 100mg of Cu/In-H-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main tube port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of the N-phenylformamide to be 22% by gas chromatography.
Comparative example 6
Putting 100mg of Mn/In-H-2 catalytic material and a stirrer into a reaction, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main pipe port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating a catalyst and a supernatant, and calculating the yield of the N-phenylformamide to be 32% by gas chromatography.
Comparative example 7
a. 160mg of ZnO is dispersed in 10mL of methanol, 10mL of 0.01-1M zinc chloride aqueous dispersion is added, and after stirring for 10 hours, the catalytic material Zn/ZnO is obtained by washing, centrifuging and drying.
b. Putting 100mg of Zn/ZnO catalytic material and a stirrer into a reaction, adding 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main pipe port, sealing the system, magnetically stirring at 30 ℃ for reaction for 8 hours, stopping the reaction, cooling to room temperature, adding biphenyl as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of the N-phenylformamide to be 26% by gas chromatography.
Comparative example 8
a. Taking 344mg CeO 2 Dispersing in 10mL of methanol, adding 10mL of 0.01-1M zinc chloride aqueous dispersion, stirring for 10h, washing, centrifuging and drying to obtain catalytic material Zn/CeO 2 。
b. 100mg of Zn/CeO 2 The catalytic material and a stirrer are placed in a reaction, 1mL of DMF, 1mmol of aniline and 2mmol of phenylsilane are added, carbon dioxide is introduced, a balloon is connected to a main pipe port, then a system is sealed, the reaction is stopped after magnetic stirring reaction is carried out for 8 hours at the temperature of 30 ℃, biphenyl is added as an internal standard after cooling to the room temperature, the catalyst and the supernatant are centrifugally separated, and the yield of N-phenylformamide is 8.5% through gas chromatography. Example 7
Putting 100mg of Zn/In-H-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of morpholine (or cyclohexylamine, p-methylaniline, p-chloroaniline and p-methoxyaniline) and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main pipe port, sealing the system, magnetically stirring at 30 ℃ for 8 hours, stopping the reaction, cooling to room temperature, adding sym-trimethoxybenzene as an internal standard, centrifuging to separate a catalyst and a supernatant, and calculating the yield of corresponding N-formylation products to be 99% (92%, 79%, 85% and 95%) by nuclear magnetism.
Example 8
Putting 100mg of Zn/In-H-2 catalytic material and a stirrer into a reaction tube, adding 1mL of DMF, 1mmol of N-methylaniline and 2mmol of phenylsilane, introducing carbon dioxide, connecting a balloon at a main pipe port, sealing the system, magnetically stirring at 30 ℃ for reaction for 24 hours, stopping the reaction, cooling to room temperature, adding sym-trimethoxybenzene as an internal standard substance, centrifugally separating the catalyst and the supernatant, and calculating the yield of N-methylformanilide to be 98% by nuclear magnetism.
Exemplary embodiments of the present invention are now compared and tabulated below, including but not limited to some exemplary examples of different metal monoatomic and substrate expansion applicability, as shown in table 1.
TABLE 1
The above description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the present invention in any way. All the modifications and embodiments based on the technical solutions or techniques of the present invention without creative efforts shall fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A zinc monoatomic catalyst which has a metal monoatomic atom containing a Zn monoatomic atom and a carrier supporting the metal monoatomic atom, the carrier being indium oxide.
2. The catalyst according to claim 1, wherein the Fourier transform infrared spectrum of the catalyst is 700-2800 cm -1 With broad peaks in between.
3. The catalyst of claim 1 or 2, having a raman spectrum at 327 ± 2cm -1 、387±2cm -1 、415±2cm -1 、561±2cm -1 、595±2cm -1 Has a characteristic peak at least at one, two or all of them.
4. A process for the preparation of the catalyst according to any one of claims 1 to 3, characterized in that it comprises the following steps:
a. respectively dispersing transition metal salt and organic amine micromolecules in deionized water, sequentially adding the transition metal salt and the organic amine micromolecules into preheated deionized water, heating, stirring, cooling, centrifugally washing, and drying the obtained precipitate;
b. and c, performing high-temperature calcination on the precipitate obtained in the step a, wherein the high-temperature calcination is performed in a hydrogen argon atmosphere, air or nitrogen atmosphere at the temperature of 200-400 ℃.
c. And d, dispersing the product obtained in the step b in an organic solvent, dropwise adding the aqueous dispersion of the metal zinc salt, stirring for a certain time, and centrifugally washing and drying to obtain the Zn monoatomic catalyst.
5. The method according to claim 4, wherein the transition metal salt in step a is selected from one or more of indium chloride, indium nitrate and indium acetylacetonate.
6. The preparation method according to claim 4, wherein the organic amine molecules in step a are selected from one or more of hexamethylenetetramine, ethylenediamine, dicyandiamide, urea, and cetyltrimethylammonium bromide.
7. The preparation method according to claim 4, wherein the metal zinc salt in step c is selected from one or more of zinc chloride, zinc nitrate and zinc acetylacetonate.
8. Use of a catalyst according to any one of claims 1 to 3 for the catalytic preparation of N-formyl compounds, the catalytic substrate being CO 2 And amine compounds.
9. The application of claim 8, wherein the amount of the catalyst used in the catalytic reaction is 1-500% of the mass of the amine compound, the reaction temperature is 20-40 ℃, the reaction pressure is normal pressure, and the reaction time is 5-24h; the amine compound is selected from one or more of aniline, morpholine, cyclohexylamine, N-methylaniline, p-chloroaniline and p-methoxyaniline.
10. The use according to claim 9, wherein the reaction temperature is ambient temperature.
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