CN116422318A - Indium oxide-based catalyst and application thereof in catalyzing DMF to prepare N-formyl compound - Google Patents

Indium oxide-based catalyst and application thereof in catalyzing DMF to prepare N-formyl compound Download PDF

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CN116422318A
CN116422318A CN202310434564.5A CN202310434564A CN116422318A CN 116422318 A CN116422318 A CN 116422318A CN 202310434564 A CN202310434564 A CN 202310434564A CN 116422318 A CN116422318 A CN 116422318A
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indium oxide
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dmf
hydroxyl
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陈玥光
李佳磊
汪乐余
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Beijing University of Chemical Technology
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
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Abstract

The invention discloses an indium oxide-based catalyst, a preparation method thereof and application thereof In preparing N-formyl compound by catalysis, wherein the catalyst comprises a nano indium oxide matrix, and In the indium oxide: the mass ratio of O is less than the stoichiometric ratio 2:3, the Fourier transform infrared spectrum of the catalyst is 3000-4000cm ‑1 Is stored betweenIn the characteristic peak of hydroxyl, the X-ray photoelectron spectroscopy test shows that the coverage of hydroxyl on the surface of the indium oxide is 40-60%, namely, the indium oxide has higher hydroxyl coverage; optionally, the nano indium oxide matrix supports a metal M selected from one or more combinations of Zn, co, al, ag, pd. The indium oxide-based catalytic material can efficiently catalyze N-formylation reaction of DMF on amine compounds under the conditions of air atmosphere, no additive, no need of anhydrous and anaerobic harsh reaction conditions and the like.

Description

Indium oxide-based catalyst and application thereof in catalyzing DMF to prepare N-formyl compound
Technical Field
The invention relates to the field of chemical industry, in particular to an indium oxide-based catalyst, a preparation method thereof and application thereof in preparing an N-formyl compound by catalyzing amines and DMF.
Background
N, N-Dimethylformamide (DMF) is a common chemical reagent, and has low raw material cost and large industrial yield. DMF is used as a safe, stable, cheap and easily available N-formylation reagent, meets the requirements of green and safe chemical technology, and has important scientific research and industrial significance. Since the amide bond of DMF is very stable and has strong chemical inertness, the preparation of N-formylation products by utilizing the transamidation reaction of DMF generally needs to be performed under strictly anhydrous and anaerobic conditions, and the reaction time is long, and additional assistants or additives are needed. For example, in 2012, mouraBIT et al used boric acid (B (OH) 3 ) Metal-free catalyst for transamidation, DMF as formylating agent, and benzylamine (BnNH) 2 ) As a reactant, water was mixed in an amount of 1-2 and reacted at 140℃and 150℃for 20 hours, respectively, to obtain 67% and 83% of N-benzylformamide. But homogeneous catalysts increase the cost of subsequent separation and purification and are difficult to recycle. In 2015, das et al prepared a silica gel (H 2 SO 4 –SiO 2 ) As a solid acid catalyst, DMF is reacted with various aromatic amines at 70℃for 6-8h and converted into the corresponding N-formylated product in good yield. However, the operation process of the reaction is quite severe, the operation is required in a glove box, and the protection of Ar gas is required in the reaction process, so that the production cost is increased. Therefore, the development of a novel efficient heterogeneous catalyst for N-formylation of amine compounds by DMF is an urgent problem to be solved.
In the applicant's prior chinese invention patent application "a zinc monoatomic catalyst, a method for preparing the same and its use in the catalytic preparation of N-formyl compounds" (application number: 202211425694.4), a zinc monoatomic catalyst treated by a reducing atmosphere was described, and the inventors of the present application further found, based on the study of this prior application, that a non-stoichiometric, cubic indium oxide support matrix treated by a non-reducing atmosphere, and the zinc monoatomic catalyst supported by the indium oxide matrix (the metal-support interface has a metal-interface O anchored coordination structure) were able to catalyze DMF to form N-formyl compounds with a higher hydroxyl coverage (40-60%) and completed the present application. That is, the prior application (application number 202211425694.4) differs from the key technology for preparing the catalyst of the present patent, resulting in different structural characteristics of the catalyst; in addition, the previous patent application is applied to the preparation of the N-formyl compound by taking CO2 as a reactant, the present patent application is used for preparing the N-formyl compound by taking DMF as a reactant and no homogeneous cocatalysts such as phenylsilane and the like are needed, so that the chemical reaction paths and reaction mechanisms for preparing the N-formyl compound are different from 2 patents. It is noted that the applicant, which is incorporated in its entirety into the specification of the present application and as part of the same, enjoys the right to make amendments and/or presentation of comments to the application's application documents based on what is described in the prior application.
Disclosure of Invention
One of the problems to be solved by the invention is to provide a catalytic synthesis technology for preparing an N-formyl compound, which comprises the steps of using DMF to realize N-formylation reaction of an amine compound, avoiding using N-formylation reagents with high cost, more byproducts and strong corrosion to equipment such as acyl halide, anhydride, formic acid and the like, and provide a novel catalyst and a synthesis method thereof. In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect, the invention relates to an oxide-based catalyst comprising a nano-indium oxide matrix In which is: the mass ratio of O is less than the stoichiometric ratio 2:3, the Fourier transform infrared spectrum of the catalyst is 3000-4000cm -1 The characteristic peak is provided between the indium oxide surface hydroxyl coverage of 40-60% (preferably 40-50%) as shown by X-ray photoelectron spectroscopy test, namely, the indium oxide surface hydroxyl coverage is higher; optionally, the nano indium oxide matrix supports a metal M selected from one or more combinations of Zn, co, al, ag, pd. The existence of the characteristic peakThe catalyst provided by the invention has rich hydroxyl groups, so that more sites are provided for adsorption and activation of reactant molecules, the activity of the catalyst is increased, the reaction process is accelerated, the reactant molecules can be catalyzed cooperatively by multiple sites through the interaction of the oxide and the metal, and the reaction yield is improved.
In a preferred embodiment of the present invention, the metal M is Zn.
In a preferred embodiment of the present invention, the substrate is cubic indium oxide.
In a preferred embodiment of the invention, the substrate is porous sheet indium oxide.
In a preferred embodiment of the invention, the metal monoatoms or nanoparticles carried on the surface of the substrate are anchored by the O atoms of the metal-support interface, i.e. the metal M and the substrate interface have an M-O coordination structure.
In a preferred embodiment of the invention, the metal M is a monoatomic.
Another aspect of the invention relates to a method for preparing the above catalyst, comprising the steps of:
a. respectively dispersing indium-based metal salt and organic weak alkaline micromolecules in a proton solvent, sequentially adding the materials into the proton solvent with a certain temperature, heating and stirring, naturally cooling, centrifugally washing, and preserving the temperature of the precipitate in a vacuum drying oven for 8-12h;
b. c, carrying out high-temperature calcination treatment on the precipitate obtained in the step a, wherein the high-temperature calcination is carried out in an air atmosphere at 200-550 ℃ for 1-6h to obtain a powdery sample;
c. optionally, dispersing the powdery sample obtained in the step b in a reducing solvent, slowly adding a precursor salt solution of the metal M, stirring for a certain time, centrifugally washing, and drying in vacuum to obtain the oxide supported metal catalyst.
In a preferred embodiment of the present invention, the indium-based metal salt in step a includes, but is not limited to, inCl 3 、In(NO 3 ) 3 、In(acac) 3 Etc.
In a preferred embodiment of the present invention, the organic weakly basic small molecules described in step a include, but are not limited to, hexamethylenetetramine (HMTA), triethanolamine (TEOA), tetrabutylammonium bromide, melamine, and the like.
In a preferred embodiment of the present invention, the precursor salt of metallic zinc in step c includes, but is not limited to, znCl 2 、(CH 3 COO) 2 Zn、ZnSO 4 、Zn(NO 3 ) 2 、Zn(acac) 2 (zinc acetylacetonate), and the like.
In a preferred embodiment of the present invention, the specific reaction conditions of step a are: dispersing 2-8mmol of metal indium salt and organic weak alkaline micromolecules in 10-80mL of proton solvent respectively, sequentially adding the solution into the proton solvent of 50-120 ℃ for constant temperature heating, continuously stirring for 1-4h, naturally cooling, washing, centrifuging and drying.
In a preferred embodiment of the invention, the temperature of step b is 200-400 ℃. In this preferred temperature range, it contributes to an increase in the catalytic activity of the catalyst.
In a preferred embodiment of the present invention, the specific reaction conditions of step c are: dispersing the powdered sample obtained in step b in a reducing solvent (including but not limited to CH 3 OH、C 2 H 5 OH), slowly adding 0.01-2M of precursor dispersion liquid of metal zinc salt, stirring, soaking for 5-12h, washing for multiple times, centrifuging, and preserving heat for 8-12h in a vacuum drying oven.
It is another object of the present invention to provide the use of the above catalyst for the catalytic preparation of N-formyl compounds, the catalyzed substrates being DMF and amine compounds. The catalyst prepared by the invention can realize the efficient catalysis of N-formylation reaction of DMF on amine compounds under the conditions of air atmosphere and no additive, and compared with the prior art, the catalyst has the advantages of simple operation, simple process, no use of acyl halide and anhydride substances with high price and more byproducts and formic acid with equipment corrosiveness as formylation reagents, environmental friendliness and reduced cost.
In a preferred embodiment of the invention, the reaction temperature in the catalytic reaction is 100-180 ℃, the reaction pressure is normal pressure, the catalyst is used in an amount of 1-500% of the mass of the amine compound, and the reaction time is 8-24h.
In a preferred embodiment of the present invention, the amine compound used in the catalytic reaction is
Figure BDA0004191556560000031
One or a combination of more of the above.
The invention has the beneficial effects that: the atomic structure and the electronic structure of the surface of the nano indium oxide matrix are regulated by optimizing the high-temperature calcination treatment method, and a series of nano In with different content of hydroxyl sites is obtained 2 O 3 And the matrix structure regulates and controls the interaction between the carrier and the single-atom metal Zn. Researches show that Zn/In with highest surface hydroxyl content does not need the reaction condition of removing water and oxygen and does not need additional additives 2 O 3 T200 can efficiently catalyze N-formylation reaction of DMF to aniline in air atmosphere, and the reaction operation and subsequent product collection and purification process are simple. In addition, through a series of characterization and control experiments, the nanometer In is found 2 O 3 The matrix carries Zn monoatomic composite catalyst, and the surface hydroxyl content and the catalytic performance of the catalyst are positively correlated. The indium oxide-based catalytic material of the invention can be realized in an air atmosphere (no O is needed 2 、N 2 Protective atmosphere such as Ar) and the like, and does not need any additive, and the N-formylation reaction of DMF to amine compounds is efficiently catalyzed under the condition of no need of harsh reaction conditions such as anhydrous oxygen-free and the like. The use of N-formylating reagent with high cost, more byproducts and strong corrosiveness to equipment such as acyl halide, anhydride, formic acid and the like is avoided. The new thought for regulating and controlling the interaction between the oxide and the metal is provided, and valuable experimental references are provided for constructing efficient active sites of the catalyst.
Drawings
Fig. 1: zn/In example 1 2 O 3 T200, zn/In example 2 2 O 3 T400, in example 3 2 O 3 T200, zn/In comparative example 1 2 O 3 -X-ray diffraction pattern of T600.
Fig. 2: zn/In example 1 2 O 3 -transmission electron microscopy of T200 composite catalytic material.
Fig. 3: zn/In example 1 2 O 3 -spherical aberration correction high-resolution transmission electron microscopy of T200 composite catalytic material and atomic intensity distribution map of corresponding region, marked zinc monoatoms in circle.
Fig. 4: zn/In example 2 2 O 3 -transmission electron microscopy of T400 composite catalytic material.
Fig. 5: zn/In comparative example 1 2 O 3 Transmission electron microscopy of T600 composite catalytic material.
Fig. 6: zn/In comparative example 1 2 O 3 -spherical aberration correcting high resolution transmission electron microscopy of T600 composite catalytic material and atomic intensity profile of corresponding region, marked zinc atoms in circles.
Fig. 7: zn/In example 1 2 O 3 T200, zn/In example 2 2 O 3 T400, zn/In comparative example 1 2 O 3 -fourier transform infrared spectrum of T600 catalytic material. At 602cm -1 、565cm -1 、541cm -1 、434cm -1 The left and right peaks are cubic In 2 O 3 Is characterized by an absorption peak. At 3435cm -1 The characteristic peak observed at this point is attributed to stretching vibration of the surface hydroxyl group at 1622cm -1 The small peaks observed here can be attributed to flexural vibration of the surface hydroxyl groups. From the comparison, it can be concluded that Zn/In has the lowest calcination temperature 2 O 3 The T200 composite catalytic material has a relatively higher hydroxyl content, whereas the surface hydroxyl content varies with the calcination temperature.
Fig. 8: zn/In example 1 2 O 3 T200, zn/In example 2 2 O 3 T400, zn/In comparative example 1 2 O 3 -X-ray photoelectron spectroscopy of the O1s orbital of the T600 catalytic material. Wherein the O partial peak at 529.8-530.1eV can be attributed to an O atom In-O-In (i.e., in 2 O 3 Lattice O), and In 2 O 3 The O vacancies of the material surface are located at 531.2-531.8eV (i.e., in 2 O 3 Central vacancy O V ) The peak position of O In the surface-OH (hydroxyl) is 532.0-532.1eV (i.e. In 2 O 3 Hydroxyl O) of (c). It is obvious from the above that the difference in the content of-OH (hydroxyl oxygen) on the surfaces of the three materials is consistent with the result obtained by the Fourier transform infrared spectrum. Example 1Zn/In by integral area calculation 2 O 3 Hydroxyl content of-T200 In 2 O 3 49%, i.e. with higher hydroxyl coverage, zn/In example 2 2 O 3 -the hydroxyl content in T400 is slightly reduced to 46%; whereas In comparative example 1Zn/In 2 O 3 The hydroxyl content of-T600 is only In 2 O 3 3% of the total, has very low hydroxyl coverage.
Detailed Description
Example 1
a. 1-10mmol of InCl is added into 10mL of deionized water 3 2-20mmol of HMTA is taken as a precipitator, and then added into 80mL of proton solvent preheated to a specified temperature for constant temperature heating, continuously stirred and naturally cooled, and the precipitate is washed for multiple times, centrifuged and dried.
b. Fully grinding the dried solid, heating to 200-350 ℃ In a muffle furnace, calcining for 2-4h to obtain non-stoichiometric indium oxide matrix precursor (the existence of hydroxyl In the material can be seen In an infrared spectrogram with non-stoichiometric ratio, and the existence of a small amount of lattice oxygen defects is contained, and the actual material proportion of In to O is less than the stoichiometric ratio of 2:3), which is recorded as In 2 O 3 -T200；
c. Weigh 200-600mg of In prepared 2 O 3 Adding alcohol solvent into T200 to obtain carrier dispersion liquid, and preparing ZnCl with 0.01-2M 2 Slowly injecting the aqueous dispersion into the carrier dispersion liquid In a stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain the Zn/In supported oxide matrix catalytic material Zn/In 2 O 3 -T200。
Example 2
a. 1-10mmol of InCl is added into 10mL of deionized water 3 2-20mmol HMTA is taken as precipitant, and then added into 80mL proton solvent preheated to the specified temperature for constant temperature heating, and the reaction is continuedStirring and naturally cooling, washing centrifugal precipitation for multiple times, and drying.
b. Grinding the dried solid, heating to 400-550deg.C In a muffle furnace, and calcining to obtain non-stoichiometric indium oxide matrix precursor, denoted as In 2 O 3 -T400；
c. Weigh 200-600mg of In prepared 2 O 3 Adding alcohol solvent into T400 to obtain carrier dispersion liquid, and preparing ZnCl with 0.01-2M 2 Dispersing liquid, slowly injecting the dispersing liquid into carrier dispersing liquid In stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain Zn/In as oxide matrix catalytic material carrying Zn 2 O 3 -T400。
Comparative example 1
a. 1-10mmol of InCl is added into 10mL of deionized water 3 2-20mmol of HMTA is taken as a precipitator, and then added into 80mL of proton solvent preheated to a specified temperature for constant temperature heating, continuously stirred and naturally cooled, and the precipitate is washed for multiple times, centrifuged and dried.
b. Grinding the dried solid, heating to 600-750deg.C In a muffle furnace, and calcining for 2-4 hr to obtain non-stoichiometric indium oxide matrix precursor, denoted as In 2 O 3 -T600；
c. Weigh 200-600mg of In prepared 2 O 3 Adding alcohol solvent into T600 to obtain carrier dispersion liquid, and preparing ZnCl with 0.01-2M 2 Dispersing liquid, slowly injecting the dispersing liquid into carrier dispersing liquid In stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain Zn/In as oxide matrix catalytic material carrying Zn 2 O 3 -T600。
Example 3
a. 1-10mmol of InCl is added into 10mL of deionized water 3 2-20mmol of HMTA is taken as a precipitator, and then added into 80mL of proton solvent preheated to a specified temperature for constant temperature heating, continuously stirred and naturally cooled, and the precipitate is washed for multiple times, centrifuged and dried.
b. Grinding the dried solid, heating to 200-350deg.C In a muffle furnace, calcining for 2-4 hr to obtain non-stoichiometric indium oxide matrix precursor, denoted In 2 O 3 -T200；
c. Weigh 200-600mg of In prepared 2 O 3 Adding alcohol solvent into T200 to obtain carrier dispersion liquid, and preparing Co (NO) of 0.01-2M 3 ) 2 ·6H 2 Slowly injecting the O aqueous dispersion into the carrier dispersion liquid In a stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain the Co-supported oxide matrix catalytic material Co/In 2 O 3 -T200。
Example 4
a. 1-10mmol of InCl is added into 10mL of deionized water 3 2-20mmol of HMTA is taken as a precipitator, and then added into 80mL of proton solvent preheated to a specified temperature for constant temperature heating, continuously stirred and naturally cooled, and the precipitate is washed for multiple times, centrifuged and dried.
b. Grinding the dried solid, heating to 200-350deg.C In a muffle furnace, calcining for 2-4 hr to obtain non-stoichiometric indium oxide matrix precursor, denoted In 2 O 3 -T200；
c. Weigh 200-600mg of In prepared 2 O 3 Adding alcohol solvent into T200 to obtain carrier dispersion liquid, and preparing Al (NO) of 0.01-2M 3 ) 3 Slowly injecting the aqueous dispersion into the carrier dispersion liquid In a stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain the Al/In oxide matrix catalytic material carrying Al 2 O 3 -T200。
Example 5
100mg Zn/In of example 1 was weighed 2 O 3 The T200 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 96% as calculated by gas chromatography.
Example 6
Weigh 100mg In example 1 2 O 3 The T200 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mm of anhydrous DMF are added into the reaction tube after ultrasonic dispersionThe ol aniline is connected with condensed water, a balloon sealing system is connected at the opening of the condensed water pipe, and the mixture is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 63.3% as calculated by gas chromatography.
Example 7
100mg Zn/In of example 2 was weighed 2 O 3 The T400 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 74% as calculated by gas chromatography.
Comparative example 2
100mg Zn/In comparative example 1 was weighed 2 O 3 The T600 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 27% as calculated by gas chromatography.
Example 8
100mg Co/In of example 3 was weighed 2 O 3 The T200 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 65.4% as calculated by gas chromatography.
Example 9
100mgAl/In example 4 was weighed 2 O 3 The T200 catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the reaction is finished, adding biphenyl internal standard substances into the mixture and centrifuging the mixture,the yield of N-phenylformamide was about 65.1% as calculated using gas chromatography.
Comparative example 3
a. 200-600mg TiO 2 Adding alcohol solvent to obtain carrier dispersion liquid, and preparing ZnCl of 0.01-2M 2 Slowly injecting the aqueous dispersion into the carrier dispersion liquid in a stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain the catalytic material Zn/TiO 2 。
b. 100mg Zn/TiO of comparative example 3 was weighed 2 The catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 35.2% as calculated by gas chromatography.
Comparative example 4
a. 200-600mg SiO was weighed 2 Adding alcohol solvent to obtain carrier dispersion liquid, and preparing ZnCl of 0.01-2M 2 Slowly injecting the aqueous dispersion into the carrier dispersion liquid in a stirring state, continuously stirring and soaking, centrifugally washing for multiple times, and drying to obtain the catalytic material Zn/SiO 2 。
b. 100mg Zn/SiO of comparative example 4 was weighed out 2 The catalyst is placed in a reaction tube, 1mL of anhydrous DMF and 1mmol of aniline are added into the reaction tube after ultrasonic dispersion, condensed water is connected, a balloon sealing system is connected to a condensation tube orifice, and the reaction tube is placed in a heating sleeve to react for 10 hours under the constant temperature of 160 ℃ under magnetic stirring. After the completion of the reaction, a biphenyl internal standard was added thereto and centrifuged, and the yield of N-phenylformamide was about 30.5% as calculated by gas chromatography.
Example 10
100mg Zn/In of example 1 was weighed 2 O 3 Placing the T200 catalyst in a reaction tube, adding 1mL anhydrous DMF and 1mmol morpholine (or cyclohexylamine, p-methylaniline, p-chloroaniline and p-methoxyaniline) into the reaction tube after ultrasonic dispersion, introducing condensed water, connecting a balloon sealing system at a condensation tube orifice, and placing the reaction tube in a heating sleeve to magnetically stir and react for 10h at the constant temperature of 160 ℃. After the reaction is finished, adding trimesoyloxyThe yield of N-phenylformamide was about 99.9% (97.5%, 91.2%, 76.4%, 73.0%) using nuclear magnetism as an internal standard of alkylbenzene and centrifugation.
Representative examples of the present invention and representative examples of the extended applicability of the substrate are now shown in comparison and juxtaposition, including but not limited to, a portion of the different metal monoatoms and carriers, as shown in Table 1.
TABLE 1
Figure BDA0004191556560000081
Figure BDA0004191556560000091
The foregoing description of the preferred embodiment of the invention is merely illustrative of the invention and is not intended to be in any way limiting. All the schemes and embodiments based on the scheme or technology of the invention are within the scope of the technical scheme protection of the invention under the premise of any improvement, modification and no creative achievement.

Claims (10)

1. An oxide-based catalyst comprising a nano-indium oxide matrix, in which In: the mass ratio of O is less than the stoichiometric ratio 2:3, the Fourier transform infrared spectrum of the catalyst is 3000-4000cm -1 The characteristic peaks of hydroxyl exist between the indium oxide and the glass, and X-ray photoelectron spectroscopy test shows that the coverage of hydroxyl on the surface of the indium oxide is 40-60%; optionally, the nano indium oxide matrix supports a metal M selected from one or more combinations of Zn, co, al, ag, pd.
2. The catalyst of claim 1, wherein the metal M is Zn.
3. The catalyst of claim 1, wherein the substrate is cubic indium oxide.
4. The catalyst of claim 1, the matrix porous sheet indium oxide.
5. The catalyst of claim 1, wherein the metal monoatoms or nanoparticles supported on the surface of the substrate are anchored by the O atoms of the metal-support interface, i.e., the metal M and the substrate interface have an M-O coordination structure.
6. The catalyst of claim 1, wherein the metal M is a single atom.
7. A process for preparing the catalyst of any one of claims 1 to 6, comprising the steps of:
a. respectively dispersing indium-based metal salt and organic weak alkaline micromolecules in a proton solvent, sequentially adding the materials into the proton solvent with a certain temperature, heating and stirring, naturally cooling, centrifugally washing, and preserving the temperature of the precipitate in a vacuum drying oven for 8-12h;
b. c, carrying out high-temperature calcination treatment on the precipitate obtained in the step a, wherein the high-temperature calcination is carried out in an air atmosphere at 200-550 ℃ for 1-6h to obtain a powdery sample;
c. optionally, dispersing the powdery sample obtained in the step b in a reducing solvent, slowly adding a precursor salt solution of the metal M, stirring for a certain time, centrifugally washing, and drying in vacuum to obtain the oxide supported metal catalyst.
8. The process of claim 7, wherein the metal precursor salt in step c is selected from ZnCl 2 、(CH 3 COO) 2 Zn、ZnSO 4 、Zn(NO 3 ) 2 、Zn(acac) 2 (zinc acetylacetonate) and combinations of one or more thereof.
9. The preparation method according to claim 8, wherein the temperature of the step b is 200-400 ℃.
10. The catalyst of any one of claims 1 to 6 for the catalytic preparation of N-formyl compoundsThe catalyzed substrate is DMF and amine compound, and the amine compound used in the catalytic reaction is
Figure FDA0004191556550000011
One or a combination of more of the above.
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