Supported metal cluster catalyst and method for its preparation

Abstract

The application discloses a supported metal cluster catalyst and a preparation method thereof. The supported metal cluster catalyst is metal clusters wrapped in an aerogel carrier. In the application, the metal clusters are wrapped in the aerogel in situ in the process of synthesizing the aerogel, and a stable catalyst is obtained. When the catalyst is applied to a carbon dioxide hydroformylation reaction, the integration of carbon dioxide capture and efficient utilization can be realized without adding an external additive. The catalyst has excellent catalytic activity and selectivity, and the regeneration process is simple, environment-friendly and recyclable, so the catalyst has great industrial application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalytic chemistry, and particularly relates to a supported metal cluster catalyst and a preparation method thereof. BACKGROUND

[0002] Atomically precise metal clusters are a kind of catalysts with uniform size, precise structure and accurate number of atoms, which are different from nanoparticles and atoms. The number of starting atoms is determined, the arrangement of internal atoms is between crystal and amorphous, and the arrangement of surface atoms depends on the metal bond with the bottom layer of atoms and the covalent bond of the surface ligand. Therefore, the variability of electronic structure and spatial structure provides a material basis for regulating the catalytic performance. The unique geometric structure and electronic structure of precise metal clusters provide a new catalytic research system for precisely constructing catalyst active sites at the atomic level, understanding the catalytic reaction mechanism at the molecular level, and regulating the catalytic reaction process.

[0003] The structural stability of metal clusters with precise structure under catalytic reaction conditions is a problem restricting the application of metal cluster catalysts. At present, metal clusters are mainly used in mild reactions in the field of catalysis. In high temperature reactions, the precise structure of the cluster is easily destroyed, and the active center is lost, resulting in a decrease in catalytic activity and selectivity, which is the main reason why the application range of precise metal clusters is limited to mild reactions. The support effect is also an effective method to improve the stability of metal cluster catalysts. The support has a strong interaction with the clusters on its surface or in its pores, affecting the geometric and electronic characteristics of the metal body, and thus affecting the catalytic activity of the metal cluster catalyst. At the same time, the support can anchor the metal cluster to avoid the aggregation of the metal cluster, thereby improving the stability of the metal cluster catalyst as a whole in the actual catalytic process. Therefore, there is an urgent need for a method to improve the catalytic stability of metal clusters to apply metal cluster catalysts to a wider range of catalytic reactions and to more severe catalytic reaction conditions.

[0004] In view of the above, we aim to develop a method to improve the catalytic stability of metal clusters, so that metal clusters can be applied to more severe catalytic reaction conditions and a wider range of catalytic reactions. SUMMARY

[0005] The object of the present application is to provide a supported metal cluster catalyst and a preparation method thereof, which has high catalytic stability and can be applied to more severe catalytic reaction conditions and a wider range of catalytic reactions.

[0006] In order to achieve the above object, the present application adopts the following technical solution: a supported metal cluster catalyst, wherein the supported metal cluster catalyst is a metal cluster wrapped in an aerogel support with a network structure.

[0007] Further, the metal cluster is gold, silver, copper, palladium, platinum, ruthenium, iridium, nickel cluster or alloy cluster of the above metals.

[0008] Further, the aerogel carrier is silica, titania aerogel or silica and titania composite aerogel.

[0009] A preparation method of a supported metal cluster catalyst, comprising the following steps:

[0010] (1) mixing solvent A with mercaptan to prepare solution A; mixing metal source with solvent B to prepare solution B; adding solution B into solution A under stirring, then mixing triphenylphosphine with solvent A to prepare solution C and adding into the mixed solution, and then adding sodium borohydride solution into the mixed solution to generate metal cluster by reduction;

[0011] (2) preparing solution D by mixing material source, solvent C and water in a certain ratio, adding catalyst A into solution D to hydrolyze, then adding catalyst B and the metal cluster prepared in step (1), and after standing for a certain time, the gel is formed, and after drying, the aerogel coated with catalyst is obtained.

[0012] Further, the solvent A in step (1) is hydrocarbon derivative, dichloromethane, trichloromethane or 1,4-dioxane, and the solvent B is alcohol, methanol, ethanol or isopropanol.

[0013] Further, the metal source in step (1) is one or a mixture of two or more of gold salt, silver salt, copper salt, platinum salt, palladium salt, iridium salt, ruthenium salt or nickel salt.

[0014] Further, the mercaptan in step (1) is one or a mixture of two or more of 2-phenylethyl mercaptan, 2,4-dimethylbenzenethiol, 4-tert-butylbenzenethiol, cyclohexanethiol, 1,3-benzenedithiol, adamantane mercaptan, 2,5-dimethylbenzenethiol, 2-chlorobenzenethiol, 2,4-dichlorobenzenethiol, 4-acetamidobenzenethiol, 4-hydroxybenzenethiol, 2-bromobenzenethiol, etc.

[0015] Further, the material source in step (2) is silicon source or titanium source; the solvent C is alcohol, methanol, ethanol or isopropanol, or hydrocarbon, dichloromethane or toluene, or amide, N,N-dimethylformamide or N,N-dimethylacetamide; and the mass ratio of the material source, solvent and water is 1:1:0.5-1:20:5.

[0016] Further, the catalyst A in step (2) is inorganic acid, hydrochloric acid or sulfuric acid, or = or inorganic base, ammonia or sodium carbonate; the catalyst B is organic acid, acetic acid, oxalic acid or succinic acid, or is organic base, tetramethyl ethylenediamine or triethylamine.

[0017] Further, the drying method in step (2) is oven drying or supercritical drying.

[0018] In the present application, the metal clusters are in-situ wrapped in aerogel during the synthesis of aerogel, obtaining a stable catalyst. It is applied to the catalytic reaction of CO2 and CO resource molecules, realizing high conversion and high selectivity to obtain high value-added chemicals. The metal clusters in the aerogel before and after the reaction maintain structural stability, and the catalyst has excellent cycle stability and good industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is the UV-visible absorption spectrum of the catalyst prepared in Example 13 before and after the reaction in Example 15.

[0020] Figure 2 is the scanning electron microscope photo of the catalyst prepared in Example 13 before and after the reaction in Example 15.

[0021] Figure 3 is the powder X-ray diffraction spectrum of the catalyst prepared in Example 13 before and after the reaction in Example 15.

[0022] Figure 4 is the X-ray photoelectron spectrogram of the catalyst prepared in Example 13 before and after the reaction in Example 15.

[0023] Figure 5 is the catalytic performance of the catalyst prepared in Example 13 in the formylation reaction of carbon monoxide and secondary amine. DETAILED DESCRIPTION

[0024] In order to enable the personnel in the technical field to better understand the scheme of the present application, the technical scheme in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the personnel in the field without creative labor should belong to the protection scope of the present application.

[0025] It is to be understood that the terminology of the specification and claims, and of the above summary, are used by way of example. It is intended that the specification and claims be construed in accordance with the definition of terms provided herein. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0026] The supported metal cluster catalyst is a supported catalyst with metal clusters encapsulated in an aerogel support. The metal species is gold, silver, copper, palladium, platinum, ruthenium, iridium, nickel cluster and alloy cluster. The aerogel support is silica, titania and other material aerogel. The supported metal cluster catalyst prepared in this application can be applied to the catalytic conversion of CO and CO2, including CO hydroformylation, CO formylation, CO hydrogenation, CO2 hydroformylation, CO2 hydrogenation. The specific implementation is as follows:

[0027] Example 1

[0028] 0.048 g of nickel chloride (NiCl2·6H2O) and 0.129 g of tetraoctylammonium bromide (TOAB) were weighed and dissolved in 15 mL of tetrahydrofuran (THF) to form solution A, which was stirred in an ice bath.

[0029] 0.14 mL of 2-phenylethanethiol was added to solution A, and the mixture was stirred until uniform to obtain solution B.

[0030] 5 mL of an aqueous solution containing 0.0767 g of sodium borohydride (NaBH4) was added to solution B, and the mixture was stirred until uniform to obtain solution C.

[0031] Solution C was rotary evaporated at 40 ℃. The sample was washed with ethanol for 3-5 times, and then dissolved and separated with acetonitrile to obtain solution D.

[0032] Solution D was rotary evaporated at 40 ℃, and the remaining solid was dissolved and separated with dichloromethane (CH2Cl2) to obtain solution E. Solution E was slowly blown dry with nitrogen (N2) to obtain nickel clusters.

[0033] 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF) were weighed and mixed and stirred until uniform. 0.5 mL of hydrochloric acid (HCl) was added as a catalyst. After hydrolysis at 50 ℃ for 5 hours, 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal clusters were added. After a period of time, the gel was formed, and supercritical drying was carried out at 70 ℃ and 11 MPa. After drying, it was taken out for standby, and nickel clusters were obtained.

[0034] Example 2

[0035] Take 0.02 g of silver nitrate (AgN03) and add it to 5 mL of methanol, sonicate until dissolved to obtain solution A.

[0036] Take 0.0135 mL of 1,3-benzenedithiol and add it to 10 mL of dichloromethane (CH2Cl2), continuously stir until mixed evenly to obtain solution B.

[0037] Add solution A to solution B and keep stirring.

[0038] Take 0.2 g of triphenylphosphine (C 18 H 15 P) and dissolve it in 1 mL of dichloromethane (CH2Cl2), then add it to the above mixed solution.

[0039] After stirring for 10 minutes, dissolve 0.0105 g of sodium borohydride (NaBH4) in 0.5 mL of ultrapure water, then add it to the mixed solution and keep stirring for 12 hours.

[0040] Centrifuge the mixed solution at high speed, discard the supernatant, and then repeatedly wash the precipitate with ethanol several times. After drying at 50 °C for 12 hours, take it out and reserve it for use, to obtain silver clusters.

[0041] Take 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF), mix and stir until evenly mixed, then add 0.5 mL of hydrochloric acid as a catalyst. After hydrolysis at 50 °C for 5 hours, add 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal clusters, and let it stand for a while until the gel is formed. Then, perform supercritical drying at 70 °C and 11 MPa. After drying, take it out and reserve it for use.

[0042] Example 3

[0043] Take 0.6748 g of tetraoctylammonium bromide (TOAB) and add it to 30 mL of tetrahydrofuran (THF) to obtain solution A.

[0044] Take 1 g of chloroauric acid (HAuCl4·3H2O) and add it to 10 mL of tetrahydrofuran (THF) to obtain solution B.

[0045] Add solution B to solution A, stir vigorously for 30 minutes, then reduce the stirring speed, add 1.02 mL of phenylethanethiol, and continue stirring for 3 hours until it is colorless. Then, add 8 mL of ice water and 0.528 g of sodium borohydride (NaBH4) under ice bath conditions, and continue stirring for 12 hours to obtain solution C.

[0046] The solution C was transferred to a separatory funnel, THF and TOAB were separated by ice water, the remaining solution was centrifuged, washed, dried, and the platinum cluster was obtained.

[0047] 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF) were weighed, mixed and stirred uniformly, 0.5 mL of hydrochloric acid was added as a catalyst, hydrolysis was carried out at 50°C for 5 hours, 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal cluster were added, and the gel was formed after a period of time. After that, supercritical drying was carried out at 70°C and 11 MPa. After drying, it was taken out for standby.

[0048] Example 4

[0049] 0.6748 g of tetraoctyl ammonium bromide (TOAB) was weighed and added to 30 mL of tetrahydrofuran (THF) to obtain solution A.

[0050] 1 g of chloroplatinic acid (H2PtCl6) was weighed and added to 10 mL of tetrahydrofuran (THF) to obtain solution B.

[0051] Solution B was added to solution A, and after stirring vigorously for 30 minutes, the stirring speed was reduced, 1.02 mL of 2,4-dichlorobenzene sulfhydryl was added, and stirring was continued for 3 hours until it was colorless. 8 mL of ice water and 0.528 g of sodium borohydride (NaBH4) were added under ice bath conditions, and stirring was continued for 12 hours to obtain solution C.

[0052] The solution C was transferred to a separatory funnel, THF and TOAB were separated by ice water, the remaining solution was centrifuged, washed, dried, and the platinum cluster was obtained.

[0053] 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF) were weighed, mixed and stirred uniformly, 0.5 mL of hydrochloric acid was added as a catalyst, hydrolysis was carried out at 50°C for 5 hours, 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal cluster were added, and the gel was formed after a period of time. After that, supercritical drying was carried out at 70°C and 11 MPa. After drying, it was taken out for standby.

[0054] Example 5

[0055] 0.6748 g of tetraoctyl ammonium bromide (TOAB) was weighed and added to 30 mL of tetrahydrofuran (THF) to obtain solution A.

[0056] Take 1 g of palladium chloride (PdCl2) and add 10 mL of tetrahydrofuran (THF) to obtain solution B.

[0057] Add solution B to solution A, stir vigorously for 30 minutes, then reduce the stirring speed, add 1.02 mL of adamantane thiol, continue stirring for 3 hours until colorless, add 8 mL of ice water and 0.528 g of sodium borohydride (NaBH4) under ice bath conditions, and continue stirring for 12 hours to obtain solution C.

[0058] Transfer solution C to a separatory funnel, separate tetrahydrofuran (THF) and tetraoctylammonium bromide (TOAB) with ice water, centrifuge the remaining solution, wash and dry to obtain the palladium cluster.

[0059] Take 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF), mix and stir until uniform, add 0.5 mL of hydrochloric acid as a catalyst, hydrolyze at 50°C for 5 hours, then add 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal cluster, stand for a period of time until the gel is formed, and then perform supercritical drying at 70°C and 11 MPa. After drying, take out for use.

[0060] Example 6

[0061] Take 0.6748 g of tetraoctylammonium bromide (TOAB) and add 30 mL of tetrahydrofuran (THF) to obtain solution A.

[0062] Take 1 g of ruthenium chloride (RuCl3) and add 10 mL of tetrahydrofuran (THF) to obtain solution B.

[0063] Add solution B to solution A, stir vigorously for 30 minutes, then reduce the stirring speed, add 1.02 mL of 4-tert-butyl phenyl mercaptan, continue stirring for 3 hours until colorless, add 8 mL of ice water and 0.528 g of sodium borohydride (NaBH4) under ice bath conditions, and continue stirring for 12 hours to obtain solution C.

[0064] Transfer solution C to a separatory funnel, separate tetrahydrofuran (THF) and tetraoctylammonium bromide (TOAB) with ice water, centrifuge the remaining solution, wash and dry to obtain the palladium cluster.

[0065] Take 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), 14.6 g of N,N-dimethylformamide (DMF), mix and stir uniformly, then add 0.5 mL of hydrochloric acid as catalyst, hydrolyze at 50°C for 5 hours, then add 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal cluster, stand for a period of time, and after the gel is formed, perform supercritical drying at 70°C and 11 MPa. After drying, take out for standby use.

[0066] Example 7

[0067] Take 0.6748 g of tetraoctyl ammonium bromide (TOAB) and add 30 mL of tetrahydrofuran (THF) to obtain solution A.

[0068] Take 1 g of iridium chloride (IrCl3) and add 10 mL of tetrahydrofuran (THF) to obtain solution B.

[0069] Add solution B to solution A, stir vigorously for 30 minutes, then reduce the stirring speed, add 1.02 mL of 4-acetamidobenzenethiol, continue stirring for 3 hours until colorless, add 8 mL of ice water and 0.528 g of sodium borohydride (NaBH4) under ice bath conditions, and continue stirring for 12 hours to obtain solution C.

[0070] Transfer solution C to a separatory funnel, separate tetrahydrofuran (THF) and tetraoctyl ammonium bromide (TOAB) with ice water, and centrifuge, wash, and dry the remaining solution to obtain an iridium cluster.

[0071] Take 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), 14.6 g of N,N-dimethylformamide (DMF), mix and stir uniformly, then add 0.5 mL of hydrochloric acid as catalyst, hydrolyze at 50°C for 5 hours, then add 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal cluster, stand for a period of time, and after the gel is formed, perform supercritical drying at 70°C and 11 MPa. After drying, take out for standby use.

[0072] Example 8

[0073] Take 0.1 g of tetraethylammonium tetrafluoroborate (C8H 12 CuF6N4P) and 0.1 g of triphenylphosphine (C 18 H 15 P) and add 4 mL of acetonitrile and 1 mL of dichloromethane (CH2Cl2) to obtain solution A.

[0074] Dissolve 100 mg of sodium borohydride (NaBH4) in 5 mL of methanol to obtain solution B

[0075] After continuously stirring solution A until complete dissolution, 0.03 mL of 1-phenylethanethiol was added to solution A to obtain solution C, and after stirring for 20 minutes, solution B was added to solution C. After reaction for 3 hours, centrifugal separation was performed to obtain copper clusters.

[0076] After weighing 1.08 g of deionized water, 8.32 g of tetraethyl orthosilicate (TEOS), and 14.6 g of N,N-dimethylformamide (DMF), the mixture was stirred uniformly, 0.5 mL of hydrochloric acid was added as a catalyst, and after hydrolysis at 50°C for 5 hours, 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal clusters were added. After a period of time, the gel was formed, and supercritical drying was performed at 70°C and 11 MPa. After drying, it was taken out for use

[0077] Example 9

[0078] 0.02 g of silver nitrate (AgNO3) was weighed into 5 mL of methanol, and ultrasonic was performed until dissolution to obtain solution A.

[0079] 0.0135 mL of 1,3-benzenedithiol was taken into 10 mL of dichloromethane (CH2Cl2), and continuously stirred and mixed uniformly to obtain solution B.

[0080] Solution A was added to solution B, and stirring was maintained.

[0081] 0.2 g of triphenylphosphine (C 18 H 15 P) was weighed and dissolved in 1 mL of dichloromethane (CH2Cl2), and the solution was added to the above mixed solution.

[0082] After stirring for 10 minutes, 0.0105 g of sodium borohydride (NaBH4) was dissolved in 0.5 mL of ultrapure water, and then added to the mixed solution, and stirring was maintained for 12 hours.

[0083] The mixed solution was centrifuged at high speed, the supernatant was discarded, and the precipitate was washed repeatedly with ethanol for several times. After drying at 50°C for 12 hours, it was taken out for use to obtain silver clusters.

[0084] After weighing 1.58 g of deionized water, 10.3 g of titanium butylate, and 18.4 g of anhydrous ethanol, the mixture was stirred uniformly, and after hydrolysis at 30°C for 5 hours, 0.5 mL of hydrochloric acid and 0.03 g of metal clusters were added. After a period of time, the gel was formed, and drying was performed at 90°C for 24 hours. After drying, it was taken out for use.

[0085] Example 10

[0086] Take 0.02 g of silver nitrate (AgNO3) and add it to 5 mL of methanol, and perform ultrasonic until dissolved, to obtain solution A.

[0087] Take 0.0135 mL of 1,3-benzenedithiol and add it to 10 mL of dichloromethane (CH2Cl2), and continuously stir to mix evenly, to obtain solution B.

[0088] Add solution A to solution B, and keep stirring.

[0089] Take 0.2 g of triphenylphosphine (C 18 H 15 P), and dissolve it in 1 mL of dichloromethane (CH2Cl2), and add the solution to the above mixed solution.

[0090] After stirring for 10 minutes, dissolve 0.0105 g of sodium borohydride (NaBH4) in 0.5 mL of ultrapure water, and then add it to the mixed solution, and keep stirring for 12 hours.

[0091] Centrifuge the mixed solution at high speed, pour off the supernatant, and then repeatedly wash the precipitate with ethanol for multiple times, and take it out after drying at 50 ℃ for 12 hours, to obtain silver clusters.

[0092] Take 1.58 g of deionized water, 2.3 g of butyl titanate, 9.6 g of tetraethyl orthosilicate (TEOS), and 18.4 g of anhydrous ethanol, mix and stir evenly, then add 0.5 mL of hydrochloric acid as a catalyst, hydrolyze at 50 ℃ for 5 hours, then add 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal clusters, and stand for a period of time until the gel is formed, then perform supercritical drying at 70 ℃ and 11 MPa. After drying, take it out for use.

[0093] Example 11

[0094] Take 0.04 g of chloroauric acid (HAuCl4·3H2O) and 0.2 g of tetraoctylammonium bromide (TOAB), and dissolve them in 15 mL of toluene to obtain solution A. Take 0.06 g of silver nitrate (AgNO3) and dissolve it in 3 mL of methanol to obtain solution B.

[0095] Mix solution A and solution B, and stir vigorously for 5 minutes. Then, add 0.05 g of bis-(diphenylphosphine) methane (DPPM) and 50 µL of tert-butyl mercaptan (tBu-SH), to form a colorless solution.

[0096] Continue stirring for 30 minutes, then add 2 mL of aqueous sodium borohydride solution (0.02 mg), and stir vigorously. The reaction is carried out for 12 hours.

[0097] The mixed solution was centrifugally separated, repeatedly washed with n-hexane, and taken out for standby, to obtain the gold-silver alloy cluster.

[0098] 1.58 g of deionized water, 2.3 g of butyl titanate, 9.6 g of tetraethyl orthosilicate (TEOS), and 18.4 g of anhydrous ethanol were weighed, mixed, and stirred uniformly, 0.5 mL of hydrochloric acid was added as a catalyst, hydrolysis was carried out at 50°C for 5 hours, 0.5 mL of tetramethyl ethylenediamine (TEMED) and 0.03 g of metal clusters were added, and the gel was formed after a period of time. Supercritical drying was carried out at 70°C and 11 MPa. After drying, it was taken out for standby.

[0099] Example 12

[0100] 0.08 g of chloroauric acid (HAuCl4·3H2O) and 0.1 g of tetraoctylammonium bromide (TOAB) were weighed into 20 mL of dichloromethane, and stirred vigorously to obtain solution A. After 15 minutes, 0.034 g of copper chloride (CuCl2) was added to solution A, and stirring was continued to obtain solution B.

[0101] 0.1 g of bis(diphenylphosphine) methane (DPPM) and 0.1 g of adamantane thiol were weighed into solution B, stirred for 30 minutes, 0.06 g of sodium borohydride was added, and stirring was continued for 12 hours to obtain dark solution C.

[0102] Solution C was centrifuged to obtain a precipitate, which was repeatedly washed with n-hexane, and taken out for standby at 30°C to obtain gold-copper alloy clusters.

[0103] 1.58 g of deionized water, 10.3 g of butyl titanate, and 18.4 g of anhydrous ethanol were weighed, mixed, and stirred uniformly, hydrolysis was carried out at 30°C for 5 hours, 0.5 mL of hydrochloric acid and 0.03 g of metal clusters were added, and the gel was formed after a period of time. Drying was carried out at 90°C for 24 hours. After drying, it was taken out for standby.

[0104] Example 13

[0105] 0.01 g of silver nitrate (AgNO3) and 0.016 g of copper acetylacetonate were weighed into 5 mL of methanol, and ultrasonicated until dissolved to obtain solution A.

[0106] 0.0135 mL of 1,3-benzenedithiol was taken into 10 mL of dichloromethane (CH2Cl2), and stirred to mix uniformly to obtain solution B.

[0107] Solution A was added to solution B, and stirring was continued.

[0108] 0.2 g of triphenylphosphine (C 18 H15 P) was dissolved in 1 mL of dichloromethane (CH2Cl2) and the solution was added to the above mixed solution.

[0109] After stirring for 10 minutes, 0.0105 g of sodium borohydride (NaBH4) was dissolved in 0.5 mL of ultrapure water and then added to the mixed solution, and stirring was maintained for 12 hours.

[0110] The mixed solution was centrifuged at high speed, the supernatant was discarded, and the precipitate was repeatedly washed with ethanol several times. After drying at 50°C for 12 hours, the silver-copper alloy cluster was taken out and reserved for use.

[0111] After mixing and stirring uniformly, 1.58 g of deionized water, 10.3 g of butyl titanate, and 18.4 g of anhydrous ethanol were hydrolyzed at 30°C for 5 hours. Then, 0.5 mL of hydrochloric acid and 0.03 g of metal clusters were added, and the gel was allowed to form after a period of rest. The gel was dried at 90°C for 24 hours. After drying was completed, the product was taken out and reserved for use.

[0112] Example 14

[0113] 0.024 g of nickel chloride (NiCl2·6H2O), 0.012 g of copper chloride (CuCl2), and 0.1290 g of tetraoctylammonium bromide (TOAB) were weighed and dissolved in 15 mL of tetrahydrofuran to form solution A, which was stirred in an ice bath.

[0114] 0.14 mL of phenylethyl mercaptan was added to solution A, and the mixture was stirred uniformly to obtain solution B.

[0115] 5 mL of an aqueous solution containing 0.0767 g of NaBH4 was added to solution B, and the mixture was stirred uniformly to obtain solution C.

[0116] Solution C was rotary evaporated at 40°C. The sample was washed with ethanol for 3-5 times, and then dissolved and separated with acetonitrile to obtain solution D.

[0117] Solution D was rotary evaporated at 40°C, and the remaining solid was dissolved and separated with dichloromethane to obtain solution E. Solution E was slowly blown dry with nitrogen (N2), and a brown-black precipitate was obtained, which was a copper-nickel alloy cluster.

[0118] After mixing and stirring uniformly, 1.58 g of deionized water, 10.3 g of butyl titanate, and 18.4 g of anhydrous ethanol were hydrolyzed at 30°C for 5 hours. Then, 0.5 mL of hydrochloric acid and 0.03 g of metal clusters were added, and the gel was allowed to form after a period of rest. The gel was dried at 90°C for 24 hours. After drying was completed, the product was taken out and reserved for use.

[0119] Example 15

[0120] Take 0.2 g of silver copper alloy cluster catalyst prepared in Example 13 into 10 mL of isopropyl alcohol (IPA) solution, after mixing and stirring uniformly, add 0.2 mL of aniline (An), to obtain solution A, transfer solution A to a high temperature and high pressure reaction kettle, fill in 4 MPa carbon monoxide (CO), under the temperature of 150 ℃, react for 12 hours under intense stirring, to obtain product formanilide.

[0121] The UV-Vis absorption spectra of the catalyst before and after reaction are shown in Figure 1 , the scanning electron microscope photos of the catalyst before and after reaction are shown in Figure 2 , the powder X-ray diffraction spectra of the catalyst before and after reaction are shown in Figure 3 , the X-ray photoelectron spectra of the catalyst before and after reaction are shown in Figure 4 , and the catalytic performance of the catalyst in the formylation reaction of carbon monoxide and secondary amine is shown in Figure 5 .

[0122] Example 16

[0123] Take 0.2 g of gold copper alloy cluster catalyst prepared in Example 12 into 10 mL of N,N-dimethylformamide (DMF) solution, after mixing and stirring uniformly, add 0.2 mL of phenethylamine (PEA), to obtain solution A, transfer solution A to a high temperature and high pressure reaction kettle, fill in 4 MPa carbon dioxide and hydrogen (CO2:H2 = 1:1), under the temperature of 100 ℃, react for 16 hours under intense stirring, to obtain product N-benzylformamide.

[0124] Example 17

[0125] Take 0.2 g of gold silver alloy cluster catalyst prepared in Example 11, after granulation (40 mesh-60 mesh), load into a reaction tube with a diameter of 0.5 cm, under the reaction conditions of 2.7 MPa and 180 ℃, pass in carbon monoxide (CO), nitrogen (N2) and dimethylamine (DMA), to obtain product N,N-dimethylformamide (DMF). The composition of the raw gas is: CO:N2 = 1:1 (volume ratio), DMA:CO = 1:18 (molar ratio).

[0126] Example 18

[0127] Take 0.2 g of copper nickel alloy cluster catalyst prepared in Example 14, after granulation (40 mesh-60 mesh), load into a reaction tube with a diameter of 0.5 cm, under the reaction conditions of 3 MPa and 160 ℃, pass in carbon dioxide (CO2), nitrogen (N2), hydrogen (H2) and dimethylamine (DMA), to obtain product N,N-dimethylformamide (DMF). The composition of the raw gas is: CO2:N2:H2 = 1:1:1 (volume ratio), DMA:CO2 = 1:18 (molar ratio).

[0128] Example 19

[0129] Example 19

[0130] Example 20

[0131] Example 20

[0132] Example 21

[0133] Example 21

[0134] It should be understood that the application is only described by way of example and can be modified within the scope and spirit of the application. The above describes a preferred embodiment of the application in detail. It should be understood that those skilled in the art can make many modifications and changes according to the concept of the application without creative labor. Therefore, any technical solution obtained by logical analysis, reasoning or limited test based on the prior art according to the concept of the application should be within the protection scope defined by the claims.

Claims

1. The application of a supported metal cluster catalyst in the catalytic reaction of carbon monoxide with secondary aminoformylation, characterized in that: The supported metal cluster catalyst consists of metal clusters encapsulated in an aerogel support with a network structure. The metal clusters are silver and copper alloy clusters; The aerogel carrier is silica, titanium dioxide aerogel, or a composite aerogel of silica and titanium dioxide. The supported metal cluster catalyst was prepared using the following steps: (1) Mix solvent A with thiol to prepare solution A; mix metal source with solvent B to prepare solution B; add solution B to solution A while stirring, then mix triphenylphosphine with solvent A to prepare solution C, and add it to the mixed solution; then add sodium borohydride solution to the mixed solution to reduce and generate metal clusters. (2) Prepare solution D by mixing material source, solvent C and water in a certain proportion. Add catalyst A to solution D for hydrolysis. Then add catalyst B and metal clusters obtained in step (1). After standing for a certain time, wait for gel to form, and then dry to obtain aerogel encapsulating catalyst. In step (1), solvent A is dichloromethane, trichloromethane, or 1,4-dioxane, solvent B is methanol, ethanol, or isopropanol, and the metal source is a mixture of silver salt and copper salt. The material source in step (2) is a silicon source or a titanium source; the solvent C is methanol, ethanol, isopropanol, dichloromethane, toluene, N,N-dimethylformamide or N,N-dimethylacetamide; the mass ratio of the material source, solvent and water is 1:1:0.5 to 1:20:5; the catalyst A is hydrochloric acid, sulfuric acid, ammonia or sodium carbonate; the catalyst B is acetic acid, oxalic acid, succinic acid or tetramethylethylenediamine or triethylamine; The drying method in step (2) is oven drying or supercritical drying.

2. The application according to claim 1, characterized in that: The thiol in step (1) is one or a mixture of two or more of the following: 2-phenylethylthiol, 2,4-dimethylbenzylthiophenol, 4-tert-butylbenzylthiophenol, cyclohexanethiol, 1,3-benzyldithiol, adamantanethiol, 2,5-dimethylbenzylthiol, 2-chlorobenzylthiol, 2,4-dichlorobenzylthiol, 4-acetaminophenbenzylthiol, 4-hydroxybenzylthiol, and 2-bromobenzylthiol.

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