A copper-based molecular sieve catalyst, a preparation method and application thereof

Abstract

The application discloses a copper-based molecular sieve catalyst and a preparation method and application thereof. The copper-based molecular sieve catalyst comprises a molecular sieve carrier and copper nanoclusters encapsulated in the molecular sieve carrier; the molecular sieve carrier has CHA, MFI, BEA, FAU and MWW topological structures; the size of the copper nanoclusters is 0.02-5 nm; and the mass content is 0.025-5 wt%. The carrier has good hydrothermal stability, regularly adjustable channels and a high-crystallinity skeleton structure, can effectively limit the sintering and agglomeration of copper in the carrier, can inhibit the occurrence of polymerization and other side reactions through channel selection, and can improve the selectivity of furfuryl alcohol. The copper nanoclusters prepared by a coordination protection reduction method are uniform and easy to control in size, the structure of copper species is protected by a coordination agent in a subsequent crystallization process, and finally, the copper-based catalyst has high metal dispersion and good uniformity.

Description

Technical Field

[0001] This application relates to a copper-based molecular sieve catalyst, its preparation method, and its application, belonging to the field of catalysis. Background Technology

[0002] Furfuryl alcohol is an important organic chemical raw material, mainly used in the preparation of various furan-type resins (such as furfuryl alcohol resin and type II resin), furfuryl alcohol-urea-formaldehyde resin, phenolic resin, as well as anti-corrosion paints and anti-corrosion films. Plasticizers made from furfuryl alcohol exhibit better cold resistance than butyl and octyl alcohol esters. It is also a good solvent for furan resins, varnishes, and pigments, and is used as rocket fuel. In addition, it is used in the synthetic fiber, rubber, pesticide, and foundry industries.

[0003] Currently, furfural, an important biomass platform compound, is the upstream feedstock for furfuryl alcohol. It is produced via three routes: gas-phase hydrogenation, liquid-phase hydrogenation, and the Cannizaro process (auto-oxidation-reduction). Among these, liquid-phase hydrogenation offers advantages such as mild and easily controllable reaction conditions, good selectivity, and high mass transfer efficiency, making it the most promising process route.

[0004] Because furfural molecules contain both aldehyde and furan ring unsaturated bonds, highly selective hydrogenation is crucial for obtaining high-yield furfuryl alcohol and is also a challenge for large-scale production. Among various metal catalysts with hydrogenation capabilities, copper-based catalysts are not only abundant and inexpensive, but also exhibit unique advantages in the selective hydrogenation of C=O bonds. Xiamen University reported a copper-based catalyst modified with alkali metals through in-situ reduction of formic acid, achieving furfuryl alcohol yields of 80%-99% (CN109731596). China University of Petroleum (East China) reported a framework copper catalyst combined with an alkali promoter to achieve efficient hydrogenation of furfural to furfuryl alcohol at relatively low reaction temperatures (120-140℃) (CN 102603681). China Petroleum & Chemical Corporation reported the use of a copper-chromium-calcium-silicon-based high-defect catalyst for the liquid-phase hydrogenation of furfural, exhibiting good activity and selectivity (CN106582671). However, copper-based catalysts still suffer from problems such as low Taman temperatures, easy sintering of copper particles under hot reaction conditions, leading to decreased metal dispersion and shortened catalyst life. Currently, the main methods for stabilizing copper-based catalysts include confinement, alloying, and single-atomization. Among these, molecular sieves, as a silicon-based porous material with a regular nanopore structure, are good confinement supports.

[0005] In summary, it is of great significance to develop a copper-based molecular sieve catalyst with high catalytic activity, good selectivity and good stability for the selective liquid-phase hydrogenation of furfural to furfuryl alcohol under mild conditions. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing and applying a copper-based molecular sieve catalyst. This method has advantages such as simple operation, low catalyst cost, economic practicality, good stability, and high efficiency in producing furfuryl alcohol.

[0007] According to one aspect of this application, a copper-based molecular sieve catalyst is provided, the copper-based molecular sieve catalyst comprising a molecular sieve support and copper nanoclusters encapsulated in the molecular sieve support;

[0008] The molecular sieve support is selected from at least one of the molecular sieves having CHA, MFI, BEA, FAU, and MWW topologies;

[0009] The size of the copper nanoclusters is 0.02–5 nm;

[0010] Optionally, the size of the copper nanoclusters is any value among 0.05nm, 0.05nm, 1nm, 3nm, 3.5nm, and 5nm, or a range between any two.

[0011] In the copper-based molecular sieve catalyst, the mass content of the copper nanoclusters is 0.025–5 wt%.

[0012] Optionally, in the copper-based molecular sieve catalyst, the mass content of the copper nanoclusters is any value or a range between 0.025wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, and 5wt%.

[0013] The silicon-aluminum molar ratio of the molecular sieve support is 12 to 1000;

[0014] Optionally, the silicon-aluminum molar ratio of the molecular sieve support is any value among 12, 15, 30, 200, and 1000, or any value between both.

[0015] The crystallinity of the molecular sieve support is 85-100%.

[0016] According to another aspect of this application, a method for preparing the above-mentioned copper-based molecular sieve catalyst is provided, comprising the following steps:

[0017] (1) A mixture I containing copper salt, ligand, reducing agent and water was reacted and separated to obtain ligand-protected copper nanoclusters;

[0018] (2) The mixture II containing the copper nanoclusters protected by the ligand obtained in (1), the template agent, the silicon source, the aluminum source, the alkali source, and the water is treated by dry gel crystallization and calcined to obtain the copper-based molecular sieve catalyst.

[0019] The copper salt is selected from at least one of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate;

[0020] The ligand is selected from at least one of glutathione, 2-mercapto-5-n-propanepyrimidine, cysteine, penicillamine, and dodecyl mercaptan;

[0021] The reducing agent is selected from at least one of hydrazine hydrate, sodium borohydride, penicillamine, and glutathione.

[0022] The molar ratio of the copper salt to the ligand is 1:10 to 1000;

[0023] Optionally, the molar ratio of the copper salt to the ligand can be any value from 1:10, 1:50, 1:100, 1:500, 1:1000, or any range between the two.

[0024] The molar ratio of the copper salt to the reducing agent is 1:5 to 100.

[0025] Optionally, the molar ratio of the copper salt to the reducing agent is any value among 1:5, 1:10, 1:50, and 1:100, or any range between the two.

[0026] The molar ratio of the copper salt to water is 1:100 to 20000.

[0027] Optionally, the molar ratio of the copper salt to water is any value among 1:100, 1:200, 1:500, 1:1000, 1:5000, 1:10000, 1:15000, and 1:20000, or any range between two of these values.

[0028] The reaction temperature is 0–90°C;

[0029] Optionally, the temperature of the reaction is any value among 0°C, 15°C, 40°C, 55°C, 70°C, and 90°C, or a range between any two.

[0030] The reaction time is 1 to 96 hours.

[0031] Optionally, the reaction time is any value among 1h, 5h, 12h, 30h, 60h, and 96h, or a range between any two points.

[0032] Stirring is maintained during the reaction process.

[0033] The template agent is selected from at least one of ethylamine, diethylamine, triethylamine, ethylenediamine, choline chloride, hexamethyleneimine, 1,6-hexanediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide;

[0034] The silicon source is selected from at least one of amorphous silica, silica aerosol, silica liquid sol, and tetraethyl orthosilicate;

[0035] The aluminum source is selected from at least one of aluminum salts, activated alumina, alkoxyaluminum, and metakaolin.

[0036] The alkali source is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and potassium carbonate.

[0037] The molar ratio of the copper nanoclusters protected by the ligand to the template agent is 0.1–5:1–50;

[0038] The molar ratio of the copper nanoclusters protected by the ligand to the silicon source is 0.1–5:20–400;

[0039] The molar ratio of the copper nanoclusters protected by the ligand to the aluminum source is 0.1–5:0.5–200;

[0040] The molar ratio of the copper nanoclusters protected by the ligand to the alkali source is 0.1–5:0.02–50;

[0041] The molar ratio of the copper nanoclusters protected by the ligand to the water is 0.1–5:45–4000;

[0042] The molar amount of copper nanoclusters protected by the ligand is expressed as the molar amount of Cu therein.

[0043] The molar amount of the template agent is expressed as its own molar amount;

[0044] The molar amount of the silicon source is expressed as the molar amount of SiO2 therein;

[0045] The molar amount of the aluminum source is expressed as the molar amount of Al2O3 therein;

[0046] The molar amount of the alkali source is expressed as the molar amount of cations in the alkali source.

[0047] The roasting atmosphere is an air atmosphere;

[0048] The roasting temperature is 300–600°C;

[0049] Optionally, the roasting temperature is any value among 300℃, 400℃, 425℃, 500℃, and 600℃, or a range between any two points.

[0050] The roasting time is 0.2 to 72 hours.

[0051] Optionally, the roasting time is any value among 0.2h, 0.5h, 1h, 6h, 12h, 24h, 36h, and 72h, or a range between any two points.

[0052] The separation method is at least one of freeze drying and high-speed centrifugation.

[0053] Specifically,

[0054] A method for preparing a copper-based molecular sieve catalyst includes the following steps: obtaining copper nanoclusters protected by a coordination reduction method, mixing the copper nanoclusters protected by the coordination agent with the raw materials for synthesizing molecular sieves, and treating them by a dry gel crystallization method to obtain the copper-based molecular sieve catalyst.

[0055] The copper-based molecular sieve catalyst includes a molecular sieve support and an active component, copper.

[0056] The steps for preparing the ligand-protected copper nanoclusters are as follows:

[0057] a1) Dissolve copper salt, complexing agent, and reducing agent in water, heat, and stir to obtain a mixture with the following molar ratio: copper salt: complexing agent: reducing agent: water molar ratio = 1:10~1000:5~100:100~20000;

[0058] a2) The mixture obtained in step a1) is separated by centrifugation or freeze-drying to obtain copper nanoclusters protected by a ligand.

[0059] The steps for preparing copper-based molecular sieve catalysts using the dry gel crystallization method are as follows:

[0060] b1) Copper nanoclusters protected by the ligand, template agent, silicon source, aluminum source, alkali source, and water are mixed to obtain a mixture with the following molar ratio: copper nanoclusters protected by ligand: template agent: silicon source: aluminum source: alkali source: water = 0.1~5:1~50:20~400:0.5~200:0.02~50:45~4000;

[0061] b2) Dry the mixture obtained in step b1) at 80-150°C until the moisture content is less than 5%, then grind it into powder to obtain a dry gel precursor.

[0062] b3) Place the dry gel precursor obtained in step b2) in a polytetrafluoroethylene-lined crystallization vessel and crystallize it with water vapor at 110-170°C for 2-7 days.

[0063] b4) After the crystallization in step b3) is completed, the solid product is separated, washed, dried, and then calcined in air at 300-600°C to obtain the copper-based molecular sieve catalyst.

[0064] According to another aspect of this application, an application of the above-described copper-based molecular sieve catalyst is provided for the furfural hydrogenation reaction.

[0065] The furfural hydrogenation reaction includes:

[0066] Under a reducing atmosphere, raw materials containing a copper-based molecular sieve catalyst, furfural, and solvent are reacted to produce furfuryl alcohol.

[0067] The reducing atmosphere is selected from at least one of hydrogen and methane.

[0068] The solvent is selected from at least one of methanol, ethanol, isopropanol, 1-butanol, 2-butanol, 2-pentanol, tetrahydrofuran, dichloromethane, and dimethylformamide.

[0069] The mass ratio of the copper-based molecular sieve catalyst, solvent, and furfural is 1.0:4.0-500:0.2-55.

[0070] The pressure of the reducing atmosphere is 0.1–15 MPa.

[0071] The reaction temperature is 120–220°C, and the reaction time is 0.1–24 h.

[0072] Specifically,

[0073] The catalyst described above is used to catalyze the hydrogenation of furfural. The specific implementation method is as follows: a high-pressure reactor is used as the reactor for the reaction. The reaction steps are as follows: the copper-based molecular sieve catalyst is placed in the reactor, and a certain mass of solvent and substrate furfural is added to obtain a mixture with the following mass ratio: the mass ratio of copper-based molecular sieve catalyst: solvent: furfural is 1.0:4.0~500:0.2~55; the reactor is sealed and the reaction atmosphere is replaced with a reducing gas, maintaining an initial pressure of 0.1~15MPa, and the temperature is raised to 120~220℃ for 0.1~24h.

[0074] The solvent is one or more of methanol, ethanol, isopropanol, 1-butanol, 2-butanol, 2-pentanol, tetrahydrofuran, dichloromethane, and dimethylformamide; the reducing gas is one or more of hydrogen and methane.

[0075] The product, furfuryl alcohol, has a selectivity of greater than 90%.

[0076] The beneficial effects that this application can produce include:

[0077] 1) This invention provides a method for preparing a copper-based molecular sieve catalyst and using it in the liquid-phase hydrogenation reaction of furfural. The catalyst prepared by this method can significantly improve the selectivity of the target product furfuryl alcohol and reduce the generation of by-products during the reaction. The catalyst provided by this invention has the advantages of easy and precise control, good stability and high reaction efficiency, which meets the requirements of sustainable development and has broad application prospects in biomass conversion.

[0078] 2) This invention uses furfural, a platform compound, as a substrate. The raw materials are widely available, the output is large, the product has high added value, and it has wide applications in multiple fields.

[0079] 3) The copper-based catalyst prepared by this invention has the following structural advantages: First, the molecular sieve catalyst support possesses excellent hydrothermal stability, regular and tunable pores, and a highly crystalline framework structure. This not only effectively confines the sintering and agglomeration of metallic copper within it but also inhibits side reactions such as polymerization through the shape-selective function of the pores, thereby improving the selectivity of furfuryl alcohol. Second, the copper nanoclusters prepared by the coordination-protected reduction method have uniform and easily controllable sizes. During subsequent crystallization, the coordinating agent protects the copper species structure, resulting in a copper-based catalyst with high metal dispersion and good uniformity. Finally, the molecular sieve support has electronegative sites that interact with the cation phase, which can effectively regulate the acidity and alkalinity of the catalyst microenvironment through ion exchange, further enhancing product selectivity. In summary, the catalyst exhibits higher stability and reactivity. Attached Figure Description

[0080] Figure 1 This is the XRD pattern of the catalyst prepared in Example 1 of this application.

[0081] Figure 2 This is a transmission electron microscope (TEM) image of the catalyst prepared in Example 1 of this application, with a scale of 20 nm. Detailed Implementation

[0082] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0083] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0084] XRD characterization was performed using a PANalytical X'Pert PRO X-ray characterizer, nitrogen adsorption-desorption was performed using a Micromeritics ASAP 2020 adsorption characterizer, and transmission electron microscopy images were obtained using a JEM-2100 electron microscope.

[0085] Example 1

[0086] 1.87 g of copper nitrate was weighed and added to a beaker containing 360 mL of deionized water. After stirring until completely dissolved, 41 g of dodecyl mercaptan and 46.1 g of glutathione were slowly added. The mixture was sealed and stirred at 30 °C for 2 h to obtain a milky white transparent solution. After high-speed centrifugation at 20,000 rpm, copper nanoclusters protected by dodecyl mercaptan were obtained. Then, 4.9 g of copper nanoclusters, 32.5 g of tetrapropylammonium hydroxide (25 wt% aqueous solution), 300 g of silica aerosol powder, 2.1 g of aluminum nitrate, 4 g of sodium hydroxide, and 1440 g of water were weighed and mixed at 25 °C for 10 h. The mixture was then placed in a 100 °C oven for 24 h to dry the water and separate into a dry gel until the water content was less than 5%. The gel was then ground into powder. The dried gel was placed in a 100 mL crystallization vessel lined with polytetrafluoroethylene (PTFE), and 5 mL of deionized water was added outside the liner. Crystallization was carried out at 170 °C for 4 days with steam assistance, followed by washing, filtration, drying at 100 °C for 12 h, and calcination at 550 °C for 4 h to obtain the catalyst CuSi-1. Figure 1 , Figure 2 As shown, the catalyst has a highly crystalline MFI topology, and copper species are uniformly distributed inside the support without forming large-sized nanoparticles.

[0087] Examples 2-7

[0088] Example 2 differs from Example 1 only in that 32g of cysteine ​​is used instead of dodecathiol as a ligand to obtain catalyst CuSi-2;

[0089] Example 3 differs from Example 1 only in that an equimolar amount of silica sol is used as the silicon source to obtain CuSi-3;

[0090] Example 4 differs from Example 1 only in that the preparation of the dry gel involves drying the water in a 120°C oven for 48 hours until the water content is less than 2%, thus obtaining CuSi-4.

[0091] Example 5 differs from Example 1 only in that the template agent is replaced with an equimolar amount of tetraethylammonium hydroxide, and the molecular sieve support has a BEA topology, resulting in CuSi-5.

[0092] Example 6 differs from Example 1 only in that the crystallization conditions are water vapor-assisted crystallization at 120°C for 6 days to obtain CuSi-6;

[0093] Example 7 differs from Example 1 only in that 0.44 g of copper nitrate was used, and an equimolar amount of aluminum isopropoxide was used as the aluminum source to obtain CuSi-7.

[0094] Comparative Example 1

[0095] Comparative Example 1 differs from Example 1 only in that no aluminum source is added during the preparation process, resulting in the catalyst CuSi-deAl;

[0096] Comparative Example 2

[0097] Comparative Example 1 differs from Example 1 only in that no alkali source is added during the preparation process, resulting in the catalyst CuSi-deNa;

[0098] Comparative Example 3

[0099] Comparative Example 1 differs from Example 1 only in that a mixture containing copper nanoclusters, template agent, silicon source, aluminum source, alkali source and water is crystallized at 170°C for 4 days under autogenous pressure in a 500mL closed reactor, then washed, filtered, dried at 100°C for 12h, and calcined at 550°C for 4h to obtain the catalyst CuSi-HT.

[0100] Comparative Example 4

[0101] Comparative Example 4: Using commercially available H-ZSM-5 as a support with a silicon-to-aluminum ratio of 100:1, copper nitrate solution was loaded onto the support by an equal-volume impregnation method. The copper loading was the same as that of CuSi-1. The solution was dried at 100°C for 12 h and calcined at 550°C for 4 h to obtain the catalyst CuSi-IM.

[0102] Comparative Example 5

[0103] Comparative Example 5: Using commercial H-ZSM-5 as a support with a silicon-to-aluminum ratio of 100:1, copper nitrate solution was loaded onto the support by deposition precipitation. The copper loading was the same as that of CuSi-1. After centrifugation, drying at 100℃ for 12 h and calcination at 550℃ for 4 h, the catalyst CuSi-DE was obtained.

[0104] Reaction Example 1

[0105] The catalytic conversion experiments were conducted in a stainless steel reactor under the following conditions: Furfural hydrogenation was carried out using catalysts prepared in Examples 1-7 and Comparative Examples 1-2, with a catalyst dosage of 1.0 g, solvent of 20 g ethanol, and 4.0 g furfural. The reactor was sealed, and the atmosphere was replaced with 1 MPa hydrogen gas. The temperature was raised to 150 °C, and the reaction was carried out for 3 h. The results of the catalytic hydrogenation of furfural on different copper-based catalysts are shown in Table 1.

[0106] Table 1 Results of furfural hydrogenation catalyzed by different copper-based catalysts

[0107]

[0108] Table 1 compares the results of furfural hydrogenation reaction on different copper-based catalysts. The reaction data show that the encapsulated copper nanocluster molecular sieve catalyst exhibits better reactivity and higher furfural selectivity compared to samples synthesized without the addition of Na and Al, samples synthesized by hydrothermal crystallization, and catalysts prepared by conventional equal-volume impregnation and deposition-precipitation methods.

[0109] Reaction Example 2

[0110] The effects of reaction temperature, reaction pressure, and reaction solvent on the catalytic results were investigated. Except for the reaction conditions specifically noted in Table 2, the other reaction conditions were the same as in Reaction Example 1. The results of the catalytic hydrogenation of furfural in Example 1 are shown in Table 2:

[0111] Table 2 Results of furfural hydrogenation reaction catalyzed by CuSi-1 catalyst under different reaction conditions

[0112]

[0113]

[0114] As can be seen from the reaction data in Table 2, the catalyst in Example 1 exhibited a selectivity of not less than 90% for furfuryl alcohol under different reaction temperatures, pressures, and reaction solvents.

[0115] Reaction Example 3

[0116] The cyclic stability of the catalyst was investigated. The reaction conditions were the same as in Example 1. After the first catalytic performance evaluation, the solid catalyst was centrifuged, washed with water, dried, and directly used for the next cycle reaction evaluation. The results of the catalytic furfural hydrogenation cycle reaction in Examples 1 and 2 are shown in Table 3.

[0117] Table 3 Results of the catalytic reaction of furfural hydrogenation in a cycling process.

[0118]

[0119]

[0120] As can be seen from the reaction data in Table 3, the encapsulated copper nanocluster molecular sieve catalyst has good structural stability and exhibits excellent performance in multiple furfural hydrogenation cycles.

[0121] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. The use of a copper-based molecular sieve catalyst in the reaction of liquid-phase hydrofurfuryl alcohol, characterized in that, The preparation method of the copper-based molecular sieve catalyst comprises the following steps: (1) a mixture I containing a copper salt, a coordination agent, a reducing agent and water is reacted, separated, and a coordination agent-protected copper nanocluster is obtained; The coordination agent is selected from at least one of glutathione, 2-mercapto-5-n-propanol pyrimidine, cysteine, penicillamine and dodecanethiol; (2) a mixture II containing the coordination agent-protected copper nanocluster obtained in (1), a template agent, a silicon source, an aluminum source, an alkali source and water is treated by a dry gel crystallization method, and calcined to obtain the copper-based molecular sieve catalyst; The copper-based molecular sieve catalyst comprises a molecular sieve carrier and copper nanoclusters encapsulated in the molecular sieve carrier; The molecular sieve carrier is selected from at least one of molecular sieves with CHA, MFI, BEA, FAU and MWW topological structures; The size of the copper nanocluster is 0.02-5 nm; In the copper-based molecular sieve catalyst, the mass content of the copper nanocluster is 0.025-5 wt%.

2. The application of claim 1, wherein The silica-alumina molar ratio of the molecular sieve carrier is 12-1000; The crystallinity of the molecular sieve carrier is 85-100%.

3. The application of claim 1, wherein The copper salt is selected from at least one of copper nitrate, copper acetate, copper chloride, copper carbonate and copper sulfate; The reducing agent is selected from at least one of hydrazine hydrate, sodium borohydride, penicillamine and glutathione.

4. The application of claim 1, wherein The molar ratio of the copper salt to the coordination agent is 1:10-1000; The molar ratio of the copper salt to the reducing agent is 1:5-100; The molar ratio of the copper salt to water is 1:100-20000.

5. The application of claim 1, wherein The reaction temperature is 0-90℃; The reaction time is 1-96h.

6. The application of claim 1, wherein The template agent is selected from at least one of ethylamine, diethylamine, triethylamine, ethylenediamine, choline chloride, hexamethyleneimine, 1,6-hexanediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide; The silicon source is selected from at least one of amorphous silicon dioxide, silicon aerosol, silicon liquid sol and tetraethyl orthosilicate; The aluminum source is selected from at least one of an aluminum salt, active aluminum oxide, alkoxy aluminum and metakaolin; The alkali source is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate.

7. The application of claim 1, wherein The molar ratio of the coordination agent-protected copper nanocluster to the template agent is 0.1-5:1-50; The molar ratio of the coordination agent-protected copper nanocluster to the silicon source is 0.1-5:20-400; The molar ratio of the coordination agent-protected copper nanocluster to the aluminum source is 0.1-5:0.5-200; The molar ratio of the coordination agent-protected copper nanocluster to the alkali source is 0.1-5:0.02-50; The molar ratio of the coordination agent-protected copper nanoclusters to the water is 0.1-5:45-4000; The molar amount of the coordination agent-protected copper nanoclusters is calculated based on the molar amount of Cu; The molar amount of the template agent is calculated based on the molar amount of the template agent itself; The molar amount of the silicon source is calculated based on the molar amount of SiO2 in the silicon source; The molar amount of the aluminum source is calculated based on the molar amount of Al2O3 in the aluminum source; The molar amount of the alkali source is calculated based on the molar amount of the cation in the alkali source.

8. The use according to claim 1, wherein, The atmosphere of the calcination is an air atmosphere; The temperature of the calcination is 300-600℃; The time of the calcination is 0.2-72h.

Images