High entropy oxide molecular sieve interface coupling catalyst, preparation method and application

Abstract

The present invention discloses a method for preparing a high-entropy oxide molecular sieve interface coupling catalyst: 1. preparing a high-entropy metal oxide; 2. preparing an H-MCM-22 molecular sieve; 3. ball-milling the high-entropy metal oxide, the H-MCM-22 molecular sieve and zirconium oxide balls to obtain a mixed powder; 4. tableting, crushing and screening the mixed powder to obtain a high-entropy oxide molecular sieve interface coupling catalyst. The present invention also discloses a high-entropy oxide molecular sieve interface coupling catalyst prepared by the above method and its application. The method for preparing a high-entropy oxide molecular sieve interface coupling catalyst of the present invention is composed of a high-entropy oxide composed of multi-component metals and a molecular sieve with acidic structure regulation capability, which significantly improves the C8 in the CO2 hydrogenation reaction through interfacial synergy. + The catalyst has high selectivity of components; the catalyst synthesis process is simple, the catalytic activity is high, and the product distribution is adjustable, making it suitable for large-scale preparation of highly selective liquid fuels.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon dioxide resource utilization and synthetic fuel, relates to a method for preparing a high-entropy oxide molecular sieve interface coupling catalyst, and also relates to a high-entropy oxide molecular sieve interface coupling catalyst prepared by the above preparation method and its application. Background Art

[0002] With the continuous growth of global energy demand and the advancement of carbon neutrality goals, the resource utilization of carbon dioxide has become an important direction for green and low-carbon transformation. + The carbon chain length distribution of aviation fuel components is C8~C 16 Petroleum-based jet fuel mainly contains about 20% normal alkanes, 40% isoalkanes, 20% cycloalkanes and 20% aromatics. The total content of isoalkanes and cycloalkanes accounts for as much as 80%, while the main component of bio-based jet fuel is isoalkanes (about 90%).

[0003] The core difficulty of carbon dioxide hydrogenation to produce aviation kerosene is that the CO2 molecule is highly stable and requires high energy consumption to activate; the product needs to be precisely controlled to be C8~C 16 Traditional catalysts for hydrocarbons (containing 80% isomeric / cyclic components) are limited by their selectivity and stability. Existing iron- and copper-based catalysts still have significant deficiencies in catalytic performance, CC coupling ability, and product distribution control, making it difficult to meet the practical needs of efficient jet fuel production. Therefore, the development of new, efficient, and stable catalyst systems has become a key issue that needs to be addressed. Currently, oxide / zeolite bifunctional catalysts, represented by In2O3 / H-ZSM-5 developed by the Shanghai Advanced Research Institute of the Chinese Academy of Sciences, have made significant progress in the one-step synthesis of gasoline, light olefins, and light aromatics from CO2 hydrogenation, but conversion rates are low and further processing is required to obtain the ideal jet fuel components.

[0004] High-entropy oxides (HEOs) are novel oxide materials composed of five or more metal elements in nearly equimolar proportions. Due to the high entropy effect and the synergistic effect of multiple metals, HEOs possess abundant active sites and tunable electronic structures. They also effectively inhibit sintering and reduce carbon deposition at high temperatures, significantly improving their catalytic activity, selectivity, and stability. The molecular sieve MCM-22 has an MWW topology. Its two-dimensional pores, supercage confinement effect, and tunable acidity allow it to achieve the desired effect on intermediate carbon numbers (e.g., C8~C10) in reactions such as methanol conversion. 16The high selectivity of high entropy oxides with MCM-22 can effectively activate CO2 through the multi-metal synergistic effect, inhibit the sintering of active components and reduce carbon deposition, and selectively screen C8~C 16 The two technologies work together to not only achieve CO2 activation, chain growth, and structural regulation, but also significantly improve the selectivity and stability of the target product while reducing energy consumption, providing an efficient and sustainable technical path for decarbonization in the aviation industry. Summary of the Invention

[0005] The first purpose of the present invention is to provide a method for preparing a high entropy oxide molecular sieve interface coupling catalyst, which is composed of a high entropy oxide composed of multi-component metals and a molecular sieve with acidic structure control ability (such as MCM-22), and significantly improves the C8 + The catalyst prepared by the present invention has the advantages of simple synthesis process, high catalytic activity, adjustable product distribution, excellent stability, etc., and is suitable for large-scale preparation of highly selective liquid fuels, especially for the green synthesis of aviation fuels.

[0006] The second object of the present invention is to provide a high entropy oxide molecular sieve interface coupling catalyst prepared by the above preparation method.

[0007] The third object of the present invention is to provide an application of the above-mentioned high entropy oxide molecular sieve interfacial coupling catalyst.

[0008] The first technical solution adopted by the present invention is a method for preparing a high entropy oxide molecular sieve interfacial coupling catalyst, and the specific method is as follows:

[0009] Step 1, preparing high entropy metal oxide;

[0010] Step 2, preparing H-MCM-22 molecular sieve;

[0011] Step 3, respectively weighing a high entropy metal oxide and H-MCM-22 molecular sieve, and then placing the high entropy metal oxide, H-MCM-22 molecular sieve and zirconia balls in a ball mill for ball milling to obtain a mixed powder;

[0012] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0013] The present invention is also characterized in that:

[0014] The specific method of step 1 is as follows:

[0015] Step 1.1. Preparing a precursor solution: dissolving zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate, and chromium nitrate in a molar ratio of 0.35±M:0.30:0.20±M:0.10:0.05 in a mixed solution of anhydrous ethanol and deionized water in a ratio of 1:1, where m ranges from 0 to 0.1 and the total molar concentration of the metals in the solution does not exceed 0.05 mol / L. Stirring for 1 to 2 hours to obtain a precursor solution;

[0016] Step 1.2, chelation reaction: add citric acid to the precursor solution at a total molar ratio of citric acid to metal of 1.5:1, and stir magnetically at 60°C for 2 h to form a metal-citric acid complex;

[0017] Step 1.3, forming a wet sol: Place the metal-citrate complex in a 60°C water bath, slowly add aqueous ammonia to adjust the pH to 4-5, and continue stirring for 2-4 hours until the solution gradually becomes viscous to obtain a wet sol;

[0018] Step 1.4, drying and calcining: The wet sol is transferred to a vacuum drying oven for drying to obtain a dry gel, which is ground into a fine powder and then placed in a muffle furnace for a first high-temperature calcination. After naturally cooling to room temperature, the powder is ground again until uniform, and then a second high-temperature calcination is performed to obtain a high-entropy metal oxide.

[0019] The specific method of step 1.4 is:

[0020] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace, heated to 400°C at 2°C / min, kept warm for 2 h, cooled naturally to room temperature, and ground again until uniform. The temperature was then raised to 600°C at 5°C / min and kept warm for 4 h to obtain a high entropy metal oxide.

[0021] Step 2:

[0022] Step 2.1, preparing a synthetic sol: at room temperature, dissolve NaOH in deionized water, add sodium metaaluminate and silica sol in sequence, and continue stirring until a uniform white colloid is formed. Then, quantitatively inject hexamethyleneimine and continue stirring for 30 minutes to obtain a synthetic sol;

[0023] Step 2.2, hydrothermal crystallization: The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing solution was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0024] Step 2.3, protonation treatment: Take the above-mentioned Na-MCM-22 powder and mix it with ammonium nitrate solution, carry out ion exchange under constant temperature stirring at 80℃ for 2 hours, repeat the operation 2~3 times and then filter and separate, wash the filter cake with deionized water to pH 6.9~7.1, dry it at 100℃ for 12 hours, and then calcine it in air atmosphere at 520℃ for 4 hours to finally obtain the proton-type H-MCM-22 molecular sieve.

[0025] In step 2.1, the molar ratio of the raw materials among silica sol, sodium aluminate, hexamethyleneimine, deionized water and NaOH is 1: 0.03~0.01: 0.5: 40: 0.3.

[0026] In step 2.3, the solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution is 1 g:15 mL, and the concentration of ammonium nitrate solution is 1 mol / L.

[0027] In step 3, the mass ratio of the high entropy metal oxide to the H-MCM-22 molecular sieve is 0.2~5:1, the mass ratio of the total mass of the high entropy metal oxide and the H-MCM-22 molecular sieve to the zirconia ball is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5min~60min.

[0028] The second technical solution adopted by the present invention is that the high entropy oxide molecular sieve interfacial coupling catalyst is prepared by the above-mentioned preparation method, comprising a high entropy metal oxide and an H-MCM-22 molecular sieve, wherein the mass ratio of the high entropy metal oxide to the H-MCM-22 molecular sieve is 0.2 to 5:1;

[0029] The chemical formula of high entropy metal oxide is Zr 0.35±m Zn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value of m ranges from 0 to 0.1.

[0030] The third technical solution adopted by the present invention is the application of a high entropy oxide molecular sieve interfacial coupling catalyst, which is used for the hydrogenation of CO2 to produce aviation kerosene fractions, with a reaction temperature of 300-400°C, a reaction pressure of 3 MPa, and a mass space velocity of 1000-12000 mL·g cat -1 ·h -1 .

[0031] The present invention is also characterized in that:

[0032] The high entropy oxide molecular sieve interface coupling catalyst needs to be activated before use. The activation conditions are: under the protection of inert gas, constant temperature activation at a temperature range of 250℃~400℃ for 2h.

[0033] The beneficial effects of the present invention are:

[0034] (1) The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of the present invention covers three core processes, namely, the controllable synthesis of high entropy metal oxides, the regulation of molecular sieve topological structure and the coupling of two-phase interfaces. It has the advantages of strong universality of raw materials (adjustable precursor metal types), precise controllable process parameters (crystallization temperature ≤ 200°C), and clear product structure (phase purity > 99%). In particular, the high entropy oxide realizes uniform element distribution and controllable oxygen vacancy defect configuration molecular sieve through solvent thermal self-assembly, and obtains a 0.41 nm × 0.54 nm ten-membered ring cross-channel system through template regulation. The two can improve the reaction performance and selectivity of the catalyst through interface coupling.

[0035] (2) The high entropy oxide molecular sieve interface coupled catalyst of the present invention has excellent catalytic performance: in a fixed bed reactor (P = 3 MPa, T = 320 ° C, GHSV = 4000 h -1 ), the catalyst achieved a CO2 single-pass conversion rate of 25.3±0.8%, C8~C 16 Selectivity for linear alkanes reached 58.6-63.2% (quantitative analysis by GC-MS), and CH selectivity remained stable below 4.7%. Notably, the catalyst showed no carbon deposition (TPO carbon deposition <0.1 wt%) or sintering (SBET specific surface area decay <3%) during 1000 hours of continuous operation, demonstrating the durability necessary for industrial application.

[0036] (3) The high entropy oxide molecular sieve interface coupling catalyst of the present invention innovatively combines high entropy oxide and molecular sieve to achieve the dual functions of CO2 conversion and jet fuel component optimization. High entropy oxide effectively breaks the chemical inertness of CO2 molecules through its unique multi-metal synergistic effect. At the same time, its high entropy structure not only inhibits the sintering phenomenon of the catalyst, but also significantly reduces the formation of carbon deposits. On the other hand, the molecular sieve achieves the conversion of C8~C 16 The product is selectively screened and its acidic sites are used to promote isomerization reactions, thereby directly optimizing the jet fuel components. The innovation of this dual-functional catalytic system is that it simultaneously takes into account the activation of CO2, carbon chain growth, and precise regulation of product structure, significantly reducing energy consumption while greatly improving product selectivity and catalyst stability. DETAILED DESCRIPTION

[0037] The present invention is described in detail below with reference to specific embodiments.

[0038] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of the present invention is as follows:

[0039] Step 1: prepare high entropy metal oxide. The specific method is as follows:

[0040] Step 1.1. Preparing a precursor solution: dissolving zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate, and chromium nitrate in a molar ratio of 0.35±M:0.30:0.20±M:0.10:0.05 in a mixed solution of anhydrous ethanol and deionized water in a ratio of 1:1, where m ranges from 0 to 0.1 and the total molar concentration of the metals in the solution does not exceed 0.05 mol / L. Stirring for 1 to 2 hours to obtain a precursor solution;

[0041] Step 1.2, chelation reaction: add citric acid to the precursor solution at a total molar ratio of citric acid to metal of 1.5:1, and stir magnetically at 60°C for 2 h to form a metal-citric acid complex;

[0042] Step 1.3, forming a wet sol: Place the metal-citrate complex in a 60°C water bath, slowly add aqueous ammonia to adjust the pH to 4-5, and continue stirring for 2-4 hours until the solution gradually becomes viscous to obtain a wet sol;

[0043] Step 1.4, drying and calcining: The wet sol is transferred to a vacuum drying oven for drying to obtain a dry gel, which is ground into a fine powder and then placed in a muffle furnace for a first high-temperature calcination. After naturally cooling to room temperature, the powder is ground again until uniform, and then a second high-temperature calcination is performed to obtain a high-entropy metal oxide.

[0044] Specifically, the wet sol was transferred into a vacuum drying oven and dried at 80°C for 24 hours to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 hours to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 hours to promote the formation of a single phase of high entropy oxide, recorded as HEO, to obtain a high entropy metal oxide.

[0045] Step 2: Prepare H-MCM-22 molecular sieve. The specific method is as follows:

[0046] Step 2.1. Preparation of synthetic sol: At room temperature, dissolve NaOH in deionized water, add sodium metaaluminate and silica sol in sequence, and continue stirring until a uniform white colloid is formed. Then, quantitatively inject hexamethyleneimine and continue stirring for 30 min to obtain a synthetic sol.

[0047] The molar ratio of the raw materials of silica sol, sodium metaaluminate, hexamethyleneimine, deionized water and NaOH is 1:0.03~0.01:0.5:40:0.3, that is, the molar ratio of silicon to aluminum in the H-MCM-22 molecular sieve is 30~100.

[0048] Step 2.2, hydrothermal crystallization: The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0049] Step 2.3, protonation treatment: Take the above-mentioned Na-MCM-22 powder and mix it with ammonium nitrate solution, carry out ion exchange under constant temperature stirring at 80℃ for 2 hours, repeat the operation 2~3 times and then filter and separate, wash the filter cake with deionized water to pH 6.9~7.1, dry it at 100℃ for 12 hours, and then calcine it in air atmosphere at 520℃ for 4 hours to finally obtain the proton-type H-MCM-22 molecular sieve.

[0050] The solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution is 1 g:15 mL, and the concentration of ammonium nitrate solution is 1 mol / L.

[0051] Step 3, respectively weighing a high entropy metal oxide and H-MCM-22 molecular sieve, and then placing the high entropy metal oxide, H-MCM-22 molecular sieve and zirconia balls in a ball mill for ball milling to obtain a mixed powder;

[0052] Among them, the mass ratio of high entropy metal oxide to H-MCM-22 molecular sieve is 0.2~5:1, the mass ratio of the total mass of high entropy metal oxide and H-MCM-22 molecular sieve to zirconia ball is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5min~60min.

[0053] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0054] The high entropy oxide molecular sieve interface coupling catalyst of the present invention is prepared by the above-mentioned preparation method, comprising a high entropy metal oxide and an H-MCM-22 molecular sieve, wherein the mass ratio of the high entropy metal oxide to the H-MCM-22 molecular sieve is 0.2-5:1;

[0055] Furthermore, the chemical formula of high entropy metal oxide is Zr 0.35±mZn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value of m ranges from 0 to 0.1.

[0056] The high entropy oxide molecular sieve interfacial coupling catalyst prepared by the present invention is used for the preparation of aviation kerosene fraction by CO2 hydrogenation, with a reaction temperature of 300-400°C, a reaction pressure of 3 MPa, and a mass space velocity of 1000-12000 mL·g cat -1 ·h -1 .

[0057] Furthermore, the high entropy oxide molecular sieve interface coupling catalyst of the present invention needs to be activated before use, and the activation conditions are: constant temperature activation at a temperature range of 250°C to 400°C for 2 hours under the protection of inert gas.

[0058] Example 1

[0059] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0060] Step 1: Preparation of Zr 0.45 Zn 0.30 In 0.10 Mg 0.10 Cr 0.05 O x : 0.9660 g Zr(NO3)4·5H2O, 0.2841 g Zn(NO3)2·6 H2O, 0.2094 g In(NO3)3·5 H2O, 0.1282 g Mg(NO3)2·6 H2O, and 0.1001 g Cr(NO3)3·9 H2O were dissolved in a mixed solvent of 50 mL anhydrous ethanol and 50 mL deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution;

[0061] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 2 h to form a metal-citric acid complex. The precursor solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 2 h until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0062] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-1.

[0063] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 30. The specific method is as follows:

[0064] At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.68 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0065] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0066] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out at 80℃ under constant temperature stirring for 2 h. The operation was repeated 3 times and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (30) molecular sieve.

[0067] Step 3: Weigh 0.17 g of high entropy metal oxide HEO-1 and 0.85 g of H-MCM-22 (30) molecular sieve in a mass ratio of 1:5, and then place the high entropy metal oxide, H-MCM-22 (30) molecular sieve and zirconia balls in a ball mill for ball milling. The ball-to-material ratio (mass ratio) is 10:1, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min to obtain a mixed powder;

[0068] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0069] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to methanol. The activation conditions were: at a space velocity of 1000 mL·gcat -1 ·h -1 Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas, argon, was switched to the feed gas and introduced into the fixed-bed reactor. Catalytic evaluation was performed at a reaction temperature of 300°C and a pressure of 3 MPa. The reaction products were directly analyzed and detected online by chromatography. H₂, N₂, and CO₂ were detected by a TCD detector, and hydrocarbons and oxygenated compounds were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0070] Example 2

[0071] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0072] Step 1: Preparation of Zr 0.45 Zn 0.30 In 0.10 Mg 0.10 Cr 0.05 O x : 0.9660 g Zr(NO3)4·5H2O, 0.2841 g Zn(NO3)2·6 H2O, 0.2094 g In(NO3)3·5 H2O, 0.1282 g Mg(NO3)2·6 H2O, and 0.1001 g Cr(NO3)3·9 H2O were dissolved in a mixed solvent of 50 mL anhydrous ethanol and 50 mL deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution;

[0073] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 2 h to form a metal-citric acid complex. The solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 4 h until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0074] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-1.

[0075] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 50. The specific method is as follows:

[0076] At room temperature, 3.0 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0077] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0078] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out at 80℃ under constant temperature stirring for 2 h. The operation was repeated twice and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (50) molecular sieve.

[0079] Step 3, weighing 0.25g of high entropy metal oxide HEO-1 and 0.75g of H-MCM-22 (50) molecular sieve respectively according to the mass ratio of 1: 3, and then placing the high entropy metal oxide, H-MCM-22 (50) molecular sieve and zirconia balls in a ball mill for ball milling, with a ball-to-material ratio (mass ratio) of 10: 1, a ball milling speed of 600 rpm / min, and a ball milling time of 15min to obtain a mixed powder;

[0080] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0081] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to aviation kerosene. The activation conditions were: at a space velocity of 3600 mL·gcat -1 ·h -1Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas, argon, was switched to the feed gas and introduced into the fixed-bed reactor. The reaction temperature was adjusted to 320°C and the reaction pressure was adjusted to 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. H2, N2, and CO2 were detected by a TCD detector, and hydrocarbons and oxygenated compounds were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0082] Example 3

[0083] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0084] Step 1: Preparation of Zr 0.35 Zn 0.30 In 0.20 Mg 0.10 Cr 0.05 O x : 0.7513 g Zr(NO3)4·5H2O, 0.2841 g Zn(NO3)2·6 H2O, 0.4188 g In(NO3)3·5 H2O, 0.1282 g Mg(NO3)2·6 H2O, and 0.1001 g Cr(NO3)3·9 H2O were dissolved in a mixed solvent of 50 mL anhydrous ethanol and 50 mL deionized water, and stirred for 2 h until the solution became completely transparent to obtain a precursor solution;

[0085] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 1 h to form a metal-citric acid complex. The precursor solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 3 h until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0086] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-2.

[0087] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 50. The specific method is as follows:

[0088] At room temperature, 3.0 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0089] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0090] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out at 80℃ under constant temperature stirring for 2 h. The operation was repeated 3 times and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (50) molecular sieve.

[0091] Step 3, weigh 0.5 g of high entropy metal oxide HEO-2 and 0.5 g of H-MCM-22 (50) molecular sieve respectively according to the mass ratio of 1: 1, and then place the high entropy metal oxide, H-MCM-22 (50) molecular sieve and zirconia balls in a ball mill for ball milling, with a ball-to-material ratio (mass ratio) of 10: 1, a ball milling speed of 600 rpm / min, and a ball milling time of 30 min to obtain a mixed powder;

[0092] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0093] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to aviation kerosene. The activation conditions were: at a space velocity of 4000 mL gcat -1 h -1Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas, argon, was switched to the feed gas and introduced into the fixed-bed reactor. The reaction temperature was adjusted to 320°C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. H₂, N₂, and CO₂ were detected by a TCD detector, and hydrocarbons and oxygenated compounds were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0094] Example 4

[0095] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0096] Step 1: Preparation of Zr 0.35 Zn 0.30 In 0.20 Mg 0.10 Cr 0.05 O x : 0.7513 g Zr(NO3)4·5H2O, 0.2841 g Zn(NO3)2·6 H2O, 0.4188 g In(NO3)3·5 H2O, 0.1282 g Mg(NO3)2·6 H2O, and 0.1001 g Cr(NO3)3·9 H2O were dissolved in a mixed solvent of 50 mL anhydrous ethanol and 50 mL deionized water, and stirred for 2 h until the solution became completely transparent to obtain a precursor solution;

[0097] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 1 hour to form a metal-citric acid complex. The solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 2 hours until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0098] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-2.

[0099] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 100. The specific method is as follows:

[0100] At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.20 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0101] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0102] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out under constant temperature stirring at 80℃ for 3 h. The operation was repeated 3 times and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and then calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (100) molecular sieve.

[0103] Step 3, weigh 0.75g of high entropy metal oxide HEO-2 and 0.25g of H-MCM-22 (100) molecular sieve respectively according to the mass ratio of 3: 1, and then place the high entropy metal oxide, H-MCM-22 (100) molecular sieve and zirconia balls in a ball mill for ball milling, with a ball-to-material ratio (mass ratio) of 10: 1, a ball milling speed of 600 rpm / min, and a ball milling time of 60 min to obtain a mixed powder;

[0104] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0105] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to aviation kerosene. The activation conditions were: at a space velocity of 6000 mL·gcat -1 ·h -1Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas, argon, was switched to the feed gas and introduced into the fixed-bed reactor. The reaction temperature was adjusted to 340°C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography, with H2, N2, and CO2 detected by a TCD detector, and hydrocarbons and oxygenated compounds detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0106] Example 5

[0107] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0108] Step 1: Preparation of Zr 0.25 Zn 0.30 In 0.30 Mg 0.10 Cr 0.05 O x : 0.5367gZr(NO3)4·5H2O, 0.2841gZn(NO3)2·6 H2O, 0.6283gIn(NO3)3·5 H2O, 0.1282gMg(NO3)2·6 H2O, and 0.1001gCr(NO3)3·9H2O were dissolved in a mixed solvent of 50 mL of anhydrous ethanol and 50 mL of deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution;

[0109] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 2 h to form a metal-citric acid complex. The precursor solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 2 h until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0110] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-3.

[0111] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 100. The specific method is as follows:

[0112] At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.20 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0113] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0114] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out at 80℃ under constant temperature stirring for 2 h. The operation was repeated 3 times and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and then calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (100) molecular sieve.

[0115] Step 3, weigh 0.85g of high entropy metal oxide HEO-3 and 0.17g of H-MCM-22 (100) molecular sieve respectively according to the mass ratio of 5:1, and then place the high entropy metal oxide, H-MCM-22 (100) molecular sieve and zirconia balls in a ball mill for ball milling, with a ball-to-material ratio (mass ratio) of 10:1, a ball milling speed of 600 rpm / min, and a ball milling time of 15min to obtain a mixed powder;

[0116] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0117] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: at a space velocity of 10000 mL·gcat -1 ·h -1Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas, argon, was switched to the feed gas and introduced into the fixed-bed reactor. The reaction temperature was adjusted to 360°C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. H₂, N₂, and CO₂ were detected by a TCD detector, and hydrocarbons and oxygenated compounds were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0118] Example 6

[0119] The preparation method of the high entropy oxide molecular sieve interface coupling catalyst of this embodiment is as follows:

[0120] Step 1: Preparation of Zr 0.25 Zn 0.30 In 0.30 Mg 0.10 Cr 0.05 O x : 0.5367gZr(NO3)4·5H2O, 0.2841gZn(NO3)2·6 H2O, 0.6283gIn(NO3)3·5 H2O, 0.1282gMg(NO3)2·6 H2O, and 0.1001gCr(NO3)3·9H2O were dissolved in a mixed solvent of 50 mL of anhydrous ethanol and 50 mL of deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution;

[0121] 1.576 g of citric acid was added to the precursor solution at a molar ratio of citric acid to total metal of 1.5:1. The mixture was magnetically stirred at 60°C for 2 h to form a metal-citric acid complex. The solution was then placed in a 60°C water bath and ammonia was slowly added dropwise to adjust the pH to 4-5. Stirring was continued for 2 h until the solution gradually became viscous and formed a transparent or translucent sol, thereby obtaining a wet sol.

[0122] The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace and heated to 400°C at a rate of 2°C / min and kept warm for 2 h to remove organic matter and nitrate ions. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600°C at a rate of 5°C / min and kept warm for 4 h to promote the formation of a high-entropy oxide single phase, which was recorded as HEO-3.

[0123] Step 2: Prepare H-MCM-22 molecular sieve with a silicon-aluminum ratio of 50. The specific method is as follows:

[0124] At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) were added in sequence. Stirring was continued until a uniform white colloid was formed. Then, 12.65 g of hexamethyleneimine was added and stirring was continued for 30 min to obtain a synthetic sol.

[0125] The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined at 540°C in static air for 4 h to obtain Na-MCM-22 powder.

[0126] Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in the ratio of m(H-MCM-22): V(NH4NO3)=1 g:15 mL, and ion exchange was carried out at 80℃ under constant temperature stirring for 2 h. The operation was repeated 3 times and then filtered and separated. The filter cake was washed with deionized water to a pH of 6.9~7.1, dried at 100℃ for 12 h, and calcined in air atmosphere at 520℃ for 4 h to finally obtain proton-type H-MCM-22 (50) molecular sieve.

[0127] Step 3, weigh 0.75g of high entropy metal oxide HEO-3 and 0.25g of H-MCM-22 (50) molecular sieve respectively according to the mass ratio of 3:1, and then place the high entropy metal oxide, H-MCM-22 (50) molecular sieve and zirconia balls in a ball mill for ball milling, with a ball-to-material ratio (mass ratio) of 10:1, a ball milling speed of 600 rpm / min, and a ball milling time of 30min to obtain a mixed powder;

[0128] Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

[0129] The high entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed bed reactor to evaluate the catalytic reaction of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: at a space velocity of 12000 mL·gcat -1 ·h -1Under an argon atmosphere, the temperature was increased from room temperature to 320°C at a rate of 10°C / min for 2 hours. After activation, the activation gas was switched from argon to feed gas and introduced into the fixed-bed reactor. The reaction temperature was adjusted to 340°C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. H2, N2, and CO2 were detected by TCD, and hydrocarbons and oxygenated compounds were detected by FID. The catalytic evaluation results are shown in Table 1.

[0130] Table 1 Catalytic evaluation results of high entropy oxide molecular sieve interfacial coupling catalysts obtained in Examples 1 to 6

[0131]

[0132] As can be seen from Table 1, the new catalyst coupled with high entropy oxide and molecular sieve exhibits good catalytic performance in the carbon dioxide hydrogenation reaction, which is specifically manifested in the following aspects:

[0133] (1) High CO2 conversion rate: In all examples, the CO2 conversion rate ranged from 17.5% to 25.9%, with Example 5 (25.9%) and Example 3 (25.3%) performing the best, indicating that the catalyst had good activity;

[0134] (2) Moderate CO selectivity: The CO selectivity is between 43.3% and 55.7%, indicating that the catalyst has a certain selectivity regulation ability, which can inhibit side reactions to a certain extent and improve the selectivity of the target product;

[0135] (3) The distribution of hydrocarbon products tends to be medium- and long-chain hydrocarbons: As can be seen from the table, the selectivity of CH4 is relatively low (2.6%~4.7%), indicating that there are fewer methane by-products, reflecting good carbon chain growth ability; C2-C7 and C8-C 16 The proportion of C8-C 16 (heavy hydrocarbons) in Example 3 is as high as 64.5%, indicating that the catalyst has strong selectivity in the direction of aromatics, which is conducive to the production of high-value-added heavy aromatics.

[0136] In summary, the high-entropy oxide and molecular sieve (such as H-MCM-22) coupling catalyst achieves a high CO2 conversion rate and excellent hydrocarbon distribution by regulating the metal ratio, acidic sites and interface synergy, especially showing good potential in the synthesis of heavy alkanes or aromatics, and has high application prospects.

[0137] The present invention regulates the electronic structure and surface alkalinity of active sites by adjusting the ratio of metal elements in the high-entropy oxide; regulates the strength and distribution of acidic sites by adjusting the silicon-aluminum ratio of the H-MCM-22 molecular sieve, thereby regulating the product distribution; determines the degree of interfacial synergistic effect between the two phases by adjusting the mass ratio of the high-entropy oxide to the molecular sieve; and regulates the degree of coupling by adjusting the length of ball milling time, thereby further affecting the close contact between the high-entropy oxide and the molecular sieve in terms of spatial structure and the electron transfer synergistic effect.

[0138] The results show that a moderate degree of interfacial coupling can promote the effective conversion of intermediate species between HEO and ZEO, significantly improve the CC coupling efficiency, and thus be beneficial to the C8-C 12 The catalyst showed good activity, selectivity and stability in a fixed bed reactor (P = 3 MPa, T = 320 ° C, GHSV = 4000 h -1 ), the catalyst achieved a CO2 single-pass conversion rate of 25.3±0.8%, C8-C 16 Selectivity for linear alkanes reached 56.8-63.2% (quantitative analysis by GC-MS), and CH4 selectivity remained stable below 4.7%. Notably, the catalyst showed no carbon deposition (TPO carbon deposition <0.1 wt%) or sintering (SBET surface area decay <3%) during 1000 hours of continuous operation, demonstrating the durability necessary for industrial application and promising applications in CO2 resource utilization and green synthetic fuels.

Claims

1. A method for preparing a high entropy oxide molecular sieve interfacial coupling catalyst, characterized in that: The specific method is as follows: Step 1: prepare high entropy metal oxide; the chemical formula of the high entropy metal oxide is Zr 0.35± m Zn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value of m ranges from 0 to 0.1; Step 2, preparing H-MCM-22 molecular sieve; Step 3, respectively weighing a high entropy metal oxide and H-MCM-22 molecular sieve, and then placing the high entropy metal oxide, H-MCM-22 molecular sieve and zirconia balls in a ball mill for ball milling to obtain a mixed powder; Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interfacial coupling catalyst.

2. The method for preparing the high entropy oxide molecular sieve interface coupling catalyst according to claim 1, characterized in that: The specific method of step 1 is as follows: Step 1.

1. Preparing a precursor solution: dissolving zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate, and chromium nitrate in a molar ratio of 0.35±M:0.30:0.20±M:0.10:0.05 in a mixed solution of anhydrous ethanol and deionized water in a ratio of 1:1, where m ranges from 0 to 0.1 and the total molar concentration of the metals in the solution does not exceed 0.05 mol / L. Stirring for 1 to 2 hours to obtain a precursor solution; Step 1.2, chelation reaction: add citric acid to the precursor solution at a total molar ratio of citric acid to metal of 1.5:1, and stir magnetically at 60°C for 2 h to form a metal-citric acid complex; Step 1.3, forming a wet sol: Place the metal-citrate complex in a 60°C water bath, slowly add aqueous ammonia to adjust the pH to 4-5, and continue stirring for 2-4 hours until the solution gradually becomes viscous to obtain a wet sol; Step 1.4, drying and calcining: The wet sol is transferred to a vacuum drying oven for drying to obtain a dry gel, which is ground into a fine powder and then placed in a muffle furnace for a first high-temperature calcination. After naturally cooling to room temperature, the powder is ground again until uniform, and then a second high-temperature calcination is performed to obtain a high-entropy metal oxide.

3. The method for preparing the high entropy oxide molecular sieve interface coupling catalyst according to claim 2, characterized in that: The specific method of step 1.4 is: The wet sol was transferred to a vacuum drying oven and dried at 80°C for 24 h to obtain a dry gel. After grinding into fine powder, the powder was placed in a muffle furnace, heated to 400°C at 2°C / min, kept warm for 2 h, cooled naturally to room temperature, and ground again until uniform. The temperature was then raised to 600°C at 5°C / min and kept warm for 4 h to obtain a high entropy metal oxide.

4. The method for preparing the high entropy oxide molecular sieve interface coupling catalyst according to claim 1, characterized in that: The specific method of step 2 is as follows: Step 2.

1. Preparation of synthetic sol: At room temperature, dissolve NaOH in deionized water, add sodium metaaluminate and silica sol in sequence, and continue stirring until a uniform white colloid is formed. Then, quantitatively inject hexamethyleneimine and continue stirring for 30 min to obtain a synthetic sol. Step 2.2, hydrothermal crystallization: The synthesized sol was transferred to a polytetrafluoroethylene-lined autoclave and dynamically crystallized at 150°C for 72 h with a stirring rate of 300 rpm. After the crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The resulting crystallized product was separated and repeatedly washed with deionized water until the washing liquid was neutral. After forced air drying at 120°C for 12 h, the product was calcined in static air at 540°C for 4 h to obtain Na-MCM-22 powder. Step 2.3, protonation treatment: Take the above-mentioned Na-MCM-22 powder and mix it with ammonium nitrate solution, carry out ion exchange under constant temperature stirring at 80℃ for 2 hours, repeat the operation 2~3 times and then filter and separate, wash the filter cake with deionized water to pH 6.9~7.1, dry it at 100℃ for 12 hours, and then calcine it in air atmosphere at 520℃ for 4 hours to finally obtain the proton-type H-MCM-22 molecular sieve.

5. The method for preparing the high entropy oxide molecular sieve interface coupling catalyst according to claim 4, characterized in that: In the step 2.1, the molar ratio of the raw materials among the silica sol, sodium aluminate, hexamethyleneimine, deionized water and NaOH is 1:0.03~0.01:0.5:40:0.

3.

6. The method for preparing the high entropy oxide molecular sieve interfacial coupling catalyst according to claim 4, characterized in that: The solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution in step 2.3 is 1 g:15 mL, and the concentration of the ammonium nitrate solution is 1 mol / L.

7. The method for preparing the high entropy oxide molecular sieve interfacial coupling catalyst according to claim 1, characterized in that: In step 3, the mass ratio of the high entropy metal oxide to the H-MCM-22 molecular sieve is 0.2 to 5: 1, the mass ratio of the total mass of the high entropy metal oxide and the H-MCM-22 molecular sieve to the zirconia ball is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min to 60 min.

8. High entropy oxide molecular sieve interface coupling catalyst, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7, comprising a high entropy metal oxide and an H-MCM-22 molecular sieve, wherein the mass ratio of the high entropy metal oxide to the H-MCM-22 molecular sieve is 0.2 to 5:

1.

9. The use of the high entropy oxide molecular sieve interfacial coupling catalyst according to claim 8, characterized in that: The high entropy oxide molecular sieve interfacial coupling catalyst is used for CO2 hydrogenation to produce aviation kerosene fractions, with a reaction temperature of 300-400°C, a reaction pressure of 3 MPa, and a mass space velocity of 1000-12000 mL·g cat -1 ·h -1 .

10. The use of the high entropy oxide molecular sieve interfacial coupling catalyst according to claim 9, characterized in that: The high entropy oxide molecular sieve interface coupling catalyst needs to be activated before use, and the activation conditions are: constant temperature activation at a temperature range of 250°C to 400°C for 2 hours under inert gas protection.

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