Chiral-metal defect coupling catalyst, preparation method and application thereof, and preparation method of fuel

Abstract

The invention relates to the technical field of catalysts, in particular to a chiral-metal defect coupling catalyst, a preparation method and application thereof and a preparation method of fuel. The chiral structure and the metal defect structure are coupled and synergistically constructed in the same metal oxide catalyst, so that the chiral-metal defect coupled catalyst has the advantages of the chiral structure and the metal defect structure, and shows excellent catalytic performance in photocatalytic reaction. Wherein the metal defect structure can regulate and control the energy band structure of the metal oxide, improve the visible light absorption capacity, promote the electron-hole separation efficiency and improve the spin photocatalytic reaction activity. A chiral spinning structure can generate a CISS effect, electron-hole recombination is further inhibited, the service life of a carrier is prolonged, a spinning triplet-state reaction intermediate is formed through a spinning filtering effect in a photocatalytic synthesis fuel reaction so as to improve the reaction rate, the fuel substrate conversion rate and the fuel selectivity, and the chiral spinning structure is especially suitable for photocatalytic synthesis of high-density fuel and has a wide application prospect. And the prepared fuel meets the requirements of aerospace.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a chiral-metal defect coupling catalyst, a preparation method and application thereof, and a fuel preparation method. BACKGROUND

[0002] With the rapid development of aerospace industry, the requirements for chemical propellants are continuously improved, therefore, researching high-density and high-calorific-value high-density fuels has become a key direction for promoting the aerospace industry. Photochemistry as a mild, efficient and environmentally friendly chemical method plays an important role in the field of green chemistry. At present, photochemical synthesis of high-density fuels has attracted widespread attention. For example, Zn / La-doped TiO2 as a photocatalyst can catalyze the cycloaddition reaction of norbornadiene to generate tetracycloheptane under light; Rh(CO)4Cl2 as a photocatalyst can catalyze the isomerization reaction of dicyclopentadiene and its substitutes to generate pentacyclo[5.3.0.0 2,6 .0 3,9 .0 5,8 ] decane under light. However, in the process of catalytic synthesis of high-density fuels by the current photocatalysts, the conversion rate of fuel substrates and the selectivity of fuel products are low, and the catalytic effect is poor, which cannot meet the needs of aerospace vehicles. SUMMARY

[0003] In view of this, the present application aims to provide a chiral-metal defect coupling catalyst, a preparation method and application thereof, and a fuel preparation method. The chiral-metal defect coupling catalyst provided by the present application has excellent catalytic effect on the catalytic synthesis of high-density fuels from fuel substrates, high reaction rate, high conversion rate of fuel substrates, high selectivity and high yield of fuel products, and can meet the needs of aerospace.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides a chiral-metal defect coupling catalyst, characterized in that it comprises a metal oxide with chiral structure and metal defect structure.

[0005] Preferably, the metal oxide comprises TiO2 and / or ZnO.

[0006] The present application also provides a preparation method of the chiral-metal defect coupling catalyst according to the above-mentioned technical solutions, comprising the following steps: mixing an inducing agent, a metal source and a solvent, carrying out a solvothermal reaction, and then calcining to obtain the chiral-metal defect coupling catalyst; the inducing agent comprises a multi-hydroxyl chiral inducing agent, or a mixture of a multi-hydroxyl inducing agent and a chiral inducing agent.

[0007] Preferably, the metal source comprises a titanium source and / or a zinc source. The polyhydroxyl chiral inducer includes a first saccharide and / or a first polyol; The first saccharide includes glucose and / or fructose; The first polyol includes at least one of L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R) 1,2,3,4-butanetetrol, (S) 1,2,3,4-butanetetrol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, 1,2-propanediol, and 1,2-butanediol; The mass ratio of the metal source and the polyhydroxyl chiral inducer is 1:0.03-10; The chiral inducer includes an amino acid, a hydroxyl acid, a second saccharide, and a second polyol; The amino acid includes at least one of L-alanine, D-alanine, L-serine, D-serine, L-valine, D-valine, L-leucine, D-leucine, L-tyrosine, and L-cysteine; The hydroxyl acid includes at least one of L-lactic acid, D-lactic acid, L-tartaric acid, and D-tartaric acid; The second saccharide includes glucose and / or fructose; The second polyol includes at least one of L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R) 1,2,3,4-butanetetrol, (S) 1,2,3,4-butanetetrol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, 1,2-propanediol, and 1,2-butanediol; The mass ratio of the metal source and the chiral inducer is 1:0.03-12; The polyhydroxyl inducer includes a third polyol, and the third polyol includes at least one of glycerol, propylene glycol, 1,3-propanediol, ethylene glycol, 1,2-butanediol, and 1,4-butanediol; The solid-liquid ratio of the metal source and the polyhydroxyl inducer is 1 g:0.5-80 mL; The solvent includes a lower alcohol and / or water; and the lower alcohol includes at least one of methanol, ethanol, propanol, isopropanol, and ethylene glycol; The temperature of the solvothermal reaction is 60-300°C, and the time is 1-50 h; The temperature of the calcination is 200-700°C, and the time is 1-30 h.

[0008] The application further provides application of the chiral-metal defect coupled catalyst in preparation of fuel.

[0009] Preferably, the fuel comprises high-density fuel.

[0010] Preferably, the fuel comprises polycyclic aerospace fuel.

[0011] Preferably, the polycyclic aerospace fuel comprises at least one of 2,2,4b,6,6,8b-hexamethyltetracyclo[4.4.0.0 2,5 .0 3 ,4 ]dodecane, 2,2,7,7,8a,8b-hexamethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane, 2,8b-dimethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane, pentacyclo[8.2.1.1 4,7 .0 2,9 .08 ,3 ]tetradecane, pentacyclo[5.3.0.0 2,6 .0 3,9 .0 5,8 ]decane, 2,8b-dimethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane and tetracycloheptane.

[0012] The application further provides a preparation method of fuel, when a fuel substrate is a mixture of ketone and olefin, the preparation method comprises the following steps: mixing the fuel substrate, a catalyst and an organic solvent, and performing a cycloaddition reaction under light conditions to obtain a fuel precursor; performing a hydrodeoxygenation reaction on the fuel precursor to obtain fuel. When the fuel substrate is an olefin, the preparation method comprises the following steps: mixing the fuel substrate, a catalyst and an organic solvent, and performing a cycloaddition reaction under light conditions to obtain fuel. The catalyst is the chiral-metal defect coupled catalyst in the above technical solution or the chiral-metal defect coupled catalyst prepared by the preparation method in the above technical solution.

[0013] Preferably, the olefin comprises at least one of dicyclopentadiene, alpha-pinene, cyclohexene, norbornene and norbornadiene. The ketone comprises at least one of isophorone and cyclohexenone.

[0014] The mass of the catalyst is 1-20% of the mass of the fuel substrate. The organic solvent includes at least one of halogenated hydrocarbon, nitrile solvent, lower alcohol, furan solvent and alkane solvent. The temperature of the cycloaddition reaction is -10-70 DEG C, and the time is 1-48h.

[0015] Compared with metal defect catalysts and chiral catalysts, the chiral-metal defect coupling catalysts of the application have the advantages of both, and exhibit excellent catalytic performance in photocatalytic reactions. The metal defect structure can adjust the energy band structure of the metal oxide (TiO2 and / or ZnO), improve the visible light absorption capacity, promote the electron-hole separation efficiency, and improve the spin photocatalytic reaction activity. The chiral spin structure can produce CISS effect, further inhibit electron-hole recombination, prolong the carrier lifetime, and form spin triplet intermediates in the photocatalytic synthesis of fuel reaction through spin filtering effect to improve the reaction rate, fuel substrate conversion rate, fuel selectivity and total yield (up to 97%). The chiral-metal defect catalysts provided by the application have the advantages of mild conditions and high efficiency and specificity in the photocatalytic synthesis of fuel substrates, and exhibit excellent catalytic performance in the catalytic synthesis of high-density fuels. The synthesized fuel meets the conditions of high-density fuel and meets the needs of aerospace, and has high industrial application value.

[0016] The preparation method of the chiral-metal defect coupling catalyst provided by the application is simple in process and easy to operate, the raw materials are widely available and low in cost, and is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 Circular dichroism spectra of catalysts prepared for Example 2 (denoted as L-TiO2), Example 5 (denoted as D-TiO2) and Comparative Example 3 (denoted as DL-TiO2); Figure 2 EPR graph of the chiral-metal defect coupling TiO2 catalyst prepared for Example 2. DETAILED DESCRIPTION

[0018] The application provides a chiral-metal defect coupling catalyst, which comprises a metal oxide with chiral structure and metal defect structure.

[0019] The chiral-metal defect coupling catalyst has excellent photocatalytic performance, and is especially suitable for photocatalytic reaction to synthesize fuel, catalyzes fuel substrates to synthesize high-density fuel, has high selectivity of fuel products, and has a total yield of up to 97%, and has excellent catalytic performance in catalyzing synthesis of high-density fuel, and can meet the needs of aerospace.

[0020] The application further provides a preparation method of the chiral-metal defect coupling catalyst.

[0021] Unless otherwise specified, the materials and equipment used in the application are commercially available in the art.

[0022] In the application, the metal source can include a titanium source and / or a zinc source; the titanium source can include a titanium salt and / or an organic titanium, and can specifically include at least one of titanium oxalate, titanium chloride, titanium acetate, titanium nitrate, titanium sulfate and tetrabutyl titanate; and the zinc source can include a zinc salt, and can specifically include at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc carbonate.

[0023] In the application, the multi-hydroxyl chiral inducer can include a first saccharide substance and / or a first polyhydric alcohol. In the application, the first saccharide substance can include glucose and / or fructose. In the application, the first polyhydric alcohol can include at least one of L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R) 1,2,3,4-butanetetrol, (S) 1,2,3,4-butanetetrol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, 1,2-propanediol and 1,2-butanediol. In the application, the mass ratio of the metal source and the multi-hydroxyl chiral inducer can be 1:0.03-10, and can also be 1:0.3-5, and can specifically be 1:0.03, 1:0.1, 1:0.375, 1:0.46, 1:0.5, 1:0.75, 1:0.92, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0024] In the present application, the chiral inducer can include an amino acid, a hydroxy acid, a second saccharide, and a second polyol. In the present application, the amino acid can include at least one of L-alanine, D-alanine, L-serine, D-serine, L-valine, D-valine, L-leucine, D-leucine, L-tyrosine, and L-cysteine. In the present application, the hydroxy acid can include at least one of L-lactic acid, D-lactic acid, L-tartaric acid, and D-tartaric acid. In the present application, the second saccharide can include glucose and / or fructose. In the present application, the second polyol can include at least one of L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R) 1,2,3,4-butanetetrol, (S) 1,2,3,4-butanetetrol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, D-arabitol, L-threitol, D-threitol, D-galactitol, L-fucitol, 1,2-propanediol, and 1,2-butanediol. In the present application, the mass ratio of the metal source and the chiral inducer can be 1:0.03~12, and can be 1:0.3~5, and can be specifically 1:0.03, 1:0.1, 1:0.375, 1:0.46, 1:0.5, 1:0.75, 1:0.92, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, or 1:12.

[0025] In the present application, the polyhydroxy inducer can include a third polyol including at least one of glycerol, propylene glycol, 1,3-propanediol, ethylene glycol, 1,2-butanediol, and 1,4-butanediol. In the present application, the solid-liquid ratio of the metal source and the polyhydroxy inducer can be 1g:0.5~80mL, and can be 1g:10~40mL, and can be specifically 1g:0.5mL, 1g:1mL, 1g:5mL, 1g:10mL, 1g:12.5mL, 1g:15mL, 1g:15.3mL, 1g:20mL, 1g:25mL, 1g:30mL, 1g:30.6mL, 1g:40mL, 1g:50mL, 1g:60mL, 1g:70mL, or 1g:80mL.

[0026] In this invention, the solvent may include lower alcohols and / or water; the lower alcohols may include at least one of methanol, ethanol, propanol, isopropanol and ethylene glycol. In this invention, the solid-liquid ratio of the metal source and the solvent can be 1g:0.1~200mL, or 1g:50~120mL, specifically 1g:0.1mL, 1g:5mL, 1g:10mL, 1g:20mL, 1g:30mL, 1g:40mL, 1g:50mL, 1g:60mL, 1g:70mL, 1g:75mL, 1g:80mL, 1g:90mL, 1g:92mL, 1g:100mL, 1g:110mL, 1g:120mL, 1g:130mL, 1g:140mL, 1g:150mL, 1g:160mL, 1g:170mL, 1g:180mL, 1g:190mL, or 1g:200mL.

[0027] In this invention, the mixing may involve mixing the inducer and the solvent, and then mixing the solvent with the inducer.

[0028] In this invention, the temperature of the solvothermal reaction can be 60~300℃, or 150~250℃, specifically 60℃, 80℃, 100℃, 120℃, 150℃, 180℃, 200℃, 220℃, 240℃, 250℃, 280℃, or 300℃; the time of the solvothermal reaction can be 1~50h, or 20~30h, specifically 1h, 4h, 6h, 10h, 12h, 15h, 18h, 20h, 22h, 24h, 28h, 30h, 32h, 34h, 36h, 40h, 42h, 45h, or 50h; the solvothermal reaction can be carried out in a polytetrafluoroethylene-lined solvothermal reactor.

[0029] After the solvothermal reaction is completed, the present application can further comprise: cooling the reaction liquid obtained by the solvothermal reaction to room temperature, solid-liquid separation, washing and centrifuging the obtained solid with water and ethanol respectively, drying, grinding, to obtain a solvothermal reaction product (catalyst precursor, chiral polyhydroxy metal). The present application does not have special limitations for the solid-liquid separation, and any solid-liquid separation method known to those skilled in the art can be used, such as filtration, suction filtration or centrifugal separation. In the present application, the number of washing can be 2-10 times, which can be specifically 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times. In the present application, the drying temperature can be 50-90℃, which can be specifically 50℃, 60℃, 70℃, 80℃ or 90℃; the drying time can be 5-24h, which can be specifically 5h, 8h, 10h, 12h, 15h, 20h, 22h or 24h. In the present application, the particle size of the solvothermal reaction product can be ≤20μm, and can also be 0.1-20μm, and can further be 5-10μm.

[0030] In the present application, the calcination temperature can be 200-700℃, and can also be 400-500℃, which can be specifically 200℃, 250℃, 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃ or 700℃; the calcination time can be 1-30h, and can also be 4-10h, which can be specifically 1h, 3h, 4h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, 24h, 25h, 28h or 30h; the calcination atmosphere is air; the calcination can be carried out in a muffle furnace.

[0031] After the calcination is completed, the present application can further comprise: cooling the calcination product obtained by the calcination to room temperature to obtain a chiral-metal defect coupled catalyst. The present application does not have special limitations for the cooling, and any cooling method known to those skilled in the art can be used, such as natural cooling.

[0032] The present application also provides the use of the chiral-metal defect coupled catalyst described in the above technical solution or the chiral-metal defect coupled catalyst prepared by the preparation method described in the above technical solution in the preparation of fuel. In the present application, the chiral-metal defect coupled catalyst can be used for photochemical synthesis of fuel.

[0033] In the present application, the fuel can comprise high-density fuel, and the high-density fuel can comprise polycyclic aerospace fuel; the polycyclic aerospace fuel can comprise 2,2,4b,6,6,8b-hexamethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane, 2,2,7,7,8a,8b-hexamethyltetracyclo[4.4.0.02,5 .0 3,4 ]dodecane, 2,8b-dimethyltetracyclo[4.4.0.0 2 ,5 .0 3,4 ]dodecane, pentacyclo[8.2.1.1 4,7 .0 2,9 .08 ,3 ]tetradecane, pentacyclo[5.3.0.0 2,6 .0 3,9 .0 5,8 ]decane, 2,8b-dimethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane and tetracycloheptane.

[0034] The application also provides a preparation method of a fuel, when a fuel substrate is a mixture of a ketone and an olefin, the preparation method comprising the following steps: mixing the fuel substrate, a catalyst and an organic solvent to perform a cycloaddition reaction under light to obtain a fuel precursor; the catalyst is the chiral-metal defect coupled catalyst in the above technical solution or the chiral-metal defect coupled catalyst prepared by the preparation method in the above technical solution; performing a hydrodeoxygenation reaction on the fuel precursor to obtain the fuel.

[0035] The application mixes the fuel substrate, a catalyst and an organic solvent to perform a cycloaddition reaction under light to obtain a fuel precursor; the catalyst is the chiral-metal defect coupled catalyst in the above technical solution or the chiral-metal defect coupled catalyst prepared by the preparation method in the above technical solution.

[0036] In the application, the olefin can include at least one of dicyclopentadiene, alpha-pinene, cyclohexene, norbornene and norbornadiene. In the application, the ketone can include at least one of isophorone and cyclohexenone. In the application, the fuel substrate can include a mixture of alpha-pinene and cyclohexenone, or a mixture of alpha-pinene and isophorone. In the application, the molar ratio of the olefin and the ketone can be 1:0.1-10, and can also be 1:1-3, and can be specifically 1:0.1, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0037] In the application, the mass of the catalyst can be 1-20% of the mass of the fuel substrate, and can also be 3-10%, and can be specifically 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.

[0038] In the present application, the organic solvent can include at least one of halogenated hydrocarbon, nitrile solvent, lower alcohol, furan solvent and alkane solvent, and can specifically include at least one of dichloromethane, acetonitrile, methanol, ethanol, tetrahydrofuran, n-pentane and cyclohexane. The present application does not have special limitation on the amount of the organic solvent, and can ensure that the cycloaddition reaction proceeds smoothly.

[0039] In the present application, the wavelength of the light can be ultraviolet light or full waveband light, and the wavelength of the ultraviolet light can be 365 nm. The light can be irradiated by an LED light strip, and can specifically be irradiated by an LED light strip with a wavelength of 365 nm or an LED light strip with a full waveband spectrum.

[0040] In the present application, the temperature of the cycloaddition reaction can be -10-70℃, and can also be 20-70℃, and can specifically be -10℃, 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃ or 70℃. The time of the cycloaddition reaction can be 1-48h, and can also be 10-20h, and can specifically be 1h, 3h, 6h, 10h, 12h, 15h, 18h, 20h, 24h, 28h, 30h, 32h, 36h, 40h, 42h or 48h.

[0041] After the cycloaddition reaction is completed, the present application can further include: removing the solvent from the reaction system obtained by the cycloaddition reaction by rotary evaporation to obtain a fuel precursor. The present application does not have special limitation on the conditions for removing the solvent by rotary evaporation, and can remove all the solvent.

[0042] After the fuel precursor is obtained, the present application performs a hydrodeoxygenation reaction on the fuel precursor to obtain a fuel.

[0043] In the present application, the hydrodeoxygenation reaction can include: mixing the fuel precursor, a hydrogenation catalyst and an organic solvent, introducing a protective atmosphere, introducing hydrogen, and performing a hydrodeoxygenation reaction.

[0044] In the present application, the hydrogenation catalyst can include a palladium catalyst and a molecular sieve. In the present application, the palladium catalyst can include at least one of Pd / C, Pd / Al2O3 and Pd / Si. In the present application, the molecular sieve can include at least one of H-Y molecular sieve, H-β molecular sieve and ZSM-5 molecular sieve. In the present application, the mass ratio of the palladium catalyst to the molecular sieve can be 1:5-20, and can also be 1:8-15, and can specifically be 1:5, 1:8, 1:10, 1:12, 1:15, 1:18 or 1:20.

[0045] In the present application, the mass ratio of the fuel precursor and the palladium catalyst can be 1:0.001-0.02, and can also be 1:0.002-0.01, and can be specifically 1:0.001, 1:0.002, 1:0.003, 1:0.005, 1:0.008, 1:0.01, 1:0.012, 1:0.015, 1:0.018 or 1:0.02.

[0046] In the present application, the mass ratio of the fuel precursor and the molecular sieve can be 1:0.005-0.4, and can also be 1:0.01-0.2, and can be specifically 1:0.005, 1:0.01, 1:0.05, 1:0.02, 1:0.025, 1:0.03, 1:0.035 or 1:0.04.

[0047] In the present application, the organic solvent can include at least one of an alkane solvent and an ester solvent, and can specifically include at least one of cyclohexane, n-hexane, n-heptane and ethyl acetate. The present application does not have special limitation on the amount of the organic solvent, and can ensure that the hydrodeoxygenation reaction can be carried out smoothly.

[0048] In the present application, the introduction time of the protective atmosphere can be 10-60 min, and can also be 20-50 min, and can be further 30-40 min. In the present application, the protective atmosphere can include nitrogen, argon or helium.

[0049] In the present application, the number of times of introducing the hydrogen can be 3-5 times, and can be specifically 3 times, 4 times or 5 times, and the pressure of the hydrogen introduced at a time can be 0.5-3 MPa, and can also be 1-2 MPa, and can be specifically 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa or 3 MPa.

[0050] In the present application, the temperature of the hydrodeoxygenation reaction can be 120-160℃, and can also be 130-140℃, and can be specifically 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃ or 160℃; and the time of the hydrodeoxygenation reaction can be 12-36 h, and can also be 20-30 h, and can be specifically 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, 32 h, 34 h or 36 h.

[0051] After the hydrodeoxygenation reaction is completed, the present application can further include: sequentially subjecting the reaction liquid obtained by the hydrodeoxygenation reaction to vacuum distillation to obtain a fuel. In the present application, the temperature of the vacuum distillation can be 50-200℃, and the pressure can be -0.01--0.07 MPa.

[0052] When the fuel substrate is an olefin, the method for preparing the fuel comprises the following steps: mixing the fuel substrate, the catalyst and the organic solvent, and performing a cycloaddition reaction under light conditions to obtain the fuel; the catalyst is the chiral-metal defect coupled catalyst described in the above technical solution or the chiral-metal defect coupled catalyst prepared by the preparation method described in the above technical solution. After the cycloaddition reaction is completed, the present application can further comprise: sequentially performing rotary evaporation to remove the solvent and vacuum distillation on the reaction system obtained by the cycloaddition reaction to obtain the fuel. In the present application, the temperature of the vacuum distillation can be 50-200 DEG C, and the pressure can be-0.01--0.07 MPa. In the present application, when the fuel substrate is an olefin, the other preparation conditions of the fuel are the same as the preparation conditions of the fuel precursor, which will not be described one by one here.

[0053] In order to further illustrate the present application, the chiral-metal defect coupled catalyst, the preparation method and application thereof, and the method for preparing the fuel provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the protection scope of the present application.

[0054] Example 1 Preparation of the chiral-metal defect coupled TiO2 catalyst: 10 mL of glycerol and 0.3 g of L-tartaric acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoroethylene-lined autoclave, and reacted at 180 DEG C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water and ethanol and centrifuged 6 times, dried at 60 DEG C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace and calcined at 450 DEG C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain the chiral-metal defect coupled TiO2 catalyst.

[0055] Example 2 Preparation of the chiral-metal defect coupled TiO2 catalyst: 20 mL of glycerol and 0.6 g of L-tartaric acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoroethylene-lined autoclave, and reacted at 180 DEG C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water and ethanol and centrifuged 6 times, dried at 60 DEG C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace and calcined at 450 DEG C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain the chiral-metal defect coupled TiO2 catalyst.

[0056] Example 3 Preparation of chiral-metal defect coupled TiO2catalyst: 20 mL of glycerol and 0.6 g of L-malic acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0057] Example 4 Preparation of chiral-metal defect coupled TiO2catalyst: 20 mL of glycerol and 0.6 g of L-malic acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0058] Example 5 Preparation of chiral-metal defect coupled TiO2catalyst: 20 mL of glycerol and 0.6 g of L-malic acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0059] Example 6 Preparation of chiral-metal defect coupled TiO2catalyst: 1.093 g of D-sorbitol was added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, after which the mixed solution was moved into a polytetrafluoro-lined autoclave and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0060] Example 7 Preparation of chiral-metal defect coupled TiO2catalyst: 1.093 g of D-sorbitol was added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, after which the mixed solution was moved into a polytetrafluoro-lined autoclave and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0061] Example 8 Preparation of chiral-metal defect coupled ZnO catalyst: 10 mL of glycerol and 0.3 g of L-tartaric acid were added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, after which the mixed solution was moved into a polytetrafluoro-lined autoclave and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0062] Example 9 Preparation of chiral-metal defect coupled ZnO catalyst: 20 mL of glycerol and 0.6 g of L-tartaric acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0063] Example 10 Preparation of chiral-metal defect coupled ZnO catalyst: 20 mL of glycerol and 0.6 g of L-tartaric acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0064] Example 11 Preparation of chiral-metal defect coupled ZnO catalyst: 20 mL of glycerol and 0.6 g of L-tartaric acid were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0065] Example 12 Preparation of chiral-metal defect coupled ZnO catalyst: 1.093 g of D-sorbitol was added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0066] Example 13 Preparation of chiral-metal defect coupled ZnO catalyst: 1.093 g of D-sorbitol was added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled ZnO catalyst.

[0067] Example 14 Preparation of chiral-metal defect coupled TiO2catalyst: 10 mL of propylene glycol and 0.243 g of L-cysteine were added to 60 mL of absolute ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoro-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, and naturally cooled to room temperature to obtain a chiral-metal defect coupled TiO2catalyst.

[0068] Example 15 Preparation of chiral-metal defect coupled TiO2catalyst: 0.365 g D-galactitol was added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoroethylene-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, naturally cooled to room temperature, and a chiral-metal defect coupled ZnO catalyst was obtained.

[0069] Example 16 Preparation of chiral-metal defect coupled ZnO catalyst: 10 mL of glycerol and 0.263 g of L-leucine were added to 60 mL of anhydrous ethanol, stirred until completely dissolved, then 0.8 mL of tetrabutyl titanate was added and stirred until clear, the mixed solution was moved into a polytetrafluoroethylene-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 450°C for 6 h in an air atmosphere, naturally cooled to room temperature, and a chiral-metal defect coupled TiO2catalyst was obtained.

[0070] Example 17 Preparation of chiral-metal defect coupled ZnO catalyst: 0.997 g of D-fucitol was added to 60 mL of deionized water, stirred until completely dissolved, then 0.654 g of zinc acetate was added and stirred until clear, the mixed solution was moved into a polytetrafluoroethylene-lined autoclave, and reacted at 180°C for 24 h, cooled to room temperature, centrifuged, the obtained solid was washed with deionized water, ethanol, and centrifuged 6 times, dried at 60°C for 12 h, put into a mortar and ground to a particle size of 0.1-20 μm, then the solvothermal reaction product was placed in a muffle furnace, calcined at 400°C for 6 h in an air atmosphere, naturally cooled to room temperature, and a chiral-metal defect coupled ZnO catalyst was obtained.

[0071] Comparative Example 1 Preparation of n-type TiO2catalyst: the difference from the preparation method of the chiral-metal defect coupled TiO2in Example 1 is only that no glycerol and L-tartaric acid are added.

[0072] Comparative Example 2 Preparation of p-type TiO2catalyst: the difference from the preparation method of the chiral-metal defect coupled TiO2in Example 1 is only that no L-tartaric acid is added.

[0073] Comparative Example 3 Preparation of TiO2 catalyst: the difference between the preparation method of the chiral-metal defect coupled TiO2 in Example 2 is that L-tartaric acid is replaced by DL-tartaric acid.

[0074] Comparative Example 4 Preparation of chiral n-type TiO2 catalyst: the difference between the preparation method of the chiral-metal defect coupled TiO2 in Example 1 is that no glycerol is added.

[0075] Comparative Example 5 Preparation of n-type ZnO catalyst: the difference between the preparation method of the chiral-metal defect coupled ZnO in Example 8 is that no glycerol and L-tartaric acid are added.

[0076] Comparative Example 6 Preparation of p-type ZnO catalyst: the difference between the preparation method of the chiral-metal defect coupled ZnO in Example 8 is that no L-tartaric acid is added.

[0077] Comparative Example 7 Preparation of ZnO catalyst: the difference between the preparation method of the chiral-metal defect coupled ZnO in Example 8 is that L-tartaric acid is replaced by DL-tartaric acid.

[0078] Comparative Example 8 Preparation of chiral n-type ZnO catalyst: the difference between the preparation method of the chiral-metal defect coupled ZnO in Example 8 is that no glycerol is added.

[0079] Figure 1 The circular dichroism spectrum of the catalyst prepared for Example 2 (denoted as L-TiO2), Example 5 (denoted as D-TiO2) and Comparative Example 3 (denoted as DL-TiO2) shows that the chiral-metal defect coupled TiO2 catalyst has a good mirror image relationship of chirality and strong chiral optical activity.

[0080] Figure 2 The EPR graph of the chiral-metal defect coupled TiO2 catalyst prepared for Example 2 shows that the chiral-metal defect coupled TiO2 catalyst has a clear Ti defect peak, proving that it has a clear metal defect structure.

[0081] Application Example 1 The catalysts prepared in Examples 1-12 and Comparative Examples 1-6 are respectively used to catalyze the cycloaddition of fuel substrates under light conditions to obtain polycyclic high-density fuel precursors, and then the polycyclic high-density fuel is obtained by hydrodeoxygenation, and the specific steps are as follows: Fuel precursor preparation step: a fuel substrate solution with a concentration of 1 mol / L (solvent: acetonitrile) was added into a quartz glass test tube, then 5% of the mass of the fuel substrate was added as catalyst, nitrogen was bubbled for 0.5 h under stirring, then a condenser tube was inserted and the circulating condensate water was turned on to maintain a temperature of 20°C, a 365 nm LED lamp was used for irradiation for 12 h, and the solvent was removed by rotary evaporation to obtain the fuel precursor.

[0082] Fuel precursor hydrodeoxygenation step: 10 g of the fuel precursor, 0.03 g of Pd / C, 0.3 g of H-Y type molecular sieve (Catalyst Factory of Nankai University), and 40 mL of cyclohexane were stirred uniformly, the obtained mixture was placed into a hydrogenation kettle, the hydrogenation kettle was tightly closed, then inert gas was bubbled for 30 min, then 1 MPa H2was bubbled for 3 times for atmosphere replacement, then 1 MPa H2was bubbled, and reaction was carried out at 120°C for 24 h, and then the product was obtained by vacuum distillation at 50-200°C and -0.01 to -0.07 MPa.

[0083] When the fuel precursor is α-pinene: isophorone with a molar ratio of 1:1, the fuel precursor is a mixed isomer of 2,2,4b,6,6,8b-hexamethyldecahydro-1,3-methyldibenzo-8(1H)-one and 2,2,7,7,8a,8b-hexamethyldecahydro-1,3-methylenedibenzenene-5(2H)-one, and the fuel is a mixed isomer of 2,2,4b,6,6,8b-hexamethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane and 2,2,7,7,8a,8b-hexamethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane. When the fuel precursor is α-pinene: cyclohexenone with a molar ratio of 1:1, the fuel precursor is a mixed isomer of 2,2,8b-trimethyldecahydro-1,3-methyldibenzobrida-5(2H)-one and 2,2,8-trimethyl-decahydro-1,3-methyldibenzenene-8(1H)-one, and the fuel is 2,8b-dimethyltetracyclo[4.4.0.0 2,5 .0 3,4 ]dodecane.

[0084] The reaction liquid was analyzed by gas chromatography-mass spectrometry to qualitatively detect the structure of the product and calculate the reaction conversion rate, and the results are shown in Table 1. The types of the fuel substrate and the polycyclic high-density fuel precursor are shown in Table 1.

[0085] Application Example 2 The catalyst prepared in Example 2 was used to catalyze the cycloaddition of the fuel substrate under light conditions to obtain a polycyclic high-density fuel, and the specific steps are as follows: In a quartz glass test tube, a fuel substrate solution with a concentration of 1 mol / L (solvent: acetonitrile) is added, then 5% of the mass of the fuel substrate of the catalyst is added, nitrogen is bubbled for 0.5 h under stirring, then a condenser tube is inserted and the circulating condensate water is opened to maintain the temperature at 20℃, a 365 nm LED lamp strip is used for irradiation for 12 h, the solvent is removed by rotary evaporation, and multi-ring high-density fuel is obtained by vacuum distillation at 50-200℃ and -0.01 to -0.07 MPa. When the fuel substrate is norbornene, the fuel is pentacyclo[8.2.1.1 4,7 .0 2,9 .0 8,3 ]tetradecane. When the fuel substrate is norbornadiene, the fuel is tetracycloheptane. When the fuel substrate is dicyclopentadiene, the fuel is pentacyclo[5.3.0.0 2,6 .0 3,9 .0 5,8 ]decane.

[0086] The reaction solution is analyzed by using a gas chromatograph-mass spectrometer analyzer, qualitative detection of the structure of the product is carried out, and the total fuel yield is calculated, and the results are shown in Table 1.

[0087] Table 1 is the ring addition reaction conditions and total fuel yield results of different catalysts and different fuel substrates under light conditions.

[0088] As can be seen from Table 1, the chiral-metal defect coupled catalysts described in the present application are generally superior to the TiO2 and ZnO catalysts before modification in the comparative examples, which proves that the chiral-metal defect coupled catalysts described in the present application can enhance the photocatalytic reaction performance, have excellent photocatalytic performance, and are especially suitable for the synthesis of high-density fuel by photocatalytic reaction, with a total fuel yield as high as 97%, meeting the needs of aerospace.

[0089] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A chiral-metal defect coupling catalyst, characterized in that, This includes metal oxides with chiral structures and metallic defect structures.

2. The chiral-metal defect coupling catalyst according to claim 1, characterized in that, The metal oxides include TiO2 and / or ZnO.

3. The method for preparing the chiral-metal defect coupling catalyst according to claim 1 or 2, characterized in that, Includes the following steps: An inducing agent, a metal source, and a solvent are mixed, subjected to a solvothermal reaction, and then calcined to obtain a chiral-metal defect coupling catalyst; the inducing agent includes a polyhydroxy chiral inducing agent, or a mixture of a polyhydroxy inducing agent and a chiral inducing agent.

4. The preparation method according to claim 3, characterized in that, The metal source includes a titanium source and / or a zinc source; The polyhydroxy chiral inducer includes a first sugar and / or a first polyol; The first carbohydrate substance includes glucose and / or fructose; The first polyol includes at least one selected from L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R)1,2,3,4-butanetetrol, (S)1,2,3,4-butanetetrol, D-arabinitol, L-threitol, D-threitol, D-galactitol, L-fucoitol, 1,2-propanediol, and 1,2-butanediol; The mass ratio of the metal source to the polyhydroxy chiral inducer is 1:0.03~10; The chiral inducing agents include amino acids, hydroxy acids, secondary sugars, and secondary polyols; The amino acid includes at least one of L-alanine, D-alanine, L-serine, D-serine, L-valine, D-valine, L-leucine, D-leucine, L-tyrosine, and L-cysteine. The hydroxy acid includes at least one of L-lactic acid, D-lactic acid, L-tartaric acid, and D-tartaric acid; The second type of carbohydrate includes glucose and / or fructose; The second polyol includes at least one of L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, (R)1,2,3,4-butanetetrol, (S)1,2,3,4-butanetetrol, D-arabinitol, L-threitol, D-threitol, D-galactitol, L-fucoitol, L-mannitol, D-mannitol, L-sorbitol, D-sorbitol, D-arabinitol, L-threitol, D-threitol, D-galactitol, L-fucoitol, 1,2-propanediol, and 1,2-butanediol; The mass ratio of the metal source to the chiral inducer is 1:0.03~12; The polyhydroxy inducer includes a third polyol, which includes at least one of glycerol, propylene glycol, 1,3-propanediol, ethylene glycol, 1,2-butanediol, and 1,4-butanediol. The solid-liquid ratio of the metal source and the polyhydroxy inducer is 1g:0.5~80mL; The solvent includes lower alcohols and / or water; the lower alcohols include at least one of methanol, ethanol, propanol, isopropanol, and ethylene glycol; The solvothermal reaction is carried out at a temperature of 60~300℃ for a time of 1~50h; The roasting temperature is 200~700℃, and the time is 1~30h.

5. The application of the chiral-metal defect coupling catalyst according to claim 1 or 2 or the chiral-metal defect coupling catalyst prepared by the preparation method according to claim 3 or 4 in the preparation of fuels.

6. The application according to claim 5, wherein the fuel comprises a high-density fuel.

7. The application according to claim 5 or 6, characterized in that, The fuel includes polycyclic aerospace fuel.

8. The application according to claim 7, characterized in that, The polycyclic aerospace fuel includes 2,2,4b,6,6,8b-hexamethyltetracyclo[4.4.0.0]. 2,5 .0 3,4 Dodecane, 2,2,7,7,8a,8b-hexamethyltetracyclo[4.4.0.0] 2,5 .0 3,4 Dodecane, 2,8β-dimethyltetracyclo[4.4.0.0] 2,5 .0 3,4 Dodecane, pentacyclic [8.2.1.1] 4,7 .0 2,9 .08 ,3 Tetradecane, Pentane [5.3.0.0] 2,6 .0 3,9 .0 5,8 [Decadecane, 2,8β-dimethyltetracyclo[4.4.0.0]] 2,5 .0 3,4 At least one of dodecane and tetracycloheptane.

9. A method for preparing a fuel, characterized in that, When the fuel substrate is a mixture of ketones and olefins, the preparation method includes the following steps: mixing the fuel substrate, catalyst and organic solvent, and carrying out a cycloaddition reaction under light irradiation to obtain a fuel precursor; and carrying out a hydrodeoxygenation reaction on the fuel precursor to obtain fuel; When the fuel substrate is an olefin, the preparation method includes the following steps: mixing the fuel substrate, catalyst and organic solvent, and carrying out a cycloaddition reaction under light irradiation to obtain fuel; The catalyst is the chiral-metal defect coupling catalyst according to claim 1 or 2, or the chiral-metal defect coupling catalyst prepared by the preparation method according to claim 3 or 4.

10. The preparation method according to claim 9, characterized in that, The olefins include at least one of dicyclopentadiene, α-pinene, cyclohexene, norbornene, and norbornadiene; The ketones include at least one of isophorone and cyclohexenone; The mass of the catalyst is 1-20% of the mass of the fuel substrate; The organic solvent includes at least one of halogenated hydrocarbons, nitrile solvents, lower alcohols, furan solvents, and alkane solvents; The cycloaddition reaction is carried out at a temperature of -10 to 70°C for a time of 1 to 48 hours.

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