A sheet-shaped AlOOH material, a preparation method and application thereof

Abstract

The application provides a flaky AlOOH material, a preparation method and application thereof. The preparation method of the flaky AlOOH material comprises the following steps: mixing a precursor of an aluminum salt, a precipitator and a structure directing agent, and then performing hydrothermal reaction and calcination to obtain the AlOOH material. The application also provides the application of the AlOOH material as a catalyst, preferably for catalyzing hydrogenation reaction, which can activate hydrogen under mild conditions (for example, T=80 DEG C, P(H2)=2.0 MPa), realize catalytic hydrogenation reaction of olefins and alkynes, and the conversion rate can be up to 100%.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalytic chemical engineering, in particular to a sheet-shaped AlOOH material, a preparation method and application thereof. BACKGROUND

[0002] Hydrogen activation is a key step in catalytic hydrogenation reactions, which is very important in the petrochemical industry. This method has been well developed on transition metal complexes, metal-based heterogeneous catalysts 1 and non-metal N, S, B or P heteroatom-doped carbon-based catalysts 2-6. In 2006, W. Stephan's group first reported a new H2 activation mode, i.e. hindered Lewis acid-base pair. Early studies on hindered Lewis acid-base pairs were mainly on molecular homogeneous complexes, such as boron phosphide hydride, which is not only expensive, but also not conducive to catalyst recovery and product purification. Therefore, it is of great significance to develop heterogeneous catalysts with hindered Lewis acid-base pair activity. Hindered Lewis acid-base pairs have been successfully constructed on the surface of noble metal-based heterogeneous catalysts. For example, after H2 treatment of zeolite NaY containing platinum nanoparticles (Ptx / NaY), a hindered Lewis acid-base pair composed of sodium hydride (NaH) and hydroxyl protons O(H+) bound to the framework was formed. Gold nanoparticles and molecular Lewis bases (e.g. imine and butyronitrile) can also form a hindered Lewis acid-base pair. In addition, in recent years, hindered Lewis acid-base pairs have also been successfully constructed on the surfaces of reducible metal oxides CeO2, In2O3(OH) and NiOx. + H - ) and hydroxyl protons O(H + ) bound to the framework. Gold nanoparticles and molecular Lewis bases (e.g. imine and butyronitrile) can also form a hindered Lewis acid-base pair. In addition, in recent years, hindered Lewis acid-base pairs have also been successfully constructed on the surfaces of reducible metal oxides CeO2, In2O 3-x (OH) y and NiOx.

[0003] Boehmite (AlOOH) is one of the main components of bauxite, which is abundant in nature and widely used in adsorbents, porous materials, catalyst supports, etc. However, boehmite is a main group metal hydroxide and is difficult to reduce, and there is no report on the construction of a hindered Lewis acid-base pair on its surface.

[0004] In the patent "Preparation method and application of sheet-shaped aluminum oxide with porous structure", carboxylic acid and anhydrous ethanol are used as solvents, and γ-Al2O3 is obtained. In our application, polyols are used as structure directing agents, and AlOOH structure is obtained. Polyols have strong reducing properties and play an important role in the construction of AlOOH surface defect sites. Surface defect sites are the reason for the high activity of catalysts. In our system, there is no need to add acid as a cosolvent, because polyols themselves have the function of structure directing agents. In the patent, the ester generated by esterification of carboxylic acid and ethanol is the structure directing agent. In patent 2, a layered composite oxide is mentioned, which needs to add acid to adjust the precipitation rate of two metals. SUMMARY

[0005] To solve the above technical problems, the present application provides the following technical solutions:

[0006] A preparation method of an AlOOH material, the preparation method comprising mixing a precursor of an aluminum salt, a precipitant and a structure-directing agent, and then performing hydrothermal reaction and calcination to obtain the AlOOH material.

[0007] According to an embodiment of the present application, the preparation method specifically comprises the following steps:

[0008] The precursor of the aluminum salt is dissolved in a solvent to obtain a first solution, and the precipitant is dissolved in the structure-directing agent to obtain a second solution, and then the first solution and the second solution are mixed uniformly; the mixed solution is subjected to hydrothermal reaction to obtain a gel; and the gel is dried and calcined to obtain the AlOOH material.

[0009] According to an embodiment of the present application, the precursor of the aluminum salt is selected from at least one of Al(NO3)3·9H2O, Al2(SO4)3 and AlCl3.

[0010] According to an embodiment of the present application, the solvent is selected from water and ethanol, and preferably is deionized water.

[0011] According to an embodiment of the present application, the precipitant is selected from at least one of urea, ammonia and sodium hydroxide, and preferably is urea.

[0012] According to an embodiment of the present application, the structure-directing agent is selected from a polyhydric alcohol.

[0013] Preferably, the polyhydric alcohol is selected from at least one of ethylene glycol, glycerol, 1,2-propanediol and 1,3-propanediol, and for example is ethylene glycol.

[0014] According to an embodiment of the present application, the amount of the precursor of the aluminum salt and the solvent is not specifically limited, and a known amount in the art can be selected, as long as the first solution can be obtained.

[0015] According to an embodiment of the present application, the molar ratio of the precursor of the aluminum salt to the precipitant is 20:(1-100), for example 20:20, 20:40, 20:60, 20:80 or 20:100.

[0016] According to an embodiment of the present application, the molar volume ratio of the precipitant to the structure-directing agent is (1-100) mmol:30 mL, for example 20 mmol:30 mL, 40 mmol:30 mL, 60 mmol:30 mL, 80 mmol:30 mL or 100 mmol:30 mL.

[0017] According to an embodiment of the present application, the structure-directing agent is used to induce the formation of the sheet-like structure of the AlOOH material.

[0018] According to an embodiment of the present application, the mixing is optionally performed by a method known in the art, such as stirring mixing. Exemplarily, the conditions of the mixing are stirring at room temperature for 0.1-2h, such as stirring at room temperature for 1h, wherein the room temperature refers to 10-40℃, such as 10℃, 20℃, 30℃, 40℃.

[0019] According to an embodiment of the present application, the hydrothermal reaction is performed under a closed condition.

[0020] Preferably, the closed condition is selected from an air atmosphere.

[0021] According to an embodiment of the present application, the conditions of the hydrothermal reaction include constant temperature reaction at 150-200℃ for 1-10h, such as constant temperature reaction at 180℃ for 5h.

[0022] According to an embodiment of the present application, the drying is optionally performed by a method known in the art, such as vacuum drying. Exemplarily, the vacuum drying includes vacuum drying at 50-90℃ for 1-12h, preferably vacuum drying at 80℃ for 12h.

[0023] According to an embodiment of the present application, the preparation method further comprises washing with the solvent until neutral, such as pH of 6.5-7.5, before drying.

[0024] According to an embodiment of the present application, the calcination includes primary calcination, or further includes secondary calcination.

[0025] Preferably, the conditions of the primary calcination include air atmosphere, calcination temperature of 300-500℃, preferably 350-450℃, such as 350℃, 400℃, 450℃; and calcination time of 1-8h, preferably 1-6h, such as 4h.

[0026] Preferably, the conditions of the secondary calcination include hydrogen atmosphere and / or inert atmosphere, calcination temperature of 300-500℃, preferably 350-450℃, such as 350℃, 400℃, 450℃; and calcination time of 1-8h, preferably 1-6h, such as 4h.

[0027] According to an embodiment of the present application, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere.

[0028] The present application also provides an AlOOH material, which is obtained by the above preparation method.

[0029] According to an embodiment of the present application, the AlOOH material has a sheet structure, for example, has a sheet structure substantially as shown in Figure 2 any of b-c in the specification.

[0030] According to an embodiment of the present application, the AlOOH material has diffraction peaks at least including (020), (120), (031), (200), (002), for example, has diffraction peaks substantially as shown in Figure 1 AlOOH-U2, AlOOH-U3, AlOOH-U4 in the specification.

[0031] According to an embodiment of the present application, the AlOOH material has surface defect sites, which can realize catalytic activation of H2. Preferably, the defect sites refer to surface containing OH vacancies.

[0032] The present application also provides a catalyst, which comprises the sheet AlOOH material as described above.

[0033] The present application also provides an application of the catalyst as described above, preferably for catalyzing hydrogenation reaction, for example, for catalyzing hydrogenation reaction of aromatic hydrocarbon containing unsaturated substituent.

[0034] According to an embodiment of the present application, the aromatic hydrocarbon containing unsaturated substituent has a structural formula as shown in formula (A):

[0035]

[0036] wherein, R1 is selected from alkyl, alkoxy, -NH2, H, -X, -Ar; X is selected from F, Cl, Br; for example, R1 is selected from methyl, n-butyl, methoxy;

[0037] R2 is selected from unsaturated substituent, for example, is vinyl, styryl, acetylenyl, phenylacetylenyl.

[0038] Preferably, the aromatic hydrocarbon containing unsaturated substituent is selected from at least one of the following compounds:

[0039]

[0040] The present application also provides a catalytic hydrogenation reaction, which comprises the following steps:

[0041] The catalyst and the substrate as described above are added into a reaction device, H2 is filled into the reaction device, and catalytic hydrogenation reaction is carried out to obtain hydrogenated product.

[0042] According to an embodiment of the present application, the substrate is selected from aromatic hydrocarbon containing unsaturated substituent, which has the meaning as described above.

[0043] According to an embodiment of the present application, the substrate can be mixed with the organic solvent first, and then added into the reaction device.

[0044] Preferably, the organic solvent is selected from at least one of tetrahydrofuran (THF), ethanol, 1,2-dioxane, water, cyclohexane, and the like.

[0045] According to an embodiment of the present application, the mass molar ratio of the catalyst and the substrate is 50mg:(0.1-1)mmol, for example, 50mg:0.2mmol.

[0046] According to an embodiment of the present application, the reaction device can be selected from the reaction devices known in the art, as long as the catalytic hydrogenation reaction can be achieved. Illustratively, the catalytic hydrogenation reaction is carried out in a high-pressure reaction kettle, for example, a stainless steel reaction kettle with a polytetrafluoroethylene lining, for example, with a volume of 16mL.

[0047] According to an embodiment of the present application, the reaction pressure of the catalytic hydrogenation reaction is not higher than 5Mpa, for example, 1Mpa, 2Mpa, 3Mpa, 4Mpa, 5Mpa.

[0048] According to an embodiment of the present application, the conditions of the catalytic hydrogenation reaction include: the reaction temperature is not higher than 100℃, for example, 60℃, 70℃, 80℃, 90℃; the reaction time is 1-10h, for example, 2h, 4h, 6h, 8h, 10h.

[0049] According to an embodiment of the present application, the reaction device further comprises an internal standard agent.

[0050] Preferably, the internal standard agent is selected from n-decane, n-dodecane.

[0051] Further, the amount of the internal standard agent can be selected from the amounts known in the art, for example, 40μL.

[0052] According to an embodiment of the present application, after the catalytic hydrogenation reaction is completed, the post-treatment can be carried out according to the methods known in the art, for example, the hydrogenated product is rapidly cooled to room temperature (for example, 10-40℃).

[0053] According to an embodiment of the present application, the conversion rate of the aromatic hydrocarbon containing unsaturated substituent is not less than 90%, preferably, 90%-100%.

[0054] Advantages

[0055] The AlOOH material of the present application is prepared by using urea as a precipitant and polyhydric alcohol as a structure directing agent, and through different atmosphere calcination. The material has a sheet structure, and as a catalyst, it can activate hydrogen under mild conditions (e.g. T = 80℃, P(H2) = 2.0 MPa) to realize the catalytic hydrogenation reaction of olefins and alkynes, and the conversion rate can be as high as 100%. BRIEF DESCRIPTION OF DRAWINGS

[0056] Figure 1 XRD patterns of the AlOOH materials of Comparative Example 1 and Examples 1-3.

[0057] Figure 2 TEM electron micrographs (a-d) and EDS element mapping (e-f) of the AlOOH materials of Comparative Example 1 and Examples 1-3; wherein (a) AlOx-U1; (b) AlOOH-U2; (c) AlOOH-U3; (d) AlOOH-U4; (e) and (f) are EDS element mapping of the catalyst AlOOH-U2.

[0058] Figure 3 EPR spectra of the AlOOH materials of Comparative Example 1 and Examples 1-3.

[0059] Figure 4 Gas chromatograms of the products of the catalytic hydrogenation reaction of the application examples. DETAILED DESCRIPTION

[0060] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustratively and explain the present application, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of the present application.

[0061] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0062] Comparative Example 1

[0063] Preparation of catalyst: 20 mmol of Al (NO3) 3.9H2O and 20 mmol of urea were dissolved in 30 mL of deionized water and ethylene glycol, respectively. Then the aqueous solution of aluminum nitrate was added to the urea ethylene glycol solution, and stirred at room temperature for 1 h to mix uniformly. Subsequently, the above mixture was transferred to a Teflon-lined 100 mL autoclave, and heated to 180 °C in a blast oven for 5 h. After the reaction, the reactor was cooled to room temperature naturally, and the reaction product was separated by centrifugation to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried in a vacuum drying oven at 80 °C overnight to obtain a white solid, which was calcined in a muffle furnace in air at 350 °C for 4 h to obtain a white powder, denoted as AlOx-U1.

[0064] Hydrogenation reaction: The conversion of styrene catalyzed by AlOx-U1 was 21.9% under the conditions of 80 °C, 2 MPa of H2 pressure, and 6 h of reaction time, wherein the ratio of AlOx-U1 to styrene was 50 mg: 0.2 mmol.

[0065] Example 1

[0066] Preparation of catalyst: 20 mmol of Al (NO3) 3.9H2O and 40 mmol of urea were dissolved in 30 mL of deionized water and ethylene glycol, respectively. Then the aqueous solution of aluminum nitrate was added to the urea ethylene glycol solution, and stirred at room temperature for 1 h to mix uniformly. Subsequently, the above mixture was transferred to a Teflon-lined 100 mL autoclave, and heated to 180 °C in a blast oven for 5 h. After the reaction, the reactor was cooled to room temperature naturally, and the reaction product was separated by centrifugation to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried in a vacuum drying oven at 80 °C overnight to obtain a white solid, which was calcined in a muffle furnace in air at 350 °C for 4 h to obtain a white powder, denoted as AlOx-U1.

[0067] Hydrogenation reaction: The conversion of styrene catalyzed by AlOx-U1 was 21.9% under the conditions of 80 °C, 2 MPa of H2 pressure, and 6 h of reaction time, wherein the ratio of AlOx-U1 to styrene was 50 mg: 0.2 mmol.

[0068] Example 2

[0069] Preparation of catalyst: 20 mmol of Al (NO3) 3.9H2O and 60 mmol of urea were dissolved in 30 mL of deionized water and ethylene glycol, respectively. Then the aqueous solution of aluminum nitrate was added to the urea ethylene glycol solution, and stirred at room temperature for 1 h until the mixture was homogeneous. Subsequently, the above mixture was transferred to a Teflon-lined 100 mL autoclave, and heated to 180 °C in a blast oven for 5 h. After the reaction, the reactor was cooled to room temperature naturally, and the reaction product was separated by centrifugation to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried in a vacuum drying oven at 80 °C overnight to obtain a white solid, which was calcined in a muffle furnace in air at 350 °C for 4 h to obtain a white powder, which was labeled as AlOOH-U3.

[0070] Hydrogenation reaction: The conversion of styrene catalyzed by AlOOH-U3 was 99% under the conditions of 80 °C, 2 MPa of H2 pressure, and 6 h of reaction time, wherein the ratio of AlOOH-U3 to styrene was 50 mg: 0.2 mmol.

[0071] Example 3

[0072] Preparation of catalyst: 20 mmol of Al (NO3) 3.9H2O and 80 mmol of urea were dissolved in 30 mL of deionized water and ethylene glycol, respectively. Then the aqueous solution of aluminum nitrate was added to the urea ethylene glycol solution, and stirred at room temperature for 1 h until the mixture was homogeneous. Subsequently, the above mixture was transferred to a Teflon-lined 100 mL autoclave, and heated to 180 °C in a blast oven for 5 h. After the reaction, the reactor was cooled to room temperature naturally, and the reaction product was separated by centrifugation to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried in a vacuum drying oven at 80 °C overnight to obtain a white solid, which was calcined in a muffle furnace in air at 350 °C for 4 h to obtain a white powder, which was labeled as AlOOH-U4.

[0073] Hydrogenation reaction: The conversion of styrene catalyzed by AlOOH-U4 was 48.8% under the conditions of 80 °C, 2 MPa of H2 pressure, and 6 h of reaction time, wherein the ratio of AlOOH-U4 to styrene was 50 mg: 0.2 mmol.

[0074] Test Example 1

[0075] Figure 1 The XRD spectra of the AlOOH materials of Comparative Example 1 and Examples 1-3 are shown in FIG. 1. Figure 1 As can be seen from FIG. 1, the AlOx-U1 did not form an AlOOH crystal structure.

[0076] Figure 2The images shown are TEM (ad) and EDS (ef) elemental surface scans of the AlOOH materials in Comparative Example 1 and Examples 1-3; where a represents AlOx-U1; b represents AlOOH-U2; c represents AlOOH-U3; d represents AlOOH-U4; and e and f represent EDS elemental surface scans of the catalyst AlOOH-U2.

[0077] from Figure 2 As can be seen from the ad, except for AlOx-U1, all of them have obvious lamellar structures.

[0078] Figure 3 The EPR spectra of AlOOH materials in Comparative Example 1 and Examples 1-3 are obtained by... Figure 3 It is known that the surface of the AlOOH material in Examples 1-3 contains defect sites with OH vacancies, which can achieve catalytic activation of H2.

[0079] Example 4

[0080] Catalyst preparation: 20 mmol Al(NO3)3·9H2O and 40 mmol urea were dissolved in 30 mL deionized water and ethylene glycol, respectively. Then, an aqueous solution of aluminum nitrate was added to the urea-ethylene glycol solution, and the mixture was stirred thoroughly for 1 h at room temperature until homogeneous. The mixture was then transferred to a 100 mL hydrothermal reactor with a polytetrafluoroethylene liner and heated to 180 °C in an explosion-proof oven for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The reactants in the reactor were centrifuged to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried overnight in a vacuum drying oven at 80 °C to obtain a white solid, which was then calcined in an air atmosphere in a muffle furnace at 350 °C for 4 h to obtain a white powder. This powder was then calcined again in a tube furnace under a hydrogen atmosphere at 300 °C for 4 h, denoted as AlOOH-U2-H2-300.

[0081] Hydrogenation reaction: At 80℃, H2 pressure of 2MPa, and reaction time of 6h, the conversion rate of styrene hydrogenation using the above-mentioned AlOOH-U2-H2-300 catalyst was 99%, wherein the ratio of AlOOH-U2-H2-300 to styrene was 50mg:0.2mmol.

[0082] Example 5

[0083] Preparation of catalyst: 20 mmol of Al (NO3) 3.9H2O and 40 mmol of urea were dissolved in 30 mL of deionized water and ethylene glycol, respectively. Then the aqueous solution of aluminum nitrate was added to the urea ethylene glycol solution, and stirred at room temperature for 1 h until the mixture was homogeneous. Subsequently, the above mixture was transferred to a Teflon-lined 100 mL autoclave, and heated to 180 °C in a blast oven for 5 h. After the reaction, the autoclave was cooled to room temperature, and the reaction mixture was separated by centrifugation to obtain a translucent gel-like solid, which was washed with deionized water until neutral. The gel was dried in a vacuum oven at 80 °C overnight to obtain a white solid, which was calcined in a muffle furnace in air at 350 °C for 4 h to obtain a white powder. The white powder was further calcined in a tube furnace in argon at 450 °C for 4 h, and was denoted as AlOOH-U2-Ar-450.

[0084] Hydrogenation reaction: The conversion of styrene catalyzed by AlOOH-U2-Ar-450 was 100% under the conditions of 80 °C, 2 MPa of H2 pressure, and 4 h of reaction time, wherein the ratio of AlOOH-U2-Ar-450 to styrene was 50 mg:0.2 mmol.

[0085] As can be seen from Example 4, the AlOOH-U2-H2-300 catalyst still has stable catalytic performance after being treated at high temperature in a reactive atmosphere (secondary calcination treatment in a hydrogen atmosphere); as can be seen from Example 5, the AlOOH-U2-Ar-450 catalyst can produce more defect vacancies under an inert atmosphere, and the catalytic activity is improved, and the conversion of styrene can be achieved in 4 h.

[0086] Application Example

[0087] The AlOOH-U2 of Example 1 was used as a catalyst for hydrogenation reaction of the alkynes or alkenes listed in Table 1 as substrates to obtain the products corresponding to Table 1, and the conditions and results of the catalytic hydrogenation reaction are listed in Table 1. As can be seen, the AlOOH of the application can be used as a catalyst for hydrogenation reaction of different alkynes or alkenes, and has strong substrate universality.

[0088] Table 1 Hydrogenation reaction of alkenes and alkynes catalyzed by AlOOH-U2 a

[0089]

[0090] a: Reaction conditions: substrate (0.2 mmol), THF (2 mL), AlOOH-U2 catalyst (50 mg), rotation speed (600 rpm); n-decane as an internal standard; conversion and selectivity were obtained by gas chromatography analysis (such as Figure 4b: n-dodecane as internal standard.

[0091] The above described exemplary embodiments of the present application. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An AlOOH material, characterized in that, The AlOOH material has a plate-like structure; the surface of the AlOOH material contains defect sites, which can achieve catalytic activation of H2; the defect sites refer to OH vacancies on the surface; The AlOOH material is prepared by the following method: an aluminum salt precursor, a precipitant and a structure directing agent are mixed and then subjected to hydrothermal reaction and calcination to obtain the AlOOH material. The preparation method specifically includes the following steps: The aluminum salt precursor is dissolved in a solvent to obtain a first solution, and the precipitant is dissolved in a structure directing agent to obtain a second solution. The first and second solutions are then mixed evenly. The mixture is subjected to a hydrothermal reaction to obtain a gel. The gel is then dried and calcined to obtain the AlOOH material.

2. The AlOOH material according to claim 1, characterized in that, The aluminum salt precursor is selected from at least one of Al(NO3)3·9H2O, Al2(SO4)3, and AlCl3; The solvent is selected from water and ethanol; The precipitant is selected from at least one of urea, ammonia, and sodium hydroxide; The structure-directing agent is selected from polyols; The polyol is selected from at least one of ethylene glycol, glycerol, 1,2-propanediol, and 1,3-propanediol.

3. The AlOOH material according to claim 1, characterized in that, The molar ratio of the aluminum salt precursor to the precipitant is 20:1-100; The molar volume ratio of the precipitant to the structure directing agent is 1-100 mmol: 30 mL; The structure-directing agent is used to induce the formation of a layered structure in the AlOOH material.

4. The AlOOH material according to claim 1, characterized in that, The hydrothermal reaction is carried out under closed conditions; The airtight conditions are selected from the air atmosphere; The conditions for the hydrothermal reaction include: constant temperature reaction at 150-200℃ for 1-10 hours; The preparation method further includes washing with the solvent until neutral before drying.

5. The AlOOH material according to claim 1, characterized in that, The calcination includes a single calcination, or may further include a double calcination; The conditions for the first calcination include: calcination temperature of 300~500℃ in air atmosphere; calcination time of 1~8h; The conditions for the secondary calcination include: calcination temperature of 300~500℃ under a hydrogen atmosphere and / or an inert atmosphere; and calcination time of 1~8h. The inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, and argon atmosphere.

6. A catalyst, characterized in that, The catalyst comprises the AlOOH material according to any one of claims 1-5.

7. The application of the catalyst according to claim 6 in catalytic hydrogenation reaction.

8. The application according to claim 7, characterized in that, The catalytic hydrogenation reaction is a catalytic hydrogenation reaction of aromatic hydrocarbons containing unsaturated substituents.

9. The application according to claim 8, characterized in that, The aromatic hydrocarbon containing unsaturated substituents has the structural formula shown in formula (A): （A）， Wherein, R1 is selected from alkyl, alkoxy, -NH2, H, -X, -Ar; X is selected from F, Cl, Br; R2 is selected from unsaturated substituents.

10. The application according to claim 8, characterized in that, The aromatic hydrocarbon containing the unsaturated substituent is selected from at least one of the following compounds: , , , , , , , , , , , , .

11. A catalytic hydrogenation reaction, characterized in that, The reaction includes the following steps: The catalyst and substrate described in claim 6 are added to a reaction apparatus, which is then filled with H2 to carry out a catalytic hydrogenation reaction to obtain the hydrogenated product. The substrate is selected from aromatic hydrocarbons containing unsaturated substituents, and the aromatic hydrocarbons containing unsaturated substituents have the structural formula shown in formula (A): （A）， Wherein, R1 is selected from alkyl, alkoxy, -NH2, H, -X, -Ar; X is selected from F, Cl, Br; R2 is selected from unsaturated substituents; The reaction pressure of the catalytic hydrogenation reaction is not higher than 5 MPa; The conditions for the catalytic hydrogenation reaction include: a reaction temperature not exceeding 100℃; and a reaction time of 1-10 hours. The conversion rate of the aromatic hydrocarbons containing unsaturated substituents is over 90%.

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