SBA-16-DC-UiO-66 composite material as well as preparation method and application thereof

Abstract

The invention provides an SBA-16-DC-UiO-66 composite material as well as a preparation method and application thereof, and belongs to the technical field of transfer hydrogenation reaction catalyst materials. According to the invention, 3-(triethoxy silyl) propyl succinic anhydride is used as a carboxyl functional reagent and is subjected to co-condensation with tetraethoxysilane to prepare the double-carboxyl functional mesoporous silica SBA-16-DC with adjustable aperture, high specific surface area and excellent hydrothermal stability, metal ion binding sites of the carrier are increased, and the mesoporous silica SBA-16-DC has the advantages of high specific surface area, high specific surface area and excellent hydrothermal stability. Steric hindrance is provided for UiO-66 growth to inhibit agglomeration, the mass transfer efficiency can be enhanced through a mesoporous confinement effect, and the efficiency of catalyzing a furfural transfer hydrogenation reaction and the yield of a catalytic product are remarkably improved; carboxyl on the surface of SBA-16-DC can effectively adsorb Zr < 4 + >, the dispersion uniformity and stability of the active component UiO-66 in the carrier are improved, the problems of agglomeration and loss are avoided, and the catalytic performance and stability of the composite material are remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of transfer hydrogenation reaction catalyst materials, and in particular to an SBA-16-DC@UiO-66 composite material and a preparation method and application thereof. Background Art

[0002] Developing renewable resources to replace traditional petrochemical raw materials has become an inevitable choice for achieving sustainable development. Biomass resources stand out due to their abundant reserves, carbon neutrality and directional conversion characteristics. Among them, hemicellulose, as a key component of wood fiber biomass, can be efficiently converted into the platform compound furfural through hydrolysis-dehydration reaction. Furfural can be further derived into high-value chemicals such as furfural alcohol (FA) and 2-methylfuran through catalytic hydrogenation, building the core hub of the biorefining industry chain. However, the coexistence of C=O and C=C bonds in the furfural molecule leads to severe selectivity challenges in its hydrogenation process: how to accurately activate the C=O bond under mild conditions while inhibiting the reduction of the C=C bond and the destruction of the furan ring structure has become a key technical bottleneck restricting the industrial production of bio-based furfural alcohol.

[0003] Current research on catalytic transfer hydrogenation systems focuses on the development of solid catalysts, covering materials such as metal oxides (such as MgO, Al2O3), metal organic frameworks (MOFs), heteropoly acids (such as phosphotungstic acid) and structured supports (such as zeolite molecular sieves). MOFs materials have shown unique advantages in the field of heterogeneous catalysis due to their designable pore structure, rich acid and base active sites and other characteristics. However, their inherent defects are also significant: insufficient mechanical strength leads to structural collapse during recycling, and active components are easily lost. Therefore, providing a MOFs catalyst for catalytic furfural transfer hydrogenation with high mechanical strength and stable active components that are not easily lost is a problem that needs to be solved in the existing technology. Summary of the Invention

[0004] The object of the present invention is to provide an SBA-16-DC@UiO-66 composite material and a preparation method and application thereof. The SBA-16-DC@UiO-66 composite material provided by the present invention is.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides an SBA-16-DC@UiO-66 composite material, which includes a carrier and an active component; the carrier is dicarboxyl-functionalized mesoporous silica SBA-16-DC, and the active component is UiO-66;

[0007] The SBA-16-DC is prepared by co-condensation of a carboxyl functionalization reagent and an inorganic silicon source;

[0008] The loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 65 to 140 mg / g.

[0009] Preferably, the SBA-16-DC@UiO-66 composite material is a microporous material with an average pore diameter of 0.6 to 1.4 nm.

[0010] Preferably, the loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 70 to 120 mg / g.

[0011] Preferably, the carboxyl functionalization agent is 3-(triethoxysilyl)propylsuccinic anhydride TPDD, and the inorganic silicon source is tetraethyl orthosilicate TEOS.

[0012] The present invention also provides a method for preparing the SBA-16-DC@UiO-66 composite material described in the above technical solution, comprising the following steps:

[0013] (1) After mixing F127, water and concentrated hydrochloric acid, n-butanol is added, and then TEOS and TPDD are added under heating conditions, and constant temperature stirring, a first hydrothermal reaction and a first post-treatment are carried out in sequence to obtain a first intermediate;

[0014] (2) mixing the first intermediate obtained in step (1) with dilute sulfuric acid, and then performing acid treatment and a second post-treatment in sequence to obtain SBA-16-DC;

[0015] (3) immersing the SBA-16-DC obtained in step (2) into a ZrCl4 solution, and sequentially performing ultrasonication and drying to obtain a solid mixture;

[0016] (4) The solid mixture obtained in step (3) is mixed with terephthalic acid and N,N-dimethylformamide, and then deionized water and acetic acid are added, and a second hydrothermal reaction and a second post-treatment are performed in sequence to obtain an SBA-16-DC@UiO-66 composite material.

[0017] Preferably, the temperature of the first hydrothermal reaction in step (1) is 80-120° C., and the time of the first hydrothermal reaction is 20-28 hours.

[0018] Preferably, the temperature of the acid treatment in step (2) is 85 to 95° C., and the time of the acid treatment is 20 to 28 hours.

[0019] Preferably, the mass ratio of SBA-16-DC to ZrCl4 in the ZrCl4 solution in step (3) is 1:(1.4-2.4).

[0020] Preferably, the temperature of the second hydrothermal reaction in step (4) is 100-140° C., and the time of the second hydrothermal reaction is 20-28 h.

[0021] The present invention also provides an application of the SBA-16-DC@UiO-66 composite material described in the above technical solution or the SBA-16-DC@UiO-66 composite material prepared by the preparation method in catalyzing the transfer hydrogenation reaction of furfural.

[0022] The present invention provides an SBA-16-DC@UiO-66 composite material, which is prepared by co-condensing 3-(triethoxysilyl)propylsuccinic anhydride (TPDD) as a carboxyl functionalization reagent with tetraethyl orthosilicate (TEOS). The obtained composite material has a double carboxyl functionalized mesoporous silica (SBA-16-DC) with adjustable pore size, high specific surface area and excellent hydrothermal stability. The SBA-16-DC increases the metal ion binding sites of the carrier, provides steric hindrance for the growth of UiO-66 and inhibits agglomeration. The SBA-16-DC composite material can enhance the mass transfer efficiency through the mesopore confinement effect, significantly improving the efficiency of the catalytic transfer hydrogenation reaction of furfural and the yield of the catalytic product. The carboxyl groups on the surface of the SBA-16-DC can effectively adsorb Zr 4+ , which improves the dispersion uniformity and stability of the active component UiO-66 in the carrier, avoids agglomeration and loss problems, and significantly improves the catalytic performance and stability of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a transmission electron microscopy image of the SBA-16-DC@UiO-66 composite material prepared in Example 1 of the present invention;

[0024] Figure 2 This is the XPS graph of the SBA-16-DC@UiO material prepared in Example 1 of the present invention, where Figure 2 (a) is Si 2p, Figure 2 (b) is Zr 3d, Figure 2 (c) is C1s, Figure 2 (d) is O1s, Figure 2 Middle (e) is a wide scan image. DETAILED DESCRIPTION

[0025] The present invention provides an SBA-16-DC@UiO-66 composite material, which includes a carrier and an active component; the carrier is dicarboxyl-functionalized mesoporous silica SBA-16-DC, and the active component is UiO-66;

[0026] The SBA-16-DC is prepared by co-condensation of a carboxyl functionalization reagent and an inorganic silicon source;

[0027] The loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 65 to 140 mg / g.

[0028] In the present invention, unless otherwise specified, the raw materials used are conventional commercial products in the field.

[0029] In the present invention, the SBA-16-DC@UiO-66 composite material is a microporous material; the average pore diameter of the SBA-16-DC@UiO-66 composite material is preferably 0.6 to 1.6 nm, more preferably 0.8 to 1.1 nm. Controlling the average pore diameter of the SBA-16-DC@UiO-66 composite material within this range allows for better loading of the UiO-66 active component, facilitates rapid diffusion of reactant molecules within the pores, and improves the mechanical strength of the support.

[0030] In the present invention, the loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite is preferably 70 to 120 mg / g, more preferably 80 to 110 mg / g. The present invention controls the loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite within the above range to provide sufficient active sites, improve the dispersion of the active component UiO-66, and avoid pore clogging, thereby achieving high catalytic activity.

[0031] In the present invention, the carboxyl functionalization agent is preferably 3-(triethoxysilyl)propyl succinic anhydride TPDD; and the inorganic silicon source is preferably tetraethyl orthosilicate TEOS.

[0032] The present invention also provides a method for preparing the SBA-16-DC@UiO-66 composite material described in the above technical solution, comprising the following steps:

[0033] (1) Polyethylene glycol-polypropylene glycol-polyethylene glycol diacrylate F127, water, and concentrated hydrochloric acid are mixed, n-butanol is added, and then TEOS and TPDD are added under heating conditions, and constant temperature stirring, a first hydrothermal reaction, and a first post-treatment are performed in sequence to obtain a first intermediate;

[0034] (2) mixing the first intermediate obtained in step (1) with dilute sulfuric acid, and then performing acid treatment and a second post-treatment in sequence to obtain SBA-16-DC;

[0035] (3) immersing the SBA-16-DC obtained in step (2) into a ZrCl4 solution, and sequentially performing ultrasonication and drying to obtain a solid mixture;

[0036] (4) The solid mixture obtained in step (3) is mixed with terephthalic acid and N,N-dimethylformamide, and then deionized water and acetic acid are added, and a second hydrothermal reaction and a second post-treatment are performed in sequence to obtain an SBA-16-DC@UiO-66 composite material.

[0037] The present invention mixes F127, water and concentrated hydrochloric acid, adds n-butanol, then adds TEOS and TPDD under heating conditions, and sequentially performs constant temperature stirring, a first hydrothermal reaction and a first post-treatment to obtain a first intermediate.

[0038] In the present invention, the mass fraction of the concentrated hydrochloric acid is preferably 36%. In the present invention, the ratio of the mass of the F127 to the volume of concentrated hydrochloric acid is preferably 1.5 g: (4 to 10) mL. In the present invention, the volume ratio of the TEOS and TPDD is preferably 6.72: (0.2 to 1.2). In the present invention, the heating temperature is preferably 35 to 55°C, more preferably 45°C. In the present invention, the temperature of the constant temperature stirring is preferably 35 to 55°C, more preferably 45°C; the constant temperature stirring time is preferably 20 to 28 hours. The present invention obtains an SBA-16 material with a more regular pore structure through constant temperature stirring.

[0039] In the present invention, the temperature of the first hydrothermal reaction is preferably 80-120°C, more preferably 90-110°C; and the duration of the first hydrothermal reaction is preferably 20-28 hours, more preferably 22-26 hours. The present invention controls the temperature and duration of the hydrothermal reaction within the above ranges to achieve a better grafting rate of the functionalized reagent TPDD.

[0040] In the present invention, the first post-treatment is preferably to cool the product of the first hydrothermal reaction to room temperature, centrifuge, wash with deionized water and wash with ethanol in sequence, and then dry at 50-70° C. for 10-14 hours to obtain a first intermediate.

[0041] After obtaining the first intermediate, the present invention mixes the first intermediate with dilute sulfuric acid, and then performs acid treatment and a second post-treatment in sequence to obtain SBA-16-DC.

[0042] In the present invention, the mass fraction of the dilute sulfuric acid is preferably 48%. In the present invention, the ratio of the mass of the first intermediate to the volume of the dilute sulfuric acid is preferably 1 g: (100-150) mL, more preferably 1 g: (110-140) mL. In the present invention, the ratio of the mass of the first intermediate to the volume of the dilute sulfuric acid is controlled within the above range to achieve more complete hydrolysis of the template F127.

[0043] In the present invention, the temperature of the acid treatment is preferably 85-95°C; the time of the acid treatment is preferably 20-28 hours, more preferably 22-26 hours. The temperature and time of the acid treatment are controlled within the above ranges to obtain a higher carboxyl conversion rate.

[0044] In the present invention, the second post-treatment is preferably washing the acid-treated product with water until the pH value of the eluent reaches 7, followed by washing with ethanol and drying at 50-70° C. for 10-14 h to obtain SBA-16-DC.

[0045] After obtaining SBA-16-DC, the present invention immerses the SBA-16-DC in a ZrCl4 solution, and sequentially performs ultrasonication and drying to obtain a solid mixture.

[0046] In the present invention, the mass ratio of SBA-16-DC to ZrCl4 in the ZrCl4 solution is preferably 1:(1.4-2.4), more preferably 1:(1.5-2.2). In the present invention, the ultrasonication time is preferably 0.5-2 hours, and the ultrasonication power is preferably 150-300W. Ultrasound is used to better adsorb ZrCl4 onto the carboxyl groups on the surface of SBA-16-DC. In the present invention, the drying temperature is preferably 50-70°C, and the drying time is preferably 10-14 hours.

[0047] After obtaining the solid mixture, the present invention mixes the solid mixture with terephthalic acid and N,N-dimethylformamide, and then adds deionized water and acetic acid to carry out a second hydrothermal reaction to obtain a carboxyl-functionalized SBA-16-loaded UIO-66 composite material.

[0048] In the present invention, the mass ratio of ZrCl₄ to terephthalic acid in the ZrCl₄ solution is preferably (1.4-2.4):(0.8-1.5). In the present invention, the mass ratio of terephthalic acid to acetic acid is preferably 1 g:(5-20) mL. The present invention controls the mass ratio of terephthalic acid to acetic acid within the above range to better dissolve the terephthalic acid in the system.

[0049] In the present invention, the temperature of the second hydrothermal reaction is preferably 100-140°C, more preferably 110-130°C; the time of the second hydrothermal reaction is preferably 20-28 hours, more preferably 22-26 hours. The present invention controls the temperature and time of the second hydrothermal reaction within the above ranges to better form the UiO-66 active component on the support surface.

[0050] After the second hydrothermal reaction is completed, the product of the second hydrothermal reaction is preferably washed with N,N-dimethylformamide, washed with ethanol, and dried in sequence to obtain an SBA-16-DC@UiO-66 composite material.

[0051] The present invention also provides an application of the SBA-16-DC@UiO-66 composite material described in the above technical solution or the SBA-16-DC@UiO-66 composite material prepared by the preparation method in catalyzing the transfer hydrogenation reaction of furfural.

[0052] This invention utilizes a one-pot-prepared dicarboxyl-functionalized SBA-16 as a carrier (SBA-16-DC), followed by in situ synthesis of UiO-66-functionalized SBA-16. Compared to traditional loading methods, this composite material exhibits three key advantages: ① The dicarboxyl functional groups inhibit UiO-66 aggregation through a "molecular anchoring" effect; ② The pore environment optimizes the diffusion pathways of reactants; and ③ The interface between the rigid silicon-based framework and the flexible MOFs synergistically enhances mechanical stability.

[0053] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0054] Example 1

[0055] A SBA-16-DC@UiO-66 composite material, which is a microporous material with an average pore diameter of 0.8 to 1.1 nm and includes a carrier and an active component; the carrier is dicarboxyl-functionalized mesoporous silica SBA-16-DC, and the active component is UiO-66;

[0056] The SBA-16-DC is prepared by co-condensing a carboxyl functionalization reagent and an inorganic silicon source.

[0057] The loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 93.5 mg / g; the carboxyl functionalization reagent is 3-(triethoxysilyl)propyl succinic anhydride TPDD; and the inorganic silicon source is tetraethyl orthosilicate TEOS;

[0058] The preparation method of the above-mentioned SBA-16-DC@UiO-66 composite material comprises the following steps:

[0059] (1) Place 1.5 g of F127, 72 mL of water, and 7 mL of 36% hydrochloric acid in a 250 mL beaker and stir vigorously at room temperature. After the F127 is completely dissolved, add 5.5 mL of n-butanol to obtain a clear solution.

[0060] The clarified solution was heated to 45° C., 6.72 mL of TEOS and 0.6 mL of TPDD were added, and the mixture was stirred at a constant temperature of 45° C. for 24 hours. The mixture was then transferred to a polytetrafluoroethylene-lined hydrothermal synthesis reactor and subjected to a first hydrothermal reaction at a constant temperature of 100° C. for 24 hours. The product of the first hydrothermal reaction was then cooled to room temperature and centrifuged. The resulting solid was washed with deionized water and ethanol, and dried at 60° C. for 12 hours to obtain a first intermediate as a white powdery solid.

[0061] The mass ratio of the F127 to the volume of concentrated hydrochloric acid is 1.5 g:7 mL; the volume ratio of the TEOS to TPDD is 6.72:0.6;

[0062] (2) 1.0 g of the white powdery first intermediate of step (1) was mixed with 120 mL of 48 wt% H2SO4 solution, heated to 95°C, and subjected to acid treatment for 24 hours. The acid-treated product was filtered, and the resulting solid was washed with water until the pH value of the eluate reached 7, then washed twice with ethanol, and the resulting solid was dried at 60°C overnight to obtain SBA-16-DC;

[0063] The ratio of the mass of the first intermediate to the volume of dilute sulfuric acid is 1 g:120 mL;

[0064] (3) 1.0 g of the SBA-16-DC obtained in step (2) was immersed in an equal volume of ZrCl4 solution, ultrasonicated at 200 W for 1 h, and then dried at 60 ° C for 12 h to obtain a solid mixture;

[0065] The mass ratio of SBA-16-DC to ZrCl4 in the ZrCl4 solution is 1:1.73;

[0066] (4) The solid mixture obtained in step (3) was mixed with 1.25 g of terephthalic acid and 75 mL of N,N-dimethylformamide at room temperature and stirred vigorously. Subsequently, 0.5 mL of deionized water and 12.5 mL of acetic acid were added, and then transferred to a polytetrafluoroethylene-lined hydrothermal synthesis reactor, heated to 120° C., and a second hydrothermal reaction was carried out at a constant temperature for 24 hours. Subsequently, the product of the hydrothermal reaction was washed twice with N,N-dimethylformamide and ethanol, and dried at 60° C. to obtain a white solid SBA-16-DC@UiO-66 composite material;

[0067] The mass ratio of ZrCl4 to terephthalic acid in the ZrCl4 solution is 1.73:1.25; the mass ratio of terephthalic acid to acetic acid is 1g:10mL.

[0068] Figure 1 This is a transmission electron microscope image of the SBA-16-DC@UiO-66 composite material prepared in Example 1. Figure 1 As can be seen, the surface of the composite material remains smooth, with no MOF particles formed. This indicates that UiO-66 was synthesized within the pores of SBA-16. TEM images reveal the pore structure of the support and the dispersion of the metal. Some samples exhibit an ordered hexagonal structure with parallel pore channels, indicating that the original body-centered cubic mesostructure has been maintained.

[0069] Figure 2 This is the XPS graph of the SBA-16-DC@UiO composite material prepared in Example 1, where Figure 2 (a) is Si 2p, Figure 2 (b) is Zr 3d, Figure 2 (c) is C1s, Figure 2 (d) is O1s, Figure 2 (e) is a wide scan image. Figure 2 It can be seen that the main elements on the surface of the SBA-16-DC@UiO composite material sample prepared in Example 1 are Si, Zr, C and O, among which the Zr element comes from UiO-66.

[0070] Example 2

[0071] The SBA-16-DC@UiO-66 composite material was prepared according to the method of Example 1, except that 0.2 mL of TPDD was added.

[0072] Example 3

[0073] The SBA-16-DC@UiO-66 composite material was prepared according to the method of Example 1, except that 0.8 mL of TPDD was added.

[0074] Example 4

[0075] The SBA-16-DC@UiO-66 composite material was prepared according to the method of Example 1, except that 1.2 mL of TPDD was added.

[0076] Comparative Example 1

[0077] A composite material was prepared according to the method of Example 1, except that 0.625 g of terephthalic acid was added.

[0078] Comparative Example 2

[0079] A composite material was prepared according to the method of Example 1, except that 2.5 g of terephthalic acid was added.

[0080] Comparative Example 3

[0081] The SBA-16@UiO-66 composite material was prepared by using mesoporous silica SBA-16 with a particle size of 2.5 to 4.0 nm purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. as a carrier; the preparation steps of the SBA-16@UiO-66 composite material were as follows:

[0082] (1) 1.0 g of the purchased mesoporous silica was immersed in an equal volume of ZrCl4 solution, ultrasonicated at 200 W for 1 h, and then dried at 60 ° C for 12 h to obtain a solid mixture;

[0083] The mass ratio of SBA-16 to ZrCl4 in the ZrCl4 solution is 1:1.73;

[0084] (2) The solid mixture obtained in step (1) was mixed with 1.25 g of terephthalic acid and 75 mL of N,N-dimethylformamide at room temperature and stirred vigorously. Subsequently, 0.5 mL of deionized water and 12.5 mL of acetic acid were added, and then transferred to a polytetrafluoroethylene-lined hydrothermal synthesis reactor, heated to 120°C, and a second hydrothermal reaction was carried out at a constant temperature for 24 hours. Subsequently, the product of the hydrothermal reaction was washed twice with N,N-dimethylformamide and ethanol, and dried at 60°C to obtain a solid SBA-16@UiO-66 composite material.

[0085] The corresponding composite materials in Examples 1 to 4 and Comparative Examples 1 to 3 were used as catalysts for the transfer hydrogenation of furfural to prepare furfuryl alcohol. The steps were as follows: 0.55 mL of furfural, 80 mg of catalyst, and 10 mL of isopropyl alcohol were added to a reactor. The reactor was then sealed and heated to a predetermined temperature while magnetically stirring. After the reaction reached a predetermined time, it was transferred to ice water to stop the reaction. After cooling to room temperature, the resulting liquid product was analyzed by gas chromatography (GC). A JN.SE-54 capillary column (30 m × 0.32 mm × 0.25 μm) was used with naphthalene as the internal standard. A standard curve was drawn based on the known concentrations of furfural and furfuryl alcohol to obtain the content of each component in the product. The temperature program for GC analysis was set as follows: first, a constant temperature of 60°C for 3 min, then a temperature increase rate of 5°C / min from 60°C to 180°C, and finally a constant temperature of 180°C for 10 min. The inlet and detector temperatures were 250°C and 270°C, respectively. The used catalyst was washed twice with deionized water and ethanol, then dried for later use. To evaluate the catalyst's cyclic stability, it was reused five times. Finally, the furfural conversion and furfuryl alcohol selectivity were calculated using the formula.

[0086] The yields of furfuryl alcohol prepared using the corresponding composite materials prepared in Examples 1 to 4 and Comparative Examples 1 to 3 as catalysts were detected by gas chromatography (GC) and are shown in Table 1.

[0087] The corresponding composite materials of Examples 1 to 4 and Comparative Examples 1 to 3 after the above reaction were recovered and recycled as catalysts. After recycling for 5 times, the yield of the prepared furfuryl alcohol is shown in Table 1.

[0088] Table 1 Catalytic performance of the corresponding composite materials of Examples 1 to 4 and Comparative Examples 1 and 2

[0089]

[0090] As shown in Table 1, when the composite material prepared in Example 1 was used as a catalyst, the conversion rate of furfural reached 100% and the selectivity of furfuryl alcohol reached 99.7%. After five cycles of experiments, the catalytic ability of the composite material remained essentially unchanged.

[0091] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A SBA-16-DC@UiO-66 composite material, characterized in that The SBA-16-DC@UiO-66 composite material includes a carrier and an active component; the carrier is dicarboxyl functionalized mesoporous silica SBA-16-DC, and the active component is UiO-66; The SBA-16-DC is prepared by co-condensation of a carboxyl functionalization reagent and an inorganic silicon source; The loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 65 to 140 mg / g.

2. The SBA-16-DC@UiO-66 composite material according to claim 1, characterized in that The SBA-16-DC@UiO-66 composite material is a microporous material with an average pore diameter of 0.6 to 1.6 nm.

3. The SBA-16-DC@UiO-66 composite material according to claim 1, characterized in that The loading amount of the active component UiO-66 in the SBA-16-DC@UiO-66 composite material is 70 to 120 mg / g.

4. The SBA-16-DC@UiO-66 composite material according to claim 1, characterized in that The carboxyl functionalization reagent is 3-(triethoxysilyl)propyl succinic anhydride TPDD, and the inorganic silicon source is tetraethyl orthosilicate TEOS.

5. A method for preparing the SBA-16-DC@UiO-66 composite material according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Polyethylene glycol-polypropylene glycol-polyethylene glycol diacrylate F127, water, and concentrated hydrochloric acid are mixed, n-butanol is added, and then TEOS and TPDD are added under heating conditions, and constant temperature stirring, a first hydrothermal reaction, and a first post-treatment are performed in sequence to obtain a first intermediate; (2) mixing the first intermediate obtained in step (1) with dilute sulfuric acid, and then performing acid treatment and a second post-treatment in sequence to obtain SBA-16-DC; (3) immersing the SBA-16-DC obtained in step (2) into a ZrCl4 solution, and sequentially performing ultrasonication and drying to obtain a solid mixture; (4) The solid mixture obtained in step (3) is mixed with terephthalic acid and N,N-dimethylformamide, and then deionized water and acetic acid are added, and a second hydrothermal reaction and a second post-treatment are performed in sequence to obtain an SBA-16-DC@UiO-66 composite material.

6. The preparation method according to claim 5, characterized in that The temperature of the first hydrothermal reaction in step (1) is 80-120° C., and the time of the first hydrothermal reaction is 20-28 hours.

7. The preparation method according to claim 5, characterized in that The temperature of the acid treatment in step (2) is 85-95° C., and the time of the acid treatment is 20-28 hours.

8. The preparation method according to claim 5, characterized in that The mass ratio of SBA-16-DC and ZrCl4 in the ZrCl4 solution in step (3) is 1:(1.4-2.4).

9. The preparation method according to claim 5, characterized in that The temperature of the second hydrothermal reaction in step (4) is 100-140° C., and the time of the second hydrothermal reaction is 20-28 hours.

10. Use of the SBA-16-DC@UiO-66 composite material according to any one of claims 1 to 4 or the SBA-16-DC@UiO-66 composite material prepared by the preparation method according to any one of claims 5 to 9 in catalyzing the transfer hydrogenation reaction of furfural.

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