MOFs derived bimetallic mesoporous Cu / Ni-MNC material and preparation method thereof

Abstract

The invention discloses an MOFs (Metal-Organic Frameworks) derived bimetallic mesoporous Cu / Ni-MNC (Metal Nitrocellulose) material and a preparation method thereof. The method comprises the following steps: adding a metal salt mixed solution into an organic ligand solution, standing, centrifuging and drying to obtain a Cu / Ni-ZIF material; the preparation method comprises the following steps: adding a Cu / Ni-ZIF-TA material into ethanol, then adding a methanol solution of tannic acid, stirring at room temperature for different times, centrifuging and drying to obtain a Cu / Ni-ZIF-TA material; and the Cu / Ni-ZIF-TA material is calcined, and the bimetallic mesoporous Cu / Ni-MNC material is obtained. Compared with a traditional synthesis template method, an activation method and the like, the method is easy and convenient to operate, safe and environmentally friendly; on one hand, due to introduction of low-boiling-point Zn, agglomeration of nanoparticles at high temperature is inhibited, and on the other hand, etching treatment of tannic acid and nitrogen doping enable the material to have different degrees of defects. The material shows excellent catalytic performance in hydrogenation reduction reaction of furfural, and has a good application prospect.

Description

Technical Field

[0001] The invention relates to the field of porous materials, and in particular to a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material and a preparation method thereof. Background Art

[0002] Metal-Organic Frameworks (MOFs) are porous materials with a periodic network structure formed by self-assembly of metal ions or metal clusters and organic ligands through coordination bonds. Compared with traditional porous materials, metal-organic frameworks (MOFs) have significant advantages in specific surface area, porosity adjustability and uniform dispersion of metal sites. By pyrolyzing MOFs at high temperatures, some of its composition and pore structure can be retained, thereby synthesizing porous metal-carbon composites with excellent chemical and thermal stability. This type of composite material has shown broad application prospects in catalysis and many other fields.

[0003] The preparation of most MOFs-derived carbon materials depends on high-temperature calcination. However, for MOFs-derived materials obtained by direct calcination, metal particles tend to aggregate during the calcination process as the pyrolysis temperature increases, and the specific surface area of ​​the obtained carbon material also decreases sharply, which greatly limits the improvement of mass transfer rate.

[0004] At present, the research on preparing MOFs-derived porous carbon materials mainly focuses on the restricted pyrolysis method. For example, Hou et al. used Fe / ZIF-8 covered with SiO2 as a precursor and cleverly used the difference in thermal stability of different materials to prepare single-atom nitrogen-doped carbon materials with "overhanging eaves" structure and abundant micropores and mesopores (Hou, C.-C.; Zou, L.; Sun, L.; Zhang, K.; Liu, Z.; Li, Y.; Li, C.; Zou, R.; Yu, J.; Xu, Q. Single-Atom Iron Catalysts on Overhang-Eave Carbon Cages for High-Performance Oxygen Reduction Reaction. Angew. Chem. Int. Ed. 2020, 59(19), 7384–7389.); In order to further enrich the pore structure, etchants are introduced to construct open pores and hollow structures in MOF to improve the accessibility of active sites. For example, Li et al. used xylenol orange (XO) as a chelating agent to directional etch to destroy the coordination bonds (Zn-2-MIM) in ZIF-8, and constructed ZIF-8 with a unique open pore structure as a pyrolysis precursor. Through a one-step high-temperature carbonization method, the prepared Fe / NC material has mesopores and macropores, accounting for 86.5% of the total pore volume. (Li, J.; Xia, W.; Xu, X.; Jiang, D.; Cai, Z.-X.; Tang, J.; Guo, Y.; Huang, X.; Wang, T.; He, J.; Han, B.; Yamauchi, Y. Selective Etching of Metal–Organic Frameworks for Open Porous Structures: Mass-Efficient Catalysts with Enhanced Oxygen Reduction Reaction for Fuel Cells. J. Am. Chem. Soc. 2023, 145(50), 27262–27272.) Similarly, Cai et al. selected cyanuric acid (CA) with appropriate chelating ability and molecular size as a surface modifier and etchant to selectively etch ZIF-67 from the inside to the outside to form a hollow nanoframe, which was then calcined in a reducing atmosphere to further obtain a mesoporous carbonized framework composed of small-sized metal nanoparticles.(Cai, Z.-X.; Wang, Z.-L.; Xia, Y.-J.; Lim, H.; Zhou, W.; Taniguchi, A.; Ohtani, M.; Kobiro, K.; Fujita, T.; Yamauchi, Y. Tailored Catalytic Nanoframes from Metal–Organic Frameworks by Anisotropic Surface Modification and Etching for the Hydrogen Evolution Reaction. Angew. Chem. Int. Ed. 2021, 60(9), 4747–4755.) However, existing literature reports all involve further acid treatment to remove the aggregated metal particle components to obtain the final metal-porous carbon material. The more complicated steps limit the application of such methods in the field of heterogeneous catalysis. In summary, there are still many challenges in preparing MOFs-derived metal-carbon composites with highly exposed active sites and excellent mass transfer efficiency through simple and green methods. Summary of the invention

[0005] In order to solve the problems existing in the existing methods and technologies, the object of the present invention is to provide a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material and a preparation method thereof.

[0006] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0007] The present invention provides a method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC, comprising the following steps:

[0008] (1) adding an organic ligand to an aqueous solution of a surfactant and dissolving the organic ligand uniformly by ultrasonication to obtain an organic ligand solution; dissolving a zinc salt, a copper salt and a nickel salt in deionized water to obtain a metal salt mixed solution;

[0009] (2) mixing the metal salt solution and the organic ligand solution in step (1), stirring evenly, standing, centrifuging to obtain a precipitate, and drying to obtain a Cu / Ni-ZIF material;

[0010] (3) adding the Cu / Ni-ZIF material described in step (2) to anhydrous ethanol, and uniformly dispersing it by ultrasonication to obtain a suspension A; dissolving an organic acid in anhydrous methanol, and uniformly dispersing it to obtain a solution B; mixing the suspension A and the solution B, and stirring them at room temperature to obtain a Cu / Ni-ZIF-TA material;

[0011] (4) The Cu / Ni-ZIF-TA material of step (3) is heated and calcined in an inert atmosphere to obtain the MOFs-derived bimetallic mesoporous Cu / Ni-MNC material. Furthermore, the organic ligand of step (1) is 2-methylimidazole, and the concentration of the organic ligand solution is 2.6-2.8 mol / L.

[0012] Furthermore, the surfactant in step (1) is hexadecyltrimethylammonium bromide (CTAB), and its concentration in the organic ligand solution is 0.46-0.48 mmol / L.

[0013] Furthermore, in the metal salt solution of step (1), the zinc salt, copper salt and nickel salt are zinc acetate, copper acetate and nickel acetate respectively, the concentration of zinc acetate is 0.26-0.28 mol / L, the concentration of copper acetate is 0.02-0.04 mol / L, and the concentration of nickel acetate is 0.01-0.02 mol / L.

[0014] Furthermore, the organic acid in step (1) is tannic acid, and the concentration of the organic acid in solution B is 2.6-2.8 mol / L.

[0015] Furthermore, in step (2), the volume ratio of the metal salt solution to the organic ligand solution is 1:1; the standing time is 120-180 minutes; and the drying temperature is 60-70°C.

[0016] Preferably, the stirring temperature in step (2) is 25-30° C., the stirring speed is 10-20 rpm / min, and the stirring time is 1-2 min.

[0017] Preferably, the centrifugal speed in step (2) is 8000-9000 r / min, and the centrifugal time is 4-6 min.

[0018] Furthermore, in step (3), the mass volume ratio of the CuNi-ZIF material to anhydrous ethanol is 7-9:1 mg / mL.

[0019] Furthermore, the mass volume of the tannic acid and anhydrous methanol in step (3) is 2-4 mg / mL.

[0020] Preferably, in step (3), the mass ratio of the CuNi-ZIF material to tannic acid is 3.5-4.5:1.

[0021] Preferably, the stirring time at room temperature in step (3) is 0-120 min.

[0022] Furthermore, the inert atmosphere in step (4) is an argon atmosphere; the calcination temperature is 900° C., the calcination time is 3 h, and the heating rate is 5° C. / min.

[0023] The present invention provides a MOFs-derived bimetallic mesoporous Cu / Ni-MNC composite material prepared by the above-mentioned preparation method.

[0024] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0025] (1) The present invention is easy to operate, environmentally friendly, and has good versatility.

[0026] (2) The material prepared by the present invention constructs defect units in the etching process, and the subsequent high-temperature pyrolysis process zinc evaporation and nitrogen doping further amplify the defects, thereby forming a mesoporous structure, which is conducive to efficient mass transfer.

[0027] (3) In the process of MOFs precursor synthesis, the present invention introduces bimetallic components through an in-situ encapsulation method, and utilizes the difference in internal and external thermal stability to form a hollow porous structure loaded with bimetallic components through one-step pyrolysis, which can expose active sites at a high density. At the same time, the synergistic catalytic effect of the bimetallic sites improves the catalytic reaction activity and selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 X-ray powder diffraction (PXRD) curves of 1# / 2# / 3# / 4# / 5# / 6#Cu / Ni-MNC materials obtained in Examples 1 / 2 / 3 / 4 / 5 / 6;

[0029] Figure 2 The following are scanning electron microscope (SEM) images of the materials obtained in Example 1; wherein (a) is a scanning electron microscope (SEM) image of the 1#Cu / Ni-MNC material obtained in Example 1; (b) is a SEM image of the 2#Cu / Ni-MNC material obtained in Example 2; (c) is a SEM image of the 3#Cu / Ni-MNC material obtained in Example 3; (d) is a SEM image of the 4#Cu / Ni-MNC material obtained in Example 4; (e) is a SEM image of the 5#Cu / Ni-MNC material obtained in Example 5; (f) is a SEM image of the 6#Cu / Ni-MNC material obtained in Example 6;

[0030] Figure 3Figures are transmission electron microscope (TEM) images, wherein (a) is a transmission electron microscope (TEM) image of the CuNi-ZIF-900 material obtained by directly calcining CuNi-ZIF; (b) is a TEM image of the 1#Cu / Ni-MNC material obtained in Example 1; (c) is a TEM image of the 2#Cu / Ni-MNC material obtained in Example 2; (d) is a TEM image of the 3#Cu / Ni-MNC material obtained in Example 3; (e) is a TEM image of the 4#Cu / Ni-MNC material obtained in Example 4; (f) is a TEM image of the 5#Cu / Ni-MNC material obtained in Example 5; (g) is a TEM image of the 6#Cu / Ni-MNC material obtained in Example 6; (h) is a TEM image of the 7#Cu / Ni-MNC material obtained in Example 7;

[0031] Figure 4 The nitrogen adsorption-desorption isotherms of 1# / 2# / 3# / 4# / 5# / 6#Cu / Ni-MNC materials obtained in Examples 1 / 2 / 3 / 4 / 5 / 6;

[0032] Figure 5 are SEM images of Examples 8 to 13; wherein (a) is the SEM image of the 8#Cu / Ni-MNC material obtained in Example 8, (b) is the SEM image of the 9#Cu / Ni-MNC material obtained in Example 9; (c) is the SEM image of the 10#Cu / Ni-MNC material obtained in Example 10; (d) is the SEM image of the 11#Cu / Ni-MNC material obtained in Example 11; (e) is the SEM image of the 12#Cu / Ni-MNC material obtained in Example 12; (f) is the SEM image of the 13#Cu / Ni-MNC material obtained in Example 13;

[0033] Figure 6 This is a graph showing the performance test results of the 1#Cu-MNC material obtained in Example 1 for catalyzing the hydrogenation reaction of furfural at different reaction times. DETAILED DESCRIPTION

[0034] The specific implementation of the present invention is further described below in conjunction with examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are processes that are not particularly described in detail below, they can be implemented or understood by those skilled in the art with reference to the prior art. If the manufacturer of the reagents or instruments used is not indicated, they are deemed to be conventional products that can be purchased commercially.

[0035] Example 1

[0036] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0037] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0038] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0039] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 10 min. Centrifuge the resulting CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0040] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is increased to 900°C at 5°C / min, calcined at 900°C for 3h, and taken out after cooling to room temperature, finally obtaining the MOFs-derived Cu / Ni-MNC material (labeled as 1#Cu / Ni-MNC material), which is a black solid. The obtained 1#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0041] Figure 1 This is the PXRD spectrum of the 1#Cu / Ni-MNC material obtained in this example. Figure 1 It can be seen that the PXRD peak of 1#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0042] Figure 2 (b) is the SEM image of the 1#Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0043] Figure 3(b) is the TEM image of the 1#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0044] Figure 4 (a) is the nitrogen adsorption and desorption test results of the 1#Cu / Ni-MNC material obtained in this example and the CuNi-ZIF-900 obtained by directly calcining CuNi-ZIF (CuNi-ZIF-900 is obtained by calcining the CuNi-ZIF in step (2) of Example 1 at 900°C for 3h). Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 1#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0 =0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0045] Example 2

[0046] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0047] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0048] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0049] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 20 min. Centrifuge the resulting CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0050] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is raised to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (labeled as 2#Cu / Ni-MNC material), which is a black solid. The obtained 2#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0051] Figure 1 This is the PXRD spectrum of the 2#Cu / Ni-MNC material obtained in this example. Figure 1 It can be seen that the PXRD peak of 2#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0052] Figure 2 (c) is the SEM image of the 2#Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0053] Figure 3 (c) is the TEM image of the 2#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0054] Figure 4 This is the nitrogen adsorption and desorption test result of the 2#Cu / Ni-MNC material obtained in this example. Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 2#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0=0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0055] Example 3

[0056] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0057] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0058] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0059] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 30 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0060] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is raised to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (labeled as 3#Cu / Ni-MNC material), which is a black solid. The obtained 3#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0061] Figure 1 This is the PXRD spectrum of the 3#Cu / Ni-MNC material obtained in this example. Figure 1It can be seen that the PXRD peak of 3#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0062] Figure 2 (d) is the SEM image of the 3#Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0063] Figure 3 (d) is the TEM image of the 3#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0064] Figure 4 This is the nitrogen adsorption and desorption test result of the 3#Cu / Ni-MNC material obtained in this example. Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 3#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0 =0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0065] Example 4

[0066] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0067] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0068] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0069] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 40 min. Centrifuge the resulting CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0070] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is increased to 900°C at 5°C / min, calcined at 900°C for 3h, and taken out after cooling to room temperature, finally obtaining the MOFs-derived Cu / Ni-MNC material (labeled as 4#Cu / Ni-MNC material), which is a black solid. The obtained 4#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0071] Figure 1 is the PXRD spectrum of 4#Cu / Ni-MNC material obtained in this example. Figure 1 It can be seen that the PXRD peak of 4#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0072] Figure 2 (e) is a SEM image of the 4#Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0073] Figure 3 (e) is a TEM image of the 4#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0074] Figure 4 This is the nitrogen adsorption and desorption test result of the 4#Cu / Ni-MNC material obtained in this example. Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 4#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0 =0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0075] Example 5

[0076] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0077] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0078] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0079] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 50 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0080] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is raised to 900°C at 5°C / min, calcined at 900°C for 3h, and taken out after cooling to room temperature, finally obtaining the MOFs-derived Cu / Ni-MNC material (labeled as 5#Cu / Ni-MNC material), which is a black solid. The obtained 5#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0081] Figure 1 is the PXRD spectrum of 5#Cu / Ni-MNC material obtained in this example. Figure 1 It can be seen that the PXRD peak of 5#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0082] Figure 2 (f) is a SEM image of the 5#Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0083] Figure 3 (f) is the TEM image of the 5#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0084] Figure 4 This is the nitrogen adsorption and desorption test result of the 5#Cu / Ni-MNC material obtained in this example. Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 5#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0 =0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0085] Example 6

[0086] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0087] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0088] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0089] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0090] (4) The CuNi-ZIF-TA material obtained in step (3) is placed in a quartz boat in a tube furnace, argon is used as the calcination atmosphere, the temperature is increased to 900°C at 5°C / min, calcined at 900°C for 3h, and taken out after cooling to room temperature, finally obtaining the MOFs-derived Cu / Ni-MNC material (labeled as 6#Cu / Ni-MNC material), which is a black solid. The obtained 6#Cu / Ni-MNC material can be directly used in heterogeneous catalysis.

[0091] Figure 1 is the PXRD spectrum of the 6#Cu / Ni-MNC material obtained in this example. Figure 1 It can be seen that the PXRD peak of 6#Cu / Ni-MNC material at 25.3° corresponds to the (002) crystal plane of carbon, indicating that the catalyst is completely carbonized during the pyrolysis process, and no obvious metal peak is found. This indicates that these copper and nickel species are very small in size and highly dispersed, and may exist in the form of single atoms.

[0092] Figure 2 (g) is a SEM image of the #6Cu / Ni-MNC material obtained in this example. It can be observed that the material has a truncated dodecahedral morphology, a rough surface, and a particle size of about 230 nm.

[0093] Figure 3 (g) is the TEM image of the 6#Cu / Ni-MNC material obtained in this example. Figure 3 It can be seen that the material is composed of a thin outer shell and a porous internal network, and no obvious aggregation of metal particles is found.

[0094] Figure 4 This is the nitrogen adsorption and desorption test result of the 6#Cu / Ni-MNC material obtained in this example. Figure 4 It can be seen that the nitrogen adsorption of the material obtained after etching increases significantly. The hysteresis loop shows that the 6#Cu / Ni-MNC material is rich in mesopores and has a low relative pressure range (P / P 0 <0.1) shows a significant nitrogen adsorption capacity, indicating that the calcined material has well preserved the microporous structure of ZIF-8. 0 =0.95-1.0), the nitrogen adsorption isotherm also shows an obvious continuous upward trend, which may be related to the existence of large pores in the material. Therefore, the material has the characteristics of a micropore-mesopore-macroporous multi-level pore structure.

[0095] Example 7

[0096] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0097] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0098] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0099] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 2 h. Centrifuge the resulting CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0100] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 7#Cu / Ni-MNC material), which was a black solid.

[0101] Example 8

[0102] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0103] (1) 2-Methylimidazole (2.24 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0104] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0105] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0106] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 8#Cu / Ni-MNC material), which was a black solid.

[0107] Example 9

[0108] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0109] (1) 2-Methylimidazole (3.36 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0110] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0111] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0112] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 9#Cu / Ni-MNC material), which was a black solid.

[0113] Example 10

[0114] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0115] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.4 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0116] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0117] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0118] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 10#Cu / Ni-MNC material), which was a black solid.

[0119] Embodiment 11

[0120] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0121] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.5 g), copper acetate (0.03 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0122] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0123] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0124] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, and taken out after cooling to room temperature, finally obtaining the MOFs-derived Cu / Ni-MNC material (marked as 11#Cu / Ni-MNC material), which was a black solid.

[0125] Example 12

[0126] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0127] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and ultrasonically dispersed to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.05 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and ultrasonically dispersed to obtain a metal salt mixed solution;

[0128] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0129] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0130] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 12#Cu / Ni-MNC material), which was a black solid.

[0131] Embodiment 13

[0132] This embodiment provides a method for preparing a MOFs-derived Cu / Ni-MNC material, comprising the following steps:

[0133] (1) 2-Methylimidazole (1.12 g) was added to 5 ml of a hexadecyltrimethylammonium bromide aqueous solution (0.17 g / L), and the mixture was dispersed uniformly by ultrasonication to obtain an organic ligand solution; zinc acetate (0.3 g), copper acetate (0.07 g) and nickel acetate (0.01 g) were dissolved in deionized water (5 ml), and the mixture was dispersed uniformly by ultrasonication to obtain a metal salt mixed solution;

[0134] (2) adding the metal salt mixed solution in step (1) to the 2-methylimidazole solution, standing for 120 min to obtain a CuNi-ZIF suspension, centrifuging the obtained CuNi-ZIF suspension at 9000 r / min for 4 min, taking a precipitate, and then washing it with deionized water and anhydrous ethanol for several times, respectively, and drying it in an oven at 60° C. for 12 h to obtain a CuNi-ZIF material;

[0135] (3) Weigh 400 mg of the CuNi-ZIF material obtained in step (2) and disperse it in 10 mL of anhydrous ethanol, and ultrasonicate for 5 min to obtain a light pink suspension. Disperse 20 mg of tannic acid in 10 mL of anhydrous methanol and add it to the light pink suspension. Stir at room temperature for 60 min. Centrifuge the obtained CuNi-ZIF-TA suspension and dry it to obtain a CuNi-ZIF-TA material.

[0136] (4) The CuNi-ZIF-TA material obtained in step (3) was placed in a quartz boat in a tube furnace, argon was passed as the calcination atmosphere, the temperature was increased to 900°C at 5°C / min, calcined at 900°C for 3h, cooled to room temperature and then taken out to finally obtain the MOFs-derived Cu / Ni-MNC material (marked as 13#Cu / Ni-MNC material), which was a black solid.

Claims

1. A method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material, characterized in that: The steps include: (1) adding an organic ligand to an aqueous solution of a surfactant and dissolving the organic ligand uniformly by ultrasonication to obtain an organic ligand solution; dissolving three transition metal salts in deionized water to obtain a metal salt mixed solution; (2) mixing the metal salt mixed solution and the organic ligand solution in step (1), stirring evenly, standing, centrifuging to obtain a precipitate, and drying to obtain a Cu / Ni-ZIF material; (3) adding the Cu / Ni-ZIF material described in step (2) to anhydrous ethanol, and uniformly dispersing it by ultrasonication to obtain a suspension A; dissolving an organic acid in anhydrous methanol, and uniformly dispersing it to obtain a solution B; mixing the suspension A and the solution B, and stirring them at room temperature to obtain a Cu / Ni-ZIF-TA material; (4) The Cu / Ni-ZIF-TA material of step (3) is heated and calcined in an airtight environment to obtain the MOFs-derived bimetallic mesoporous Cu / Ni-MNC material.

2. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (1), the organic ligand is a basic organic ligand, and the concentration of the organic ligand solution is 2.6-2.8 mol / L.

3. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (1), the surfactant is an anionic surfactant, and its concentration in the organic ligand solution is 0.46-0.48 mmol / L; the anionic surfactant is selected from hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride.

4. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (1), in the metal salt mixed solution, the three transition metal salts are zinc salt, copper salt and nickel salt, respectively, the concentration of zinc salt is 0.26-0.28 mol / L, the concentration of copper salt is 0.02-0.04 mol / L, and the concentration of nickel salt is 0.01-0.02 mol / L; the zinc salt is selected from zinc acetate, zinc nitrate or zinc chloride; the copper salt is selected from copper acetate, copper nitrate or copper chloride; the nickel salt is selected from nickel acetate, nickel nitrate or nickel chloride.

5. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (2), the volume ratio of the metal salt solution to the organic ligand solution is 3-1:1; the standing time is 120-180 min; the drying temperature is 60-70° C.; and the organic ligand is selected from 2-methylimidazole or 1-methylimidazole.

6. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (3), the mass volume ratio of the CuNi-ZIF material to anhydrous ethanol is 7-9:1 mg / mL, and the mass volume ratio of the organic acid to anhydrous methanol is 2-4 mg / mL; the organic acid is selected from tannic acid or cyanuric acid.

7. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (3), the mass ratio of the CuNi-ZIF material to the organic acid is 3.5-4.5:

1.

8. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (3), the stirring time at room temperature is 0-120 min.

9. The method for preparing a MOFs-derived bimetallic mesoporous Cu / Ni-MNC material according to claim 1, characterized in that: In step (4), the inert atmosphere is an argon atmosphere; the calcination temperature is 700-900°C, the calcination time is 1-3h, and the heating rate is 2-6°C / min.

10. A MOFs-derived bimetallic mesoporous Cu / Ni-MNC material prepared by the preparation method according to any one of claims 1 to 9.

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