Copper-iron bimetallic MOFs material, preparation method and application thereof and method for preparing N-substituted pyrrole compound

Abstract

The application relates to the technical field of metal organic framework materials, in particular to a copper-iron bimetallic MOFs material, a preparation method and application thereof and a method for preparing N-substituted pyrrole compounds. The copper-iron bimetallic MOFs material comprises: a bimetallic center formed by Fe and Cu containing two or more valence states; and an organic ligand which is hybridized with the bimetallic center through a coordination bond to form a three-dimensional network structure crystal; wherein the copper-iron bimetallic MOFs material contains only L acid and the amount of the L acid is 100-600 micromoles per gram ‑1 The copper-iron bimetallic MOFs material contains only L acid sites and is used as a catalyst for synthesizing N-substituted pyrrole compounds, has the outstanding characteristics that the reaction efficiency of furan compounds and amine compounds is high and the yield is high under mild conditions, and high efficiency and high yield of the reaction are realized.

Description

Technical Field

[0001] This invention relates to the field of metal-organic framework materials technology, specifically to a copper-iron bimetallic MOF material, its preparation method and application, and a method for preparing N-substituted pyrrole compounds. Background Technology

[0002] Over the past few decades, the world has become increasingly reliant on petroleum as a primary source of chemicals and energy. Due to increasing industrial demand and dwindling petroleum reserves, conversion strategies for producing fine chemicals and biofuels from primary biomass have attracted widespread attention from scientists. Lignocellulose can be readily converted into platform compounds containing specific functional groups, including furans and benzene rings, providing a promising entry point for downstream processing. While researchers have made significant efforts in recent years to develop new catalytic routes and processes to convert platform compounds into various high-density biosynthetic fuels, developing new conversion methods orthogonal to or complementary to existing green and sustainable chemical synthesis approaches remains a crucial industrial challenge.

[0003] Nitrogen heterocycles, particularly functionalized pyrroles, are important structural units in a large number of naturally occurring and pharmacologically active molecules, widely used in the core structures of bioactive substances such as vitamins, anticancer drugs, and antibacterial drugs. Patent document CN103288701A discloses a 1,5-diarylpyrrole derivative prepared by reacting a 1,4-dicarbonyl compound with an amine compound under protic acid catalysis; the yields in most examples are around 40-60%. Traditional N-substituted pyrrole methods typically use substituted ketones, aldehydes, or amines as substrates, most of which are derived from petrochemical resources, and the reaction yields are relatively low. Exploring the construction of pyrrole derivatives based on biomass is therefore more important.

[0004] The heterogeneous catalytic dehydrogenation coupling reaction of bio-secondary alcohols with amino alcohols, pioneered in literature [Nat. Chem. 2013, 5, 140-144; Catal. Sci. Technol. 2014, 4, 4188-4192], has become an important method for constructing pyrrole skeletons. Despite the high yields, the costly and potentially toxic iridium species, requiring separation and recovery, still present challenges to establishing greener and more sustainable synthetic methods.

[0005] Recently, it has been reported that the condensation of aromatic amines with furan to prepare pyrrole under mild conditions can be achieved using a solid acid H-type zeolite Y catalyst [ACS Catal. 2017, 7, 959.]. Studies have confirmed that the Brønsted acid site (protic acid) is the key catalytic site for the catalyst, and the reaction follows the classic Paal-Knorr reaction pathway. CN111574424B reports a method for preparing N-arylpyrrole compounds using a catalyst containing a Lewis acid. The catalyst is synthesized via a sol-gel method, using a mesoporous molecular sieve SBA15 as a support and loading Hf as the core metal element. However, this method suffers from uneven metal element distribution and easy leaching. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of low product selectivity of N-substituted pyrrole compounds or the need for expensive metal catalysts in existing technologies. This invention provides a copper-iron bimetallic MOF material, its preparation method, and its application in the preparation of N-substituted pyrrole compounds. This copper-iron bimetallic MOF material contains only L-acid sites and is used as a catalyst for the synthesis of N-substituted pyrrole compounds. Under mild conditions, it exhibits outstanding characteristics such as high reaction efficiency and high yield for furan and amine compounds, achieving high reaction efficiency and high product yield.

[0007] To achieve the above objectives, a first aspect of the present invention provides a copper-iron bimetallic MOF material, the copper-iron bimetallic MOF material comprising:

[0008] A bimetallic center formed by Fe and Cu containing two or more valence states; and

[0009] Organic ligands that hybridize with bimetallic centers through coordination bonds to form a three-dimensional network structure crystal;

[0010] The copper-iron bimetallic MOFs material contains only L-acid, and the amount of L-acid is 100-600 μmol·g. -1 .

[0011] A second aspect of the present invention provides a method for preparing the copper-iron bimetallic MOFs material of the present invention, the method comprising the following steps:

[0012] S1. Dissolve organic ligands and Cu salts in a solvent, crystallize, separate, and first dry to obtain Cu-based MOFs materials formed by Cu and organic ligands;

[0013] S2. Contact the Cu-based MOFs material from step S1 with an aqueous alcohol mixture containing elemental Fe and Fe salt; separate and perform a second drying to obtain the copper-iron bimetallic MOFs material.

[0014] A third aspect of the present invention provides the application of the copper-iron bimetallic MOFs material described herein in the synthesis of pyrrole compounds.

[0015] A fourth aspect of the present invention provides a method for preparing N-substituted pyrrole compounds, the method comprising:

[0016] In the presence of a liquid diluent, furan compounds and amine compounds are contacted with a catalyst; the catalyst contains the copper-iron bimetallic MOF material described in this invention.

[0017] Through the above technical solution, the copper-iron bimetallic MOFs material of the present invention has both metals bonded to organic ligands, and due to the interaction between the two metals, the valence state of the metals changes, forming more vacant coordination sites. The copper-iron bimetallic MOFs material contains only Lewis acid sites. According to a preferred embodiment of the present invention, the crystal surface of the copper-iron bimetallic MOFs material exhibits a regularly rough or uneven morphology; more preferably, the rough morphology covers the crystal surface of the copper-iron bimetallic MOFs material in a network pattern; or the rough morphology covers the crystal surface of the copper-iron bimetallic MOFs material in particles.

[0018] The copper-iron bimetallic MOFs material described in this invention is used to synthesize pyrrole compounds (e.g., N-substituted pyrrole compounds) with high reaction efficiency and high selectivity.

[0019] In existing technologies, conventional catalytic methods for preparing N-substituted pyrrole compounds use Brønsted acid (protic acid) as a catalyst. This method is susceptible to the influence of the presence or absence of water in the reaction system. However, in this invention, the method for preparing N-substituted pyrrole compounds uses the copper-iron bimetallic MOFs material described herein as a catalyst. Since the copper-iron bimetallic MOFs material contains only Lewis acid sites, it can catalytically convert furans and amines into N-substituted pyrrole compounds under mild reaction conditions, preventing the formation of byproducts such as 3-methyl-2-cyclopentenone. This method exhibits high selectivity. Furthermore, because it uses a catalytic material containing Lewis acid, it is less likely to corrode equipment at high temperatures. Simultaneously, the mild reaction conditions do not damage the structure of the copper-iron bimetallic MOFs material, thus providing a new approach to the application of MOFs in catalysis.

[0020] The preparation method of the copper-iron bimetallic MOFs material of this invention creatively incorporates elemental iron, utilizing the concept of self-reduction of multivalent transition metals. Under the influence of elemental iron, the modified solution acquires reducing properties, maximizing the effectiveness of the reducing components. Furthermore, in addition to its reducing effect, metallic iron provides more vacancy sites, increasing the acidity of the material, resulting in the multivalent copper-iron bimetallic MOFs material containing only L-acids. In the copper-iron bimetallic MOFs material of this invention, metal ions and carboxylic acid ligands form a binuclear metal slurry structure at the nodes. During the preparation process, coordinated water molecules are easily removed, forming open metal centers that serve as catalytic centers. Attached Figure Description

[0021] Figure 1 This is a scanning electron microscope (SEM) image of Cu-BTC in Example 1;

[0022] Figure 2 This is a scanning electron microscope (SEM) image of the Fe-Cu-BTC obtained in Example 1;

[0023] Figure 3 The image shows a scanning electron microscope (SEM) image of Fe-Cu-BTC-8 obtained in Example 8.

[0024] Figure 4(a) shows the X-ray photoelectron spectroscopy (XPS) of Cu 2p3 / 2 of Cu-BTC and Fe-Cu-BTC obtained in Example 1; Figure 4(b) shows the X-ray photoelectron spectroscopy (XPS) of Fe 2p of Cu-BTC and Fe-Cu-BTC obtained in Example 1.

[0025] Figure 5 The images show the pyridine desorption infrared (Py-FTIR) images of Cu-BTC and Fe-Cu-BTC obtained in Example 1.

[0026] Figure 6 The images show the XRD patterns of Cu-BTC and Fe-Cu-BTC obtained in Example 1. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] In this invention, MOFs materials refer to metal-organic framework materials or metal-organic skeleton materials.

[0029] In this invention, the metal center refers to the metal ion used to form the coordination complex in MOF materials.

[0030] The first aspect of this invention provides a copper-iron bimetallic MOF material, which comprises:

[0031] A bimetallic center formed by Fe and Cu containing two or more valence states; and

[0032] Organic ligands that hybridize with bimetallic centers through coordination bonds to form a three-dimensional network structure crystal;

[0033] The copper-iron bimetallic MOFs material contains only L-acid with an acid content of 100-600 μmol·g. -1 Both metals are bonded to organic ligands, and due to the interaction between the two metals, the valence state of the metals changes, forming more empty coordination sites. The copper-iron bimetallic MOFs material contains only Lewis acid sites.

[0034] In this invention, the total acid content in the copper-iron bimetallic MOFs material can be selected within a wide range. According to a preferred embodiment of this invention, the L acid content in the bimetallic MOFs material is 150-400 μmol·g. -1 .

[0035] In this invention, the range of types of organic ligands that can be selected is relatively wide. According to a preferred embodiment of this invention, the organic ligand is selected from at least one of the following: trimellitic acid, terephthalic acid, phthalic acid, biphenyl-3,4,5-tricarboxylic acid, 1,4-naphthalenedicarboxylic acid, biphenylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, 4,4,4-tris(N,N-di(4-carboxyphenyl)-amino)triphenylamine, 3,3,5,5-biphenyltetracarboxylic acid, imidazole, 2-methylimidazolium, 2-nitroimidazolium, and 2-nitroimidazolium derivatives; preferably at least one of trimellitic acid and terephthalic acid.

[0036] According to a preferred embodiment of the present invention, in the copper-iron bimetallic MOFs material, the node metal Cu has two valence states, preferably, the molar ratio of divalent Cu to monovalent copper is 0.01-5.

[0037] According to a preferred embodiment of the present invention, the molar ratio of Cu to Fe is (1-200):1, preferably (1-80):1.

[0038] In this invention, the molar ratio of the organic ligand to the metallic Cu can be selected over a wide range. According to a preferred embodiment of this invention, the molar ratio of the metallic Cu to the organic ligand is 0.1-10.

[0039] According to a preferred embodiment of the present invention, the copper-iron bimetallic MOF material crystal has a polyhedral structure.

[0040] According to a preferred embodiment of the present invention, the crystal size of the copper-iron bimetallic MOFs material is 5-20 μm.

[0041] According to a preferred embodiment of the present invention, the surface of the copper-iron bimetallic MOF material crystal exhibits a regular rough or uneven morphology, preferably the rough morphology covers the surface of the copper-iron bimetallic MOF material crystal in a network pattern; or the rough morphology covers the surface of the copper-iron bimetallic MOF material crystal in the form of particles.

[0042] All copper-iron bimetallic MOFs materials possessing the aforementioned features of this invention can achieve the objectives of this invention, and there are no special requirements for their preparation methods. In accordance with a preferred embodiment of this invention, a second aspect of this invention provides a method for preparing the copper-iron bimetallic MOFs material described above, the method comprising the following steps:

[0043] S1. Dissolve organic ligands and Cu salts in a solvent, crystallize, separate, and first dry to obtain Cu-based MOFs materials formed by Cu and organic ligands;

[0044] S2. Contact the Cu-based MOFs material from step S1 with an aqueous alcohol mixture containing elemental Fe and Fe salt; separate and perform a second drying to obtain the copper-iron bimetallic MOFs material.

[0045] The preparation method of the copper-iron bimetallic MOFs material of this invention creatively incorporates elemental iron, utilizing the concept of self-reduction of multivalent transition metals. Under the influence of elemental iron, the modified solution acquires reducing properties, maximizing the effectiveness of the reducing components. Furthermore, in addition to its reducing effect, metallic iron provides more vacancy sites, increasing the acidity of the material, resulting in the multivalent copper-iron bimetallic MOFs material containing only L-acids. In the copper-iron bimetallic MOFs material of this invention, metal ions and carboxylic acid ligands form a binuclear metal slurry structure at the nodes. During the preparation process, coordinated water molecules are easily removed, forming open metal centers that serve as catalytic centers.

[0046] In this invention, in step S1, the organic ligand and Cu salt can be dissolved in a solvent to obtain a solution containing the organic ligand and a solution containing the Cu salt, respectively. Then, the solution containing the organic ligand and the solution containing the Cu salt are mixed and reacted to obtain Cu-based MOFs materials.

[0047] In this invention, the crystallization conditions in step S1 can be selected from a wide range. According to a preferred embodiment of this invention, the crystallization conditions include: a crystallization temperature of 30-150℃, preferably 60-110℃; and a reaction time that can be reasonably determined according to actual needs. Preferably, the crystallization time is 3-24h, preferably 10-20h.

[0048] In this invention, the range of selectable first drying conditions in step S1 is relatively wide. According to a preferred embodiment of this invention, the drying conditions include: a drying temperature of 70-200℃, and a drying time of 2-48h that can be reasonably determined according to actual needs; preferably, the drying is carried out in steps, with the first drying condition including: a temperature of 70-100℃ and a time of 1-24h; and the second drying condition including: a temperature of 120-200℃ and a time of 1-24h.

[0049] In this invention, the range of selectable contact conditions in step S2 is relatively wide. According to a preferred embodiment of this invention, the contact conditions include: a contact temperature of 30-150℃, preferably 50-90℃; and a contact time that can be reasonably determined according to actual needs, with a contact time of 3-24h, preferably 3-10h.

[0050] In this invention, the Cu salt is selected from at least one of the soluble salts of metallic Cu.

[0051] In this invention, the Fe salt is selected from at least one of the soluble salts of metallic Fe.

[0052] In this invention, the range of solvents that can be selected in step S1 is relatively wide. According to a preferred embodiment of this invention, the solvent is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, triethylamine, hydrofluoric acid, tetrahydrofuran, methanol, ethanol and deionized water.

[0053] In step S2, the alcohol in the water-alcohol mixture is selected from C1-C5 monohydric or polyhydric alcohols, preferably at least one of methanol, ethanol, propanol and ethylene glycol.

[0054] In this invention, the surface of the copper-iron bimetallic MOF material crystal exhibits a regularly occurring rough or uneven morphology; the rough morphology forms a network covering the surface of the copper-iron bimetallic MOF material crystal; or the rough morphology forms particles covering the surface of the copper-iron bimetallic MOF material crystal. The surface morphology of the copper-iron bimetallic MOF material crystal can be controlled by selecting the organic ligand and the anion in the salt containing the second metal. According to a preferred embodiment of the invention, in step S1, the organic ligand is selected from trimesic acid and / or terephthalic acid; in step S2, the anion in the Fe salt is selected from at least one of chloride ions and sulfate ions.

[0055] In this invention, the ratio of solvent to Cu salt in step S1 can be selected from a wide range. According to a preferred embodiment of this invention, the ratio of solvent to salt containing the first metal is 5-100 mL solvent / 1.0 g Cu salt.

[0056] According to a preferred embodiment of the present invention, in step S2, the molar ratio of elemental Fe to soluble Fe salt is 1:0.1-10.

[0057] According to a preferred embodiment of the present invention, in step S2, the ratio of Fe salt used is 5-200 mL solvent / 1.0 g.

[0058] A third aspect of this invention provides the application of the copper-iron bimetallic MOFs material described herein in the synthesis of pyrrole compounds. The copper-iron bimetallic MOFs material described herein is used to synthesize pyrrole compounds (e.g., N-substituted pyrrole compounds) with high reaction efficiency and high selectivity.

[0059] A fourth aspect of the present invention provides a method for preparing N-substituted pyrrole compounds, the method comprising:

[0060] In the presence of a liquid-phase diluent, furan compounds and amine compounds are contacted with a catalyst containing the copper-iron bimetallic MOFs material described in this invention. Using the copper-iron bimetallic MOFs material as a catalyst, due to its greater number of Lewis acid sites, the method achieves the catalytic conversion of furan compounds and amine compounds into N-substituted pyrrole compounds under mild reaction conditions, preventing the generation of byproducts (such as 3-methyl-2-cyclopentenone). This method exhibits high selectivity. Furthermore, because it uses a catalytic material containing Lewis acids, it is less likely to corrode equipment at high temperatures. Simultaneously, the mild reaction conditions do not damage the structure of the copper-iron bimetallic MOFs material, thus providing a new approach to the application of MOFs in catalysis.

[0061] In this invention, the range of furan compounds is relatively wide. According to a preferred embodiment of this invention, the furan compounds are selected from at least one of 2-methylfuran, 2,5-dimethylfuran, and furan, and are preferably biomass-based furan compounds.

[0062] In this invention, the range of amine compounds that can be selected is relatively wide. According to a preferred embodiment of this invention, the amine compounds are selected from at least one of aniline, p-methoxyaniline, 3-fluoroaniline, 3-methoxyaniline, m-toluidine, o-phenylenediamine, o-toluidine, n-butylamine, 3-nitroaniline, 4-nitroaniline, p-trifluoromethylaniline, p-chloroaniline, p-hydroxyaniline, n-hexylamine, furfurylamine, 2-thiophene methylamine, and benzylamine.

[0063] In this invention, the liquid phase diluent can be selected from a wide range of types. According to a preferred embodiment of this invention, the liquid phase diluent is selected from at least one of anhydrous methanol, anhydrous ethanol, propanol, isopropanol, n-butanol, toluene, cyclohexane, dichloromethane, tetrahydrofuran, acetone, and methyl isobutyl ketone, preferably at least one of anhydrous methanol, isopropanol, tetrahydrofuran, and methyl isobutyl ketone.

[0064] In this invention, the contact conditions between furan compounds, amine compounds and catalyst can be selected over a wide range. According to a preferred embodiment of this invention, the contact conditions include: a temperature of 100-220℃, preferably 120-200℃; and a reaction time that can be reasonably determined according to actual needs, with a reaction time of 1-24h, preferably 4-16h.

[0065] In this invention, the mass ratio of furan compounds to catalyst can be selected from a wide range. According to a preferred embodiment of this invention, the mass ratio of furan compounds to catalyst is 1-80:1, preferably 2-20:1.

[0066] In this invention, the mass ratio of furan compounds to amine compounds can be selected from a wide range. According to a preferred embodiment of this invention, the mass ratio of furan compounds to amine compounds is 1-300:1, preferably 5-100:1.

[0067] In this invention, the mass ratio of the liquid phase diluent to the furan compound can be selected within a wide range. According to a preferred embodiment of this invention, the mass ratio of the liquid phase diluent to the furan compound is 0-200:1, preferably 5-50:1.

[0068] In this invention, the N-substituted pyrrole compounds of the reaction product were qualitatively and quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS), and the conversion rate of soluble carbohydrates in the product was analyzed by high-performance liquid chromatography (HPLC). The GC-MS system was an Agilent 7890A from Agilent Technologies, USA, with an HP-5 nonpolar capillary column (30m, 0.53mm). The gas chromatograph was an Agilent 7890B, with a flame ionization detector (FID) and an SE-54 capillary column (30m, 0.53mm). HPLC analysis was performed using an Agilent 1200 system with a SHODEX SC1011 sugar column (8×300mm).

[0069] In this invention, the acid content and type of the catalyst are determined using the pyridine adsorption infrared method (Nicolet Model 710 spectrometer). The specific operating steps are as follows: a) Sample pretreatment: The sample (approximately 30 mg) is compressed into a thin disc with a diameter of 13 mm and placed in an infrared sample cell. The sample is then pretreated in a vacuum chamber at 150°C for 1 hour. After the sample cell cools to room temperature, the infrared data of the sample is scanned as background. b) Pyridine adsorption: Pyridine vapor is introduced into the in-situ under room temperature and vacuum conditions until adsorption reaches equilibrium; the adsorption time is 1 hour. c) Pyridine desorption: After adsorption, a vacuum is applied at 100°C until the internal pressure no longer changes; the desorption time is 40 minutes, and the infrared absorption spectra are scanned and recorded. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption-infrared absorption spectrum. The acid content of the sample is semi-quantitatively calculated based on the spectrum.

[0070]

[0071]

[0072] Where r and w are the diameter (cm) and mass (g) of the catalyst disc, respectively, and A is the integral value of absorbance at a specified wavenumber peak based on the scanned pyridine adsorption-infrared absorption spectrum. IMEC is the integral molar extinction coefficient, with IMECL being 2.22 and IMECB being 1.67.

[0073] In this invention, the XRD measurement method for bimetallic MOF materials is as follows: the phase composition of the sample is analyzed using a Rigaku Ultima IV X-ray powder diffractometer (Japan), with a CuKα ray source. Nickel filter, 2θ scanning range 3°-75°, operating voltage 35KV, current 25mA, scanning rate 10° / min.

[0074] In this invention, the surface element binding energy was measured on a Thermo X-ray photoelectron spectrometer (ESCALAB-250), and C1s = 284.6 eV was used as an internal standard to correct the measured element signal.

[0075] In this invention, an inductively coupled plasma atomic emission spectrometer (ICP) model Varian725-ES is used to dissolve the analytical sample in hydrofluoric acid to detect the element content.

[0076] In this invention, the conversion formula for furan compounds uses 2,5-dimethylfuran as an example:

[0077] Conversion rate of 2,5-dimethylfuran % = (molar amount of 2,5-dimethylfuran participating in the reaction) / (molar amount of 2,5-dimethylfuran substrate) × 100%.

[0078] The formula for calculating the yield of N-substituted pyrrole products, using 2,5-dimethylfuran as a substrate, is as follows:

[0079] Yield % of N-substituted pyrrole product = (molar amount of N-substituted pyrrole produced in the reaction) / (molar amount of 2,5-dimethylfuran substrate) × 100%.

[0080] The selectivity % of the product N-substituted pyrrole = (molar amount of N-substituted pyrrole produced in the reaction) / (molar amount of 2,5-dimethylfuran produced in the reaction) × 100%.

[0081] To facilitate understanding of the present invention, the following embodiments are provided. However, these embodiments are merely for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0082] Example 1

[0083] S1. Weigh 3g of trimesic acid (BTC) and add it to a mixture of 70mL anhydrous ethanol and 40mL LDM. Stir thoroughly for 20min. Weigh 6g of copper nitrate trihydrate and dissolve it in 70mL H2O. Mix the two solutions together, stir thoroughly, and place the mixture in a reaction vessel. Crystallize at 85℃ for 20h. After crystallization, cool to room temperature, centrifuge to remove the mother liquor, and wash with ethanol. Drying is carried out in two stages: the first stage is at 75℃ for 4h, and the second stage is at 130℃ for 10h. After drying, Cu-BTC is obtained.

[0084] S2. Weigh 0.2 g of ferrous sulfate and dissolve it in 20 mL of water. Add 0.1 g of iron powder, stir for 20 min, then add 80 mL of ethanol and stir thoroughly for 20 min to obtain an iron-containing solution. Weigh 2.0 g of Cu-BTC prepared in step S1 and add it to the iron-containing solution. Then place it in a water bath at 75 °C and react for 6 h. Afterward, centrifuge to remove the mother liquor, wash with ethanol and water alternately, and dry to obtain Fe-Cu-BTC.

[0085] SEM image of Cu-BTC as follows Figure 1 As shown, it exhibits an octahedral crystal form with a smooth surface.

[0086] SEM images of Fe-Cu-BTC are shown below. Figure 2 As shown, it exhibits an octahedral crystal form, with particles attached to the crystal surface and distributed in a uniform network.

[0087] The X-ray photoelectron spectroscopy (XPS) spectra of Cu-BTC and Fe-Cu-BTC are shown in Figure 4. Cu-BTC eluted at 935.0 eV, corresponding to Cu(II)2p 3 / 2This indicates that Cu in the Cu-BTC structure exists in the form of Cu(II). After modification with ferrous sulfate and iron powder, the Fe-Cu-BTC sample showed a new characteristic peak at 933.1 eV, corresponding to the Cu 2p of Cu(I). 3 / 2 Binding energy; the molar ratio of Cu(II) to Cu(I) is 1.18. The Fe-Cu-BTC elution positions at Fe 2p are 711.5 eV and 726.2 eV, which are 1.4 eV and 2.5 eV shifts compared to the elution positions of ferrous sulfate at 710.1 eV and 723.7 eV.

[0088] Infrared spectra of pyridine desorption from Cu-BTC and Fe-Cu-BTC are shown below. Figure 5 As shown. Infrared desorption of pyridine Figure 5 The calculated total acidity of Cu-BTC is 64.2 μmol·g. -1 The total acidity of Fe-Cu-BTC is 224.6 μmol·g. -1 , and by Figure 5 It is known that Fe-Cu-BTC contains only Lewis acid.

[0089] From Figure 4 and Figure 5 The results show that the present invention provides Fe-Cu-BTC metal-organic framework (MOF) material, in which both Fe and Cu metals are bonded to BTC organic ligands, and due to the interaction between the two metals, the valence state is changed, forming more empty coordination sites. The pyridine desorption infrared spectrum shows that the modified material Fe-Cu-BTC contains only L acid.

[0090] The Fe / Cu ratio of the sample was determined to be 0.18 (molar ratio) using inductively coupled plasma atomic emission spectrometry (ICP).

[0091] Depend on Figure 6 It can be seen that the characteristic peak positions of the Fe-Cu-BTC sample and the Cu-BTC sample are consistent, indicating that they have the same crystal form.

[0092] Example 2

[0093] S1. Weigh 3g of terephthalic acid (BDC) and add it to a mixture of 50mL tetrahydrofuran and 60mL water, stirring thoroughly for 20min. Weigh 6g of copper nitrate trihydrate and dissolve it in 60mL H2O. Mix the two solutions together, stir thoroughly, and then place the mixture in a reaction vessel for crystallization at 85℃ for 20h. After crystallization, cool to room temperature, centrifuge to remove the mother liquor, and wash with ethanol. Drying is carried out in two stages: the first stage is at 75℃ for 4h, and the second stage is at 130℃ for 10h. After drying, Cu-BDC is obtained.

[0094] S2. Weigh 0.2g of ferrous sulfate and dissolve it in 20mL of water. Add 0.1g of iron powder, stir for 20min, then add 80mL of ethanol and stir thoroughly for 20min to obtain an iron-containing solution. Weigh 2.0g of Cu-BDC prepared in step S1 and add it to the above iron-containing solution. Then place it in a water bath at 75℃ and react for 6h. Afterward, centrifuge to remove the mother liquor, wash with ethanol and water alternately, and dry to obtain Fe-Cu-BDC.

[0095] The SEM, XPS, and XRD patterns of sample Fe-Cu-BDC were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio of the sample to be 0.15 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 1.10. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BDC contained only L acid, and the calculated L acid content was 210.8 μmol·g. -1 .

[0096] Example 3

[0097] The method of Example 1 was followed, except that in step S2, the content of ferrous sulfate added was 0.5g, and the other conditions were the same as in Example 1; Fe-Cu-BTC-3 was obtained.

[0098] The SEM, XPS, and XRD patterns of sample Fe-Cu-BTC-3 were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio to be 0.21 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 0.85. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-3 contained only L acid, and the calculated L acid content was 256.9 μmol·g. -1 .

[0099] Example 4

[0100] The method of Example 1 was followed, except that in step S2, the amount of iron powder added was 0.2g, and the other conditions were the same as in Example 1; Fe-Cu-BTC-4 was obtained.

[0101] The SEM, XPS, and XRD patterns of sample Fe-Cu-BTC-4 were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio to be 0.24 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 0.56. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-4 contained only L acid, and the calculated L acid content was 240.6 μmol·g. -1 .

[0102] Example 5

[0103] The method of Example 1 is followed, except that in step S2, the reaction temperature of Cu-BTC with the iron-containing solution is 40°C, and the other conditions are the same as in Example 1; Fe-Cu-BTC-5 is obtained.

[0104] The SEM, XPS, and XRD patterns of sample Fe-Cu-BTC-5 were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio of the sample to be 0.13 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 1.59. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-5 contained only L acid, and the calculated L acid content was 190.7 μmol·g. -1 .

[0105] Example 6

[0106] The method of Example 1 is followed, except that in step S2, the reaction temperature of Cu-BTC with the iron-containing solution is 100°C, and the other conditions are the same as in Example 1; Fe-Cu-BTC-6 is obtained.

[0107] The SEM, XPS, and XRD patterns of sample Fe-Cu-BTC-6 were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio to be 0.15 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 0.77. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-6 contained only L acid, and the calculated L acid content was 203.7 μmol·g. -1 .

[0108] Example 7

[0109] The method of Example 1 is followed, except that in step S2, 0.2g of ferric sulfate is added instead of 0.2g of ferrous sulfate, and the other conditions are the same as in Example 1; Fe-Cu-BTC-7 is obtained.

[0110] The SEM, XPS, and XRD patterns of sample Fe-Cu-BTC-7 were similar to those of Fe-Cu-BTC in Example 1. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio of the sample to be 0.11 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 1.89. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-7 contained only L acid, and the calculated L acid content was 172.3 μmol·g. -1 .

[0111] Example 8

[0112] The method of Example 1 was followed, except that in step S2, 0.2g of ferrous chloride was added instead of 0.2g of ferrous sulfate, and the other conditions were the same as in Example 1; Fe-Cu-BTC-8 was obtained.

[0113] The XPS and XRD patterns of sample Fe-Cu-BTC-8 are similar to those of Fe-Cu-BTC in Example 1. SEM images are shown below. Figure 3 As shown, the crystal is octahedral with uniformly distributed particles on its surface. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio of the sample to be 0.17 (molar ratio). XPS determined the molar ratio of Cu(II) to Cu(I) to be 1.28. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-8 contains only L acid, and the calculated L acid content is 236.1 μmol·g. -1 .

[0114] Example 9

[0115] The method of Example 1 was followed, except that in step S2, 0.2g of ferric chloride was added instead of 0.2g of ferrous sulfate, and the other conditions were the same as in Example 1; Fe-Cu-BTC-9 was obtained.

[0116] The XPS and XRD patterns of sample Fe-Cu-BTC-9 were similar to those of Fe-Cu-BTC in Example 1. The SEM image was similar to that of the sample in Example 8. Inductively coupled plasma atomic emission spectrometry (ICP) determined the Fe / Cu ratio to be 0.10. XPS determined the Cu(II) to Cu(I) molar ratio to be 2.10. Pyridine desorption infrared spectroscopy revealed that Fe-Cu-BTC-9 contained only L acid, and the calculated L acid content was 175.9 μmol·g. -1 .

[0117] Examples 10-18

[0118] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC-n or Fe-Cu-BDC (from Examples 1-9), 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The conversion rate of 2,5-dimethylfuran and the yield of the target product 2,5-dimethyl-1-phenylpyrrole were analyzed and are shown in Table 1.

[0119] Table 1 Catalytic evaluation results of Examples 10-18

[0120]

[0121] Example 19

[0122] The method of Example 10 was followed, except that 0.1g of Fe-Cu-BTC prepared in Example 1 was used as the catalyst, and the other conditions were the same as in Example 10.

[0123] The conversion rate of 2,5-dimethylfuran was 99%, and the yield of N-substituted pyrrole compounds was 98.3%.

[0124] Example 20

[0125] The method of Example 10 was followed, except that 0.6g of Fe-Cu-BTC prepared in Example 1 was used as the catalyst, and the other conditions were the same as in Example 10.

[0126] The conversion rate of 2,5-dimethylfuran was 98.2%, and the yield of N-substituted pyrrole compounds was 97.5%.

[0127] Example 21

[0128] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC (from Example 1), 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 140 °C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0129] The conversion rate of 2,5-dimethylfuran was 95.9%, and the yield of N-substituted pyrrole compounds was 96.1%.

[0130] Example 22

[0131] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC from Example 1, 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 190°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0132] The conversion rate of 2,5-dimethylfuran was 99.6%, and the yield of N-substituted pyrrole compounds was 92.3%.

[0133] Example 23

[0134] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC from Example 1, 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 15 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0135] The conversion rate of 2,5-dimethylfuran was 99.5%, and the yield of N-substituted pyrrole compounds was 91.2%.

[0136] Example 24

[0137] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC from Example 1, 1.5 g of 2,5-dimethylfuran, and 0.5 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0138] The conversion rate of 2,5-dimethylfuran was 99.2%, and the yield of N-substituted pyrrole compounds was 97.3%.

[0139] Example 25

[0140] Using 2,5-dimethylfuran and aniline as substrates and tetrahydrofuran as the reaction solvent, 0.2 g of Fe-Cu-BTC from Example 1, 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0141] The conversion rate of 2,5-dimethylfuran was 98.7%, and the yield of N-substituted pyrrole compounds was 96.6%.

[0142] Example 26

[0143] Using 2,5-dimethylfuran and aniline as substrates and methyl isobutyl ketone as the reaction solvent, 0.2 g of Fe-Cu-BTC (from Example 1), 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0144] The conversion rate of 2,5-dimethylfuran was 97.3%, and the yield of N-substituted pyrrole compounds was 98%.

[0145] Example 27

[0146] Using 2-methylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC from Example 1, 1.5 g of 2-methylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2-methylfuran and the yield of the target product, 2-methyl-1-phenylpyrrole.

[0147] The conversion rate of 2-dimethylfuran was 97.4%, and the yield of N-substituted pyrrole compounds was 97.8%.

[0148] Example 28

[0149] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of Fe-Cu-BTC (from Example 1), 1.5 g of 2,5-dimethylfuran, 0.5 g of deionized water, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170°C for 10 h. The reaction solution was analyzed to obtain the conversion rate of 2,5-dimethylfuran and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole.

[0150] The conversion rate of 2,5-dimethylfuran was 98.5%, and the yield of N-substituted pyrrole compounds was 96.9%.

[0151] Example 29

[0152] The method of Example 10 is the same as that of Example 10, except that m-toluidine is used instead of aniline.

[0153] The conversion rate of 2,5-dimethylfuran was 95.0%, and the yield of N-substituted pyrrole compounds was 93.5%.

[0154] Example 30

[0155] The method of Example 10 is the same, except that n-hexylamine is used instead of aniline, and the other conditions are the same as in Example 10.

[0156] The conversion rate of 2,5-dimethylfuran was 93.8%, and the yield of N-substituted pyrrole compounds was 90.1%.

[0157] Example 31

[0158] The method of Example 10 is followed, except that p-methoxyaniline is used instead of aniline, and the other conditions are the same as in Example 31.

[0159] The conversion rate of 2,5-dimethylfuran was 90.7%, and the yield of N-substituted pyrrole compounds was 85.6%.

[0160] Comparative Example 1

[0161] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of HY(12), 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 170 °C for 10 h. Analysis of the reaction solution showed that the conversion rate of 2,5-dimethylfuran was 63.4%, and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole, was 56.1%.

[0162] Comparative Example 2

[0163] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of sulfonated carbon, 1.5 g of 2,5-dimethylfuran, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and the mixture was then stirred magnetically. The reaction was carried out at 170 °C for 10 h. Analysis of the reaction solution showed that the conversion rate of 2,5-dimethylfuran was 83.9%, and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole, was 73.7%.

[0164] Comparative Example 3

[0165] Using 2,5-dimethylfuran and aniline as substrates and methanol as the reaction solvent, 0.2 g of sulfonated carbon, 1.5 g of 2,5-dimethylfuran, 0.5 g of deionized water, and 1.0 g of aniline were stirred in a high-pressure reactor. Nitrogen gas at 1 MPa was introduced to prevent boiling of the organic solvent. The temperature was raised to the preset temperature using a programmed heating mantle, and the mixture was then stirred magnetically. The reaction was carried out at 170 °C for 10 h. Analysis of the reaction solution showed that the conversion rate of 2,5-dimethylfuran was 60.5%, and the yield of the target product, 2,5-dimethyl-1-phenylpyrrole, was 51.6%.

[0166] Comparative Example 4

[0167] The method of Example 10 is the same as that of Example 10, except that 0.2g of Cu-BTC prepared according to the method of Example 1 is used instead of 0.2g of Fe-Cu-BTC prepared in Example 1, and the other conditions are the same as those of Example 10.

[0168] Analysis of the reaction solution showed that the conversion rate of 2,5-dimethylfuran was 70.5%, and the yield of the target product 2,5-dimethyl-1-phenylpyrrole was 61.9%.

[0169] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. The application of copper-iron bimetallic MOFs materials in the catalytic conversion of furan and amine compounds to prepare N-substituted pyrrole compounds, characterized in that, The copper-iron bimetallic MOFs material includes: A bimetallic center formed by Fe and Cu containing two or more valence states; and Organic ligands that hybridize with bimetallic centers through coordination bonds to form a three-dimensional network structure crystal; The copper-iron bimetallic MOFs material contains only L-acid with an acid content of 150-400 µmol•g. -1 .

2. The application according to claim 1, wherein, The organic ligand is selected from at least one of the following: trimellitic acid, terephthalic acid, phthalic acid, biphenyl-3,4,5-tricarboxylic acid, 1,4-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, 4,4,4-tris(N,N-di(4-carboxyphenyl)-amino)triphenylamine, 3,3,5,5-biphenyltetracarboxylic acid, imidazole, 2-methylimidazolium, 2-nitroimidazolium, and 2-nitroimidazolium derivatives; and / or In the copper-iron bimetallic MOFs, metallic Cu has two valence states; and / or The molar ratio of metallic Cu to metallic Fe is (1-200):1; and / or The molar ratio of metallic Cu to organic ligands is 0.1-10.

3. The application according to claim 2, wherein, The organic ligand is at least one of trimesic acid and terephthalic acid; and / or The molar ratio of divalent Cu to monovalent copper is 0.01-5; and / or The molar ratio of metallic Cu to metallic Fe is (1-80):1; and / or The molar ratio of metallic Cu to organic ligands is 0.1-10.

4. The application according to any one of claims 1-3, wherein, The copper-iron bimetallic MOFs material crystal has a polyhedral structure; and / or The crystal size of the copper-iron bimetallic MOFs material is 5-20 μm.

5. The application according to any one of claims 1-3, wherein, The surface of the copper-iron bimetallic MOFs material crystals exhibits a regular rough or uneven morphology. The roughened morphology forms a network covering the crystal surface of the copper-iron bimetallic MOFs material; or The rough morphology consists of particles covering the crystal surface of the copper-iron bimetallic MOFs material.

6. The application according to any one of claims 1-3, wherein, The preparation method of the copper-iron bimetallic MOFs material includes the following steps: S1. Dissolve organic ligands and Cu salts in a solvent, crystallize, separate, and first dry to obtain Cu-based MOFs materials formed by Cu and organic ligands; S2. Contact the Cu-based MOFs material from step S1 with an aqueous alcohol mixture containing elemental Fe and Fe salt; separate and perform a second drying to obtain the copper-iron bimetallic MOFs material.

7. The application according to claim 6, wherein, In step S1, the crystallization conditions include: a crystallization temperature of 30-150℃; and / or a crystallization time of 3-24h; and / or In step S1, the first drying conditions include: a drying temperature of 70-200℃; and / or a drying time of 2-48 hours; and / or In step S2, the contact conditions include: a contact temperature of 30-150℃; and / or a contact time of 3-24h.

8. The application according to claim 6, wherein, The Cu salt is selected from at least one of the soluble salts of metallic Cu; and / or The Fe salt is selected from at least one of the soluble salts of metallic Fe; and / or In step S1, the solvent is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, triethylamine, hydrofluoric acid, tetrahydrofuran, methanol, ethanol, and deionized water; and / or In step S2, the alcohol in the water-alcohol mixture is selected from C1-C5 monohydric or polyhydric alcohols, preferably at least one of methanol, ethanol, propanol and ethylene glycol.

9. The application according to claim 6, wherein, In step S1, the organic ligand is selected from trimesic acid and / or terephthalic acid; and / or In step S2, the anion in the Fe salt is selected from at least one of chloride ions and sulfate ions.

10. The application according to claim 6, wherein, In step S1, the ratio of solvent to Cu salt is 5-100 mL solvent / 1.0 g Cu salt; and / or In step S2, the molar ratio of elemental Fe to soluble Fe salt is 1:0.1-10; In step S2, the ratio of Fe salt used is 5-200 mL solvent / 1.0 g.

11. A method for preparing N-substituted pyrrole compounds, characterized in that, The method includes: In the presence of a liquid diluent, furan compounds, amine compounds, and catalysts are contacted; the catalyst contains the copper-iron bimetallic MOF material as described in any one of claims 1-10.

12. The method according to claim 11, wherein, The furan compounds are selected from 2-methylfuran, 2,5-methylfuran, and 2,5-methylfuran. At least one of dimethylfuran and furan; and / or The amine compounds are selected from aniline, p-methoxyaniline, and 3 Fluoroaniline, 3 Methoxyaniline, m-toluidine, o-phenylenediamine, o-toluidine, n-butylamine, 3 Nitroaniline, 4 Nitroaniline, p-trifluoromethylaniline, p-chloroaniline, p-hydroxyaniline, n-hexylamine, furfurylamine, 2 At least one of thiophene methylamine and benzylamine; and / or The liquid phase diluent is selected from at least one of anhydrous methanol, anhydrous ethanol, propanol, isopropanol, n-butanol, toluene, cyclohexane, dichloromethane, tetrahydrofuran, acetone, and methyl isobutyl ketone.

13. The method according to claim 12, wherein, The furan compound is a biomass-based furan compound; and / or The liquid phase diluent is at least one of anhydrous methanol, isopropanol, tetrahydrofuran, and methyl isobutyl ketone.

14. The method according to claim 11, wherein, Contact conditions include: temperature of 100-220℃; reaction time of 1-24h; and / or The mass ratio of furan compounds to catalyst is 1-80:1; and / or The mass ratio of furans to amines is 1-300:1; and / or The mass ratio of solvent to furan compound is 0-200:1.

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