Metal organic framework material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalysis, and discloses a metal organic framework material and a preparation method and application thereof.The metal organic framework material has the structure shown in the formula (1), in the formula (1), R is selected from halogen, nitryl and C1-C6 alkyl; m1, M2, M3 and M4 are respectively and independently selected from Co and / or Fe. When the metal organic framework material is used for olefin hydroformylation reaction, the conversion rate of olefin and the selectivity of aldehyde can be effectively improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of catalysis technology, and in particular to a metal organic framework material and a preparation method and application thereof. Background Art

[0002] Metal-organic frameworks (MOFs) are coordination polymers produced by the self-assembly of multidentate organic building blocks with inorganic clusters. They have applications in gas adsorption, sensing applications, drug delivery, and catalysis. Due to their chemical and structural diversity, their applications in catalysis have great potential. Despite the increasing number of MOF-related reports, the study of MOF-based catalysts is still in its infancy. Many studies have focused on the synthesis of MOFs with catalytically active sites with well-defined structures.

[0003] Hydroformylation is the reaction of olefins and synthesis gas (CO+H2) to generate aldehydes or alcohols under the action of transition metal catalysts. In the prior art, the catalysts for hydroformylation are mainly homogeneous catalysts, but the recovery of homogeneous catalysts is difficult, and the loss of metal active components and ligands in the catalyst is serious. In order to reduce the cost of catalysts, researchers have also developed heterogeneous catalysts, but the catalytic performance of existing heterogeneous catalysts is low. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems in the prior art that homogeneous catalysts in hydroformylation reactions are difficult to recover and heterogeneous catalysts have poor catalytic effects, and to provide a metal organic framework material and a preparation method and application thereof.

[0005] In order to achieve the above object, the first aspect of the present invention provides a metal organic framework material having a structure shown in formula (1):

[0006]

[0007] Wherein, R is selected from halogen, nitro, C1-C6 alkyl; M1, M2, M3 and M4 are each independently selected from Co and / or Fe.

[0008] The second aspect of the present invention provides a method for preparing a metal organic framework material, wherein the method comprises: in the presence of a solvent, causing a metal precursor to undergo a coordination reaction with a ligand, wherein the metal precursor is a cobalt precursor and / or an iron precursor, and the ligand has a structure shown in formula (2):

[0009]

[0010] Wherein, R is selected from halogen, nitro, and C1-C6 alkyl.

[0011] The third aspect of the present invention provides a metal organic framework material prepared by the above method.

[0012] A fourth aspect of the present invention provides a catalyst comprising a metal organic framework material and an active component;

[0013] Alternatively, the catalyst comprises a reaction product of a metal organic framework material and an active component;

[0014] Wherein, the metal organic framework material is the metal organic framework material described above.

[0015] The fifth aspect of the present invention provides the use of the above-mentioned metal organic framework material, the above-mentioned catalyst and the metal organic framework material prepared by the above-mentioned method in a hydroformylation reaction.

[0016] A sixth aspect of the present invention provides a method for hydroformylation reaction, which comprises: in the presence of the above-mentioned catalyst, under hydroformylation reaction conditions, contacting olefin, carbon monoxide and hydrogen with the catalyst to carry out hydroformylation reaction.

[0017] Through the above technical solution, the present invention achieves the following beneficial effects:

[0018] (1) The catalyst composed of the metal organic framework material and the active component of the present invention can effectively improve the conversion rate of olefins and the selectivity of aldehydes when used in the hydroformylation reaction of olefins. The activity of the catalyst of the present invention is significantly higher than that of homogeneous / heterogeneous catalysts. Particularly preferably, the catalyst of the present invention can effectively improve the selectivity of terminal products when catalyzing olefins with substituents. For example, when catalyzing vinyl acetate, the selectivity of 3-acetoxypropionaldehyde can be significantly improved.

[0019] (2) The catalyst separation method of the present invention is simple and can be used repeatedly, which is more conducive to environmental protection and reduces industrial costs. It improves its synthesis efficiency, reduces synthesis costs, and is more conducive to large-scale industrial use.

[0020] (3) After being reused 10 times, the catalyst of the present invention can still keep the olefin conversion rate and aldehyde selectivity basically unchanged. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a scanning electron microscope image of Co-TER prepared in Preparation Example 1;

[0022] Figure 2 is a scanning electron microscope image of Fe-TER prepared in Preparation Example 2;

[0023] Figure 3 is a scanning electron microscope image of MOF-5 prepared in comparative preparation example 2;

[0024] Figure 4 1 and 2 are XRD patterns of Co-TER of Preparation Example 1, Fe-TER of Preparation Example 2, and MOF-5 of Comparative Preparation Example 2. DETAILED DESCRIPTION

[0025] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0026] The first aspect of the present invention provides a metal organic framework material having a structure shown in formula (1):

[0027]

[0028] Wherein, R is selected from halogen, nitro, C1-C6 alkyl; M1, M2, M3 and M4 are each independently selected from Co and / or Fe.

[0029] In the present invention, in formula (1), R represents a substituent on the benzene ring.

[0030] The inventors of the present invention have found that when the R group in formula (1) is a halogen, a nitro group, or a C1-C6 alkyl group, the metal organic framework material can achieve better results when used in a hydroformylation reaction. The inventors speculate that this may be because the R group of the present invention can play a steric limiting and switching role, which is beneficial to improving the conversion rate of the raw materials and the selectivity of aldehydes in the hydroformylation reaction. In particular, when used in the hydroformylation reaction of olefins with substituents, the coordination mode of the olefins with substituents can be effectively controlled at the terminal position, thereby improving the selectivity of aldehydes.

[0031] In the present invention, the C1-C6 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, or isohexyl.

[0032] According to the present invention, preferably, R is selected from Br, Cl, I, nitro, C1-C3 alkyl.

[0033] The second aspect of the present invention provides a method for preparing a metal organic framework material, wherein the method comprises: in the presence of a solvent, causing a metal precursor to undergo a coordination reaction with a ligand, wherein the metal precursor is a cobalt precursor and / or an iron precursor, and the ligand has a structure shown in formula (2):

[0034]

[0035] Wherein, R is selected from halogen, nitro, and C1-C6 alkyl.

[0036] According to the present invention, preferably, R is selected from Br, Cl, I, nitro, C1-C3 alkyl.

[0037] According to the present invention, the cobalt precursor can be any substance containing cobalt elements that can provide coordination with the ligand. Preferably, the cobalt precursor is a cobalt salt, more preferably a divalent metal salt of the cobalt element, and further preferably a cobalt nitrate (e.g., Co(NO3)2) and / or a cobalt chloride (e.g., CoCl2).

[0038] According to the present invention, the iron precursor can be any substance containing an iron element that can provide a coordination compound with the ligand. Preferably, the iron precursor is an iron salt, more preferably a divalent metal salt of iron, and further preferably an iron nitrate (e.g., Fe(NO3)2) and / or an iron chloride (e.g., FeCl2).

[0039] According to the present invention, preferably, the solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide and N,N-diethylformamide.

[0040] According to the present invention, preferably, the molar ratio of the metal precursor to the ligand calculated as the metal element is 0.5: 1-2.0: 1. In the present invention, the molar ratio of the metal precursor to the ligand calculated as the metal element can be 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1, 1: 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2: 1, and the range of any two of the above points.

[0041] According to the present invention, preferably, the amount of solvent used per gram of ligand is 100-500 mL (for example, 100 mL, 110 mL, 150 mL, 200 mL, 300 mL, 400 mL, 500 mL, and ranges consisting of any two of the above points).

[0042] According to the present invention, preferably, the conditions of the coordination reaction include: temperature of 50-200° C., preferably 70-150° C., and time of 0.5-72 h, preferably 20-30 h.

[0043] According to the present invention, preferably, the coordination reaction is carried out under an inactive atmosphere, and more preferably, the inactive atmosphere includes an inert atmosphere and / or a nitrogen atmosphere, wherein the inert atmosphere can be at least one of a helium atmosphere, a neon atmosphere, and an argon atmosphere.

[0044] The third aspect of the present invention provides a metal organic framework material prepared by the above method.

[0045] A fourth aspect of the present invention provides a catalyst comprising a metal organic framework material and an active component;

[0046] Alternatively, the catalyst comprises a reaction product of a metal organic framework material and an active component;

[0047] Wherein, the metal organic framework material is the metal organic framework material described above.

[0048] According to the present invention, the active component can be any active component used in the hydroformylation homogeneous reaction. Preferably, the active component is Co2(CO)8.

[0049] According to the present invention, preferably, the weight ratio of the active component to the metal organic framework material is 1: 1-1000, more preferably 1: 2-200. The weight ratio of the active component to the metal organic framework material can be 1: 1, 1: 2, 1: 3, 1: 4, 1: 5, 1: 6, 1: 7, 1: 8, 1: 9, 1: 10, 1: 100, 1: 200, 1: 500, 1: 1000, and a range consisting of any two of the above points.

[0050] In the present invention, the metal organic framework material and the active component can be directly added to the reaction system for catalytic reaction; the reaction product of the metal organic framework material and the active component can also be added to the reaction system for catalytic reaction. Usually, when the first catalytic reaction is carried out, the metal organic framework material and the active component are directly added to the reaction system for catalytic reaction. After the first reaction is completed, the catalyst in the reaction system (i.e., the reaction product of the metal organic framework material and the active component) is recovered, and the recovered catalyst is added to the reaction system to continue the catalytic reaction.

[0051] The present invention also provides a method for preparing a supported catalyst, which comprises contacting a metal organic framework material and an active component for loading in the presence of a solvent and synthesis gas; wherein the metal organic framework material is the metal organic framework material described above.

[0052] According to the method for preparing the supported catalyst of the present invention, the active component can be any active component used in the homogeneous hydroformylation reaction. Preferably, the active component is Co2(CO)8.

[0053] According to the method for preparing a supported catalyst of the present invention, preferably, the volume ratio of carbon monoxide to hydrogen is 0.2-5:1, preferably 0.3-3:1.

[0054] According to the method for preparing the supported catalyst of the present invention, preferably, the contacting conditions include: temperature of 70-180° C., time of 0.1-2 h, and pressure of 1-7 MPa. The pressure in the present invention is gauge pressure.

[0055] According to the method for preparing a supported catalyst of the present invention, preferably, the weight ratio of the metal organic framework material to the active component is 1:1-1000, preferably 1:2-200.

[0056] According to the method for preparing a supported catalyst of the present invention, preferably, the solvent is an aromatic hydrocarbon, more preferably toluene.

[0057] The present invention also provides a supported catalyst, which includes a metal organic framework material and an active component supported on the metal organic framework material, wherein the metal organic framework material is the metal organic framework material described above.

[0058] According to the supported catalyst of the present invention, preferably, the active component is Co2(CO)8.

[0059] According to the supported catalyst of the present invention, preferably, the loading amount of the active component (Co) in the supported catalyst is 0.1-50 wt%.

[0060] The amount of active components loaded in the supported catalyst = (the weight of Co added during the preparation of the supported catalyst - the weight of Co remaining in the solution) / the weight of the metal organic framework material × 100%.

[0061] The fifth aspect of the present invention provides the use of the above-mentioned metal organic framework material, the above-mentioned catalyst and the metal organic framework material prepared by the above-mentioned method in a hydroformylation reaction.

[0062] A sixth aspect of the present invention provides a method for hydroformylation reaction, which comprises: in the presence of the above-mentioned catalyst, under hydroformylation reaction conditions, contacting olefin, carbon monoxide and hydrogen with the catalyst to carry out hydroformylation reaction.

[0063] According to the present invention, preferably, the volume ratio of carbon monoxide to hydrogen is 0.2-5: 1, more preferably 0.3-3: 1. In the present invention, the volume ratio of carbon monoxide to hydrogen can be 0.2: 1, 0.5: 1, 1: 1, 1.5: 1, 2: 1, 3: 1, 4: 1, 5: 1, and a range consisting of any two of the above points.

[0064] According to the present invention, preferably, the weight ratio of the catalyst to the olefin is 0.001-1000: 1, more preferably 0.01-100: 1. The weight ratio of the catalyst to the olefin may be 0.001: 1, 0.01: 1, 0.1: 1, 0.2: 1, 0.3: 1, 0.4: 1, 0.5: 1, 1: 1, 10: 1, 100: 1, 1000: 1, and a range consisting of any two of the above.

[0065] According to the present invention, preferably, the olefin includes an ester-substituted olefin and / or an aryl-substituted olefin; more preferably, an ester-substituted olefin with a carbon number of 4-15 and / or an aryl-substituted olefin with a carbon number of 4-15; for example, at least one of vinyl acetate, vinyl propionate, allyl propionate, vinyl butyrate, allyl butyrate, butyl butyrate, styrene, propylene, and butylene. Further preferably, the olefin is an ester-substituted olefin with a carbon number of 4-6 and / or an aryl-substituted olefin with a carbon number of 4-10.

[0066] According to the present invention, preferably, the olefin is vinyl acetate and / or styrene.

[0067] According to the present invention, preferably, the conditions of the hydroformylation reaction include: temperature of 70-180° C., time of 0.1-2 h, and pressure of 1-7 MPa.

[0068] The present invention will be described in detail below by way of examples. In the following examples,

[0069] The volume ratio of CO:H2 in the synthesis gas is 1:1.

[0070] Olefin conversion rate mol % = (the amount of olefin substance added to the reaction system - the amount of olefin substance remaining in the system) ÷ the amount of olefin substance added to the reaction system × 100%.

[0071] 3-acetoxypropionaldehyde selectivity mol% = the amount of 3-acetoxypropionaldehyde substance / (the amount of 3-acetoxypropionaldehyde substance+the amount of 2-acetoxypropionaldehyde substance)×100%;

[0072] The selectivity of phenylpropionaldehyde, mol % = the amount of phenylpropionaldehyde substance / (the amount of phenylpropionaldehyde substance+the amount of 2-methylphenylacetaldehyde substance)×100%.

[0073] Preparation Example 1

[0074] Add 2.0 g of 2-methyl-terephthalic acid, 2.9 g of Co(NO3)2·6H2O, and 200 mL of N,N-dimethylformamide to the reactor, and heat at 120°C for 24 h under nitrogen protection. Cool to room temperature, filter, wash with ethanol, and dry to obtain a yellow-green solid (metal organic framework material), which is recorded as Co-TER.

[0075] Figure 1 This is a scanning electron microscope image of Co-TER. Figure 1 It can be seen that the morphology of Co-TER is layered, and the layers are in a stacked form.

[0076] Preparation Example 2

[0077] Add 2.0 g of 2-chloro-terephthalic acid, 2.0 g of FeCl2·4H2O, and 200 mL of N,N-dimethylformamide to the reactor, and heat at 80°C for 24 hours under nitrogen protection. Cool to room temperature, filter, wash with ethanol, and dry to obtain a blue-green solid (metal organic framework material), which is recorded as Fe-TER.

[0078] Figure 2 This is a scanning electron microscope image of Fe-TER. Figure 2 It can be seen that the Fe-TER contains Fe-TER with a prismatic structure and small particles of Fe-TER, wherein the two ends of the prismatic structure are pyramidal structures. The total length of the prism (including the length of the pyramids at both ends) is about 1-15 μm, wherein the length of the single-sided pyramid is about 1-2 μm.

[0079] Comparative Preparation Example 1

[0080] The method of Preparation Example 1 was followed, except that 2-methyl-terephthalic acid was replaced with an equal molar amount of terephthalic acid.

[0081] Comparative Preparation Example 2

[0082] The method of Preparation Example 1 was followed, except that Co(NO3)2·6H2O was replaced by an equal mole of Zn(NO3)2·6H2O. The prepared metal organic framework material was designated as MOF-5.

[0083] Figure 3 The metal organic framework material MOF-5 prepared in Comparative Preparation Example 1 is composed of Figure 3 It can be seen that MOF-5 is mostly blocky.

[0084] Figure 4 The XRD patterns of Co-TER of Preparation Example 1, Fe-TER of Preparation Example 2 and MOF-5 of Comparative Preparation Example 2 are shown in Table 1. Figure 4 It can be seen that Co-TER, Fe-TER and MOF-5 have different diffraction characteristic peaks.

[0085] Comparative Preparation Example 3

[0086] The method of Preparation Example 1 was followed, except that Co(NO3)2·6H2O was replaced by an equimolar amount of ZrCl4.

[0087] In the following examples, Example A is used to illustrate the catalytic performance of a fresh catalyst, and Example B is used to illustrate the catalytic performance of a recovered catalyst.

[0088] Example 1-A

[0089] Take 1g of Co-TER, 200mg of Co2(CO)8, 5.8g of vinyl acetate, and 50mL of toluene, add them into a high-pressure closed reactor, and introduce synthesis gas, control the pressure of the synthesis gas in the reactor to 4MPa, the reaction temperature to 100℃, and react for 3h. After the reaction is completed, filter and recover the catalyst to obtain a catalyst and reaction liquid that can be used once. The reaction liquid is subjected to gas chromatography detection, and it is calculated that the conversion rate of vinyl acetate is 95.2mol%, and the selectivity of 3-acetoxypropionaldehyde is 61mol%.

[0090] Example 1-B

[0091] The catalyst (about 1 g) recovered in Example 1-A, 5.8 g of vinyl acetate, and 50 mL of toluene were added to a high-pressure closed reactor, and synthesis gas was introduced. The pressure of the synthesis gas in the reactor was controlled to be 4 MPa, the reaction temperature was 100 ° C, and the reaction was carried out for 3 hours. After the reaction was completed, the catalyst was filtered and recovered to obtain the catalyst and reaction liquid used twice. The reaction liquid was subjected to gas chromatography detection, and the conversion rate of vinyl acetate was calculated to be 95.1 mol%, and the selectivity of 3-acetoxypropionaldehyde was 60.5 mol%.

[0092] Example 2-A

[0093] Take 1g of Co-TER, 200mg of Co2(CO)8, 7.0g of styrene, and 50mL of toluene, add them into a high-pressure closed reactor, and introduce synthesis gas. The pressure of the synthesis gas in the reactor is controlled to be 4MPa, the reaction temperature is 100℃, and the reaction is carried out for 3h. After the reaction is completed, filter and recover the catalyst to obtain a catalyst and reaction liquid that can be used once. The reaction liquid is detected by gas chromatography, and the styrene conversion rate is calculated to be 96.5mol%, and the phenylpropanaldehyde selectivity is 92mol%.

[0094] Example 2-B

[0095] The catalyst (about 1g) recovered in Example 2-A, 7.0g styrene, and 50mL toluene were added to a high-pressure closed reactor, and synthesis gas was introduced, and the pressure of the synthesis gas in the reactor was controlled to be 4MPa, the reaction temperature was 100°C, and the reaction was carried out for 3h. After the reaction was completed, the catalyst was filtered and recovered to obtain the catalyst and reaction solution used twice. The reaction solution was subjected to gas chromatography detection, and the styrene conversion rate was calculated to be 96.7mol%, and the phenylpropanaldehyde selectivity was 91.7mol%.

[0096] Example 3-A

[0097] Take 1g of Fe-TER, 200mg of Co2(CO)8, 5.8g of vinyl acetate, and 50mL of toluene, add them into a high-pressure closed reactor, and introduce synthesis gas. The pressure of the synthesis gas in the reactor is controlled to be 4MPa, the reaction temperature is 100℃, and the reaction is carried out for 3h. After the reaction is completed, filter and recover the catalyst to obtain a catalyst and reaction liquid that can be used once. The reaction liquid is subjected to gas chromatography detection, and it is calculated that the conversion rate of vinyl acetate is 94.1%, and the selectivity of 3-acetoxypropionaldehyde is 60%.

[0098] Example 3-B

[0099] The catalyst (about 1 g) recovered in Example 3-A, 5.8 g of vinyl acetate, and 50 mL of toluene were added to a high-pressure closed reactor, and synthesis gas was introduced. The pressure of the synthesis gas in the reactor was controlled to be 4 MPa, the reaction temperature was 100 ° C, and the reaction was carried out for 3 hours. After the reaction was completed, the catalyst was filtered and recovered to obtain the catalyst and reaction liquid used twice. The reaction liquid was subjected to gas chromatography detection, and the conversion rate of vinyl acetate was calculated to be 94.0 mol%, and the selectivity of 3-acetoxypropionaldehyde was 60 mol%.

[0100] Example 4-A

[0101] Take 1g of Fe-TER, 200mg of Co2(CO)8, 7.0g of styrene, and 50mL of toluene, add them into a high-pressure closed reactor, and introduce synthesis gas. The pressure of the synthesis gas in the reactor is controlled to be 4MPa, the reaction temperature is 100℃, and the reaction is carried out for 3h. After the reaction is completed, filter and recover the catalyst to obtain a catalyst and reaction liquid that can be used once. The reaction liquid is detected by gas chromatography, and the styrene conversion rate is calculated to be 98.3mol%, and the phenylpropanaldehyde selectivity is 97.7mol%.

[0102] Example 4-B

[0103] The catalyst (about 1g) recovered in Example 4-A, 7.0g of styrene, and 50mL of toluene were added to a high-pressure closed reactor, and synthesis gas was introduced, and the pressure of the synthesis gas in the reactor was controlled to be 4MPa, the reaction temperature was 100°C, and the reaction was carried out for 3h. After the reaction was completed, the catalyst was filtered and recovered to obtain the catalyst and reaction solution used twice. The reaction solution was subjected to gas chromatography detection, and the styrene conversion rate was calculated to be 97.3mol%, and the phenylpropanaldehyde selectivity was 97.6mol%.

[0104] Comparative Example 1

[0105] The method of Example 1-A was followed, except that Co-TER was replaced by an equal weight of Co2(CO)8. The reaction solution was detected by gas chromatography, and the conversion of vinyl acetate was calculated to be 80.3 mol%, and the selectivity of 3-acetoxypropionaldehyde was 40 mol%.

[0106] Comparative Example 2

[0107] The method of Example 2-A was followed, except that Co-TER was replaced by an equal weight of Co2(CO)8. The reaction solution was detected by gas chromatography, and the styrene conversion rate was calculated to be 85.3 mol%, and the phenylpropanaldehyde selectivity was 67.1 mol%.

[0108] Comparative Example 3

[0109] The method of Example 1-A was followed, except that Co-TER was replaced with an equal weight of the metal organic framework material of Comparative Preparation Example 1. The reaction solution was detected by gas chromatography, and the conversion of vinyl acetate was calculated to be 83.7 mol%, and the selectivity of 3-acetoxypropionaldehyde was 47 mol%.

[0110] Comparative Example 4

[0111] The method of Example 1-A was followed, except that Co-TER was replaced with an equal weight of the metal organic framework material of Comparative Preparation Example 2. The reaction solution was detected by gas chromatography, and the conversion of vinyl acetate was calculated to be 90.3 mol%, and the selectivity of 3-acetoxypropionaldehyde was 43 mol%.

[0112] Comparative Example 5

[0113] The method of Example 1-A was followed, except that Co-TER was replaced with an equal weight of the metal organic framework material of Comparative Preparation Example 3. The reaction solution was detected by gas chromatography, and the conversion of vinyl acetate was calculated to be 75.3 mol % and the selectivity of 3-acetoxypropionaldehyde was 38.9 mol %.

[0114] Compared with the homogeneous catalysts of Comparative Examples 1-2, the heterogeneous catalysts containing metal organic framework materials of the present invention can significantly improve the conversion rate of olefins and the selectivity of aldehydes.

[0115] Compared with Comparative Example 3, it can be found that the addition of R groups to the metal organic framework material in the examples of the present invention can significantly improve the conversion rate of olefins and the selectivity of aldehydes.

[0116] Compared with Comparative Examples 4-5, it can be found that when the metal of the metal organic framework material in the embodiments of the present invention is Co or Fe, the conversion rate of olefins and the selectivity of aldehydes can be significantly improved.

[0117] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A metal organic framework material, characterized in that: The metal organic framework material has a structure shown in formula (1): Wherein, R is selected from halogen, nitro, C1-C6 alkyl; M1, M2, M3 and M4 are each independently selected from Co and / or Fe.

2. The metal organic framework material according to claim 1, wherein R is selected from Br, Cl, I, nitro, C1-C3 alkyl.

3. A method for preparing a metal organic framework material, wherein: The method comprises: in the presence of a solvent, causing a metal precursor to undergo a coordination reaction with a ligand, wherein the metal precursor is a cobalt precursor and / or an iron precursor, and the ligand has a structure shown in formula (2): Wherein, R is selected from halogen, nitro, and C1-C6 alkyl.

4. The method according to claim 3, wherein: R is selected from Br, Cl, I, nitro, C1-C3 alkyl; And / or, the cobalt precursor is a cobalt salt, preferably a cobalt nitrate and / or a cobalt chloride; And / or, the iron precursor is an iron salt, preferably an iron nitrate and / or an iron chloride; And / or, the solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide and N,N-diethylformamide.

5. The method according to claim 3, wherein: The molar ratio of the metal precursor to the ligand is 0.5:1-2:1, calculated as the metal element; and / or, the amount of the solvent used is 100-500 mL per gram of the ligand; And / or, the conditions of the coordination reaction include: temperature of 50-200° C. and time of 0.5-72 h.

6. A metal organic framework material prepared by the method according to any one of claims 3 to 5.

7. A catalyst, characterized in that The catalyst comprises a metal organic framework material and an active component; Alternatively, the catalyst comprises a reaction product of a metal organic framework material and an active component; Wherein, the metal organic framework material is the metal organic framework material described in any one of claims 1, 2, and 6.

8. The catalyst according to claim 7, wherein The active component is Co2(CO)8; And / or, the weight ratio of the active component to the metal organic framework material in the catalyst is 1:1-1000, preferably 1:2-200.

9. Use of the metal organic framework material according to any one of claims 1, 2, and 6, the catalyst according to claim 7, and the metal organic framework material prepared by the method according to any one of claims 3 to 5 in a hydroformylation reaction.

10. A method for hydroformylation reaction, characterized in that: The method comprises: in the presence of the catalyst according to claim 7 or 8, under hydroformylation reaction conditions, contacting olefin, carbon monoxide and hydrogen with the catalyst to carry out a hydroformylation reaction; Preferably, the volume ratio of carbon monoxide to hydrogen is 0.2-5:1, preferably 0.3-3:1; Preferably, the weight ratio of the catalyst to the olefin is 0.001-1000:1, preferably 0.01-100:1; Preferably, the olefin comprises an ester-substituted olefin and / or an aryl-substituted olefin; preferably vinyl acetate and / or styrene; Preferably, the conditions of the hydroformylation reaction include: temperature of 70-180° C., time of 0.1-2 h, and pressure of 1-7 MPa.

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