CN111732736B - Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof - Google Patents

Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof Download PDF

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CN111732736B
CN111732736B CN202010629615.6A CN202010629615A CN111732736B CN 111732736 B CN111732736 B CN 111732736B CN 202010629615 A CN202010629615 A CN 202010629615A CN 111732736 B CN111732736 B CN 111732736B
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史大斌
莫双铭
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Zunyi Medical University
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Abstract

Ni (II) -Salen ligand metal organic framework crystal material and a preparation method and application thereof. The chemical formula of the material is as follows: { [ Zn ]4O(L)6]·DMF·H2O}nWherein L is a dicarboxylate dianion of (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II), and N is the degree of polymerization. The metal organic framework crystal material adopts a solvent thermal synthesis method, has simple operation, low cost and high yield, and is easy for large-scale industrial production. The prepared metal organic framework crystal material has higher thermal stability (400 ℃), and the BET specific surface area is 228m2(ii) in terms of/g. At 273K and 1atm for CO2Has an adsorption capacity of 18.8m3(iv) g. In the presence of an oxidant, styrene is catalyzed in a water phase to be selectively oxidized into benzaldehyde, the yield reaches 99%, the catalyst is recycled for five times, and the activity loss is small. In the presence of tetrabutylammonium bromide, styrene oxide and CO are catalyzed by 1atm and 50 ℃ without solvent2The reaction produces styrene carbonate with a yield of 91%, and the catalyst is recycled for five times and still keeps activity. This material is a good heterogeneous catalyst.

Description

Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation and application of MOFs new materials, and particularly relates to a preparation method of a metal organic framework taking (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) as a ligand and application of the metal organic framework in the fields of gas adsorption and catalysis.
Background
Metal Organic Frameworks (MOFs) represent a class of hybrid organic-inorganic ordered network supramolecular materials, which are ordered network structures composed of organic bridging ligands and inorganic metal ions, including one-dimensional chain-like, two-dimensional layered and three-dimensional network structures. These materials consist of rigid multidentate bridging struts and metal nodes. High micropore volume, large pore size, and possibly high levels of metals that provide active sites are important features of such materials.
MOFs based on the metal Salen complex are usually prepared by a direct method, namely, the MOFs is constructed by directly using the metal complex as a connector and carrying out in-situ self-assembly on the metal complex and a metal node. As mentioned above, the metal Salen complex is a homogeneous catalyst which has excellent performance but is easy to pollute and waste, and is difficult to recycle. Thus, limiting its further application in the field of catalysis. The heterogeneous catalyst obtained by loading the mesoporous composite material is an effective means, and a metal organic framework is an excellent means by taking the heterogeneous catalyst as a basis, the MOFs is highly porous, has an ultrahigh specific surface area, and has stable physical/chemical properties, so that the MOFs is an ideal immobilized material, and the immobilized sites provided by the MOFs are far higher than other common materials, so that the immobilized capacity is stronger, and the MOFs are not easy to separate after being immobilized for multiple times and circularly used; specific active groups can be introduced into the framework to enhance the reaction capability and realize the series catalysis of multi-step reaction; and moreover, ligands can be modified to construct MOFs with specific structures so as to realize concerted catalysis. In summary, the abundant geometry of MOFs, the diversity of catalytic centers, and the tailorability give the catalyst more catalytic forms.
The heterogeneous catalyst synthesized by utilizing the MOFs preparation method immobilization strategy not only perfectly overcomes the problems of difficult recovery, instability and the like caused by the homogeneous catalyst, but also has more catalytic forms and frame structures, the application field is wider, the MOFs prepared based on the metal Salen complex gradually attracts the attention of researchers, and the related research is more and more intensive. The construction of MOFs requires the coordination self-assembly of an additional coordination point of a metal Salen complex with a metal ion or a metal cluster, and the current reports mainly focus on carboxylic acid type or pyridine type metal Salen ligands. As catalysts, such MOFs can be used to catalyze various types of reactions, such as: asymmetric silicon cyanation, photodegradation, and Diels-Alder reactions, etc. (Hu Y H, Liu C X, Wang J C, et al. organic Chemistry,2019,58(8): 4722-. For example, Jian-Fang Ma research group (Li J, Yang J, Li)u Y et al chemistry 2015,21(11):4413-4421) in 2015 Fe-Salen complex (III as organic ligand and Zn as transition metal respectively)2+、Cd2+In-situ self-assembly coordination is carried out to obtain two chiral MOFs (CMOF 1 and CMOF 2), researches find that the prepared crystal material can catalyze the degradation of 2-chlorophenol under the condition of visible light, and compared with a control homogeneous catalyst Fe-Salen complex (III), the CMOF 1 and CMOF 2 show higher catalytic activity, so that the complex not only benefits from the properties of high porosity and the like of the MOFs, but also increases the mutual contact between the catalyst and a degraded substance; the active metal center is combined with hydroxyl firstly under acidic condition and then reacts with hydrogen peroxide to obtain [ salen-Fe ]IIIOOH]And irradiating with visible light to obtain [ salen-Fe (V) ═ O]And. OH free radical, which is significantly greater than [ salen-Fe (V) ═ O]Is more reactive. The generated OH free radicals immediately react with degraded substances, thereby accelerating the reaction process and improving the catalytic efficiency.
Ying-Ying Liu research group (Wang H, Yang J, Liu Y, et al. Crystal Growth)&Design,2015,15(10):4986-4992) obtaining a porous trimetal organic framework, Fe, by in-situ self-assembly coordination of Salen complex precursor, barium chloride and sodium chloride3+Tetradentate with N, N, O, O to form a metal centre, carboxyl groups of Salen ligands with Ba2+And Na+Atoms are coordinated to generate a three-dimensional periodic network, so that a network crystal supramolecular catalyst with periodicity is obtained, and the first Fe-containing catalyst based on Schiff base ligandIIIThe research shows that the photocatalytic degradation activity of the 4-CP is higher than that of the 2-CP and the 3-CP, and the phenolic hydroxyl group is generally considered to be caused by the action of the phenolic hydroxyl group and can improve the electron density of para-position and ortho-position carbon atoms when the phenolic hydroxyl group is taken as an electron-donating group, so that the two positions are easily attacked by an electrophilic reagent, and the para-position is weaker, and the degradation activity is lower.
The dicarboxylic acid compound as an organic ligand has the characteristics of strong coordination capacity, various coordination modes, easy formation of hydrogen bonds and the like. The (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) has two carboxyl coordination sites, can form various coordination modes with metal ions or metal clusters, and can obtain MOFs materials with various structures. In addition, (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is coordinated with divalent nickel ions, and can be used as an active center to catalyze a plurality of organic reactions.
As can be seen from the literature, (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) is a novel metal Salen ligand, and the ligand is coordinated with metal ions to form a metal organic framework material and has not been reported in the literature.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a microporous metal organic framework crystal material with stable structure and higher specific surface area.
The second technical problem to be solved by the invention is to provide a preparation method of the metal organic framework crystal material, which is simple and easy to implement, low in cost, high in yield and easy for large-scale industrial production.
The third purpose of the invention is to provide the application of the metal organic framework crystal material in the fields of gas adsorption and catalysis.
The invention utilizes the characteristics that (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) has stronger coordination capability, multiple coordination modes, easy formation of hydrogen bond, aromatic ring accumulation effect and the like, and firstly uses the ligand and Zn2+Coordination forms a metal organic framework crystal material with novel structure. The material generally has porous holes and large specific surface area, and has good application prospect in the fields of catalysis, gas adsorption and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the Ni (II) -Salen ligand metal organic framework crystal material has the chemical formula { [ Zn ]4O(L)6]·DMF·H2O}nWherein L is a dicarboxylate dianion of (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II), and N is the degree of polymerization.
The crystal of the metal organic framework belongs to a monoclinic system, and the space group is I2.
The invention relates to a Ni (II) -Salen ligand metal organic framework crystal material and a preparation method and application thereof, which comprises the following steps:
(1) the divalent zinc salt compound, (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is dissolved in the solvent, evenly stirred and then added into a transparent high temperature resistant glass bottle with screw threads.
(2) Heating to raise the temperature, reacting the reactants at a certain temperature for a period of time, gradually reducing the temperature, cooling to room temperature, filtering, washing with DMF or DMA, and drying to obtain the metal organic framework crystal material.
The zinc salt compound is zinc nitrate salt, zinc chloride salt, zinc sulfate salt, zinc acetate salt and zinc perchlorate salt; the zinc ion has a valence of + 2;
the nickel ions are +2 valent;
the solvent DMF or DMA of the invention;
the molar ratio of the zinc salt compound to (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is 2: 0.8-2: 1, and the molar ratio of the zinc salt compound to the solvent is 1: 1000-1: 5000;
the reaction temperature of the invention is 80-100 ℃;
the reaction time is 1-120 hours;
the heating rate of the invention is 1-5 ℃/h.
The cooling rate of the invention is 1-10 ℃/h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the metal organic framework crystal material synthesized by the invention has novel and unique structure.
(2) The invention adopts (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) and Zn2+The salt is used as raw material, the solvent thermal synthesis method is adopted, the method is simple and easy to implement, the cost is low, and the yield is highHigh efficiency and easy large-scale industrial production.
(3) The metal organic framework crystal material has a three-dimensional network structure, porosity and specific surface area (BET specific surface area of 228 m)2The temperature is 400 ℃ at 273K under 1atm2Has an adsorption capacity of 18.8cm3(ii) in terms of/g. In the presence of an oxidant, styrene is catalyzed in a water phase to be selectively oxidized into benzaldehyde, the yield reaches 99%, the catalyst is recycled for five times, and almost no activity loss exists. In addition, in the presence of tetrabutylammonium bromide, epoxystyrene and CO are catalyzed under the solvent-free reaction conditions of 1atm and 50 DEG C2The reaction produces styrene carbonate with a yield of 91%, and the catalyst is recycled for five times, and the activity of the catalyst is still maintained. The material has good application prospect in the fields of gas adsorption, catalysis and the like.
Drawings
FIG. 1 shows the molecular structure of Ni (II) -Salen (L) ligand of the metal-organic framework crystal material of the present invention. FIG. 2 shows the coordination mode of the crystal material Ni (II) -Salen (L) of the metal-organic framework of the present invention.
FIG. 3 is a diagram of a secondary structural unit of the metal organic framework crystalline material of the present invention.
FIG. 4 is a diagram of coordination cubic units of the metal-organic framework crystal material of the present invention.
FIG. 5 is a structural diagram of a dual interpenetrating topos of a metal organic framework crystalline material of the present invention.
FIG. 6 is an infrared spectrum of the metal organic framework crystal material of the present invention.
FIG. 7 is a thermogravimetric analysis of the metal-organic framework crystalline material of the present invention.
FIG. 8N at 77K for the MOM crystalline material of the present invention2Adsorption-desorption isotherm diagram. FIG. 9 shows that the crystalline material of the metal-organic framework of the present invention has CO at 273K2The attached drawing is shown.
FIG. 10 shows that the metal organic framework crystal material of the present invention catalyzes the oxidation of styrene to generate benzaldehyde1H NMR chart.
FIG. 11 shows that the metal organic framework crystal material of the present invention catalyzes the oxidation of styrene to generate benzaldehyde13C NMR chart.
FIG. 12 shows that the metal organic framework crystal material of the present invention catalyzes epoxystyrene and CO2To styrene carbonate1H NMR chart.
FIG. 13 shows that the metal organic framework crystal material of the present invention catalyzes epoxystyrene and CO2To styrene carbonate13C NMR chart.
Detailed Description
The Ni (II) -Salen ligand metal organic framework crystal material and the preparation method and the application thereof have the following synthesis steps and structural characterization:
dissolving a divalent zinc salt compound, (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) in a solvent, uniformly stirring, adding the mixture into a threaded high-temperature-resistant glass vial, heating to slowly raise the temperature, reacting the reactant at a certain temperature for a period of time, gradually reducing the temperature, cooling to room temperature, filtering, washing with the solvent, and drying to obtain { [ Zn ]4O(L)6]·DMF·H2O}nA crystalline material. Then measuring the single crystal structure of the compound by a Rigaku RAXIS-RAPID IPX-ray diffractometer, measuring the infrared spectrum of the compound by a Nicolet Nexus 470FTIR infrared spectrometer, testing the thermogravimetric/differential thermal analysis of a sample on a Q600 SDT thermogravimetric analyzer, testing the powder X-ray diffraction on a Bruker D8X-ray diffractometer, testing the C, H, N element analysis on a German Vario EL III element analyzer, testing the nitrogen adsorption isotherm on a Quantachrome AS-1MP instrument,1h NMR and13c NMR was measured on an Agilent DD2-400 NMR spectrometer.
The specific embodiment is as follows:
{[Zn4O(L)6]·DMF·H2O}nsynthesis and characterization of
Putting Ni (II) -Salen (L) ligand (10mg, 0.0169mmol, 1.0equiv) into a 10mL transparent high-temperature-resistant glass vial with threads, sequentially adding zinc nitrate hexahydrate (10mg, 0.0338mmol, 2.0equiv) and 2mL DMF, carrying out ultrasonic treatment for 2 minutes to dissolve the ligand, screwing a bottle cap after the ligand is completely dissolved, putting the bottle cap into an automatic program-controlled heating box, heating to 80 ℃ at the heating rate of 5 ℃/h, carrying out heat preservation for 3 days, and then cooling at the cooling rate of 5 ℃/hThe yield was reduced to room temperature, filtered to give brick-red crystals, washed with DMF and dried at room temperature to give 8.0mg, 80% yield (calculated as Ni-Salen). According to C198H162N14Ni6O42Zn8The theoretical value (%) of elemental analysis was calculated as: c, 55.49; n, 4.58; h, 3.81; experimental values: c, 55.38; n, 4.64; h, 3.86. IR (4000-400 cm)-1):3435(vs),3059(w),1660(vs),1610(vs),1400(vs),1323(m),1249(w),754(w),700(w)。
Single crystal X-ray diffraction data of the obtained compound were measured on a Rigaku RAXIS-RAPID IPX-ray diffractometer and collected at room temperature. The diffractometer uses CuKalpha rays with the wavelength of
Figure BDA0002568023620000071
Working voltages and currents of 90kV and 50mA, collected in a ω -scan fashion for Lp factor correction, absorption correction using the CrystalClear program (Muller P., Herbst-Irmer R., Spek A.L., et al., International Union of Crystallographics Book Series, Oxford University Press: New York,2006, Chapter 7). Analyzing the structure by a direct method, then solving the coordinates of all non-hydrogen atoms by a difference Fourier method, obtaining organic hydrogen atoms by a theoretical hydrogenation method, and correcting the structure by a least square method. The calculation is completed by a SHELXTL program package (SHELdrick, G.M.: Crystal structure recovery with SHELXL. acta Crystalogger.2015, C71: 3-8.) on a microcomputer, and the structure of the compound is { [ Zn4O(L)6]·DMF·H2O}n. Table 1 shows the main crystallographic data of the metal-organic framework material.
TABLE 1
Figure BDA0002568023620000081
R1=Σ||Fo|-|Fc||/Σ|Fo|.wR2=[Σw(Fo2-Fc2)2/Σw(Fo2)2]1/2
FIG. 1 shows the molecular structure of the ligand Ni (II) -Salen (L). Single crystal derivatives of X-rayThe compounds were monoclinic, space group I2, as shown by the gamma ray study. Crystallographic data and structure refinement parameters are shown in table 1. Each asymmetric unit contains 6 Ni (II) -Salen ligands, 4 Zn (II) atoms, 1 coordinated water molecule and one coordinated DMF molecule. Each Zn atom is coordinated with 3 carboxyl groups, 3 carboxyl groups being derived from 3 different ligands. The secondary structural unit is a tetranuclear Zn-O octahedral structure [ Zn ]4O(CO2)6](FIG. 3). Since one Zn atom coordinates one water molecule and DMF molecule, this Zn atom is 6 coordinates and the remaining three Zn atoms are 4 coordinates, resulting in some distortion of the octahedral structure. Each secondary building block is linked to 6 ligands, both carboxyl groups of each Ni (II) -Salen ligand being represented by (kappa)112) The mode coordinates to two Zn atoms of the secondary building block (fig. 1). Topological analysis of the compound confirmed that linear ni (ii) -Salen maintained its di-connectivity, each secondary building block served as a six-link node, and that the ni (ii) -Salen ligand joined end-to-end with the secondary building blocks formed pcu lattices (fig. 4). Ni (II) -Salen is connected with secondary structural units to form a dual interpenetrating 3D network, and the topology of the network
Figure BDA0002568023620000091
The symbol is (4)12.63) (FIG. 5).
FIG. 6 is an infrared spectrum of the metal organic framework, tested on a Nicolet Nexus 470FTIR infrared spectrometer using spectrally pure potassium bromide pellets, the sample and potassium bromide were dried under an ultraviolet lamp to remove water from the surface of the sample prior to testing, with a measurement range of 4000--1. From the infrared spectrogram, 3300-3600cm-1Is the absorption peak of the stretching vibration of the O-H bond of water. Due to the coordination of the ligand and the metal, the absorption peaks of some groups are changed. 3059cm-1Is an aromatic ring; 1660 vibrating with C ═ N expansion; 1610cm-1And 1400cm-1Each being a carboxyl groupsC ═ O and upsilonasVibration of 1323cm C ═ O-1The absorption peak is the skeletal oscillation of upsilon (C ═ C) in the aromatic ring of the ligand.
FIG. 7 shows the thermogravimetric/differential thermal analysis of the metal organic framework, which is performed on a Q600 SDT thermogravimetric analyzer, after zeroing, weighing 5-10 mg of sample, placing the sample into a ceramic dry pot for measurement, and performing measurement under a nitrogen atmosphere, wherein the heating rate is set to 10 ℃/min and the temperature is increased to 800 ℃. There are two distinct weight loss stages, weight loss of 17.6% between 30-400 ℃, corresponding to loss of 1 coordinated water molecule and 1 coordinated DMF molecule, and disordered solvent molecules in the pore channel; at 400-440 ℃, there was a sharp weight loss of 22.4%, the organic ligand began to decompose and the framework began to collapse. The weight loss was completed at 700 c and there was a total weight loss of about 51.7%.
FIG. 8 is a nitrogen adsorption isotherm of the metal organic framework, which is measured on a Quantachrome AS-1MP instrument, and before the measurement, the sample is activated in vacuum at 200 ℃ for 24h to remove the guest molecules in the pore channels of the sample. Using high purity N2(99.999%) 10 at 77K -61 measurement of N in the pressure range2The amount of adsorption was calculated and the BET specific surface area was calculated. The physical adsorption-desorption isotherm is a typical microporous adsorption isotherm (type I), and the BET specific surface area thereof is calculated to be 228m2/g。
FIG. 9 shows that the metal-organic framework is aligned to CO at 0.1-1atm and 273K2The adsorption quantity of the compound is measured on a Quantachrome AS-1MP instrument, and a sample is activated for 24 hours in vacuum at 200 ℃ before the test, so that guest molecules in the pore channels of the sample are removed. Using high purity CO2(99.998%). Experimental results on CO2The adsorption capacity of (2) was 18.8m3/g。
The step of catalyzing the selective oxidation reaction of styrene and hydrogen peroxide: styrene (2mmol), 2mL of water, hydrogen peroxide (3mmol) and { [ Zn ] were charged in a 10mL parallel eggplant-shaped bottle reactor, respectively4O(L)6]·DMF·H2O}n(0.025 mol%) and reacted at 60 deg.C for 15 hr, adding ethyl acetate 1.5mL after the reaction, centrifuging reaction solution and catalyst, extracting and separating for 4 times, mixing supernatant, concentrating, separating and purifying by silica gel column chromatography to obtain benzaldehyde (eluent is petroleum ether: ethyl acetate 25:1), passing through Agilent DD2-400 NMR instrument, CDCl3TMS was an internal standard for solvent, and the structures of the target products were characterized (fig. 10 and 11).
Cyclic catalytic experiments: after each catalytic reaction is finished, centrifugally separating the catalyst by a centrifugal machine, filtering, washing the catalyst by dichloromethane and acetone in sequence, heating and activating for 24 hours in vacuum at 150 ℃ to be used as the catalyst for the next circular catalysis. The product yield of 5-cycle catalysis is 99%, 97%, 95%, 94% and 92% in sequence.
Catalysis of epoxystyrene and CO2The ring expanding reaction step (2): in a 10mL parallel eggplant-shaped bottle reactor, epoxystyrene (10mmol), tetrabutylammonium bromide (0.025mmol) and { [ Zn ] were charged4O(L)6]·DMF·H2O}n(0.05 mol%) and a jacket containing CO at the top of the condenser tube2Placing the balloon in parallel with a gas for three times, reacting at 50 ℃ for 12 hours, adding 1.5mL of ethyl acetate into a reaction system after the reaction is finished, centrifugally separating the reaction solution and a catalyst, extracting and separating for 4 times, combining supernate, concentrating, separating and purifying by silica gel column chromatography to obtain a product, purifying by column chromatography (eluent is petroleum ether: ethyl acetate 12:1), and performing Agilent DD2-400 nuclear magnetic resonance spectroscopy, CDCl3TMS was an internal standard for solvent, and the structures of the target products were characterized (fig. 12 and 13).
Cyclic catalytic experiment: styrene oxide is used as a substrate for reaction, after each catalytic reaction is finished, a centrifugal machine centrifugally separates the catalyst, the catalyst is filtered, washed by dichloromethane and acetone in sequence, and heated and activated for 24 hours in vacuum at 150 ℃ to be used as the catalyst for the next circular catalysis. The product yield of 5-cycle catalysis is 91%, 90%, 88% and 85% in sequence.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.

Claims (10)

1. A kind of Ni (C)
Figure 632137DEST_PATH_IMAGE001
)-The preparation method of the Salen ligand metal organic framework crystal material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: a divalent zinc salt compound, (b) aR, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) ((III))
Figure 371423DEST_PATH_IMAGE001
) Dissolving in a solvent, stirring uniformly, and then adding into a transparent high-temperature-resistant glass vial with threads;
step two: slowly heating to 80-100 ℃ at a heating rate of 1-5 ℃/h, reacting for 1-120 hours, gradually reducing the temperature, cooling to room temperature at a cooling rate of 1-10 ℃/h, filtering, washing with a solvent, and drying to obtain a metal organic framework crystal material; the chemical formula is as follows:
{[Zn4O(L)6]·DMF·H2O}nwherein L is: (R, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) ((III))
Figure 606095DEST_PATH_IMAGE001
) Abbreviation of dicarboxylate dianion of (a);
wherein the chemical structural formula of L is as follows:
Figure 823450DEST_PATH_IMAGE002
in the above chemical formula:
and n is the degree of polymerization.
2. Ni (according to claim 1)
Figure 827178DEST_PATH_IMAGE001
) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: the crystal of the metal organic framework belongs to a monoclinic system, and the space group isI2。
3. Ni (according to claim 1)
Figure 737365DEST_PATH_IMAGE001
) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: the zinc salt compound and (A) and (B)R, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (N- (ll-butyl-N-ethyl-p-phenylenediamine)
Figure 193754DEST_PATH_IMAGE001
) The molar ratio of the zinc salt compound to the solvent is 2: 0.8-2: 1, and the molar ratio of the zinc salt compound to the solvent is 1: 1000-1: 5000.
4. Ni (according to claim 1)
Figure 214800DEST_PATH_IMAGE001
) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: the zinc salt compound is one of zinc nitrate salt, zinc chloride salt, zinc sulfate salt, zinc acetate salt and zinc perchlorate salt.
5. Ni (according to claim 1)
Figure 807455DEST_PATH_IMAGE001
) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: the zinc ion in the zinc salt is +2 valence.
6. Ni (according to claim 1)
Figure 888544DEST_PATH_IMAGE001
) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: and the solvent in the first step and the second step is one of DMF and DMA.
7. Root of herbaceous plantA Ni (Ni) (I) prepared according to claim 1
Figure 832229DEST_PATH_IMAGE001
) -the use of a Salen ligand metal organic framework crystalline material, characterized in that: the metal organic framework crystal material catalyzes styrene to be oxidized in a water phase to generate benzaldehyde.
8. Ni (Ni) (according to claim 7)
Figure 656965DEST_PATH_IMAGE001
) -the use of a Salen ligand metal organic framework crystalline material, characterized in that: the oxidant is one of hydrogen peroxide, tert-butyl alcohol peroxide, iodobenzene oxide, peracetic acid, m-chloroperoxybenzoic acid and sodium hypochlorite.
9. A Ni (C) (prepared according to claim 1)
Figure 635286DEST_PATH_IMAGE001
) -the use of a Salen ligand metal organic framework crystalline material, characterized in that: the metal organic framework crystal material catalyzes epoxystyrene and CO in the presence of tetrabutylammonium bromide2The reaction produces styrene carbonate.
10. Ni (according to claim 9)
Figure 356117DEST_PATH_IMAGE001
) -use of a Salen ligand metal organic framework crystalline material, characterized in that: the catalytic reaction conditions are 1atm and no solvent at 50 ℃.
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