CN113000070A - Fluorine-containing super-hydrophobic modified MOFs material and application thereof as catalyst in catalytic preparation of cyclic carbonate - Google Patents

Fluorine-containing super-hydrophobic modified MOFs material and application thereof as catalyst in catalytic preparation of cyclic carbonate Download PDF

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CN113000070A
CN113000070A CN202110263337.1A CN202110263337A CN113000070A CN 113000070 A CN113000070 A CN 113000070A CN 202110263337 A CN202110263337 A CN 202110263337A CN 113000070 A CN113000070 A CN 113000070A
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uio
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韩正波
刘硕
高明亮
刘琳
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Liaoning University
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention relates to an application of super-hydrophobic modified MOFs materials in catalytic preparation of cyclic carbonate. The technical scheme is as follows: respectively taking four prepared MOFs materials (MIL-101(Cr) -NH)2,MIL‑101(Al)‑NH2,UiO‑66‑(Zr)‑NH2,UiO‑66‑(Hf)‑NH2) Activating at 150 ℃ under vacuum for 12h, putting 200mg of the activated MOFs into a container, adding 50ml of dried tolumene, ultrasonically dispersing, adding 20mmol of 4-trifluoromethylbenzaldehyde, and placing in a 120 ℃ oil bath kettle under the protection of nitrogen to react for 12h at constant temperature. After cooling to room temperature, the product was centrifuged and washed several times with tolumene and dried under vacuum at 80 ℃ overnight to give MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and UiO-66(Hf) -3F. Prepared by the inventionThe MOFs composite material has excellent hydrophobic property and can efficiently catalyze CO2Cycloaddition reaction with an epoxide.

Description

Fluorine-containing super-hydrophobic modified MOFs material and application thereof as catalyst in catalytic preparation of cyclic carbonate
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to fluorine-containing super-hydrophobic modificationApplication of MOFs materials in catalytic preparation of cyclic carbonate, in particular to preparation of a series of super-hydrophobic trifluoromethyl functionalized MOFs composite materials and CO catalysis under mild conditions2Study of cycloaddition reaction with epoxide.
Background
In 2014, the united nations reported that by 2050, global urbanization would have increased to 66% and would have led to an explosion of the population in urban areas. Such rapid growth will undoubtedly exacerbate the overlap of residential and industrial fields. CO 22As one of the major components of greenhouse gases, it is recognized as a major factor contributing to global warming. With the increase of human social activities, CO emitted from power plants, automobile exhaust, industrial production processes and the like2The amount will grow proportionally. As is well known, CO2CO released by combustion or other activity, causing global warming2Will be balanced by photosynthesis, helping to maintain the carbon cycle. However, CO2The concentration rises to a frightening proportion, which can lead to natural disasters including sea level rise, ecosystem disturbance, crop failure and species extinction, etc. Fossil fuels, on the other hand, provide a large amount of energy for our daily lives. Therefore, we are in a dilemma and there is a strong need to find a solution that can optimize both cases. Introducing CO2The capture and conversion into fine chemicals is a very sensible approach to reduce CO2The amount of discharge of (c). To date, researchers have developed to convert CO2Capture and sequestration, and the like, and the use of CO2Various chemical strategies for conversion to value-added chemicals, and the like. In particular, in recent years, CO has been introduced2The possibility of conversion into value added products has been the subject of much attention on a global scale. In this respect, CO2Has several important characteristics of fire resistance, no toxicity, low price, rich content, easy processing and the like, and the characteristics are all the advantages. However, since the element C is in the highest oxidation state and the C ═ O bond energy is high (+805kJ mol)-1) Result in CO2Is less reactive, but the high reactivity can be reduced by using highly reactive substrates and catalystsTo overcome this problem.
CO2Is a C1 resource with abundant reserves and is used for storing CO2The conversion into fine chemical products with additional value has environmental and practical significance. Epoxide with CO2The cycloaddition reaction for synthesizing the Cyclic Carbonate (CCs) is a reaction with economic value and has wide application in the fields of medicine and fine chemical engineering. CCs are widely used in the pharmaceutical, dye, lithium ion battery electrolytes, ethylene glycol synthesis intermediates, high molecular materials, polycarbonate precursors and other industries. The metal complex, the metal halide, the quaternary ammonium salt compound and the like are used as homogeneous catalysts, and the CCs are synthesized on an industrial scale under mild conditions. On the other hand, the MOFs can be applied to various reactions as a potential catalyst through elaborate design and functionalization. The structure and function of the framework can be easily regulated and controlled according to the properties of the metal nodes and the structure of the organic ligand. In recent years, such materials have attracted much attention because of their structural versatility, crystallinity, and ultrahigh specific surface area. Because MOFs have rigid frameworks and high thermal stability and chemical stability, lattice solvent molecules coordinated with metals can be removed by heating without affecting the overall structure, so that catalytic sites of the MOFs are exposed in the pore channels. Reactants can easily enter the channels of the MOFs to contact the metal sites. And metal ions are difficult to leach into solution during or after catalytic reaction. Thus, MOFs combine the advantages of metal complexes (homogeneous catalysts) in terms of reactivity and accessibility of the active sites with the recyclability of heterogeneous catalysts. Recently, MOFs are excellent catalysts in CO2Applications that capture and convert to CCs are again widely recognized. CO 22The adsorption studies of (a) show that capacity can be increased by: (a) appropriate ligand design (amino functionalized MOFs, MOFs containing N and F in the ligand); (b) synthesis of hybrid materials (MOF-CNF and MOF template carbons) using MOFs and in some cases (c) generation of open metal sites. Generally, the catalytic activity of MOF (here CO)2Cycloaddition reaction with epoxides) are derived from different structural features: (i) there are open metal coordination sites (in eliminating loosely bound solvent components)Generated after generation) as Lewis acid sites, and can be used together with Lewis base cocatalysts such as tetrabutylammonium bromide (TBABr) and the like; (ii) the organic ligand with Lewis base function added or PSM function in the synthesis process can be used as CO2Fixing the active site; (iii) lewis acid or basic defect sites exist in the interior/surface of the MOF; (iv) contactable COOH groups and the like
Figure BDA0002971003610000021
The presence of an acidic site; (v) there are accessible Lewis and
Figure BDA0002971003610000022
an acid bifunctional active site.
Due to the periodicity of the MOF self-nanoscale, the permanent porosity, the pore channels with adjustable functions and the structural diversity, MOFs can be reasonably designed and prepared so as to meet the application requirements of multiple aspects such as heterogeneous catalysis, gas storage and separation, drug delivery and the like. Researchers have been exploring various ways to control the microenvironment of MOFs to enhance CO2The catalytic performance of cycloaddition reaction with epoxide, but most of the MOFs contain weak coordination bonds and are easily destroyed by water molecules in a humid environment or a water body, and the weak coordination bonds are considered to be one of the main obstacles limiting the practical application of the MOFs. In recent years, the preparation of hydrophobic and even superhydrophobic MOFs and their composites has made rapid and promising progress, not only overcoming their inherent disadvantages and improving the stability of MOFs in humid conditions or water, but also imparting novel functions thereto, and being applicable to a variety of novel applications. Generally, a common method for constructing hydrophobic MOFs is to treat the outer surface of the MOFs by a specific method to increase the roughness of the outer surface. However, the existing methods are cumbersome and complex, and have respective limitations, such as specific surface area inhibition, demanding requirements for required instruments, etc., which will greatly limit the preparation and application of hydrophobic MOFs. The above mentioned ideas have prompted us to design and prepare MOFs catalysts with excellent hydrophobicity, large specific surface area and excellent catalytic performance.
Disclosure of Invention
The invention aims to prepare a series of super-hydrophobic modified MOFs materials by taking MOFs with grafting active sites as a substrate and carrying out PSM functionalization with 4-trifluoromethylbenzaldehyde by means of Mannich reaction.
The technical scheme adopted by the invention is as follows: a fluorine-containing super-hydrophobic modified MOFs material is prepared by taking MOFs with a grafting active site as a substrate and carrying out PSM functionalization with 4-trifluoromethylbenzaldehyde through a Mannich reaction.
The fluorine-containing super-hydrophobic modified MOFs material is used as a catalyst to catalyze CO2Use in a cycloaddition reaction with an epoxide.
The application is that the fluorine-containing super-hydrophobic modified MOFs material is used as a catalyst, and TBABr is used as a cocatalyst to catalyze CO2Use in a cycloaddition reaction with an epoxide.
The application and the method are as follows: taking an epoxide as a reaction device, taking the activated fluorine-containing super-hydrophobic modified MOFs material as a catalyst, placing TBABr in a polytetrafluoroethylene lining, sealing the lining, and introducing CO into the lining2The gas was replaced three times, the reaction was carried out at 80 ℃ for 12 hours, and the yield was determined by gas chromatography.
The catalyst is MIL-101(Cr) -NH2,MIL-101(Al)-NH2,UiO-66-(Zr)-NH2,UiO-66-(Hf)-NH2One of the materials or one of MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and UiO-66(Hf) -3F of the super-hydrophobic modified MOFs.
In the application, the epoxide is one or more of propylene oxide, butylene oxide, isobutylene oxide, epichlorohydrin, styrene oxide and cyclohexene oxide.
The invention has the beneficial effects that: the super-hydrophobic modified MOFs material prepared by the invention realizes high-efficiency catalysis on the carbon dioxide cycloaddition reaction under mild conditions. The experimental result provides a new thought and method for the design and synthesis of the hydrophobic MOF and the composite material thereof and the aspect of catalyzing organic conversion. The method has the advantages of easily available raw materials, green and environment-friendly synthesis process and simple operation, thereby having good market economic value and wide application prospect.
Drawings
FIG. 1 is a PXRD diffraction pattern of the superhydrophobic modified MOFs material of the present invention. Wherein (a) is MIL-101(Cr) -NH2And MIL-101(Cr) -3F; (b) is MIL-101(Al) -NH2And MIL-101(Al) -3F; (c) is UiO-66(Zr) -NH2And UiO-66(Zr) -3F; (d) is UiO-66(Hf) -NH2And UiO-66(Hf) -3F.
FIG. 2 is an FT-IR spectrum of the superhydrophobic-modified MOFs of the present invention. Wherein (a) MIL-101(Cr) -NH2And MIL-101(Cr) -3F; (b) MIL-101(Al) -NH2And MIL-101(Al) -3F; (c) UiO-66(Zr) -NH2And UiO-66(Zr) -3F; (d) UiO-66(Hf) -NH2And UiO-66(Hf) -3F.
FIG. 3 is a thermogravimetric analysis diagram of the superhydrophobic modified MOFs material of the present invention.
FIG. 4 is an SEM photograph of the super-hydrophobic modified MOFs material of the present invention.
FIG. 5 is an XPS spectrum of the superhydrophobic modified MOFs material of the invention.
FIG. 6 is N of the super-hydrophobic modified MOFs material of the present invention2Adsorption-desorption curve.
FIG. 7 is CO of the super-hydrophobic modified MOFs material of the invention2Adsorption-desorption curve.
FIG. 8 is a contact angle test chart of the super-hydrophobic modified MOFs material of the present invention.
FIG. 9 shows the chemical stability of the superhydrophobic modified MOFs of the present invention, wherein (a) is MIL-101(Cr) -3F, and (b) is MIL-101(Al) -NH2(c) is UiO-66(Zr) -3F, and (d) is UiO-66(Hf) -3F.
FIG. 10 shows MIL-101(Cr) -NH according to the invention2And Py-IR testing of the super-hydrophobic modified MOFs material.
FIG. 11 shows that the super-hydrophobic modified MOFs material of the invention catalyzes CO2Schematic representation of cycloaddition reaction with epoxide.
FIG. 12 is a graph showing a comparison of the cycle performance of MIL-101(Cr) -3F as a catalyst according to the present invention.
FIG. 13 is XRD of the super-hydrophobic modified MOFs material of the present invention after catalysis.
FIG. 14 shows that the super-hydrophobic modified MOFs material of the invention catalyzes CO2Mechanism diagram of cycloaddition reaction.
Table 1 shows that four super-hydrophobic modified MOFs materials of the invention catalyze CO2Cycloaddition reaction with epoxide.
Detailed Description
Example 1 Superhydrophobically modified MOFs materials
The reaction formula is as follows:
Figure BDA0002971003610000041
the preparation method comprises the following steps:
1. preparation of four initial MOFs materials (MIL-101(Cr) -NH)2,MIL-101(Al)-NH2,UiO-66-(Zr)-NH2,UiO-66-
(Hf)-NH2)。
1)MIL-101(Cr)-NH2Preparation of
Accurately weighing Cr (NO)3)3·9H2O(800mg)，H2DBC-NH2(360mg) was added to 15mL of redistilled water, followed by addition of NaOH (160mg) and vigorous stirring for 30 min. The obtained mixture is transferred to a high-pressure reaction kettle to be sealed and checked whether leakage occurs or not, and the mixture is placed into a constant-temperature oven to be insulated for 16 hours at the temperature of 150 ℃. After cooling to room temperature, the product was centrifuged, washed several times until the upper liquid was colorless, and dried under vacuum at 80 ℃ overnight.
2)MIL-101(Al)-NH2Preparation of
AlCl3·6H2Adding 560mg of O510, 2-amino terephthalic acid into 30mL of DMF, stirring at room temperature for 30min until the mixture is completely dissolved, transferring the obtained mixture into a high-pressure reaction kettle, sealing, checking whether liquid leakage exists or not, and preserving the mixture in a constant-temperature oven at 130 ℃ for 12 h. Cooling to room temperature, centrifuging, washing for multiple times, and vacuum drying the obtained solid at 80 deg.C overnight to obtain pure NH2-MIL-101(Al)。
3)UiO-66-(Zr)-NH2Preparation of
ZrCl is prepared according to a method for rapidly preparing UiO-66 reported in the literature4900mg, 702mg of 2-aminoterephthalic acid was dissolved in 60mL of DMF, 26.4mL of glacial acetic acid and 4.5mL of deionized water were added, and stirring was continued at room temperature for 10 min. Transferring the solution into a 150mL single-neck flask, heating and stirring in an oil bath at 120 ℃ for 15min, centrifuging the obtained product, washing for multiple times, and vacuum drying at 60 ℃ overnight to obtain pure UiO-66(Zr) -NH2。
4)UiO-66-(Hf)-NH2Preparation of
HfCl4750mg, 425mg of 2-aminoterephthalic acid were dissolved in 100mL of DMF, 18mL of glacial acetic acid and 2.5mL of deionized water were added, and stirring was continued at room temperature for 10 min. The solution was transferred to a 150mL single-neck flask, heated and stirred in a 120 ℃ oil bath for 15min, the resulting product was centrifuged, washed several times, and the resulting solid was dried under vacuum at 60 ℃ overnight.
2. Four super-hydrophobic modified MOFs materials (MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and
UiO-66(Hf)-3F)。
and (3) activating the initial MOFs material at 150 ℃ for 12 hours in vacuum, taking 200mg of the activated MOFs in 150mL, adding 50mL of dried tolene, performing ultrasonic dispersion, adding 20mmol of 4-trifluoromethylbenzaldehyde, and placing the mixture in an oil bath kettle at 120 ℃ for constant-temperature reaction for 12 hours under the protection of nitrogen. After cooling to room temperature, the product was centrifuged and washed several times with tolumene and dried under vacuum at 80 ℃ overnight to give MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and UiO-66(Hf) -3F.
The structure of the super-hydrophobic modified MOFs material synthesized by the invention is shown in figures 1-10. The MOF-3F material has no obvious change compared with the original MOF shape.
The test was carried out using an X-ray diffractometer, and the test results are shown in FIG. 1. In FIG. 1, it can be observed that the MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and UiO-66(Hf) -3F superhydrophobic composite materials have no structural change after being grafted by 4-trifluoromethylbenzaldehyde.
Testing by using a Fourier infrared spectrometer to obtain a test resultAs shown in fig. 2. FT-IR spectral analysis showed that, for example, MIL-101(Cr) -3F was compared to the original MIL-101(Cr) -NH2Compared with the material with 1067cm, the super-hydrophobic modified MOFs material-1A new characteristic absorption peak appears at the position corresponding to-CF in the 4-trifluoromethylbenzaldehyde molecule3Bending vibration of the C-F bond of the group. Meanwhile, MIL-101(Cr) -NH2At 847cm-1The peak of (A) belongs to-NH2The out-of-plane deformation vibration of the group N-H bond is carried out, after 4-trifluoromethylbenzaldehyde molecule grafting, the infrared absorption peak at the position almost disappears, the amino group reaction is proved to be changed into-C-N-group, and the conclusion can be drawn through FT-IR spectrum, and the 4-trifluoromethylbenzaldehyde molecule is grafted to the surface of MOF material to prepare the super-hydrophobic MOF-3F composite material.
As shown in fig. 3, the thermogravimetric analysis shows the measurement of the mass of the MOF-3F composite versus temperature change at a programmed temperature. As can be seen from the figure, the initial MOF and MOF-3F composites have similar spectra, but retain different residues at 750 ℃. This phenomenon is attributed to the change in the framework groups of MOFs resulting in a change in their TGA after 4-trifluoromethylbenzaldehyde grafting treatment.
As shown in FIG. 4, the morphology of the superhydrophobic modified MOFs material compounded by 4-trifluoromethylbenzaldehyde is consistent with the original MOF size, and the morphology is not changed.
As shown in FIG. 5, XPS test was used to study the chemical composition and elemental chemical state of the surface of the superhydrophobic-modified MOFs. Taking MIL-101(Cr) -3F treated by 4-trifluoromethylbenzaldehyde as an example, from the whole spectrum, the MIL-101(Cr) -3F contains five elements of C, N, O, Cr and F, two spectral components can be observed in a Cr 2p spectrum, are respectively positioned at 278.3 and 288.1eV, and can be classified as Cr 2p in the MIL-101(Cr) -3F3/2And Cr 2p1/2. As shown in FIG. 5c, the F1 s spectrum appears at 689.2eV, which is derived from the-CF in MOF-3F3Group, demonstration of successful grafting of 4-trifluoromethylbenzaldehyde onto MIL-101(Cr) -NH2In the skeleton. Furthermore, fig. 5d is a N1s spectrum with the position of the fitted peak at 399.6eV, which can be assigned to the conjugate-C ═ N-, from 4-trifluoromethylbenzaldehyde and-NH in MOF2Schiff base generated by group reaction can also prove that the synthesis method is effective. Four spectral components appear in the C1s spectrum, 288.3, 286.1, 285.3 and 284.7eV respectively, and can be assigned to C-O, C-C, C-N and C-C (fig. 5 e). The O1 s spectra show two chemical states, the binding energies at 534.8 and 532.8eV being attributable to O-H and Cr-O in the MOF framework. The position of the peak is slightly shifted in the literature, and can be attributed to that after 4-trifluoromethylbenzaldehyde grafting treatment, the trifluoromethyl group in the MIL-101(Cr) -3F is a strong electron-pulling group, so that the charge distribution of the MIL-101(Cr) -3F framework is influenced, and the position of the peak is shifted.
The adsorption and desorption isotherms of four MOFs before and after molecular grafting by 4-trifluoromethylbenzaldehyde are shown in FIG. 6. MIL-101(Cr) -NH2(MIL-101(Cr)-3F)、MIL-101(Al)-NH2(MIL-101(Al)-3F)、UiO-66(Zr)-NH2(UiO-66(Zr) -3F) and UiO-66(Hf) -NH2(UiO-66(Hf) -3F) has BET surface areas of 3179.3(2768.4), 1359.2(1039.5), 1248(1146) and 700.8(537.2) m2·g-1。
As shown in FIG. 7, is CO2Adsorption-desorption measurement under 273K and 298K conditions to obtain CO2Adsorption-desorption isotherms. MIL-101(Cr) -NH at 273K2(MIL-101(Cr)-3F)、MIL-101(Al)-NH2(MIL-101(Al)-3F)、UiO-66(Zr)-NH2(UiO-66(Zr) -3F) and UiO-66(Hf) -NH2CO of (UiO-66(Hf) -3F)2The adsorption amounts were 75.8(73.5), 65.9(63.7), 61.9(62.2), and 67.2(67.0) cm3 g-1MIL-101(Cr) -NH at 298K2(MIL-101(Cr)-3F)、MIL-101(Al)-NH2(MIL-101(Al)-3F)、UiO-66(Zr)-NH2(UiO-66(Zr) -3F) and UiO-66(Hf) -NH2CO of (UiO-66(Hf) -3F)2The adsorption amounts were 45.1(42.3), 38.0(32.8), 40.9(38.9), and 45.9(43.9) cm3 g-1As can be seen from the adsorption isotherm, the CO of the four MOFs materials before and after grafting2The adsorption amount is not obviously changed, and the MOF-3F is proved to have excellent CO2Adsorption capacity.
As shown in FIG. 8, wettability of superhydrophobic-modified MOFs (MOF-3F) was evaluated by CA test. The WCA of MIL-101(Cr) -3F is about 164 degrees, the WCA of MIL-101(Al) -3F is about 154 degrees, the WCA of UiO-66(Zr) -3F is about 151 degrees, and d) the WCA of UiO-66(Hf) -3F is about 153 degrees, and the CA of the four MOF-3F composite materials obtained after the 4-trifluoromethylbenzaldehyde grafting treatment is more than 150 degrees, and the four MOF-3F composite materials are determined to have the super-hydrophobic property according to the definition.
As shown in FIG. 9, four prepared superhydrophobic modified MOFs materials were tested for chemical stability. The four MOF-3F composite materials are respectively soaked in (MeOH, EtOH, dichloromethane, chloroform, tolumene, water, building water and 1M NaOH aqueous solution) for 24h, separated and dried, and PXRD test is carried out on the prepared MOF-3F composite materials, and the results show that the structures of the four MOF-3F composite materials are not changed and have excellent chemical stability after treatment by different organic solvents. In addition, the four MOF-3F are found to have excellent stability under harsh conditions (water, binding water,1M NaOH aqueous solution) by PXRD test.
As shown in FIG. 10, in order to test the synthesized material for Lewis acid and
Figure BDA0002971003610000071
acid Activity, we are on MIL-101(Cr) -NH2And MIL-101(Cr) -3F composite material were subjected to Py-IR testing. Tests show that the concentration of the active carbon is 1466 cm and 1563cm-1At a Lewis acid site of 1509cm-1Is arranged as
Figure BDA0002971003610000072
An acid active site, wherein the Lewis acid active site is derived from a coordinately unsaturated metal site in the MOF framework
Figure BDA0002971003610000073
The acidic sites may be derived from hydroxyl active sites on metal clusters in the MOF framework. The content of MIL-101(Cr) -NH can be known by Py-IR test2And Lewis acid and
Figure BDA0002971003610000074
acid content is divided intoLewis acids of 0.02940 and 0.04543mmol/g, MIL-101(Cr) -3F and
Figure BDA0002971003610000075
the acid content was 0.03960 and 0.05306mmol/g, respectively. From the results, it was found that Lewis acid of MIL-101(Cr) -3F composite material after the graft treatment with trifluoromethylbenzaldehyde and
Figure BDA0002971003610000076
the acid activity is enhanced.
Example 2 fluorine-containing superhydrophobic modified MOFs materials catalyze CO2Cycloaddition reaction with epoxides
CO by using the super-hydrophobic modified MOFs material prepared in example 1 as a catalyst2The cycloaddition reaction with the epoxide is catalyzed.
The method comprises the following steps:
first, the four resulting starting MOFs and the prepared superhydrophobic modified MOFs were vacuum activated at 120 ℃ for 12 h. Using a high-pressure reaction kettle as a reaction device, taking 10mmol of epoxide, 0.005mmol of activated catalyst and 0.1mmol of TBABr in a polytetrafluoroethylene lining, placing the materials in the high-pressure reaction kettle, sealing the high-pressure reaction kettle, and introducing 1.0MPa of CO into the high-pressure reaction kettle2The gas was replaced three times, the reaction was carried out at 80 ℃ for 12 hours, and the yield was determined by gas chromatography. The results are shown in table 1 and fig. 11 to 14.
TABLE 1
Figure BDA0002971003610000081
As shown in Table 1, entries 1-8 in Table 1, 1MPa CO at 80 deg.C2Pressure, 0.1mmol TBABr as cocatalyst, we used MIL-101(Cr) -NH2,MIL-101(Al)-NH2,UiO-66(Zr)-NH2,UiO-66(Hf)-NH2And MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F, UiO-66(Hf) -3F as heterogeneous Lewis acid catalyst for catalyzing CO under mild conditions2The propylene carbonate is prepared by cycloaddition reaction with propylene oxide, and the result can be obtainedIt is shown that the catalytic performances of the superhydrophobic modified MOFs grafted with 4-trifluoromethylbenzaldehyde (MIL-101(Cr) -3F 97.5%, MIL-101(Al) -3F 86.6%, UiO-66(Zr) -3F 84.3%, UiO-66(Hf) -3F 86.8%, respectively) are better than those of the original MOF (MIL-101(Cr) -NH-3F 86.8%, respectively)2 81.4％,MIL-101(Al)-NH2 74.4％,UiO-66(Zr)-NH270.8％,UiO-66(Hf)-NH273.9 percent) and proves that the catalytic performance of the MOF is improved after the super-hydrophobic modification. Simultaneously, after hydrophobic modification, the Lewis acid & lt/EN & gt of the MOF-3F composite material
Figure BDA0002971003610000091
The acid activity is enhanced, and the catalytic activity can be improved. In addition, after the super-hydrophobic modification, the enrichment of the catalyst on a substrate can be enhanced, the catalyst is prevented from contacting with water molecules in the air or the environment, the selectivity of the catalyst is enhanced, and the phenomena of catalyst inactivation and the like occur. In addition, through experimental results, MIL-101(Cr) -3F shows the optimal catalytic activity, probably because the hydrophobic property of MIL-101(Cr) -3F is better than that of the other three MOF-3F composite materials. Meanwhile, MIL-101(Cr) -3F has larger pore size and smaller particle size due to the inherent characteristics, so that the catalytic activity of the composite material is better than that of the other three MOF-3F composite materials. Therefore, the catalytic activity of the reaction is studied by selecting MIL-101(Cr) -3F as a catalyst. First, 0.1mmol TBABr catalyzed the reaction under the same conditions without catalyst addition with only 28.56% conversion, demonstrating that catalyst addition can greatly increase the conversion of the reaction (table 1, entry 9). At the same time, without the promoter TBABr, the conversion of the reaction was only 2.8% (as in table 1, entry 10), demonstrating that the addition of promoter was necessary. The reaction is catalyzed synergistically by the MOF catalyst and the cocatalyst TBABr, both of which are essential.
Secondly, the research on the substrate expansibility of the reaction catalyzed by MIL-101(Cr) -3F as a catalyst is carried out, epoxides (epoxybutane, oxidized isobutene, epichlorohydrin, oxidized styrene and oxidized cyclohexene) with different substituents are selected as the substrates of the reaction for the research of the catalytic performance, and the yield of CCs is reduced with the increase of the substrate sizeAt 80 ℃ and 1MPa CO2Under the pressure of 0.1mmol of TBABr as a cocatalyst, the conversions of butylene oxide, isobutylene oxide, epichlorohydrin, styrene oxide and cyclohexene oxide were 84.4%, 56.57%, 64.64%, 58.21% and 26.1%, respectively (Table 1, entries 11 to 15). This may be due to steric hindrance of the pore size and reactant steric configuration that reduces the efficiency of reactant diffusion, making it difficult to contact the catalytic sites, reducing catalytic efficiency.
As shown in FIG. 12, the superhydrophobic MIL-101(Cr) -3F composite material grafted with 4-trifluoromethylbenzaldehyde was used as a catalyst, epoxy propane was used as a substrate, and CO was added at 80 ℃ and 1MPa2The recyclability under the conditions of pressure, 0.1mmol of TBABr as cocatalyst, was investigated. When the reaction was complete, the remaining catalyst was recovered by centrifugation, washed several times with MeOH and dried, and activated in vacuo at 120 ℃ for 12h before the next round of cycling experiments. Drying As shown in FIG. 12, the prepared superhydrophobic MIL-101(Cr) -3F has almost no loss of catalytic activity after five cycles of experiments. PXRD spectrum tests show that the structure of the MIL-101(Cr) -3F composite material is not changed (FIG. 13). The MIL-101(Cr) -3F composite material has excellent cycle performance and stability proved by cycle experiments.
A possible mechanism for this reaction is shown in FIG. 14, initially, by having Lewis acidic Cr3+Center and
Figure BDA0002971003610000092
the acid-active O-H center is activated by weak coordination with the doubly-bound oxygen atom in the epoxide. At this time, Br in TBABr-Attack the C atom on the less sterically positioned side of the epoxide, which is kinetically driven, resulting in epoxide ring opening. Then, CO2The intermediate formed in the previous step is reacted by nucleophilic attack and converted to CC by intermolecular cyclization, providing the original catalyst for the next cycle.

Claims (6)

1. The fluorine-containing super-hydrophobic modified MOFs material is characterized in that: MOFs with grafting active sites are used as a substrate, and the MOFs and 4-trifluoromethylbenzaldehyde are subjected to PSM functionalization through Mannich reaction, so that a series of fluorine-containing super-hydrophobic MOF composite materials are prepared.
2. The fluorine-containing super-hydrophobic modified MOFs material of claim 1 as a catalyst for catalyzing CO2Use in a cycloaddition reaction with an epoxide.
3. The use of claim 2, wherein the fluorine-containing superhydrophobic modified MOFs material of claim 1 is used as a catalyst, and TBABr is used as a promoter to catalyze CO2Use in a cycloaddition reaction with an epoxide.
4. Use according to claim 3, characterized in that the method is as follows: taking an epoxide as a reaction device, taking the activated fluorine-containing super-hydrophobic modified MOFs material as a catalyst, placing TBABr in a polytetrafluoroethylene lining, sealing the lining, and introducing CO into the lining2The gas was replaced three times, the reaction was carried out at 80 ℃ for 12 hours, and the yield was determined by gas chromatography.
5. Use according to claim 4, wherein the catalyst is MIL-101(Cr) -NH2,MIL-101(Al)-NH2,UiO-66-(Zr)-NH2,UiO-66-(Hf)-NH2One of the materials or one of MIL-101(Cr) -3F, MIL-101(Al) -3F, UiO-66(Zr) -3F and UiO-66(Hf) -3F of the super-hydrophobic modified MOFs.
6. Use according to claim 5, wherein the epoxide is one or more of propylene oxide, butylene oxide, isobutylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide.
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