CN114225967B - Self-healing supported zirconium-based metal organic framework and preparation method and application thereof - Google Patents
Self-healing supported zirconium-based metal organic framework and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-stability self-healing load type zirconium-based metal organic framework, and preparation and application thereof; the chemical formula of the self-healing load type zirconium-based metal organic framework is as follows: { Pd (II) -bpy } x Zr 6 O 4 (OH) 4 (bpy) 6‑x Wherein x is the content of Pd (II), x is more than or equal to 0.08 and less than or equal to 0.25; bpy is 2,2 '-bipyridine-5,' 5-dicarboxylic acid. The self-healing supported zirconium-based metal organic framework is synthesized by adopting a solvothermal method, is environment-friendly, and is simple and easy to operate. The self-healing supported zirconium-based metal organic framework catalyst has the advantages of high catalytic activity, mild reaction conditions, wide substrate practicability and the like in the serial cyclization reaction of the isonitrile and the N-acyl-o-alkynyl aniline, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts and the field of organic synthesis, and particularly relates to a self-healing supported zirconium-based metal organic framework, and a preparation method and application thereof.
Background
Catalytic efficiency is one of the key parameters for evaluating the universality and practicability of an organic reaction system, and is closely related to the catalytic activity of the catalyst in the reaction process. Metallic palladium is one of the most commonly used metal catalysts in organic synthesis due to its high reactivity. In general, most palladium-catalyzed reactions involve a state transition between divalent palladium species and zero-valent palladium species, such as palladium-catalyzed oxidation, suzuki coupling, heck coupling, etc. (Q.P.Dai, B.G.Zhao, Y.H.Yang, Y.A.Shi, org.Lett.2019,21,5157;L.J.Oxtoby,J.A Gurak,S.R Wisniewski,M.D.Eastgate,K.M Engle,Trends in Chemistry,2019,1,572;Y.H.Wang,Y.F.Wu,Y.H.Li and Y.F.Tang,Chem.Sci, 2017,8,3852). However, zero-valent palladium species generated during the reaction are more likely to aggregate into palladium nanoparticles and even palladium black, thereby inactivating. In homogeneous catalytic systems, the addition of organic ligands slows down to some extent the rate of deactivation of the active palladium species, but does not fundamentally avoid deactivation of the palladium catalyst. Therefore, how to stabilize palladium catalysts to improve catalytic efficiency is a research hotspot in the field of heterogeneous catalysis.
The Metal Organic Frameworks (MOFs) are porous materials formed by self-assembly coordination of organic ligands and inorganic metals or metal clusters, and have the advantages of large specific surface area, high porosity, diversified structures and functions, good thermal stability and the like. As researchers continue to develop the field of MOFs catalysis, different types of palladium supported MOF catalysts have been developed and widely used in organic synthesis reactions (h.c. zhou.j.r.long and O.M.Yaghi, chem.Rev.2012,112,673; neha, a.; N.Antil, N.Akhtar, R.Newar, W.Begum, A.Kumar, M.Chauhan and k.manna, ACS catalyst.2021, 11,10450;J.L.Long,K.Shen and Y.W.Li,ACS Catal.2017,7,275;J.W.Li,J.H.Liao,Y.W.Ren,C.Liu,C.L.Yue,J.M.Lu and H.F.Jiang.Angew.Chem, 2019,131,17308.). Meanwhile, the use of MOFs as catalysts or catalyst precursors for the preparation of carbon materials to promote the conversion of carbon-nitrogen triple bonds has been further developed, but is mainly focused on hydration and reduction of carbon-nitrogen triple bonds, with a narrower reaction type (J.L.Long, B.L.Yin, Y.W.Li and L.J.Zhang, AIChE.,2014,60,3565;J.L.Long,K.Shen,L.Che and Y.W.Li,J.Mater.Chem.A, 2016,4,10254;P.F,Ji,K.Manna,Z.L.Lin,X.Y.Feng,A.Urban,Y.Song and W.BLin,J.Am.Chem.Soc, 2017,139,7004). Palladium-catalyzed conversion of C-N triple bonds is an effective way to build various nitrogen-containing functionalized backbones, and to avoid hydrolysis of C-N triple bonds and promote reaction progress, (sub) equivalents of base are typically added to the catalytic system under conditions where palladium catalyst readily aggregates to form palladium black, thereby greatly limiting the catalytic efficiency of the palladium catalyst (M.Knorn, E.Lutsker and O.Reiser, chem.Soc.Rev.2020,49,7730;G.Y.S.Qiu,Q.P.Ding and J.Wu,Chem.Soc.Rev, 2013,42,5257; b.r.song, b.xu, chem.soc.rev.,2017,46,1103.).
Therefore, in order to promote the rich conversion of isonitriles, it is highly desirable to develop a MOF catalyst which has good stability, high activity and simple preparation method.
Disclosure of Invention
In order to solve the defects in the prior art, one of the purposes of the invention is to provide a self-healing load type zirconium-based metal organic framework.
The second purpose of the invention is to provide the preparation method of the self-healing supported zirconium-based metal organic framework, which is simple and feasible, environment-friendly and high in yield.
The invention also aims to provide the application of the self-healing supported zirconium-based metal organic framework in the cyclization reaction of isonitrile and N-acyl-o-alkynyl aniline.
The self-healing supported zirconium-based metal organic framework shows unique state change in the catalytic process, and is different from the common heterogeneous catalyst, palladium species firstly fall off from the metal organic framework into a solution in the reaction process, and are quickly captured by ligands on the metal organic framework after participating in catalytic circulation, so that the self-healing of the catalyst is realized.
The aim of the invention is achieved by the following technical scheme:
a self-healing supported zirconium-based metal organic framework has a chemical formula: { Pd (II) -bpy } x Zr 6 O 4 (OH) 4 (bpy) 6-x Wherein x is the content of Pd (II), x is more than or equal to 0.08 and less than or equal to 0.25; bpy is 2,2 '-bipyridine-5,' 5-dicarboxylic acid.
The preparation method of the self-healing supported zirconium-based metal organic framework comprises the following steps of:
(1) ZrCl is added to 4 Dispersing 2,2 '-bipyridine-5,' 5-dicarboxylic acid and a modulator in a solvent, stirring for reaction, purifying and drying to obtain a zirconium-based metal organic framework material;
(2) Dispersing the zirconium-based metal organic framework material and palladium salt in the step (1) in an organic solvent, and stirring to obtain the self-healing supported zirconium-based metal organic framework.
Preferably, the preparation agent in the step (1) is more than one of benzoic acid, glacial acetic acid and formic acid;
preferably, the solvent of step (1) is DMF;
preferably, the temperature of the stirring reaction in the step (1) is 100-140 ℃ and the time is 16-32 hours.
Preferably, the ZrCl of step (1) 4 2,2 '-bipyridine-5,' 5-The molar ratio of dicarboxylic acid to modifier is 1:1:10 to 1:1:30.
preferably, the molar ratio of the zirconium-based metal organic framework material to the palladium salt in the step (2) is 1:1-4;
preferably, the palladium salt in step (2) is Pd (OAc) 2 、PdCl 2 、Pd(TFA) 2 At least one of them.
Preferably, the temperature of the stirring treatment in the step (2) is 30-80 ℃;
preferably, the stirring treatment in the step (2) is performed for 3 hours or more. Further, the stirring time is 3-24 hours.
Preferably, the organic solvent in the step (2) is at least one of acetonitrile, acetone and tetrahydrofuran.
The self-healing supported zirconium-based metal organic framework is used for catalyzing cyclization reaction of isonitrile and N-acyl-o-alkynyl aniline.
Preferably, the structural formula of the N-acyl-o-alkynylaniline is as follows:
wherein R is-H, -F, -CF 3 、-CH 3 、-OCH 3 。
Preferably, the cyclization reaction of the isonitrile and the N-acyl-o-alkynylaniline specifically comprises the following steps:
under inert gas atmosphere, isonitrile, N-acyl-o-alkynylaniline, self-healing supported zirconium-based metal organic framework and Li 2 CO 3 Adding the mixture into a solvent, and stirring the mixture to perform a reaction.
Compared with the prior art, the invention has the following beneficial effects:
the self-healing supported zirconium-based metal organic framework catalyst prepared by the method has the advantages of higher stability and catalytic activity in the cyclization reaction of isonitrile and N-acyl-o-alkynyl aniline, obviously improved TON value, reduced alkali content required by a system, mild reaction condition, convenient operation, wide substrate applicability and the like, can be subjected to gram-scale amplification, and has good application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of examples 1-5.
FIG. 2 is an X-ray photoelectron spectrum of example 2.
FIG. 3 is an X-ray photoelectron spectrum of example 3.
FIG. 4 is an X-ray photoelectron spectrum of example 4.
FIG. 5 is an X-ray photoelectron spectrum of example 5.
FIG. 6 is an infrared spectrum of examples 2-5.
Fig. 7 is a scanning electron microscope image of example 2.
Fig. 8 is a scanning electron microscope image of example 3.
Fig. 9 is a scanning electron microscope image of example 4.
Fig. 10 is a scanning electron microscope image of example 5.
FIG. 11 is a transmission electron microscope image of palladium black in system 1 in example 7.
FIG. 12 is a transmission electron micrograph of the post-reaction catalyst of System 2 of example 7.
FIG. 13 is a graph of the photoelectron spectrum of system 2 in example 7 after reaction.
Detailed Description
The present invention will be specifically described with reference to the following examples, but the embodiments and the scope of the present invention are not limited to the following examples.
Example 1
The preparation method of the self-healing supported zirconium-based metal organic framework comprises the following steps:
0.52 mmol of ZrCl 4 0.52 mmole of 2,2 '-bipyridine-5,' 5-dicarboxylic acid and 15.6 mmole of benzoic acid were dispersed in N, N-dimethylformamide solution, sonicated for 30 minutes, placed in an oven and reacted at 120℃for 24 hours. Cooling the reaction solution to room temperature, filtering, washing the filtered solid with N, N-dimethylformamide and acetone for multiple times, and drying at 120deg.C for 24 hr to obtain zirconium-based metal-organic frame material (denoted as UiO-67-bpy, zr) 6 O 4 (OH) 4 (bpy) 6 )。
Example 2
The preparation method of the self-healing supported metal organic framework comprises the following steps:
0.1 mmole of UiO-67-bpy and 0.1 mmole of Pd (OAc) in example 1 were each separately prepared 2 Evenly dispersed in 3 ml of acetone, pd (OAc) was slowly added 2 The solution was added dropwise to the UiO-67-bpy solution and stirred at 30℃for 6 hours to give a self-healing supported zirconium-based metal-organic framework (denoted as Pd (II) 0.08 /UiO-67-bpy，{Pd(II)-bpy} 0.08 Zr 6 O 4 (OH) 4 (bpy) 5.92 ) Wherein the supported palladium content was obtained by ICP testing.
Example 3
The preparation method of the self-healing supported metal organic framework comprises the following steps:
0.1 mmole of UiO-67-bpy and 0.2 mmole of Pd (OAc) in example 1 were each separately prepared 2 Evenly dispersed in 3 ml of acetone, pd (OAc) was slowly added 2 The solution was added dropwise to the UiO-67-bpy solution and stirred at 30℃for 6 hours to give a self-healing supported zirconium-based metal-organic framework (denoted as Pd (II) 0.09 /UiO-67-bpy，{Pd(II)-bpy} 0.09 Zr 6 O 4 (OH) 4 (bpy) 5.91 ) Wherein the supported palladium content was obtained by ICP testing.
Example 4
The preparation method of the self-healing supported zirconium-based metal organic framework comprises the following steps:
0.1 mmole of UiO-67-bpy and 0.3 mmole of Pd (OAc) in example 1 were each separately prepared 2 Evenly dispersed in 3 ml of acetone, pd (OAc) was slowly added 2 The solution was added dropwise to the UiO-67-bpy solution and stirred at 30℃for 6 hours to give a self-healing supported zirconium-based metal-organic framework (denoted as Pd (II) 0.15 /UiO-67-bpy，{Pd(II)-bpy} 0.15 Zr 6 O 4 (OH) 4 (bpy) 5.85 ) Wherein the supported palladium content was obtained by ICP testing.
Example 5
The preparation method of the self-healing supported metal organic framework comprises the following steps:
0.1 mmole of UiO-67-bpy and 0.4 mmole of Pd (OAc) in example 1 were each separately prepared 2 Evenly dispersed in 3 ml of acetone, pd (OAc) was slowly added 2 The solution was added dropwise to the UiO-67-bpy solution and stirred at 30℃for 6 hours to give a self-healing supported zirconium-based metal-organic framework (denoted as Pd (II) 0.25 /UiO-67-bpy，{Pd(II)-bpy} 0.25 Zr 6 O 4 (OH) 4 (bpy) 5.75 ) Wherein the supported palladium content was obtained by ICP testing.
The X-ray diffraction patterns of examples 1-5 are shown in FIG. 1. When the zirconium-based metal organic frameworks UiO-67-bpy are used with different levels of Pd (OAc) 2 When post-modification is carried out, the crystal form is kept unchanged, which indicates that the structure of the prepared self-healing supported metal organic framework is perfect.
The X-ray photoelectron spectra of examples 2 to 5 are shown in FIGS. 2 to 5. From the figure, it can be seen that 3d of the palladium species contained in the self-healing supported metal organic framework is prepared 3/2 And 3d 5/2 The binding energies of 343.5eV and 337.8eV, respectively, meaning that the valence state of the palladium species is +2.
The infrared spectra of examples 2-5 are shown in FIG. 6. As can be seen, when the zirconium-based metal organic frameworks UiO-67-bpy are used with different levels of Pd (OAc) 2 The structure remains unchanged when post-modification is performed.
The scanning electron microscope diagrams of examples 2 to 5 are shown in FIGS. 7 to 10. When the zirconium-based metal organic frameworks UiO-67-bpy are used with different levels of Pd (OAc) 2 In the case of the post-modification, the post-modification is carried out, the morphology of the material is kept in a perfect octahedron shape.
Example 6
Catalytic performance testing of the self-healing supported metal organic frameworks obtained in examples 2-5.
0.1 mmol of N-acyl-O-alkynylaniline, 0.15 mmol of tert-butylisonitrile, 4 mg of Pd (II) x/UiO-67-bpy catalyst, 0.03 mmol of Li 2 CO 3 1 ml of dimethyl sulfoxide solution was placed in the vial. After thoroughly removing the air from the tube, nitrogen was bubbled in and the operation was repeated three times. Subsequently, the system was left to react at 90℃with stirring for 1 hour. And after the reaction is finished, filtering and separating filter residues of the filtrate, cleaning the filter residues with acetone for three times, and sampling to perform projection electron microscope characterization. The yield of the product was determined by NMR. The results are shown in Table 1. As is clear from the results in Table 1, catalyst Pd (II) obtained in example 3 0.09 The UiO-67-bpy effect is optimal.
The reaction formula is as follows:
TABLE 1
Example 7
The catalyst Pd (II) obtained in example 3 0.09 UiO-67-bpy and Pd (OAc) 2 Comparison of catalytic properties.
TABLE 2
In System 1, 0.1 mmol of N-acyl-O-alkynylaniline was added to 0.15 mmol of t-butylisonitrile and 0.01 mmol of Pd (OAc), respectively 2 0.03 millimoles of Li 2 CO 3 And 1 ml of a mixed solution of dimethyl sulfoxide. After thoroughly removing the air from the tube, nitrogen was bubbled in, and the operation was repeated three times. Subsequently, the system was placed at 90℃and the yields of the products were measured at stirring for 20 minutes, 40 minutes and 1 hour, respectively.And palladium black formation was observed in the solution at 20 minutes of stirring reaction, indicating Pd (OAc) in system 1 2 And is unstable and easily deactivated.
A transmission electron microscope image of the palladium black in system 1 of example 7 is shown in FIG. 11. From the figure, pd (OAc) in system 1 was found 2 Is easily reduced into Pd (0), is further agglomerated into palladium black, and loses catalytic activity.
In System 2, 0.1 mmol of N-acyl-O-alkynylaniline was added to 0.15 mmol of t-butylisonitrile and 4 mg of Pd (II) 0.09 UiO-67-bpy, 0.03 mmol Li 2 CO 3 And 1 ml of a mixed solution of dimethyl sulfoxide. After thoroughly removing the air from the tube, nitrogen was bubbled in, and the operation was repeated three times. Subsequently, the system was placed at 90℃and the yields of the products were measured at stirring for 20 minutes, 40 minutes and 1 hour, respectively. The catalyst remained intact after the reaction, no formation of palladium nanoparticles and palladium black was observed, indicating Pd (II) 0.09 The stability of the UiO-67-bpy is better.
A transmission electron microscope image of the catalyst after the reaction in the system 2 in example 7 is shown in FIG. 12. The graph shows that the catalyst after the reaction maintains the good octahedral morphology, and no palladium nano particles and palladium black are generated on the surface, which proves that the catalyst can well stabilize palladium species and avoid aggregation and agglomeration of the palladium species.
The X-ray photoelectron spectrum after the reaction in the system 2 in example 7 is shown in FIG. 13. From the figure, it can be seen that the palladium species 3d in the catalyst after the reaction 3/2 And 3d 5/2 The binding energies of 343.5eV and 337.8eV indicate that the palladium species remains +2 valent and still has catalytic activity.
Example 8
0.1 mmol of N-acyl-O-alkynylaniline was added to 0.15 mmol of t-butylisonitrile and 4 mg of Pd (II), respectively 0.09 UiO-67-bpy, 0.03 mmol Li 2 CO 3 And 1 ml of dimethyl sulfoxide, and four parallel sample feeding tubes. After thoroughly removing the air from the tube, nitrogen was bubbled in, and the operation was repeated three times. Subsequently, the system was subjected to a reaction at 90℃under stirring for 15 minutes, 30 minutes, 45 minutes and 60 minutes, and was catalyzedSeparating the reagent, and detecting the concentration of metal palladium ions in the reaction liquid by flame atomic absorption. The experimental result shows that with the extension of the reaction time, the concentration of palladium ions in the solution is increased from the initial 0ppm to 14.213ppm after fifteen minutes of reaction, the concentration reaches 15.313ppm at the highest after minutes, and then the concentration of palladium ions in the solution is obviously reduced to 6.042ppm, and finally the concentration is stabilized at 3.215ppm. The change trend shows that the supported zirconium-based metal organic framework falls off from the metal organic framework firstly in the catalytic process, and the self-healing is completed after the supported zirconium-based metal organic framework participates in the reaction.
Example 9
The catalyst Pd (II) obtained in example 3 0.09 Substrate suitability test for the cyclization of N-acyl-o-alkynylaniline with t-butylisonitrile by UiO-67-bpy.
0.1 mmol of N-acyl-O-alkynylaniline containing different substituents was added to 0.15 mmol of t-butylisonitrile and 4 mg of Pd (II) 0.09 UiO-67-bpy, 0.03 mmol Li 2 CO 3 And 1 ml of a mixed solution of dimethyl sulfoxide. After thoroughly removing the air from the tube, nitrogen was bubbled in, and the operation was repeated three times. Subsequently, the system was left to react at 90℃with stirring for 1 hour. After the reaction was completed, the filtrate was filtered and the residue was separated, and the yield of the product was determined by NMR, and the experimental results are shown in table 2. As can be seen from the results of Table 2, catalyst Pd (II) obtained in example 3 0.09 The catalyst performance of the UiO-67-bpy is good, and the conversion of different types of substrates can be efficiently promoted.
TABLE 2
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The application of a self-healing supported zirconium-based metal organic framework for catalyzing cyclization reaction of isonitrile and N-acyl-o-alkynylaniline is characterized in that the self-healing supported zirconium-based metal organic framework has the chemical formula: { Pd (II) -bpy } x Zr 6 O 4 (OH) 4 (bpy) 6-x Wherein x is the content of Pd (II), x is more than or equal to 0.08 and less than or equal to 0.25; bpy is 2,2 '-bipyridine-5,' 5-dicarboxylic acid.
2. The use according to claim 1, wherein the method for preparing the self-healing supported zirconium-based metal organic framework comprises the steps of:
(1) ZrCl is added to 4 Dispersing 2,2 '-bipyridine-5,' 5-dicarboxylic acid and a modulator in a solvent, stirring for reaction, purifying and drying to obtain a zirconium-based metal organic framework material;
(2) Dispersing the zirconium-based metal organic framework material and palladium salt in the step (1) in an organic solvent, and stirring to obtain the self-healing supported zirconium-based metal organic framework.
3. The use according to claim 2, wherein the modulator of step (1) is one or more of benzoic acid, glacial acetic acid and formic acid; the solvent is DMF; the temperature of the stirring reaction is 100-140 ℃ and the time is 16-32 hours.
4. The use according to claim 2, wherein the ZrCl of step (1) 4 The molar ratio of 2,2 '-bipyridine-5,' 5-dicarboxylic acid, and modulator is 1:1:10 to 1:1:30.
5. the use according to claim 2, wherein the molar ratio of the zirconium based metal organic framework material to palladium salt of step (2) is from 1:1 to 4; the palladium salt is Pd (OAc) 2 、PdCl 2 、Pd(TFA) 2 At least one of them.
6. The use according to claim 2, wherein the temperature of the stirring treatment in step (2) is 30 ℃ to 80 ℃ and the time of the stirring treatment is 3 hours or more.
7. The use according to claim 2, wherein the organic solvent of step (2) is at least one of acetonitrile, acetone, tetrahydrofuran.
8. The use according to claim 1, wherein the N-acyl-o-alkynylaniline has the structural formula:
wherein R is-H, -F, -CF 3 、-CH 3 、-OCH 3 。
9. The use according to claim 1, wherein the cyclisation reaction of isonitrile with N-acyl-o-alkynylaniline comprises in particular:
under inert gas atmosphere, isonitrile, N-acyl-o-alkynylaniline, self-healing supported zirconium-based metal organic framework and Li 2 CO 3 Adding the mixture into a solvent, and stirring the mixture to perform a reaction.
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| US7579430B2 (en) * | 2005-09-27 | 2009-08-25 | The United States Of America As Represented By The Secretary Of The Navy | Polymeric material made from siloxane-acetylene polymer containing metal-acetylene complex |
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| CN112221540B (en) * | 2020-09-01 | 2023-07-18 | 沈阳化工大学 | Pd 2+ Supported metal organic framework composite catalyst and preparation method and application thereof |
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| US11111255B1 (en) * | 2020-03-06 | 2021-09-07 | Tongji University | Zirconium-based metal-organic framework material UiO-66(Zr), rapid room-temperature preparation method and application thereof |
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