CN117887097A - Metal organic framework material containing mixed-valence hexanuclear cerium cluster structural unit, and preparation method and application thereof - Google Patents
Metal organic framework material containing mixed-valence hexanuclear cerium cluster structural unit, and preparation method and application thereof Download PDFInfo
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- CN117887097A CN117887097A CN202410129771.4A CN202410129771A CN117887097A CN 117887097 A CN117887097 A CN 117887097A CN 202410129771 A CN202410129771 A CN 202410129771A CN 117887097 A CN117887097 A CN 117887097A
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 44
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000002924 oxiranes Chemical class 0.000 claims description 16
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical group C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000013208 UiO-67 Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001569 carbon dioxide Substances 0.000 abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- 150000007517 lewis acids Chemical class 0.000 abstract description 5
- 239000013110 organic ligand Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 150000005676 cyclic carbonates Chemical class 0.000 description 9
- 125000002524 organometallic group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- -1 4,4' -biphenyl dicarboxylic acid-N, N-dimethylformamide Chemical compound 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 108010046334 Urease Proteins 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010703 epoxide synthesis reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a metal organic framework containing mixed-valence hexanuclear cerium cluster structural units, a preparation method and application thereof, wherein the structure contains two Ce ion centers of 3 valence and 4 valence; the metal organic framework takes 4,4' -biphenyl dicarboxylic acid as an organic ligand, is prepared by a stirring method, has rapid synthesis reaction, is easy to operate, can be synthesized in batches, has an open pore structure, contains abundant catalytic sites, and can be used as Lewis acid for catalyzing carbon dioxide cycloaddition reaction of epoxide.
Description
Technical Field
The invention discloses the technical field of metal organic frame preparation, and particularly relates to a metal organic frame material containing mixed-valence hexanuclear cerium cluster structural units, and a preparation method and application thereof.
Background
The carbon dioxide content in the atmosphere is increasing due to the use of global fossil fuels, the increasing industrialization of the world, etc., and becomes a major factor of global warming. Carbon dioxide is nontoxic and readily available as a by-product of the chemical and energy industries and therefore can be used as a carbon source in industrial syntheses, such as the synthesis of N, N' disubstituted ureases, cyclic carbonates, recycled polyurethanes, and formic acid, and the like. The synthesis of cyclic carbonates using carbon dioxide and epoxides has received great attention because of their wide variety of applications as polar aprotic solvents, as electrolytic elements for batteries, or as intermediates or precursors for fine chemicals, pharmaceuticals, and polymer synthesis.
The metal organic framework material (Metal Organic Frameworks, MOFs) has good application prospect in the fields of storage, separation, sensing, catalysis and the like due to the designability of the structure and the property of the metal organic framework material.
For the reaction of synthesizing cyclic carbonate from carbon dioxide and epoxide, MOFs are widely studied in the direction of taking MOFs as catalytic materials for the reaction because of the advantages of good repeatability, stability, recoverability, environmental friendliness and the like due to the open pore structure and rich catalytic sites in the framework.
In summary, it is very interesting to provide a metal organic framework material to achieve catalysis of carbon dioxide and epoxide synthesis reactions.
Disclosure of Invention
The invention discloses a metal organic framework material containing mixed-valence hexanuclear cerium cluster structural units, a preparation method and application thereof, and the material can be used as Lewis acid in the catalytic reaction of synthesizing cyclic carbonate by carbon dioxide and epoxide.
The invention provides a metal organic framework material containing mixed-valence hexanuclear cerium cluster structural units, wherein the metal organic framework structure contains two Ce ion centers of 3 valence and 4 valence;
the invention also provides a preparation method of the metal organic framework material containing the mixed-valence hexanuclear cerium cluster structural unit, which adopts a stirring method to rapidly synthesize the metal organic framework material and comprises the following steps:
1) Dissolving ceric ammonium nitrate in deionized water to form a solution A;
2) Dissolving 4,4' -biphenyl dicarboxylic acid in N, N-dimethylformamide to form a solution B;
3) Mixing the solution A with the solution B, and stirring to form a solution C;
4) Heating solution C to form solid D;
5) Washing the solid D with N, N-dimethylformamide, soaking in acetone, filtering and drying to obtain a target product: metal organic framework materials of mixed valence hexanuclear cerium cluster structural units.
Specifically, the molar ratio of the ammonium cerium nitrate to the 4,4' -biphenyl dicarboxylic acid is 1:1.
Specifically, the heating conditions in step 4) are: heated at 100℃for 15 minutes.
Specifically, the drying conditions in step 5) are: oven dried at 80 ℃ for 2 hours.
In addition, the invention also provides an application of the metal organic framework containing the mixed valence hexanuclear cerium cluster structural unit, and particularly can be used as a catalytic material for synthesizing cyclic carbonate by using Lewis acid in the reaction of carbon dioxide and epoxide.
The preparation method of the metal organic framework containing the mixed-valence hexanuclear cerium cluster base metal provided by the invention adopts a stirring method to rapidly synthesize, and has the advantages of simple preparation process, rapid reaction and high yield; contains rich coordination unsaturated Ce (III) and Ce (IV) metal centers, and the catalyst is used as a catalytic material for synthesizing cyclic carbonate by using Lewis acid for carbon dioxide and epoxide, thus exhibiting high-efficiency catalytic activity and having wide application prospect.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as disclosed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a structural formula of an organic ligand H2BPDC used in a mixed-valence hexanuclear cerium cluster-based organometallic framework in an embodiment of the present invention;
FIG. 2 is a schematic illustration of a hexanuclear cerium cluster in a mixed-valence hexanuclear cerium cluster-based organometallic framework in an embodiment of the present invention.
FIG. 3 is a schematic representation of the coordination mode of the organic ligand H2BPDC in a mixed-valence hexanuclear cerium cluster-based organometallic framework in an embodiment of the present invention.
FIG. 4 is a schematic three-dimensional structure of a face-centered cubic framework of a mixed-valence hexanuclear cerium cluster-based organometallic framework in an embodiment of the present invention.
FIG. 5 is an X-ray photoelectron spectrum of a mixed-valence hexanuclear cerium cluster-based organometallic framework in an embodiment of the present invention.
FIG. 6 is a schematic representation of a mixed-valence hexanuclear cerium cluster-based organometallic framework catalyzed carbon dioxide cycloaddition reaction in an embodiment of the present invention.
Detailed Description
The invention is further illustrated below in connection with specific embodiments, but is not intended to limit the scope of the invention.
The embodiment provides a metal organic framework material containing mixed-valence hexanuclear cerium cluster structural units, which contains 3-valence and 4-valence Ce ion centers in the structure, has a classical 12-connection face-centered cubic topological structure of UiO-67, belongs to a cubic crystal system, and has a space group of
The embodiment provides a preparation method of the metal organic framework material containing the mixed-valence hexanuclear cerium cluster structural unit, which uses 4,4' -biphenyl dicarboxylic acid as an organic ligand, and utilizes a stirring method to rapidly synthesize a large amount of metal organic frameworks containing the mixed-valence hexanuclear cerium cluster structural unit by adjusting synthesis conditions;
the method specifically comprises the following steps:
1) Dissolving ceric ammonium nitrate in deionized water to form a solution A;
2) Dissolving 4,4' -biphenyl dicarboxylic acid in N, N-dimethylformamide to form a solution B;
3) Mixing the solution A with the solution B, and stirring to form a solution C;
4) Heating solution C to form solid D;
5) Washing the solid D with N, N-dimethylformamide, soaking in acetone, filtering and drying to obtain a target product: metal organic framework materials of mixed valence hexanuclear cerium cluster structural units.
Preferably, the molar ratio of the ceric ammonium nitrate to the 4,4' -biphenyl dicarboxylic acid is 1:1.
Preferably, the heating conditions in step 4) are: heated at 100℃for 15 minutes.
Preferably, the drying conditions in step 5) are: oven dried at 80 ℃ for 2 hours.
The metal organic framework containing the mixed-valence hexanuclear cerium cluster structural unit provided by the embodiment contains rich unsaturated Ce (III) and Ce (IV) centers, has the advantages of high selectivity and catalytic activity, adjustability, good repeatability and stability, recoverability, environmental friendliness and the like, and can be used as a catalytic material for the reaction of synthesizing cyclic carbonate from carbon dioxide and epoxide by using Lewis acid.
The specific application is as follows: placing epoxide and catalyst in a container, adding promoter, stirring, and introducing CO 2 Reacting for 12h under high pressure; or reacting for 24-48h under normal pressure. The reaction scheme is shown in FIG. 6:
the catalyst is the metal organic framework containing mixed-valence hexanuclear cerium cluster base metal, the epoxide is styrene oxide, the cocatalyst is tetrabutylammonium bromide (TBAB), the molar ratio is 0.1% of the epoxide. The inlet CO 2 The conditions for the reaction at high pressure are: CO is introduced into 2 The pressure in the container is 1.0MPa, and the temperature is 60 ℃; under normal pressure, the balloon is used for containing CO 2 The mixture was introduced into a reaction vessel at a temperature of 60 ℃.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1:
preparing a metal organic framework material of a mixed-valence hexanuclear cerium cluster structural unit:
5.48g (NH) 4 ) 2 Ce(NO 3 ) 6 (1 mmol) is dissolved in 20mL deionized water and stirred uniformly; ligand 2.42g (1 mmol) 4,4' -biphenyl dicarboxylic acid was dissolved in 60mL N, N-dimethylformamide and stirred well; will (NH) 4 ) 2 Ce(NO 3 ) 6 Pouring the solution into the stirred 4,4' -biphenyl dicarboxylic acid-N, N-dimethylformamide solution, and stirring uniformly. Heating the uniformly stirred mixed solution at 100 ℃ for 15min, washing with N, N-dimethylformamide for three times, soaking with acetone overnight, filtering, and drying in an oven at 80 ℃ for 2 hours to obtain the target product.
Example 2:
CO containing mixed-valence hexanuclear cerium cluster-based MOFs on epoxides under high pressure conditions 2 Catalytic function of cycloaddition reaction
Co was reacted with a catalyst comprising a mixed-valence hexanuclear cerium cluster-based MOF synthesized according to the procedure of example 1 2 And epoxide by high pressure reaction. 49.7mg (0.02 mmol,0.1 mol%) of a metal organic frame containing a hexanuclear cerium cluster molecular structural unit and 322mg of TBAB and 2.3mL of styrene oxide are taken, the mixture is added into a high-pressure reaction kettle, the high-pressure reaction kettle is sealed, carbon dioxide is introduced into the container to enable the pressure in the container to be 1.0MPa, the temperature is 60 ℃, and the reaction time is 12 hours, so that the product of the cyclic carbonate is obtained. The experimental results were detected by gas chromatography-mass spectrometry.
The experimental results are shown in Table 1 (1-2), and when the reaction is carried out for 12 hours, the conversion rate of the styrene oxide reaches 89.07%, while the conversion rate of the metal organic framework catalyzed reaction without the hexanuclear cerium cluster molecular structural unit under the same catalysis condition is only 48.31%.
Example 3:
CO containing mixed valence hexanuclear cerium cluster based MOF on epoxide under normal pressure condition 2 Catalytic function of cycloaddition reaction
The mixed-valence hexanuclear cerium cluster-based MOF synthesized according to the steps is used as a catalyst for CO 2 And epoxide by cycloaddition under normal pressure. 49.7mg (0.02 mmol,0.1 mol%) of a metal organic frame containing a hexanuclear cerium cluster molecular structural unit, 322mg of TBAB and 2.3mL of styrene oxide are placed in a reaction vessel, vacuumized, and filled with CO by an air balloon under normal pressure 2 And introducing the mixture into a reaction vessel, wherein the reaction temperature is 60 ℃, and the reaction time is 24 hours, 36 hours and 48 hours, so as to obtain the product of the cyclic carbonate. The experimental results were detected by gas chromatography-mass spectrometry.
The mixed valence cerium cluster-based MOF has the catalytic performance on cycloaddition reaction of carbon dioxide and styrene oxide under different reaction times. The experimental results are shown in Table 1 (3-5).
TABLE 1 Metal organic framework catalyzed oxidation of styrene and CO for six-core cerium cluster molecular building blocks 2 Cycloaddition reactivity
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to what has been described above and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A metal organic framework material containing mixed-valence hexanuclear cerium cluster structural units is characterized in that the structure of the metal organic framework material contains two Ce ion centers of 3 valence and 4 valence, has a classic 12-connection face-centered cubic topological structure of UiO-67, belongs to a cubic crystal system, and has a space group of
2. A method for preparing a metal organic framework material containing mixed-valence hexanuclear cerium cluster structural units according to claim 1, which is characterized by adopting a stirring method for rapid synthesis and comprising the following steps:
1) Dissolving ceric ammonium nitrate in deionized water to form a solution A;
2) Dissolving 4,4' -biphenyl dicarboxylic acid in N, N-dimethylformamide to form a solution B;
3) Mixing the solution A with the solution B, and stirring to form a solution C;
4) Heating solution C to form solid D;
5) Washing the solid D with N, N-dimethylformamide, soaking in acetone, filtering and drying to obtain a target product: metal organic framework materials of mixed valence hexanuclear cerium cluster structural units.
3. The method for preparing a metal organic framework of a mixed-valence hexanuclear cerium cluster structural unit according to claim 2, wherein the molar ratio of cerium ammonium nitrate to 4,4' -biphenyl dicarboxylic acid is 1:1.
4. The method for preparing a metal organic framework of a mixed-valence hexanuclear cerium cluster structural unit according to claim 2, wherein the heating conditions in the step 4) are as follows: heated at 100℃for 15 minutes.
5. The method for preparing a metal organic framework of a mixed-valence hexanuclear cerium cluster structural unit according to claim 2, wherein the drying conditions in step 5) are: oven dried at 80 ℃ for 2 hours.
6. Use of a metal-organic framework material containing mixed-valence hexanuclear cerium cluster building blocks according to claim 1, characterized in that it is used for CO under high or normal pressure 2 And catalysis in epoxide cycloaddition reactions.
7. The use of a metal organic framework material comprising mixed-valence hexanuclear cerium cluster building blocks according to claim 6, wherein the epoxide is styrene oxide.
8. The use of a metallo-organic framework of mixed-valence hexanuclear cerium cluster building blocks according to claim 6, wherein the amount of the metallo-organic framework is 0.1% of the epoxide in terms of molar ratio.
9. The use of a metal organic framework of a mixed-valence hexanuclear cerium cluster building block according to claim 6, wherein the cocatalyst is tetrabutylammonium bromide in an amount of 1mmol.
10. The method of using a metal organic framework of mixed-valence hexanuclear cerium cluster building blocks according to claim 6, wherein the reaction is carried out under high pressure, and CO is introduced 2 The pressure in the container is 1MPa, the temperature is 60 ℃, and the reaction time is 6-12h; and the reaction is carried out at normal pressure, the reaction temperature is 60 ℃, and the reaction time is 24-48h.
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