CN105732487A - Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof - Google Patents
Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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Abstract
The invention relates to a pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and a preparation method and application thereof. The technical scheme is as follows: adding Yb(NO3)3, a 5,5'-(pyridyl-2,5-disubstituted)-1,3-phthalic acid, a solvent N,N-dimethylformamide and water into a high-temperature-resistant screw glass bottle, and stirring at normal temperature; sealing the container, putting into a drying oven, and heating at 105 DEG C for 4 days; slowly cooling to room temperature to obtain colorless transparent massive crystals; and washing with N,N-dimethylformamide, filtering, and drying to obtain the target product. The pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework has favorable size selectivity and catalytic property for carbon dioxide cycloaddition reaction of epoxides.
Description
Technical field
The present invention relates to a kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application, specifically, relate to a kind of carbon dioxide cycloaddition reaction to epoxide and show preparation and the application thereof of the active metal-organic framework material with cage modle vestibule of size Selection catalysis.
Background technology
In recent years, functional metal organic framework materials has been obtained for paying close attention to the most widely as a field developed rapidly, and the most critically important reason is because them and has huge potentiality in practical application area.Multi-nuclear metal cluster compound has become as one of focus in the research of current functional material, not only due to they have the molecular structure of nano-scale, but also shows interesting optical, electrical, magnetic and catalytic property.But the current research overwhelming majority concentrates on multinuclear transition metal cluster compound, and the research of multi-kernel rare-earth cluster compound is started late.In recent years, some four discrete cores, five cores, six cores, seven cores, eight cores, nine cores, ten cores, 12 cores, 15 cores etc. are synthesized in succession.The Long Lasheng professor of Xiamen University does a lot of work in terms of high core rare earth cluster compound and rare earth-transition metal cluster compound.Utilizing threonine part, synthesized 60 core rare earth cluster compounds of four chiralitys, this is also the rare earth cluster compound that the check figure having now been found that is the highest.In recent years, along with the fast development of multi-kernel rare-earth cluster compound aspect research, using rare earth bunch as molecular structure unit complex functionality rare earth bunch metal organic frame, due to the structure of its uniqueness, abundant hole and offunctional site, cause chemist and the attention of material scholar.
Owing to for reasons such as warm industrial developments, the content of the carbon dioxide in air increases day by day, becomes the principal element causing global warming.As chemistry and the by-product of energy industry, carbon dioxide has avirulence and being readily available property, therefore can participate in commercial synthesis, such as N, the disubstituted urease of N ', cyclic carbonate, circulation polyurethane and the synthesis etc. of formic acid as carbon source.Owing to cyclic carbonate can be as aprotic, polar type solvent, the electrolysis element of battery, or as many application such as the intermediate of fine chemicals, medicine and Polymer Synthesizing or presomas, so utilizing carbon dioxide and epoxide synthesizing annular carbonate to be constantly subjected to extensive concern.
Summary of the invention
It is an object of the invention to utilize 5,5'-(pyridine radicals-2,5-two the replacement)-1,3-phthalic acid (H containing pyridine radicals4PDDI) as organic ligand, by regulation synthesis condition, utilize the method for solvent thermal to construct out the metal-organic framework material containing five core ytterbiums bunch of a kind of novelty, and study it as the Lewis acid catalyst catalytic performance to carbon dioxide cycloaddition reaction.
The technical solution used in the present invention is: a kind of metal organic frame containing five core ytterbium cluster molecule construction units, preparation method comprises the steps:
1) by 5,5'-(pyridine radicals-2,5-two replacement)-1,3-phthalic acid (H4PDDI)、Yb(NO3)3Joining in container with DMF, stirring is lower dissolves；
2) add deionized water, stir, after being sealed by container, put into baking oven, heat 4-5 days at 100-110 DEG C；
3) it is slowly cooled to room temperature, generates with or without color bulk crystals；
4) wash with DMF, filter, be dried, obtain target product.
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, in molar ratio, 5,5'-(pyridine radicals-2,5-bis-replacements)-1,3-phthalic acid (H4PDDI): Yb (NO3)3=1:1.0-1.5.
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, step 2) in, to put in baking oven after container is sealed, heating rate is 5 DEG C of min-1。
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, the described rate of temperature fall being slowly cooled to room temperature is 5 DEG C of h-1。
The metal organic frame containing five core ytterbium cluster molecule construction units of the present invention, containing abundant unsaturated Yb (III) center in structure, can carry out catalytic applications as Lewis acid catalyst to carbon dioxide cycloaddition reaction.Method is as follows: take epoxide and catalyst in container, adds or without promoter, under stirring, is passed through CO2, under high pressure react 3-6h；Described catalyst is the above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units.Reaction equation is as follows:
Described epoxide is expoxy propane, epoxy butane, allyl glycidyl ether, n-butyl glycidyl ether or styrene oxide.
In molar ratio, the consumption of described catalyst is the 0.03-0.05% of epoxide
Described promoter is tetrabutyl ammonium bromide (TBAB).
Described is passed through CO2, under high pressure reaction is: be passed through CO2Making container inner pressure is 1.0MPa, and temperature is 90-130 DEG C.
The invention has the beneficial effects as follows: the metal organic frame containing five core ytterbium cluster molecule construction units prepared by the present invention is the first metal-organic framework material constructed by five core cluster molecule construction units.And Yb (III) ion in five core ytterbiums bunch is seven coordinations or eight-coordinate, so containing abundant undersaturated Yb (III) center in structure, can be as Lewis acid site, the coordination compound making invention can show good catalytic performance as a kind of Lewis acid catalyst to the carbon dioxide cycloaddition reaction of epoxide.Again because the structure of the metal organic frame containing five core ytterbium cluster molecule construction units prepared by the present invention contains the vestibule of cage modle, when carrying out catalytic reaction, " window " on the vestibule of cage modle has interception effect to larger-size reactant, and therefore the coordination compound of the present invention shows the size selectivity catalytic performance of the carbon dioxide cycloaddition reaction to epoxide.Synthetic method is simple, has application prospect.
Accompanying drawing explanation
Fig. 1 a is the trigonal biyramid type five core Yb cluster molecule construction unit in metal-organic framework of the present invention.
Fig. 1 b is the coordination environment of Yb (III) ion in metal-organic framework of the present invention.
H in Fig. 2 a metal-organic framework of the present invention4A kind of coordination mode of PPDI part.
H in Fig. 2 b metal-organic framework of the present invention4The another kind of coordination mode of PPDI part.
Each molecular structure unit [Yb in Fig. 3 metal-organic framework of the present invention5(μ3-OH)6(O2C-)8] double cap triangular prism cylinder building blocks of being simplified to.
Fig. 4 is the three-dimension hole cavity configuration simplification figure of metal organic frame of the present invention.
Fig. 5 is the structural representation of cage modle vestibule configuration in metal-organic framework of the present invention.
Fig. 6 a is the first window of cage modle vestibule in metal organic frame of the present invention.
Fig. 6 b is the second window of cage modle vestibule in metal organic frame of the present invention.
Fig. 6 c is the third window of cage modle vestibule in metal organic frame of the present invention.
Fig. 7 is the carbon dioxide and the impact of the expoxy propane cycloaddition reaction differential responses time being catalyzed metal organic frame of the present invention.
Fig. 8 is that metal organic frame of the present invention carries out the five catalysis activity taking turns circulation catalytic reaction.
Detailed description of the invention
The embodiment 1 metal organic frame containing five core ytterbium cluster molecule construction units
By H4PDDI (0.01g, 0.025mmol) and Yb (NO3)3·5H2O (0.015g, 0.03mmol) joins in the high temperature resistant spiral mouth vial that volume is 5mL, adds 1.5mL DMF, and magnetic stirrer is dissolved, and adds 1.5ml H2O, stirs 15 minutes until slaine all dissolves mixs homogeneously with part, puts into 105 DEG C of baking ovens, at such a temperature heating 4 days, with 5 DEG C of h after being sealed by vial-1Rate of temperature fall be slowly cooled to room temperature, with or without color bulk crystals generate, with DMF wash, filter, be dried, obtain target product, i.e. contain the metal organic frame of five core ytterbium cluster molecule construction units, productivity is 50%.
The present invention synthesis metal organic complex be one by the tetrabasic carboxylic acid part H containing pyridine groups4The three-dimensional porous metals organic frame that five cores Yb cluster molecule construction unit (Fig. 1 a) of PDDI and trigonal biyramid type are built into.Yb bunch of [Yb of five core in structure5(μ3-OH)6(O2C-)8], as shown in Figure 1 b, it is to have a kind of eight molecular structure units connected.Each five core Yb oxygen clusters comprise three kinds of different Yb3+Center, one of them Yb1 and two Yb3 ions are positioned on the equatorial plane of trigonal biyramid, and also two Yb2 ions occupy the axial vertex position of trigonal biyramid.Yb1 and Yb3 is eight-coordinate, and Yb1 is and four μ3-OH group and four oxygen atom ligands, wherein four oxygen atoms are respectively from the carboxyl of four independent L1 parts；Yb3 and four μ3-OH group and four oxygen atom ligands, two of which oxygen atom comes from the hydrone of two coordinations, and two oxygen atoms come from the carboxyl of two independent L1 parts.The coordination mode of Yb1 and Yb3 presents a kind of anti-four directions prism geometric configuration, wherein a plane of anti-four directions prism is by four carboxyl oxygen atoms (Yb1) from four independent L1 parts, or is constituted (Yb3) by the oxygen atom of two oxygen atoms on two independent L1 parts and two hydrones；Another plane is then by four μ3The oxygen atom composition of-OH.Yb2 and three μ3-OH oxygen atom, the carboxyl oxygen atom of three independent L1 parts and the oxygen atom of a water of coordination form seven coordinations, show single cap octahedral coordination geometric configuration.In the structure of metal organic frame, present two kinds of connection modes between PDDI part and Yb (III) ion respectively, such as Fig. 2 a and 2b.
The abducent junction point of five core Yb bunch regarded as by carbon atom on the carboxyl of Jiang Yu Yb center coordination, can be by each molecular structure unit [Yb5(μ3-OH)6(O2C-)8] it is simplified to double cap triangular prism cylinder (Fig. 3), one eight node connected, by the bridging with PDDI part, expand around forming a kind of frame structure (Fig. 4) with cage modle vestibule.As it is shown in figure 5, a kind of octoploids structure should be presented containing the cage modle vestibule in metal organic frame of five core ytterbium cluster molecule construction units, this octahedral each summit is in occupation of five core Yb bunch.There is three kinds " window " in each cage modle vestibule structure, size is respectively(Fig. 6 a),(Fig. 6 b) and(Fig. 6 c).
Should be constructed by the Carboxylic acid ligand containing pyridine groups form containing the metal organic frame of five core ytterbium cluster molecule construction units, its crystal belongs to tetragonal crystal system, and space group is I41/amd。
The embodiment 2 metal organic frame containing the five core ytterbium cluster molecule construction units catalysis to the carbon dioxide cycloaddition reaction of epoxide
The cycloaddition reaction of carbon dioxide and epoxide is catalyzed using the metal organic frame containing five core ytterbium cluster molecule construction units of embodiment 1 preparation as catalyst.
The activation processing of catalyst: taking a certain amount of metal organic frame containing five core ytterbium cluster molecule construction units, evacuation is dried 24 hours under 50 DEG C of heating conditions.
1) impact of differential responses time
Method: taking the metal organic frame containing five core ytterbium cluster molecule construction units after the activation of 37.2mg (0.02mmol, 0.04mol%), the expoxy propane of TBAB and 50mmol of 0.075mmol joins in autoclave, seals, is passed through CO2Making container inner pressure is 1.0MPa, and temperature is 120 DEG C, and the response time is respectively 3h, 4h, 5h and 6h, obtains product Allyl carbonate.Experimental result gas chromatographic detection.
Under the differential responses time, the metal organic frame of five core ytterbium cluster molecule construction units should be contained to carbon dioxide and the catalytic performance of the cycloaddition reaction of expoxy propane.The when that experimental result being as it is shown in fig. 7, reaction is carried out 5 hours, the conversion ratio of expoxy propane has reached 87.2% (TOF:93.8h-1), even if reaction is carried out 6 hours, conversion ratio the most no longer significantly increases, so the response time of the 5 hours maximized optimal choice that is products collection efficiency.
Product Allyl carbonate nuclear-magnetism:1H-NMR(400MHz,TMS,CDCl3): δ=4.84 (m, 1H, OCH), 4.53 (t, 1H, J=8.3Hz, OCH2), 3.98 (dd, 1H, J=7.8,7.9Hz, OCH2), 1.51 (d, 3H, J=6.3Hz, CH3)ppm.13C-NMR(100MHz,CDCl3, TMS): δ=155.4 (OC (O) O), 74.6 (> CH O), 70.6 (CH2–O–),19.1(–CH3)ppm.
2) impact of catalyst amount
Method: by table 1, taking the metal organic frame containing five core ytterbium cluster molecule construction units after activation, the expoxy propane of TBAB and 50mmol of 0.075mmol joins in autoclave, seals, is passed through CO2Making container inner pressure is 1.0MPa, and temperature is 120 DEG C, reacts 5h；In molar ratio, the addition of catalyst is 0.03mol%, 0.04mol% and the 0.05mol% of expoxy propane.Experimental result gas chromatographic detection.Result such as table 1.
Table 1
| The amount of catalyst | 0.03mol% | 0.04mol% | 0.05mol% |
| The conversion ratio % of expoxy propane | 82.2 | 87.2 | 83.5 |
| TON | 548 | 436 | 334 |
| TOF(h-1) | 109.1 | 87.2 | 66.8 |
From table 1, when the amount of catalyst is 0.04mol%, the conversion ratio of epoxidation reaction is maximum, and during higher than 0.04mol%, conversion ratio does not improve and declines on the contrary, and therefore selecting the catalyst of 0.04mol% to participate in catalytic reaction is optimal choice.
3) impact of promoter
Method: taking the metal organic frame containing five core ytterbium cluster molecule construction units after activation, as table 2 adds catalyst and promoter, the expoxy propane of 50mmol joins in autoclave, seals, is passed through CO2Making container inner pressure is 1.0MPa, and temperature is 120 DEG C, reacts 5h.Experimental result gas chromatographic detection.Result such as table 2.
Table 2
| The amount of catalyst | 0 | 37.2mg (0.04mol%) | 37.2mg (0.04mol%) |
| The amount of promoter | 0.075mmol | 0 | 0.075mmol |
| The conversion ratio % of expoxy propane | 17.2 | 9.9 | 87.2 |
| TON | — | 49.5 | 436 |
| TOF(h-1) | — | 9.9 | 87.2 |
From table 2, individually metal organic frame or TBAB containing five core ytterbium cluster molecule construction units are the lowest to the catalytic effect of this reaction, and two kinds of materials exist simultaneously and just can show the catalytic performance good to carbon dioxide and epoxide cycloaddition reaction.
4) different rings oxide
Method: take the metal organic frame containing five core ytterbium cluster molecule construction units after the activation of 37.2mg (0.04mol%), TBAB and 50mmol of 0.075mmol such as the epoxide of table 3, seal, be passed through CO2Making container inner pressure is 1.0MPa, and temperature is 120 DEG C, reacts 5h.Experimental result gas chromatographic detection.Result such as table 3.
Table 3
As shown in table 3, the catalytic reaction to the cycloaddition reaction of different rings oxide of the metal organic frame containing five core ytterbium cluster molecule construction units, along with the increase of epoxide size, conversion ratio is gradually lowered.This is owing to there is cage modle vestibule in the structure of the metal organic frame containing five core ytterbium cluster molecule construction units of the present invention, can allow for reactant on vestibule and enter limited with " window " size of Lewis acid catalysis point cantact, so the conversion ratio of bigger reactant is the lowest.Therefore, the metal organic frame containing five core ytterbium cluster molecule construction units of the present invention shows size selectivity catalytic performance to the cycloaddition reaction of carbon dioxide and epoxide.
5) the recyclable recycling of catalyst in cycloaddition reaction
The recovery of catalyst: after reaction terminates, filters, is separated with reactant mixture by catalyst, washs with methanol and dichloromethane, then soaks six hours in methanol, leach, dries.
The concrete operations of circulation experiment: utilize the catalyst (0.04mol%) reclaimed and promoter TBAB (0.075mmol) to be catalyzed carbon dioxideWith the cycloaddition reaction of expoxy propane (50mmol), react 5 hours at 120 DEG C.
As shown in Figure 8, circulation experiment proceeds to the 5th takes turns experimental result, and the activity of catalyst does not the most decline.Illustrate that this contains the metal organic frame of five core ytterbium cluster molecule construction units as carbon dioxide and epoxide cycloaddition reaction catalyst reusable edible.
Claims (10)
1. the metal organic frame containing five core ytterbium cluster molecule construction units, it is characterised in that: preparation method includes walking as follows
Rapid:
1) by 5,5'-(pyridine radicals-2,5-two replacement)-1,3-phthalic acid, Yb (NO3)3Appearance is joined with N,N-dimethylformamide
In device, stirring is lower dissolves；
2) add water, stir, after being sealed by container, put into baking oven, heat 4-5 days at 100-110 DEG C；
3) it is slowly cooled to room temperature, generates crystal；
4) wash with DMF, filter, be dried, obtain target product.
Metal organic frame containing five core ytterbium cluster molecule construction units the most according to claim 1, it is characterised in that: step
Rapid 1) in molar ratio, 5,5'-(pyridine radicals-2,5-bis-replacements)-1,3-phthalic acid: Yb (NO3)3=1:1.0-1.5.
Metal organic frame containing five core ytterbium cluster molecule construction units the most according to claim 1, it is characterised in that: step
Rapid 2) in, putting in baking oven after being sealed by container, heating rate is 5 DEG C of min-1。
Metal organic frame containing five core ytterbium cluster molecule construction units the most according to claim 1, it is characterised in that: step
Rapid 3), in, the described rate of temperature fall being slowly cooled to room temperature is 5 DEG C of h-1。
5. the arbitrary described metal organic frame containing five core ytterbium cluster molecule construction units of claim 1-4 is at catalysis CO2And ring
Application in oxide cycloaddition reaction.
Application the most according to claim 5, it is characterised in that method is as follows: take epoxide and catalyst in container
In, add or without promoter, under stirring, be passed through CO2, under high pressure react 3-6h；Described catalyst
It it is the arbitrary described metal organic frame containing five core ytterbium cluster molecule construction units of claim 1-4.
Application the most according to claim 6, it is characterised in that: described epoxide be expoxy propane, epoxy butane,
Allyl glycidyl ether, n-butyl glycidyl ether or styrene oxide.
Application the most according to claim 6, it is characterised in that: in molar ratio, the consumption of described catalyst is epoxidation
The 0.03-0.05% of thing.
Application the most according to claim 6, it is characterised in that: described promoter is tetrabutyl ammonium bromide.
Application the most according to claim 6, it is characterised in that: described is passed through CO2, under high pressure reaction is: be passed through
CO2Making container inner pressure is 1.0MPa, and temperature is 90-130 DEG C.
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| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
| CN108191894A (en) * | 2018-01-12 | 2018-06-22 | 辽宁大学 | A kind of metal organic anion framework material formed based on indium and its preparation method and application |
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| CN108191894A (en) * | 2018-01-12 | 2018-06-22 | 辽宁大学 | A kind of metal organic anion framework material formed based on indium and its preparation method and application |
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