CN105646900A - Three-ligand Cd(II) metal organic framework crystal material and preparation method - Google Patents
Three-ligand Cd(II) metal organic framework crystal material and preparation method Download PDFInfo
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Abstract
The invention relates to a three-ligand Cd(II) metal organic framework crystal material and a preparation method and application thereof. The material has the following chemical formula [Cd3(L)2(L')(L'')]n, wherein L represents a 9,10-anthracenediyl-4,4'-bis(benzoic acid) bivalent anion, L' represents a 3-picolinic acid univalent anion, L'' represents a 4-picolinic acid univalent anion, and n represents the polymerization degree. The Cd(II) metal organic framework crystal material adopts a hydrothermal synthesis method and is environmentally friendly, simple and practicable, low in cost, high in yield and capable of easily achieving large-scale industrialized production. The prepared Cd(II) metal organic framework crystal material has the very good application prospect in the field of luminescence, catalysis, gas absorption, chemical sensing, high polymer material auxiliaries and the like.
Description
Technical field
The present invention relates to Cd (II) complex crystal material, particularly relate to 9,10-anthracene two base-4, Cd (II) the cadmium metal organic frame crystalline material of 4 '-dibenzoic acid, acidum nicotinicum and Isonicotinic acid three part, it is specifically related to 9,10-anthracene two base-4, the preparation method and application of Cd (II) the cadmium metal organic frame crystalline material of 4 '-dibenzoic acid dianion, acidum nicotinicum univalent anion and three parts of Isonicotinic acid univalent anion. Prepared Cd (II) cadmium metal organic frame crystalline material has good application prospect in fields such as luminescence, absorption, catalysis, chemical sensitisation, macromolecular material auxiliary agents.
Background technology
Metal organic frame (MOFs) represents the organic-inorganic ordered network supramolecular materials of a class hydridization, it is the ordered network structure being bonded by organic bridging ligand and inorganic metal ion, including one-dimensional chain, two-dimensional layer and tridimensional network. These materials are made up of many bridge works chord post and the metal node of rigidity. High micro pore volume, large aperture, and can be provided that the high-load metal of active site is the key character of this kind of material.
In recent years, metal organic frame is due to its porous, bigger serface, knot
Structure variation and the special host-guest relationship that formed by self assembly and cause the great interest of people. This kind of material is it have been reported that have the performances such as gas storage and separation, catalysis, chemical sensitisation, conduction and luminescence. As: ChampnessN.R., Schr derM.science, 1998,3:419-424; YaghiO.M., LiG.M., LiH.L.Nature, 1995,378:703-706; LiH., EddaoudiM., O ' keeffeM., etal.Nature, 1999,402:276-279; ChuiS.S., LoS.M.-F., CharmantJ.P.H., etal.Science, 1999,283:1148-1150; F �� reyG., Mellot-DraznieksC., SerreC., etal.Science, 2005,309:2040-2042; Yoon, M., Srirambalaji, R., Kim, K.Chem.Rev.2012,112:1196 1231; Yin, Z., Wang, Q.-X., Zeng, M.-H., J.Am.Chem.Soc.2012,134:4857 4863; Zeng, M.-H., Wang, Q.-X., Tan, Y.-X., etal.J.Am.Chem.Soc.2010,132:2561 2563; Bloch, E.D., Britt, D., Lee, C.; Doonan., etal.J.Am.Chem.Soc.2010,132:14382 14384.
9,10-anthracene two base-4,4 '-dibenzoic acid has strong coordination ability, multiple coordination mode as organic ligand, is easily formed the feature such as hydrogen bond and aromatic ring pi-pi accumulation effect.Acidum nicotinicum and Isonicotinic acid, except the carboxyl strong containing coordination ability, also have N coordination site, so multiple coordination mode can be formed, can make complex structure and performance variation as organic ligand, and improve the stability of coordination compound.
In known bibliographical information, it is common that with a kind of metallic ion coordination while of a kind of part and a kind of metallic ion coordination or two kinds of parts, part three kinds different is simultaneously considerably less with the report that a kind of metallic ion coordination forms metal organic frame.
Summary of the invention
The invention aims to first technical problem solved, it is provided that a kind of three part Cd (II) cadmium metal organic frame crystalline materials with multiple hole, bigger serface.
The preparation method that second technical problem to be solved of the present invention is to provide above-mentioned three part Cd (II) cadmium metal organic frame crystalline materials, the method is simple, environmentally friendly, with low cost, productivity is high, it is easy to large-scale industrial production.
3rd purpose of the present invention is in that to provide above-mentioned three part Cd (II) cadmium metal organic frame crystalline materials in luminous, catalysis, the application in the fields such as absorption, chemical sensitisation, macromolecular material auxiliary agent.
The present invention utilizes 9,10-anthracene two base-4,4 '-dibenzoic acid, acidum nicotinicum and Isonicotinic acid have stronger coordination ability, multiple coordination mode, are easily formed the feature such as hydrogen bond and Aromatic-ring stacking interaction, form Cd (II) the cadmium metal organic frame crystalline material of a novel structure first with above-mentioned part three kinds different and Cd (II) coordination. This kind of material is generally of multiple hole, bigger serface, in good application prospects in field such as luminous, catalysis, absorption, chemical sensitisation, macromolecular material auxiliary agents.
In order to achieve the above object, the present invention adopts the following technical scheme that
It is [Cd that three part Cd (II) cadmium metal organic frame crystalline materials of the present invention possess following chemical formula3(L)2(L��)(L����)]n, wherein L is 9,10-anthracene two base-4,4 '-dibenzoic acid dianion, and L ' is acidum nicotinicum univalent anion, and L ' ' is Isonicotinic acid univalent anion, and n is the degree of polymerization.
The crystal of three part Cd (II) cadmium metal organic frames of the present invention belongs to rhombic system, and space group is Pca21��
The preparation method of three part Cd (II) cadmium metal organic frame crystalline materials of the present invention, comprises the steps:
(1) by bivalence cadmium salt compound, 9,10-anthracene two base-4,4 '-dibenzoic acid, acidum nicotinicum, Isonicotinic acid are dissolved in solvent, stir, and regulate the pH value of reaction system with acid or alkali, are then added in reactor.
(2) heat temperature raising, after reactant reacts a period of time at a certain temperature, gradually reduces temperature, is cooled to room temperature, filters, washes with water, dry, prepares three part Cd (II) cadmium metal organic frame crystalline materials.
Cadmium salt compound of the present invention is nitric acid cadmium salt, chlorination cadmium salt, sulphuric acid cadmium salt, acetic acid cadmium salt and perchloric acid cadmium salt; Described cadmium ion is+divalent;
Solvent of the present invention is one or more in water, DMF, methanol, ethanol, isopropanol;
Cadmium salt compound of the present invention and 9,10-anthracene two base-4, the mol ratio of 4 '-dibenzoic acid is 1:0.1 ~ 1:0.3, and the mol ratio of cadmium salt compound and acidum nicotinicum is 1:2 ~ 1:4; The mol ratio of cadmium salt compound and Isonicotinic acid is 1:2 ~ 1:4; The mol ratio of cadmium salt compound and solvent is 1:5000 ~ 1:10000;
The pH value of reaction system of the present invention is 2 ~ 7, and alkali used is organic base or inorganic base; Organic base used is diethylamine or triethylamine; Inorganic base used is sodium carbonate or sodium hydroxide;
Acid used by the present invention is acetic acid, phosphoric acid, nitric acid, hydrochloric acid or sulphuric acid;
Water used by the present invention is deionized water;
The reaction temperature of the present invention is 80 DEG C ~ 220 DEG C;
1 ~ 240 hour response time of the present invention;
The rate of temperature fall of the present invention is 1 �� of C/h ~ 10 �� C/h.
Relative to prior art, the invention have the advantages that and beneficial effect:
(1) Cd (II) the metal organic frame crystalline material structure synthesized by the present invention is novel, unique.
(2) present invention adopts cheap 9,10-anthracene two base-4,4 '-dibenzoic acid, acidum nicotinicum, Isonicotinic acid and Cd (II) salt are raw material, adopt water (solvent) thermal synthesis method, simple, environmentally friendly, cost is low, productivity is high, it is easy to large-scale industrial production.
(3) present invention three part Cd (II) cadmium metal organic frame crystalline material has tridimensional network and porous, bigger serface, stable feature, in luminous, catalysis, gas absorption with separate, the field such as chemical sensitisation, macromolecular material auxiliary agent has good application prospect.
Accompanying drawing explanation
The crystal asymmetric cell structure chart of Fig. 1 present invention three part Cd (II) cadmium metal organic frame.
The graphics of Fig. 2 present invention three part Cd (II) cadmium metal organic frame crystal.
The infrared spectrogram of Fig. 3 present invention three part Cd (II) cadmium metal organic frame.
The thermogravimetric analysis figure of Fig. 4 present invention three part Cd (II) cadmium metal organic frame.
The solid uv absorption figure of Fig. 5 present invention three part Cd (II) cadmium metal organic frame.
The solid emissive spectrogram of Fig. 6 present invention three part Cd (II) cadmium metal organic frame.
Detailed description of the invention
The preparation method of three part Cd (II) the metal organic frame crystalline materials of the present invention, synthesizes and sign step is:
By bivalence cadmium salt compound, 9,10-anthracene two base-4,4 '-dibenzoic acid, acidum nicotinicum, Isonicotinic acid are dissolved in solvent, stir, and regulate the pH value of reaction system with acid or alkali, are then added in reactor. Heat temperature raising, reactant gradually reduces temperature after reacting one section at a certain temperature, is cooled to room temperature, filters, washes with water, dry, obtains [Cd3(L)2(L��)(L����)]nCrystalline material. Then the mono-crystalline structures of compound is surveyed with RigakuRAXIS ~ RAPIDIPX-x ray diffractometer x, compound of red external spectrum surveyed by NicoletNexus470FTIR infrared spectrometer, thermogravimetric/the differential thermal analysis of sample is tested on Q600SDT thermogravimetric analyzer, powder x-ray diffraction is tested on BrukerD8X-x ray diffractometer x, C, H, N element analysis test on Germany's VarioELIII elemental analyser, room temperature ultraviolet spectra measures on U-3100 ultraviolet-visible absorption spectroscopy instrument, and Room temperature PL spectrum is tested in HitachiF-4500 fluorescence spectrophotometer.
Specific embodiment is as follows:
[Cd3(L)2(L��)(L����)]nSynthesis and sign
By 9,10-anthracene two base-4,4 '-dibenzoic acid (42mg, 0.1mmol), Cd (NO3)2?4H2O (136mg, 0.4mmol), nicotinic acid (24mg, 0.2mmol) .gamma.-pyridinecarboxylic acid (24mg, 0.2mmol), the mixture of 20mL deionized water is placed in 100mL with in the reactor of polytetrafluoroethylsubstrate substrate, 5 �� of C/h of heating rate are heated slowly to 180 �� of C and are incubated 48 hours, then cool to room temperature with the speed of 5 �� of C/h. Obtaining light yellow flat crystal, use deionized water wash crystal, room temperature is dried, and obtains product 34mg, and productivity is 70.4% (calculating by 4,4 '-(9,10-anthracene two base)-dibenzoic acids).The Advances in crystal X-ray diffraction data of gained compound are to measure on RigakuRAXIS ~ RAPIDIPX-x ray diffractometer x, at room temperature carry out the collection of Advances in crystal X-ray diffraction data. Diffractometer is to use MoK alpha ray, wavelength is 0.71073, the running voltage of 90kV and 50mA and electric current, collect with �� scan mode and carry out Lp factor correction, and absorption correction uses CrystalClear program (M �� llerP., Herbst-IrmerR., SpekA.L., etal.InternationalUnionofCrystallographyBookSeries, OxfordUniversityPress:NewYork, 2006, Chapter7). Using direct method analytic structure, then obtain whole non-hydrogen atom coordinate with difference Fourier method, organic hydrogen atom adopts theoretical hydrogenation method to obtain, and with method of least square, structure is modified. Evaluation work completes (Sheldrick, G.M.SHELXL-97, G ttingenUniversity, Germany, 1997) with SHELXTL program package on microcomputer, compound structure be [Cd3(L)2(L��)(L����)]n. Table 1 is the predominant crystal data of this metal-organic framework material.
Table 1
R1=��||Fo|?|Fc||/��|Fo|.wR2=[��w(Fo2?Fc2)2/��w(Fo2)2]1/2
Fig. 1 is this metal organic frame crystal asymmetric cell structure chart. From structure
Figure can be seen that three bivalence Cd ions respectively with two 9,10-anthracene two base-4, the dianion coordination of 4 '-dibenzoic acid, simultaneously and acidum nicotinicum univalent anion coordination, an Isonicotinic acid univalent anion coordination. Fig. 2 is 9,10-anthracene two base-4,4 '-dibenzoic acid dianion, acidum nicotinicum univalent anion, Isonicotinic acid univalent anion respectively with Cd (II) coordination formed tridimensional network figure.
Fig. 3 is the infrared spectrum of this metal organic frame, NicoletNexus470FTIR radar stealthy materials is tested, uses specpure pressing potassium bromide troche, before test, sample and potassium bromide are dried under uviol lamp, to remove the water of sample surfaces, measure scope 4000-400cm-1. 9,10-anthracene two base-4,4 is can be seen that from infrared spectrogram '-dibenzoic acid carboxylate radical, acidum nicotinicum carboxylate radical and Isonicotinic acid carboxylate radical asymmetrical stretching vibration and symmetrical stretching vibration absworption peak respectively appear in 1584cm-1And 1366m-1, 3066m-1�� C-H for aromatic ring vibrates.
Fig. 4 be this metal organic frame thermogravimetric/differential thermal analysis test on Q600SDT thermogravimetric analyzer, after zeroing, weigh 5 ~ 10mg sample put in ceramic dry pot measure, carry out in a nitrogen atmosphere, heating rate is set to 10 DEG C/min, rises to 700 DEG C. Having two obvious zero-g periods, about lose the weight of 12% from 20 DEG C to 110 DEG C, from 400 DEG C to 500 DEG C, framework caves in, and loses the weight of about 80% altogether, is finally decomposed to oxide.
The mensuration of this metal organic frame luminescent properties, measures the solid sorbent spectrum of this material with Hitachi's U-3010 ultraviolet-visible spectrophotometer. Fig. 5 is the abosrption spectrogram of this metal organic frame. Can be seen that this material is approximately within the scope of wavelength 200 ~ 500nm and has a wider absorption band from abosrption spectrogram. With the solid emissive spectrum of HitachiF-4500 this metal organic frame of fluorescent spectrophotometer assay, use barium sulfate as reference. Fig. 6 is this material emission spectrum figure after the incident illumination of 200 ~ 400nm excites. Can be seen that this material can send strong blue light at 400 ~ 600nm from emission spectrum figure. Illustrate that this metal organic frame crystalline material can as luminescent material for producing blue light.
The above, it it is only presently preferred embodiments of the present invention, not the present invention is done any pro forma restriction, any without departing from technical solution of the present invention content, according to any simple modification, equivalent variations and modification that above example is made by the technical spirit of the present invention, all still fall within the scope of technical solution of the present invention.
Claims (7)
1. one kind one three part Cd (II) cadmium metal organic frame crystalline materials, it is characterised in that its chemical formula is: [Cd3(L)2(L��)(L����)]n, wherein L is 9,10-anthracene two base-4,4 '-dibenzoic acid dianion, and L ' is acidum nicotinicum univalent anion, and L ' ' is Isonicotinic acid univalent anion, and n is the degree of polymerization.
2. three part Cd (II) cadmium metal organic frame crystalline materials according to claim 1, it is characterised in that: the crystal of described Cd (II) cadmium metal organic frame belongs to rhombic system, and space group is Pca21��
3. the preparation method of one kind one three part Cd (II) cadmium metal organic frame crystalline materials, it is characterised in that: it comprises the steps:
1) by bivalence cadmium salt compound, 9,10-anthracene two base-4,4 '-dibenzoic acid, acidum nicotinicum, Isonicotinic acid are dissolved in solvent, stir, and the pH value regulating reaction system with alkali is 2 ~ 7, is then added in reactor; Described alkali is organic base or inorganic base;
Described cadmium salt compound is nitric acid cadmium salt, chlorination cadmium salt, sulphuric acid cadmium salt, acetic acid cadmium salt and perchloric acid cadmium salt; Described cadmium ion is+divalent;
Described solvent is one or more in water, DMF, methanol, ethanol, isopropanol;
Described cadmium salt compound and 9,10-anthracene two base-4, the mol ratio of 4 '-dibenzoic acid is 1:0.1 ~ 1:0.3, and the mol ratio of cadmium salt compound and acidum nicotinicum is 1:2 ~ 1:4; The mol ratio of cadmium salt compound and Isonicotinic acid is 1:2 ~ 1:4; The mol ratio of cadmium salt compound and solvent is 1:5000 ~ 1:10000;
2) it is heated to 80 DEG C ~ 220 DEG C, after reacting 1 ~ 240 hour, gradually reduces temperature, be cooled to room temperature, 1 �� of C/h ~ 10 �� C/h of rate of temperature fall, filter, wash with water, dry, prepare three part Cd (II) metal organic frame crystalline materials.
4. the preparation method of three part Cd (II) cadmium metal organic frame crystalline materials according to claim 3, it is characterised in that: described organic base is diethylamine or triethylamine; Described inorganic base is sodium carbonate or sodium hydroxide.
5. the preparation method of three part Cd (II) cadmium metal organic frame crystalline materials according to claim 3, it is characterised in that: described acid is acetic acid, phosphoric acid, nitric acid, hydrochloric acid or sulphuric acid.
6. the preparation method of three part Cd (II) cadmium metal organic frame crystalline materials according to claim 3, it is characterised in that: described water is deionized water.
7. three part Cd (II) cadmium metal organic frame crystalline materials described in claim 1, it is characterised in that: described three part Cd (II) cadmium metal organic frame crystalline materials application in luminous, chemical sensitisation or macromolecular material auxiliary agent.
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Cited By (4)
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| CN106010510A (en) * | 2016-07-15 | 2016-10-12 | 武汉大学 | Multifunctional rare-earth metal organic framework material used for light conversion and preparation method thereof |
| CN107973914A (en) * | 2017-11-17 | 2018-05-01 | 东北师范大学 | A kind of mixture metal organic framework photochemical catalyst for controllable free-radical polymerisation |
| CN109134518A (en) * | 2018-08-30 | 2019-01-04 | 济南大学 | A kind of Metal-organic frame Cd-MOF crystalline material and its preparation method and application |
| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010510A (en) * | 2016-07-15 | 2016-10-12 | 武汉大学 | Multifunctional rare-earth metal organic framework material used for light conversion and preparation method thereof |
| CN106010510B (en) * | 2016-07-15 | 2018-07-03 | 武汉大学 | A kind of multifunctional rare-earth metal-organic framework material converted for light and preparation method thereof |
| CN107973914A (en) * | 2017-11-17 | 2018-05-01 | 东北师范大学 | A kind of mixture metal organic framework photochemical catalyst for controllable free-radical polymerisation |
| CN109134518A (en) * | 2018-08-30 | 2019-01-04 | 济南大学 | A kind of Metal-organic frame Cd-MOF crystalline material and its preparation method and application |
| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
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Application publication date: 20160608 |