CN102952161A - Chromium-containing amorphous coordination polymer particle and preparation method thereof - Google Patents
Chromium-containing amorphous coordination polymer particle and preparation method thereof Download PDFInfo
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- CN102952161A CN102952161A CN2011102465391A CN201110246539A CN102952161A CN 102952161 A CN102952161 A CN 102952161A CN 2011102465391 A CN2011102465391 A CN 2011102465391A CN 201110246539 A CN201110246539 A CN 201110246539A CN 102952161 A CN102952161 A CN 102952161A
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Abstract
The invention relates to a chromium-containing amorphous coordination polymer particle and a preparation method thereof, and mainly provides a chromium-containing coordination polymer which has a porous structure and has a particle size within a range of 0.8-5.0 microns, and a preparation method thereof. The preparation method comprises the following steps: dissolving reactants (inorganic chromium salts and organic carboxylic acid) in a mixed organic solvent, performing a crystallization reaction of the mixed solution for 5-90 hours under a condition with a temperature of 90-200 DEG C, naturally cooling, taking out the product, performing suction filtration, washing, drying, and roasting to prepare the chromium-containing coordination polymer with a particle size within a range of 0.8-5.0 microns. The preparation process of the invention is simple, and low in cost, and can prepare the chromium-containing amorphous coordination polymer particle under a mild condition. The prepared product has a porous structure and structure defects, and has wide application prospects in aspects of adsorption, separation, catalysis, drug release, and the like.
Description
Technical field
The present invention relates to the multi-pore micron particulate material, be specifically related to a kind of amorphous ligand polymer particle of chromium and preparation method thereof that contains.
Background technology
Metal organic coordination polymer is by metal ion and organic ligand, interconnects by covalent linkage or ionic linkage, forms a unlimited class material that extends.This class material has potential actual application value at gas storage, separation, catalysis, magnetic, the aspect such as non-linear, luminous, has caused various countries scholars' extensive concern, has become in recent years the focus of new functional materials research.Recently, in the world, have several study group to prepare amorphous micron polycoordination composition granule by methods such as solvent-induced, microemulsion and solvent thermal, this class material does well in the new Application Areas such as drug release, bio-sensing.2005, the people such as U.S. Mirkin pass through to add a kind of initial solvent in the precursor solution of the metal organic ligand of another kind of metal ion and carboxylic acid functional at the Nature report, spontaneous, whole reversible a kind of novel micrometer/nanometer particle [Nature with metal-metal organic ligand of network structure of formation, 2005,438 (7068): 651-654.].The people such as U.S. Mirkin in 2009 have reported hydrogen adsorption performance [Small, 2009,5,46 of such amorphous ligand polymer particle; Chem.Soc.Rev., 2009,38,1218], caused various countries scholars' concern.
That has reported contains normally polycrystalline material of chromium ligand polymer, France F é professor rey has synthesized MIL-53-Cr and MIL-101-Cr material by hydrothermal method, and these materials show excellent properties [J.Am.Chem.Soc., 2002 aspect Chu Qing, 124,13519; Science, 2005,309,2040], Korea S scholar J hung etc. has studied pH value and the water yield to the impact [Eur.J.Inorg.Chem.2010,1043.] of synthetic chromium polymerization of olefin using catalyst polymkeric substance.The Bai Junfeng of Nanjing University in 2010 etc. have reported by direct mixing method and have synthesized the little mesopore coordination polymer material of amorphous chromium terephthalic acid, this material ligand polymer particle in 500 nanometers with interior [Cryst.Growth Des., 2010,10,2451].
But so far there are no contains the relevant report of the amorphous ligand polymer micron particle of chromium relevant for porous.Here material has than bigger serface and more textural defect, so more is conducive to gas adsorption, particularly hydrogen adsorption.
Summary of the invention
The object of the present invention is to provide a kind of amorphous ligand polymer particle of chromium that contains, namely porous contains chromium ligand polymer particle, and proposes corresponding preparation method.
For achieving the above object, the technical solution used in the present invention is:
A kind of amorphous ligand polymer particle of chromium that contains, its be have a vesicular structure contain the amorphous ligand polymer particulate material of chromium, as follows preparation,
1) inorganic chromate salt and organic carboxyl acid are dissolved in the organic solvent, every 200mL organic solvent adds 2～30mmol inorganic chromate salt and 5～30mmol organic carboxyl acid, and temperature of reaction is 90～200 ℃, and the crystallization time is 5～90 hours, naturally cools to room temperature;
2) with product collection, then suction filtration, water or organic solvent washing, 50～120 ℃ of vacuum-dryings remove guest molecule 150～550 ℃ of roastings, makes to contain the amorphous ligand polymer micron particle of chromium; It has particle size in the 0.8-5.0 micrometer range.
In the described step 1) preparation method that contains the amorphous ligand polymer particle of chromium is the solvent thermal synthesis method, inorganic chromate salt and organic carboxyl acid press the metal positively charged ion and acid ion stoichiometric ratio (0.5～2) is added; Synthesis temperature is 90～200 ℃; Generated time is 5～90 hours.
In the described step 1) the inorganic chromium salt is chromium chloride or chromium nitrate; Organic acid is terephthalic acid, m-phthalic acid, 1,3,5-benzene tricarboxylic acid, 1,2, one or more in 4-benzene tricarboxylic acid, the amino terephthalic acid of 2-, benzene tetracarboxylic acid, Isosorbide-5-Nitrae-naphthalic acid or the NDA; Solvent is one or more in DMF, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), methyl alcohol, ethanol or the ethylene glycol.
In the described step 2) drying temperature is 50～120 ℃; Operating time is adjustable at 5～24 hours.150～550 ℃ of maturing temperatures; Operating time is adjustable at 4～15 hours.
Porous provided by the present invention contains the amorphous ligand polymer particle of chromium and the preparation method has following advantage:
Among the present invention porous to contain the size of particles of the amorphous ligand polymer of chromium controlled in the 0.8-5.0 micrometer range.And have than bigger serface (greater than 200m
2/ g).
2. synthesis technique is simple, and cost is lower.The present invention adopts solvent-thermal method synthetic, the product that can obtain at short notice having higher yields.
3. the present invention can prepare a class porous and contains the amorphous ligand polymer particle of chromium under mild conditions; The porous material that has that makes has a wide range of applications at aspects such as absorption, separation, catalysis, drug release.
Description of drawings
Fig. 1 is the stereoscan photograph of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 1.
Fig. 2 is the low temperature nitrogen isothermal adsorption curve of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 1.
Fig. 3 is the low temperature hydrogen isothermal adsorption curve of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 1.
Fig. 4 is the x-ray diffractogram of powder spectrum of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 1.
Fig. 5 is the stereoscan photograph of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 2.
Fig. 6 is the low temperature nitrogen isothermal adsorption curve of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 2.
Fig. 7 is the x-ray diffractogram of powder spectrum of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 2.
Fig. 8 is the stereoscan photograph of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 3.
Fig. 9 is the low temperature nitrogen isothermal adsorption curve of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 3.
Figure 10 is the low temperature hydrogen isothermal adsorption curve of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 3.
Figure 11 is the x-ray diffractogram of powder spectrum of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 3.
Figure 12 is the stereoscan photograph of the amorphous ligand polymer particle of chromium m-phthalic acid of embodiments of the invention 4.
Figure 13 is the chromium 1,2 of embodiments of the invention 5, the stereoscan photograph of the amorphous ligand polymer particle of 4-benzene tricarboxylic acid.
Figure 14 is the chromium 1,3 of embodiments of the invention 6, the stereoscan photograph of the amorphous ligand polymer particle of 5-benzene tricarboxylic acid.
Figure 15 is the stereoscan photograph of the amorphous ligand polymer particle of the amino terephthalic acid of chromium 2-of embodiments of the invention 7.
Embodiment
To carrying out described containing on the amorphous ligand polymer particulate material of the chromium scanning electron microscope analysis real example JSM-6360LV type scanning electron microscope, voltage is 20kV, magnification be 1000-20000 doubly, specific operation process is:
Testing sample is put into dehydrated alcohol, and then ultra-sonic dispersion is added drop-wise on the test board, after the seasoning, sample is put into metal-spraying equipment, vacuumize 2 hours after, with the sample surfaces metal spraying.At last sample behind the metal spraying is put into SEM equipment, analyze.
Contain chromium amorphous ligand polymer particulate material nitrogen and the hydrogen adsorption performance test is carried out at U.S. Kang Ta company (Quantachrome Instruments) Autosorb-1 type physical adsorption appearance to described, specific operation process is:
1) takes by weighing 0.1～0.3g left and right sides sample, put into sample pool, in degassed station, descended degassed 4～24 hours in 160 ℃.
2) under 77K, carry out the test of low temperature nitrogen and hydrogen adsorption, use liquid nitrogen cooling.
Embodiment 1
1) takes by weighing the 0.133g chromium chloride and the 0.083g m-phthalic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 150 ℃ were reacted 2 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) low temperature nitrogen isothermal adsorption performance test: treatment condition be 160 ℃ degassed 6 hours.Test condition is 77K, nitrogen and hydrogen isothermal adsorption.
Embodiment 2
1) takes by weighing the 0.533g chromium chloride and the 0.166g m-phthalic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 190 ℃ were reacted 3 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) low temperature nitrogen isothermal adsorption performance test: treatment condition be 160 ℃ degassed 6 hours.Test condition is 77K, isothermal nitrogen adsorption.
Embodiment 3
1) takes by weighing the 0.533g chromium chloride and the 0.333g terephthalic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 190 ℃ were reacted 3 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) low temperature nitrogen isothermal adsorption performance test: treatment condition be 160 ℃ degassed 6 hours.Test condition is 77K, nitrogen and hydrogen isothermal adsorption.
Embodiment 4
1) takes by weighing the 0.067g chromium chloride and the 0.062g m-phthalic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 150 ℃ were reacted 2 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
1) takes by weighing 0.133g chromium chloride and 0.105g 1,2, the 4-benzene tricarboxylic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 150 ℃ were reacted 2 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
Embodiment 6
1) takes by weighing 0.133g chromium chloride and 0.105g 1,3, the 5-benzene tricarboxylic acid is dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 150 ℃ were reacted 2 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
Embodiment 7
1) takes by weighing the amino terephthalic acid of 0.133g chromium chloride and 0.135g 2-and be dissolved in 20ml N, dinethylformamide/1,4-dioxane mixed solvent (volume ratio 1: 1), magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 150 ℃ were reacted 2 days in synthetic baking oven, naturally cooled to room temperature.
2) with the product suction filtration, and with DMF washing, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
Preparation technology of the present invention is simple, and cost is low, can prepare a kind of amorphous ligand polymer micron particle of chromium (such as Fig. 1,5,8,12-15) that contains under mild conditions.Such material has higher specific surface area (244-994m
2/ g is such as Fig. 2,6 and 9), can adsorb in a large number hydrogen (＞90cm
3/ g is such as Fig. 3 and Figure 10), surpassed the amorphous ligand polymer micron particle of bibliographical information hydrogen storage property (see document Adv.Mater.2008,20 (11), 2105-2110; Small 2009,5 (1), 46-50; Adv.Mater.2009,21 (6), 674-677).Prepared have porous structure material and a textural defect, has a wide range of applications at aspects such as absorption, separation, catalysis, drug release.
Claims (8)
1. one kind contains the amorphous ligand polymer particle of chromium, it is characterized in that: as follows preparation,
1) inorganic chromate salt and organic carboxyl acid are dissolved in the organic solvent, every 200mL organic solvent adds 2～30mmol inorganic chromate salt and 5～30mmol organic carboxyl acid, and temperature of reaction is 90～200 ℃, and the crystallization time is 5～90 hours, naturally cools to room temperature;
Described inorganic chromate salt is chromium chloride or chromium nitrate; Organic acid is terephthalic acid, m-phthalic acid, 1,3,5-benzene tricarboxylic acid, 1,2, one or more in 4-benzene tricarboxylic acid, the amino terephthalic acid of 2-, benzene tetracarboxylic acid, Isosorbide-5-Nitrae-naphthalic acid or the NDA;
2) suction filtration is collected solid product, and then water or organic solvent washing, 50～120 ℃ of vacuum-dryings remove guest molecule 150～550 ℃ of roastings, makes porous and contain the amorphous ligand polymer micron particle of chromium; It has particle size in the 0.8-5.0 micrometer range.
2. according to the described amorphous ligand polymer particle of chromium that contains of claim 1, it is characterized in that: inorganic chromate salt and organic carboxyl acid are pressed metal positively charged ion and 0.5～2 interpolation of acid ion stoichiometric ratio described step 1).
3. according to the described amorphous ligand polymer particle of chromium that contains of claim 1, it is characterized in that: be 5～24 hours described time of drying, and roasting time is 4～15 hours.
4. according to the described amorphous ligand polymer particle of chromium that contains of claim 1, it is characterized in that: described organic solvent is one or more in DMF, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), methyl alcohol, ethanol or the ethylene glycol.
5. described preparation method who contains the amorphous ligand polymer particle of chromium of claim 1 is characterized in that: as follows preparation,
1) inorganic chromate salt and organic carboxyl acid are dissolved in the organic solvent, every 200mL organic solvent adds 2～30mmol inorganic chromate salt and 5～30mmol organic carboxyl acid, and temperature of reaction is 90～200 ℃, and the crystallization time is 5～90 hours, naturally cools to room temperature;
Described inorganic chromate salt is chromium chloride or chromium nitrate; Organic acid is terephthalic acid, m-phthalic acid, 1,3,5-benzene tricarboxylic acid, 1,2, one or more in 4-benzene tricarboxylic acid, the amino terephthalic acid of 2-, benzene tetracarboxylic acid, Isosorbide-5-Nitrae-naphthalic acid or the NDA;
2) with product collection, then suction filtration, water or organic solvent washing, 50～120 ℃ of vacuum-dryings remove guest molecule 150～550 ℃ of roastings, makes to contain the amorphous ligand polymer micron particle of chromium.
6. according to the described preparation method who contains the amorphous ligand polymer particle of chromium of claim 5, it is characterized in that: inorganic chromate salt and organic carboxyl acid are pressed metal positively charged ion and 0.5～2 interpolation of acid ion stoichiometric ratio described step 1).
7. according to the described preparation method who contains the amorphous ligand polymer particle of chromium of claim 5, it is characterized in that: be 5～24 hours described time of drying; Roasting time is 4～15 hours.
8. according to the described preparation method who contains the amorphous ligand polymer particle of chromium of claim 5, it is characterized in that: described organic solvent is one or more in DMF, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), methyl alcohol, ethanol or the ethylene glycol.
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| CN101337192A (en) * | 2007-07-04 | 2009-01-07 | 中国科学院大连化学物理研究所 | Meso-microporous metal-organic compound and preparation method thereof |
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| CN101289161A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Method for preparing hydrogen-storing material |
| CN101337192A (en) * | 2007-07-04 | 2009-01-07 | 中国科学院大连化学物理研究所 | Meso-microporous metal-organic compound and preparation method thereof |
| CN101269713A (en) * | 2008-04-02 | 2008-09-24 | 朱惠芬 | Dual-purpose plastic vessel for cup and bottle, and breaking method thereof |
Non-Patent Citations (3)
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