CN101337192B - Meso-microporous metal-organic compound and preparation method thereof - Google Patents
Meso-microporous metal-organic compound and preparation method thereof Download PDFInfo
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- CN101337192B CN101337192B CN2007100119576A CN200710011957A CN101337192B CN 101337192 B CN101337192 B CN 101337192B CN 2007100119576 A CN2007100119576 A CN 2007100119576A CN 200710011957 A CN200710011957 A CN 200710011957A CN 101337192 B CN101337192 B CN 101337192B
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Abstract
The invention relates to a microporous and mesoporous organometallic compound as well as the preparation method thereof, and mainly provides an organometallic compound with multilevel pores, as well as the preparation method thereof. The preparation method comprises the following steps: metal inorganic salts and organic carboxylic acid coordination polymers are dissolved in water or an organic solvent; the mixed solution is crystallized for 10-100 hours under the condition that the temperature is 100-220 DEG C; after being naturally cooled down and taken out, the reaction product is taken out; the microporous and mesoporous organo-metallic compound is prepared through suction-filtering, washing, drying and baking. The preparation process of the invention is simple, the cost is low, and the microporous and mesoporous organo-metallic compound can be prepared under mild conditions. The prepared material with the multilevel pores has wide application prospect on aspects of adsorption, separation, catalysis, etc.
Description
Technical field
The present invention relates to multistage pore size distribution material, be specifically related to a kind of middle micropore metal organic compound and preparation method thereof.
Background technology
Stephanoporate metal organic compound by metal ion and organic ligand, interconnects by covalent bond or ionic bond, the crystalline state polycrystalline material of constructing jointly with regular pore canal or opening structure.The one dimension that this material spatially forms, two dimension or three-dimensional have the infinite network structure.Because it has characteristics such as unique pore structure, bigger specific area and the little molecule of selective absorption, makes its research be subjected to various countries researcher's great attention, has obtained fast development at last decade.The F é rey group of the Yaghi group of the U.S. and France has obtained the achievement that attracts people's attention in this field.Stephanoporate metal organic compound such as MOF-117 (H.K.Chae, D.Y.Siberio-Perez, J.Kim, Y.-B.Go, M.Eddaoudi, A.J.Matzger, M.O ' Keeffe, O.M.Yaghi, Nature, 2004,427,523.) and MIL-101 (G.Ferey, C.Mellot-Draznieks, C.Serre, F.Millange, J.Dutour, S.Surble and I.Margiolaki, Science, 2005,309,2040.) have bigger specific area and pore volume, at stored-gas (particularly storage of hydrogen), divided gas flow, catalysis, nonlinear optics, there is potential application prospect aspects such as magnetics.F é rey etc. has synthesized micropore MIL-53 (Al
3+, Cr
3+), and to its adsorption property that has carried out research, this compounds not only has certain hydrogen storage property and (is respectively 3.8wt% and 3.2wt% at 77K, 16MPa), and can CO absorption
2And CH
4(G.F é rey, M.Latroche, C.Serre, F.Millange, T.Loiseau and A.Percheron-Guegan, Chem.Commun., 2003,2977.), (S.Bourrelly, P.L.Llewellyn, C.Serre, F.Millange, T.Loiseauand G.F é rey, J.Am.Chem.Soc., 2005,127,13519).The stephanoporate metal organic compound of having reported only has microcellular structure extremely mostly, has only the porous compounds of reports such as Zhou to have middle pore property (X.-S.Wang, S.Ma, D.Sun at present, S.Parkin, and H.-C.Zhou, J.Am.Chem.Soc., 2006,128,16474).But, do not see metal-organic relevant report so far relevant for the multistage pore size distribution of middle micropore.The metallo-organic compound of the middle multistage pore size distribution of micropore has bigger specific area, and appreciable mesopore duct is arranged, and so more helps molecular transport, is specially adapted to bigger organic molecule diffusion.
Summary of the invention
The object of the present invention is to provide a kind of middle micropore metal organic compound, i.e. the metallo-organic compound of the middle multistage pore size distribution of micropore, and proposition corresponding preparation method.
For achieving the above object, the technical solution used in the present invention is:
Micropore metal organic compound in a kind of, it is to have the metallo-organic compound material that middle micropore distributes, and can prepare as follows
1) metal inorganic salt and organic carboxyl acid are dissolved in water or organic solvent (every 200mL solvent adds 2～20mmol metal inorganic salt and 5～30mmol organic carboxyl acid), the crystallization temperature is 100～220 ℃, crystallization 10～100 hours cools to room temperature naturally.
2) product is collected, suction filtration, washing (water or organic solvent), 30～150 ℃ of vacuum drying are removed guest molecule 200～500 ℃ of roastings, micropore metal organic compound in making then; It has micropore and the multistage pore size distribution of mesopore, and micropore size is in 0.5～1.0nm scope; The mesopore aperture is at 2.0～40.0nm.
The multistage hole of described step 1) branch preparation methods is hydro-thermal or solvent thermal synthesis method, and metal inorganic salt and organic carboxyl acid press the metal cation and acid ion stoichiometric proportion (0.5～2) is added; Synthesis temperature is 100～220 ℃; Generated time is 10～100 hours.
Described step 1) metal inorganic salt is a chromium chloride, nickel chloride, chromic nitrate, zinc nitrate, lanthanum nitrate or aluminum nitrate; Organic acid is a formic acid, oxalic acid, M-phthalic acid or terephthalic acid (TPA); Solvent is water or N, dinethylformamide, 1.4-dioxane, ethanol or methyl alcohol.
Described step 2) baking temperature is 30～150 ℃; Operating time is adjustable at 4～20 hours.200～500 ℃ of sintering temperatures; Operating time is adjustable at 4～10 hours.
Micropore metal organic compound and preparation method have following advantage in provided by the present invention:
1. the micropore metal organic compound has than bigger serface (greater than 500m among the present invention
2/ g) with than macropore volume (greater than 0.5cm
3/ g), mesopore and micropore size distribute all narrower.
2. synthesis technique is simple, and cost is lower.The present invention adopts hydro-thermal or solvent-thermal method to synthesize the product that can obtain having higher yields at short notice.
3. the present invention can prepare micropore metal organic compound in the class under temperate condition; The multistage pore size distribution material that has that makes has a wide range of applications at aspects such as absorption, separation, catalysis.
Description of drawings
Fig. 1 is the low temperature nitrogen isothermal adsorption curve of middle micropore metal organic compound of the chromium terephthalate of specific embodiments of the invention 1;
Fig. 2 is the low temperature nitrogen isothermal adsorption curve of middle micropore metal organic compound of the terephthalic acid (TPA) aluminium of specific embodiments of the invention 2.
Fig. 3 is the low temperature nitrogen isothermal adsorption curve of middle micropore metal organic compound of the M-phthalic acid aluminium of specific embodiments of the invention 3.
The specific embodiment
Described porous material absorption property test is carried out on the ASAP of Micromeritics Instrument Corp. U.S.A (Micromeritics) 2010 type physical adsorption appearances, and specific operation process is:
1) takes by weighing 0.1～0.3g left and right sides sample, put into sample cell, in degassing station, outgased 1～8 hour down in 110 ℃.
2) then, heat up again 150～350 ℃ and continue the degassing 2～24 hours.
3) under 77K, carry out low temperature nitrogen absorption test, use liquid nitrogen cooling, adopt the micropore working procedure.
Embodiment 1
1. take by weighing the 0.53g chromium chloride and the 0.50g terephthalic acid (TPA) is dissolved in 20ml N, dinethylformamide, magnetic agitation fully dissolve it, then mixed solution are moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 190 ℃ of crystallization are 3 days in synthetic baking oven, naturally cool to room temperature.
2. with the product suction filtration, and use N, the dinethylformamide washing, 50 ℃ of oven dry, last, 250 ℃ of roastings 6 hours, obtain target product.
3. low temperature nitrogen isothermal absorption property test: treatment conditions are 110 ℃ of degassings 8 hours, heat up 200 ℃ and continue the degassing 8 hours.Test condition is 77K, isothermal nitrogen adsorption.
Embodiment 2
1. take by weighing the 0.75g aluminum nitrate and the 0.50g terephthalic acid (TPA) is dissolved in 20ml N, dinethylformamide, magnetic agitation fully dissolve it, then mixed solution are moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 190 ℃ of crystallization are 3 days in synthetic baking oven, naturally cool to room temperature.
2. with the product suction filtration, and use N, the dinethylformamide washing, 50 ℃ of oven dry, last, 350 ℃ of roastings 6 hours, obtain target product.
3. low temperature nitrogen isothermal absorption property test: treatment conditions are 110 ℃ of degassings 8 hours, heat up 300 ℃ and continue the degassing 8 hours.Test condition is 77K, isothermal nitrogen adsorption.
Embodiment 3
1. take by weighing the 0.75g aluminum nitrate and the 0.50g M-phthalic acid is dissolved in 20ml N, the mixed solution of dinethylformamide and 1.4-dioxane (1: 1), magnetic agitation is fully dissolved it, then mixed solution is moved into the stainless steel cauldron of 30ml inner liner polytetrafluoroethylene, 190 ℃ of crystallization are 3 days in synthetic baking oven, naturally cool to room temperature.
2. with the product suction filtration, and use N, the washing of N-NMF, 50 ℃ of oven dry, last, 300 ℃ of roastings 6 hours, obtain target product.
3. low temperature nitrogen isothermal absorption property test: treatment conditions are 110 ℃ of degassings 8 hours, heat up 250 ℃ and continue the degassing 8 hours.Test condition is 77K, isothermal nitrogen adsorption.
Table 1 is the pore passage structure parameter of micropore sample among the specific embodiments of the invention 1-3.
Claims (8)
1. micropore metal organic compound in a kind is characterized in that: preparation as follows,
1) metal inorganic salt and organic carboxyl acid are dissolved in water or the organic solvent, every 200mL water or organic solvent add 2～20mmol metal inorganic salt and 5～30mmol organic carboxyl acid, reaction temperature is 100～220 ℃, and the crystallization time is 10～100 hours, cools to room temperature naturally;
Described metal inorganic salt is chromium chloride, nickel chloride, chromic nitrate, zinc nitrate, lanthanum nitrate or aluminum nitrate; Organic carboxyl acid is formic acid, oxalic acid, M-phthalic acid or terephthalic acid (TPA);
2) product is collected, suction filtration, water or organic solvent washing, 30～150 ℃ of vacuum drying are removed guest molecule 200～500 ℃ of roastings then, make the metallo-organic compound material of multistage pore size distribution; It has micropore and the multistage pore size distribution of mesopore, and micropore size is in 0.5～1.0nm scope; The mesopore aperture is at 2.0～40.0nm.
2. according to the described middle micropore metal organic compound of claim 1, it is characterized in that: metal inorganic salt and organic carboxyl acid are pressed metal cation and 0.5～2 interpolation of acid ion stoichiometric proportion in the described step 1).
3. according to the described middle micropore metal organic compound of claim 1, it is characterized in that: described roasting time is 4～10 hours.
4. according to the described middle micropore metal organic compound of claim 1, it is characterized in that: described organic solvent is N, dinethylformamide, 1.4-dioxane, ethanol or methyl alcohol; Be 4～20 hours drying time.
A claim 1 described in the preparation method of micropore metal organic compound, it is characterized in that: preparation as follows,
1) metal inorganic salt and organic carboxyl acid are dissolved in water or the organic solvent, every 200mL water or organic solvent add 2～20mmol metal inorganic salt and 5～30mmol organic carboxyl acid, reaction temperature is 100～220 ℃, and the crystallization time is 10～100 hours, cools to room temperature naturally;
Described metal inorganic salt is chromium chloride, nickel chloride, chromic nitrate, zinc nitrate, lanthanum nitrate or aluminum nitrate; Organic carboxyl acid is formic acid, oxalic acid, M-phthalic acid or terephthalic acid (TPA);
2) product is collected, suction filtration, water or organic solvent washing, 30～150 ℃ of vacuum drying are removed guest molecule 200～500 ℃ of roastings then, make the metallo-organic compound material of multistage pore size distribution.
6. according to the preparation method of the described middle micropore metal organic compound of claim 5, it is characterized in that: metal inorganic salt and organic carboxyl acid are pressed metal cation and 0.5～2 interpolation of acid ion stoichiometric proportion in the described step 1).
7. according to the preparation method of the described middle micropore metal organic compound of claim 5, it is characterized in that: be 4～20 hours described drying time; Roasting time is 4～10 hours.
8. according to the preparation method of the described middle micropore metal organic compound of claim 5, it is characterized in that: described organic solvent is N, dinethylformamide, 1.4-dioxane, ethanol or methyl alcohol.
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| FR2938540B1 (en) * | 2008-11-18 | 2017-08-11 | Centre Nat Rech Scient | METHOD FOR THE HYDROTHERMAL PREPARATION OF CRYSTALLIZED POROUS ALUMINUM CARBOXYLATES OF THE "METAL-ORGANIC FRAMEWORK" TYPE |
| CN102952161A (en) * | 2011-08-25 | 2013-03-06 | 中国科学院大连化学物理研究所 | Chromium-containing amorphous coordination polymer particle and preparation method thereof |
| CN103193804B (en) * | 2013-03-17 | 2016-03-30 | 北京化工大学 | A kind of preparation method of metal organic coordination polymer material |
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| CN104667876B (en) * | 2013-11-29 | 2018-02-13 | 北京思达安新材料科技有限公司 | Serial MOF types multilevel hole material IPD mesoMOF 1~8 and preparation method thereof, and the adjusting method of mesoporous size |
| CN104710303A (en) * | 2013-12-12 | 2015-06-17 | 中国科学院大连化学物理研究所 | Spherical coordination polymer material and preparation method thereof |
| CN104525124A (en) * | 2014-12-15 | 2015-04-22 | 北京思达安新材料科技有限公司 | MOF type multistage porous material IPD-mesoMOF-10 and preparation method thereof |
| CN104587965A (en) * | 2014-12-15 | 2015-05-06 | 北京思达安新材料科技有限公司 | MOF (metal-organic framework) hierarchical porous material IPD-mesoMOF-11 and preparation method |
| CN104587966A (en) * | 2014-12-15 | 2015-05-06 | 北京思达安新材料科技有限公司 | MOF (metal-organic framework) hierarchical porous material IPD-mesoMOF-9 and preparation method |
| CN107556488B (en) * | 2017-09-30 | 2020-09-08 | 哈尔滨工业大学 | Method for synthesizing metal organic framework material MIL-53(Cr) |
| CN107987659A (en) * | 2017-12-18 | 2018-05-04 | 枣阳市旺前电泳涂料有限公司 | A kind of production technology with metal-organic cathode electrodip painting |
| CN111253351A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Controllable preparation of MIL material and application of MIL material in separation and enrichment of furan compound |
| CN109734127A (en) * | 2019-03-13 | 2019-05-10 | 西安交通大学 | A kind of monodisperse zirconium oxide porous microsphere and preparation method thereof |
| CN111450842B (en) * | 2020-05-21 | 2021-02-26 | 苏州大学 | Preparation method of micro-flower structure black lead-copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof |
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