CN109160824B - Ceramic porous material based on MOFs (metal-organic frameworks) and preparation method thereof - Google Patents
Ceramic porous material based on MOFs (metal-organic frameworks) and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ceramic porous material based on MOFs and a preparation method thereof, wherein the preparation method comprises the following steps: s1: preparing a metal organic framework material by taking a metal precursor and an organic ligand as raw materials; s2: dispersing zirconium salt in a solvent, stirring and mixing to generate transparent gel, sealing and aging, and drying to obtain xerogel; s3: calcining the dried gel at high temperature and performing ball milling to obtain ceramic powder; s4: dispersing ceramic powder and a metal organic framework material in a solvent, adding a dispersing agent, uniformly ball-milling, adding a binder, and continuously ball-milling to obtain metal organic framework-ceramic composite slurry; s5: pouring the metal organic framework-ceramic composite slurry into a mold, and drying to obtain a ceramic blank; calcining at high temperature to obtain the MOFs-based ceramic porous material; according to the invention, the MOFs material is used as a pore forming agent, so that the MOFs-ceramic composite material has high porosity and uniform pore size, an oxide formed after the MOFs material is sintered at a high temperature is bonded with zirconia in the ceramic, and the formed porous material has higher strength.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a MOFs-based porous ceramic material and a preparation method thereof.
Background
Metal organic framework Materials (MOFs), also called porous coordination polymers, refer to crystal materials formed by connecting inorganic metals or metal clusters and polydentate nitrogen-oxygen-containing organic ligands through coordination bonds, and are porous materials with high specific surface area, adjustable pore channel size and organic functionalization; compared with the conventional porous material, the metal organic framework material has the following advantages: (1) the texture performance (specific surface area and pore diameter) of the material can be effectively controlled by regulating the length and the size of the organic ligand; (2) the internal pore channel system is developed, no dead volume exists, and the pore structure is regular; therefore, the MOFs material has a wide application scene in chemical engineering and other technical fields, such as catalysis, separation, magnetism, photoelectricity, gas storage and sensing.
The porous ceramic is a ceramic material with open pore size prepared by molding and special high-temperature sintering process, has the advantages of high temperature resistance, high pressure resistance, acid-base resistance, organic medium corrosion resistance, good biological inertia, long service life and the like, is suitable for the fields of filtration and separation of various media, high-pressure gas exhaust silencing, gas distribution, electrolytic diaphragms and the like, and is widely applied to the fields of wastewater treatment, high-temperature gas filtration, sound absorbing materials, heat insulation materials and the like as a green material due to good mechanical property, chemical property and thermal stability.
The porous ceramics can be prepared by various methods, such as: pore-forming agent addition method, organic foam impregnation method and foaming method. The method of adding pore-forming agent is to utilize organic pore-forming agent to burn out or volatilize at high temperature to leave pores in the ceramic body, the method has simple process, adjustable porosity, low porosity, uneven pore size and shape distribution and pollutant emission in the preparation process. The organic foam impregnation method is to uniformly coat the prepared slurry on an organic foam reticular body by utilizing the special structure of an open-cell three-dimensional reticular framework of the organic foam, and burn off the organic foam after drying to obtain the mesh porous ceramic. The strength and elasticity of organisms in the preparation process of the method have great influence on the structure and performance of the porous material, and the prepared porous material has the defect of low strength, and is easy to generate residues and toxic gases and pollute the environment. The porosity of the porous ceramic prepared by the foaming method can be generally more than 70%, the foaming method generally adds some organic matters, the slurry is solidified after the ceramic slurry is foamed, and the organic matters can be burnt or volatilized during sintering to pollute the environment. In a word, the existing porous ceramic material has the defects of low porosity, low strength, and uneven pore size and shape distribution.
Disclosure of Invention
Aiming at least one defect or improvement requirement in the prior art, the invention provides a MOFs-based ceramic porous material and a preparation method thereof, wherein the MOFs material is used as a pore-forming agent, so that the MOFs-ceramic composite material has high porosity and uniform pore diameter; the size of the pore channel can be designed and regulated by adjusting the organic ligand used in the MOFs material so as to meet the requirements of the porous ceramic material on different pore diameters, and the porous ceramic material aims to solve the problems of low porosity, low strength, and uneven pore size and shape distribution of the existing porous ceramic material.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a MOFs-based ceramic porous material, comprising the steps of:
s1: preparing a metal organic framework material by taking a metal precursor and an organic ligand as raw materials;
s2: preparing a ceramic gel: dispersing zirconium salt in a solvent, stirring and mixing to generate transparent gel, sealing and aging for a period of time, and drying to obtain xerogel; the ceramic slurry prepared by the gel method is not easy to agglomerate and has better stability.
S3: preparing ceramic powder: calcining the dried gel at high temperature, and performing ball milling to obtain ceramic powder;
s4: dispersing ceramic powder and a metal organic framework material in a solvent, and stirring to uniformly mix the ceramic powder and the metal organic framework material, wherein the addition amount of the metal organic framework material is 30-70 wt% of the ceramic powder; adding a dispersing agent into the mixture, adding a binder after ball milling is uniform, and continuing ball milling to obtain metal organic framework-ceramic composite slurry;
the dispersant is added, so that the stability of the slurry can be improved, the particles are prevented from reuniting, and the solid content of the slurry is improved; the binder can improve the strength of the green body and prevent powder segregation.
S5: pouring the metal organic framework-ceramic composite slurry into a forming mold, and drying to obtain a ceramic blank; and calcining the ceramic blank at a high temperature to obtain the MOFs-based ceramic porous material.
Preferably, in the above production method, the molar ratio of the metal precursor to the organic ligand is (1-10): (1-10), adding a solvent for dissolving, reacting for 4-12 h at 25-75 ℃, and preparing the metal organic framework material by a coprecipitation method.
Preferably, in the preparation method, the metal precursor is one or more of sulfate, nitrate, acetate, halide or hydrate of zirconium, aluminum, magnesium and calcium; the difference between the radiuses of three metal cations of aluminum, magnesium and calcium and the radius of zirconium metal ions in the ceramic is less than 12%, and the metal cations can be used as a stabilizer to stabilize the crystal form of zirconium oxide formed after the ceramic is sintered; the MOFs material prepared by adopting the zirconium metal precursor has the advantages that the components and the crystal forms of zirconium oxide formed after sintering are consistent with those of zirconium oxide in ceramic, and the adaptability of the composite material can be improved.
The organic ligand is any one or more of aromatic carboxylic acid ligand and nitrogen-containing heterocyclic ligand.
Preferably, in the above production method, the zirconium salt is selected from any one of zirconium oxychloride, zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide and zirconium isooctanoate.
Preferably, in the above preparation method, the dispersant is selected from any one of polyethylene glycol, polyvinylpyrrolidone and terpineol, and the addition amount thereof is 2 wt% to 3 wt% of the total amount of the ceramic powder and the metal organic framework material.
Preferably, in the above preparation method, the binder is selected from any one of polyethersulfone resin, zinc phosphate, polyvinyl butyral, polyvinyl alcohol, starch, hydroxymethyl cellulose and water glass, and the addition amount thereof is 6 wt% to 10 wt% of the total amount of the ceramic powder and the metal organic framework material.
Preferably, in the preparation method, in step S3, the calcination temperature is 500 ℃ to 600 ℃, and the calcination time is 1.5 to 3 hours;
preferably, in the preparation method, in the step S5, the calcination temperature is 1200-1600 ℃, and the calcination time is 15-30 h.
Preferably, in the above preparation method, step S2, the solvent is selected from one or more of water, methanol, ethanol, isopropanol, ethylene glycol, isobutanol, and glycerol.
According to another aspect of the present invention, there is provided a MOFs-based ceramic porous material prepared by the preparation method according to any one of the above methods.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the MOFs material with a porous structure with a regular structure is used as a pore-forming agent to obtain metal organic framework-ceramic composite slurry; organic ligands in the MOFs material volatilize in the high-temperature calcination process of the ceramic blank prepared by the slurry, metal in the framework is bonded with zirconia in the ceramic in the form of oxide, and the growth of zirconia particles in the ceramic is inhibited, so that a porous structure is formed; in addition, the original pore channel structure in the MOFs material is reserved as the pore structure of the ceramic material, so that the prepared MOFs-based ceramic porous material has high porosity, uniform pore size and shape distribution, and higher strength.
(2) According to the MOFs-based ceramic porous material and the preparation method thereof, an oxide formed after the MOFs material is sintered can also be used as a sintering aid for stabilizing the crystal form of zirconia in the ceramic, and the sintering process of the ceramic in the sintering process is changed from solid-phase sintering to liquid-phase sintering, so that the sintering temperature of the ceramic is reduced, and the cost is saved.
(3) According to the MOFs-based ceramic porous material and the preparation method thereof, the size of the pore channel can be designed and regulated by adjusting the organic ligand used in the MOFs material, so that the requirements of the porous ceramic material on different pore diameters are met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
S1: respectively weighing 9.4g of zirconium chloride and 6g of trimesic acid in a 50mL beaker, adding 30mL of N, N-dimethylformamide into the beaker, continuously stirring the mixture until the mixture is completely dissolved, and reacting the mixture for 4 hours at 50 ℃; and collecting the obtained product through centrifugation and filtration, washing the product with N, N-dimethylformamide for 3 times, then transferring the product into a vacuum drying oven, and drying the product at 80 ℃ for 12 hours to finally obtain the zirconium-based metal organic framework material for later use.
S2: weighing 10g of ZrOCl2·8H2Dissolving O in 15mL of ethanol, and adding 20 vol% of deionized water to promote the dissolution of solute; stirring and mixing to generate transparent gel, sealing and aging for 8h, and drying at 40 ℃ for 12h to obtain xerogel;
s3: calcining the xerogel at 600 ℃ for 1.5 hours, and performing ball milling for 24 hours to obtain zirconia ceramic powder;
s4: dispersing 8g of zirconia ceramic powder and 2.4g (30%) of metal organic framework material in ethanol, and stirring for 1 hour to uniformly mix the ceramic powder and the metal organic framework material; adding 0.2g (2%) of polyethylene glycol (PEG400) as a dispersant to the mixture, and ball milling for a period of time; after ball milling is carried out uniformly, 1.04g (10%) of polyether sulfone resin is added as a binder to carry out ball milling continuously, so as to obtain metal organic framework-ceramic composite slurry;
s5: pouring the metal organic framework-ceramic composite slurry into a forming mold, and drying at normal temperature for 24 hours to obtain a ceramic blank; and calcining the mixture at 1600 ℃ for 15h to obtain the MOFs-based ceramic porous material.
The porosity of the MOFs-based ceramic porous material is tested by adopting a soaking medium method: firstly, the volume v of the sample is measured by a vernier caliper, and the weight m of the dried sample in air is weighed1And then immersed in distilled water to saturate the material, i.e., a heated drum is used to substantially fill the pores of the porous material with the medium. After the sample is fully saturated in a certain period of time, removing the sample, slightly wiping off the medium on the surface of the sample, and weighing the total mass m of the sample in the air by using an electronic scale2The porosity of the porous material was calculated by the following formula: f ═ m2-m1)/vρWater (W)(ii) a The porosity of the ceramic porous material based on MOFs was measured according to this method to be 45%.
The specific surface area and the pore diameter of the composite porous material are determined by a nitrogen adsorption and desorption test: vacuum degassing the synthesized composite porous material at 150 deg.C for 8h, measuring nitrogen adsorption and desorption isotherm at 77K, and determining specific surface area to be 1497m2.g-1Average pore diameter of 0.9 nm.
Testing the bending strength of the MOFs-based ceramic porous material on an ALJ-02B type manual spiral testing machine by adopting a three-point bending test method; the flexural strength of the material is 601MPa after testing.
Example two
S1: respectively weighing 9.67 aluminum sulfate and 6.8g of 2,2 '-bipyridine-5, 5' -dicarboxylic acid in a 50mL beaker, adding 30mL of absolute ethanol, continuously stirring until the absolute ethanol is completely dissolved, and reacting for 4 hours at 75 ℃; and collecting the obtained product through centrifugation and filtration, washing the product with absolute ethyl alcohol for 3 times, transferring the product into a vacuum drying oven, and drying the product at 80 ℃ for 12 hours to finally obtain the zirconium-based metal organic framework material for later use.
S2: weighing 10g of zirconium n-propoxide, dissolving the zirconium n-propoxide in 15mL of glycerol, and adding 20 vol% of deionized water to promote the dissolution of solutes; stirring and mixing to generate transparent gel, sealing and aging for 10h, and drying at 40 ℃ for 12h to obtain xerogel;
s3: calcining the xerogel at 500 ℃ for 2 hours, and performing ball milling for 24 hours to obtain zirconia ceramic powder;
s4: dispersing 8g of zirconia ceramic powder and 3.2g (40%) of metal organic framework material in ethanol, and stirring for 1 hour to uniformly mix the ceramic powder and the metal organic framework material; 0.27g (2.4%) of polyethylene glycol (PEG400) was added to the mixture as a dispersant and ball milled for a period of time; after ball milling is carried out uniformly, 1g (9%) of water glass is added as a binder to carry out ball milling continuously, so as to obtain metal organic framework-ceramic composite slurry;
s5: pouring the metal organic framework-ceramic composite slurry into a forming mold, and drying at normal temperature for 24 hours to obtain a ceramic blank; and (3) calcining at 1450 ℃ for 20h to obtain the MOFs-based ceramic porous material.
The porosity of the composite porous material is 58 percent, the average pore diameter is 2.8nm, and the breaking strength is 491 MPa.
EXAMPLE III
S1: 3.76g of calcium acetate and 6.24g of 4,4' -bipyridine are respectively weighed in a 50mL beaker, 20mL of tetrahydrofuran is added into the beaker, the mixture is continuously stirred until the mixture is completely dissolved, and the mixture is reacted for 12 hours at 25 ℃; and collecting the obtained product through centrifugation and filtration, washing the product with tetrahydrofuran for 3 times, then transferring the product into a vacuum drying oven, and drying the product at 80 ℃ for 12 hours to finally obtain the zirconium-based metal organic framework material for later use.
S2: weighing 10g of n-butyl zirconium alcohol, dissolving in 15mL of isobutanol, and then adding 20 vol% of deionized water to promote the dissolution of a solute; stirring and mixing to generate transparent gel, sealing and aging for 12h, and drying at 40 ℃ for 12h to obtain xerogel;
s3: calcining the xerogel at 500 ℃ for 6 hours, and performing ball milling for 24 hours to obtain zirconia ceramic powder;
s4: dispersing 8g of zirconia ceramic powder and 4g (50%) of metal organic framework material in ethanol, and stirring for 1h to uniformly mix the ceramic powder and the metal organic framework material; 0.31g (2.6%) of polyvinylpyrrolidone was added to the mixture as a dispersant and ball milled for a period of time; after ball milling is carried out uniformly, 0.96g (8%) of polyvinyl butyral is added as a binder to continue ball milling, and the metal organic framework-ceramic composite slurry is obtained;
s5: pouring the metal organic framework-ceramic composite slurry into a forming mold, and drying at normal temperature for 24 hours to obtain a ceramic blank; and (3) calcining at 1400 ℃ for 25h to obtain the MOFs-based ceramic porous material.
The porosity of the composite porous material is 67%, the average pore diameter is 2.2nm, and the breaking strength is 451 MPa.
Example four
S1: weighing 4.07g of magnesium nitrate and 60g of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine respectively into a 50mL beaker, adding 45mL of N, N diethylformamide into the beaker, continuously stirring the mixture until the N, N diethylformamide is completely dissolved, and reacting the mixture at 60 ℃ for 6 hours; and collecting the obtained product through centrifugation and filtration, washing the product with N, N-diethylformamide for 3 times, transferring the product into a vacuum drying oven, and drying the product at the temperature of 80 ℃ for 12 hours to finally obtain the zirconium-based metal organic framework material for later use.
S2: weighing 10g of zirconium tert-butoxide and dissolving in 15mL of isopropanol, and then adding 20 vol% of deionized water to promote the dissolution of solute; stirring and mixing to generate transparent gel, sealing and aging for 8h, and drying at 40 ℃ for 12h to obtain xerogel; s3: calcining the xerogel at 550 ℃ for 2.5 hours, and performing ball milling for 24 hours to obtain zirconia ceramic powder;
s4: dispersing 8g of zirconia ceramic powder and 4.8g (60%) of metal organic framework material in ethanol, and stirring for 1 hour to uniformly mix the ceramic powder and the metal organic framework material; 0.36g (2.8%) of polyvinylpyrrolidone was added to the mixture as a dispersant and ball milled for a period of time; after ball milling is carried out uniformly, 0.9g (7%) of polyvinyl alcohol is added as a binder to continue ball milling, and the metal organic framework-ceramic composite slurry is obtained;
s5: pouring the metal organic framework-ceramic composite slurry into a forming die, and drying at 40 ℃ for 12h to obtain a ceramic blank; and (3) calcining at 1300 ℃ for 20h to obtain the MOFs-based ceramic porous material.
The porosity of the composite porous material is 79 percent, the average pore diameter is 5.9nm, and the breaking strength is 372 MPa.
EXAMPLE five
S1: respectively weighing 15g of zirconium chloride and 10.2g of tetra (4-carboxyphenyl) porphine into a 50mL beaker, adding 30mL of trichloromethane into the beaker, continuously stirring the beaker until the trichloromethane is completely dissolved, and reacting the mixture for 8 hours at 45 ℃; and collecting the obtained product through centrifugation and filtration, washing the product with trichloromethane for 3 times, transferring the product into a vacuum drying oven, and drying the product at 80 ℃ for 12 hours to finally obtain the zirconium-based metal organic framework material for later use.
S2: weighing 10g of zirconium isopropoxide, dissolving the zirconium isopropoxide in 15mL of methanol, and adding 20 vol% of deionized water to promote the dissolution of a solute; stirring and mixing to generate transparent gel, sealing and aging for 8h, and drying at 40 ℃ for 12h to obtain xerogel;
s3: calcining the xerogel at 600 ℃ for 2 hours, and performing ball milling for 24 hours to obtain zirconia ceramic powder;
s4: dispersing 8g of zirconia ceramic powder and 5.6g (70%) of metal organic framework material in ethanol, and stirring for 1 hour to uniformly mix the ceramic powder and the metal organic framework material; adding 0.4g (3%) terpineol as a dispersant to the mixture, and ball milling for a period of time; after ball milling is carried out uniformly, 0.82g (6%) of hydroxymethyl cellulose is added as a binder to carry out ball milling continuously, so as to obtain metal organic framework-ceramic composite slurry;
s5: pouring the metal organic framework-ceramic composite slurry into a forming die, and drying at 40 ℃ for 24 hours to obtain a ceramic blank; and calcining at 1200 ℃ for 30h to obtain the MOFs-based ceramic porous material.
The porosity of the composite porous material is 85%, the average pore diameter is 8.6nm, and the breaking strength is 345 MPa.
The MOFs material with a porous structure with a regular structure is used as a pore-forming agent to obtain metal organic framework-ceramic composite slurry; organic ligands in the MOFs material volatilize in the high-temperature calcination process of the ceramic blank prepared by the slurry, metal in the framework is bonded with zirconia in the ceramic in the form of oxide, and the growth of zirconia particles in the ceramic is inhibited, so that a porous structure is formed; in addition, the original pore channel structure in the MOFs material is reserved as the pore structure of the ceramic material, so that the prepared MOFs-based ceramic porous material has high porosity, uniform pore size and shape distribution, and higher strength.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a ceramic porous material based on MOFs is characterized by comprising the following steps:
s1: preparing a metal organic framework material by taking a metal precursor and an organic ligand as raw materials;
s2: preparing a ceramic gel: dispersing zirconium salt in a solvent, stirring and mixing to generate transparent gel, sealing and aging for a period of time, and drying to obtain xerogel;
s3: preparing ceramic powder: calcining the dried gel at high temperature, and performing ball milling to obtain ceramic powder;
s4: dispersing ceramic powder and a metal organic framework material in a solvent, and stirring to uniformly mix the ceramic powder and the metal organic framework material, wherein the addition amount of the metal organic framework material is 30-70 wt% of the ceramic powder; adding a dispersing agent into the mixture, adding a binder after ball milling is uniform, and continuing ball milling to obtain metal organic framework-ceramic composite slurry;
s5: and forming the metal organic framework-ceramic composite slurry and calcining at high temperature to obtain the MOFs-based ceramic porous material.
2. The method of claim 1, wherein the molar ratio of metal precursor to organic ligand is (1-10): (1-10), adding a solvent for dissolving, reacting for 4-12 h at 25-75 ℃, and preparing the metal organic framework material by a coprecipitation method.
3. The preparation method according to claim 2, wherein the metal precursor is one or more of sulfates, nitrates, acetates, halides or hydrates thereof of zirconium, aluminum, magnesium, calcium;
the organic ligand is any one or more of aromatic carboxylic acid ligand and nitrogen-containing heterocyclic ligand.
4. The method according to claim 1, wherein the zirconium salt is selected from any one of zirconium oxychloride, zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide, and zirconium isooctanoate.
5. The method according to claim 1 or 4, wherein the dispersant is selected from any one of polyethylene glycol, polyvinylpyrrolidone and terpineol, and the amount of the dispersant added is 2 wt% to 3 wt% of the total amount of the ceramic powder and the metal organic framework material.
6. The preparation method according to claim 1 or 4, wherein the binder is selected from any one of polyether sulfone resin, zinc phosphate, polyvinyl butyral, polyvinyl alcohol, starch, hydroxymethyl cellulose and water glass, and the addition amount of the binder is 6-10 wt% of the total amount of the ceramic powder and the metal organic framework material.
7. The method of claim 1, wherein in step S3, the calcination temperature is 500 ℃ to 600 ℃ and the calcination time is 1.5 to 3 hours.
8. The method of claim 1, wherein in step S5, the calcination temperature is 1200 ℃ to 1600 ℃ and the calcination time is 15 to 30 hours.
9. The method of claim 1, wherein in step S2, the solvent is selected from one or more of water, methanol, ethanol, isopropanol, ethylene glycol, isobutanol, and glycerol.
10. A MOFs-based ceramic porous material, characterized in that it is prepared by the preparation method according to any one of the preceding claims 1 to 9.
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| CN110589786A (en) * | 2019-10-16 | 2019-12-20 | 大连理工大学 | Based on three-dimensional porous transition metal carbide Ti3C2MXene composite nano structure and general preparation method thereof |
| CN112679965B (en) * | 2019-10-17 | 2022-10-11 | 中国石油化工股份有限公司 | Metal organic framework forming body and preparation method and application thereof |
| CN111672330B (en) * | 2020-06-16 | 2022-04-08 | 北京工业大学 | Method for preparing MOF nanofiltration membrane by adopting synthesis technology after thermal annealing |
| CN114292122A (en) * | 2021-12-09 | 2022-04-08 | 华南理工大学 | Preparation method of porous ceramic |
| CN114824301A (en) * | 2022-04-26 | 2022-07-29 | 国家电投集团氢能科技发展有限公司 | Anti-antipole nitrogen-carbon carrier catalyst for proton exchange membrane fuel cell and preparation method thereof |
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