CN109160824A - A kind of ceramic porous material and preparation method thereof based on MOFs - Google Patents
A kind of ceramic porous material and preparation method thereof based on MOFs Download PDFInfo
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Abstract
The invention discloses a kind of ceramic porous material and preparation method thereof based on MOFs, the preparation method is the following steps are included: S1: using metal precursor and organic ligand as raw material, preparing metal-organic framework materials；S2: dispersing zirconates in solvent, is stirred generation clear gel, after seal aging, is dried to obtain xerogel；S3: ceramic powder is obtained after xerogel high-temperature calcination and ball milling；S4: in a solvent by ceramic powder and metal-organic framework materials dispersion, dispersing agent is added, binder is added after ball milling and continues ball milling, obtains metal organic framework-Ceramic Composite slurry；S5: metal organic framework-Ceramic Composite slurry is poured into mold, is dried to obtain ceramic idiosome；High-temperature calcination obtains the ceramic porous material based on MOFs；The present invention obtains MOFs- ceramic composite porosity height and uniform pore diameter using MOFs material as pore creating material, and the zirconium oxide in oxide and ceramics formed after the sintering of MOFs material at high temperature bonds, and the porous material strength of formation is higher.
Description
Technical field
The invention belongs to technical field of ceramic material, more particularly, to a kind of porous ceramic film material based on MOFs and
Preparation method.
Background technique
Metal-organic framework materials (MOFs), also known as Porous coordination polymer, refer to inorganic metal or metal cluster with contain
The crystalline material that the multiple tooth organic ligand of nitrogen oxygen is formed by coordination key connection is a kind of with high-specific surface area, adjustable variable orifice
The porous material of road size, organic functional；Metal-organic framework materials have following excellent compared with conventional porous material
Gesture: (1) can by regulate and control length, the size of organic ligand effectively material texture performance (specific surface area, aperture) be controlled；(2)
Internal gutter system is flourishing, no dead volume, and pore structure is regular；Therefore, MOFs material is such as urged in chemical industry and other technical fields
The fields such as change, separation, the storage of magnetism, photoelectricity, gas and sensing show wide application scenarios.
Porous ceramics is a kind of ceramic material with hatch bore diameter prepared through overmolding and special high-sintering process,
Have many advantages, such as high temperature resistant, high pressure, antiacid alkali and organic media corrosion, good biologically inert, long service life, is suitable for each
The filtering of kind of medium with separate, high pressure gas exhaust noise silencing, gas are distributed and the fields such as electrolyte membrane, due to having good machine concurrently
Tool performance, chemical and thermal stability, as a kind of green material, it is widely used in wastewater treatment, high temperature air filtration, sound-absorbing
The fields such as material, heat-insulating heat-preserving material.
There are many preparation methods of porous ceramics, such as: addition pore creating material method, Polymeric sponge method and foaming.Add
Add pore creating material method be using organic pore-forming agents at high temperature after-flame or volatilization and hole is left in ceramic body, this method work
Skill is simple, adjustable porosity section, but porosity is low, and pore size and distribution of shapes are uneven, and can exhaust emission in preparation process
Object.Polymeric sponge method is using the special construction of the three-dimensional netted skeleton of aperture possessed by organic foam, by what is prepared
Slurry is evenly coated on organic foam reticulate body, is burnt up Organic Foam Material after dry and is obtained a kind of screen like and porous ceramic.
The intensity of organism and elasticity have a significant impact to the structure and performance of porous material in this method preparation process, obtained porous
Material haves the shortcomings that intensity is not high, while being also easy to produce Remained mass and toxic gas, pollutes the environment.Foaming preparation
Porous ceramics hole rate can generally be greater than 70%, and foaming can generally add some organic matters, solid after ceramic slurry foaming
Slurrying material, these organic matters can all burn in sintering or volatilization, pollute environment.In short, existing porous ceramic film material exists
Porosity is not high, intensity is not high, the defect of pore size and distribution of shapes unevenness.
Summary of the invention
For at least one defect or Improvement requirement of the prior art, the present invention provides a kind of, and the ceramics based on MOFs are more
Porous materials and preparation method thereof obtain MOFs- ceramic composite porosity height and aperture are equal using MOFs material as pore creating material
It is even；By organic ligand used in adjusting MOFs material, the size in duct can be designed and be regulated and controled, it is porous to adapt to
Demand of the ceramic material to different pore size is not high, strong its object is to solve porosity existing for existing porous ceramic film material
Spend the problem of not high, pore size and distribution of shapes unevenness.
To achieve the above object, according to one aspect of the present invention, a kind of ceramic porous material based on MOFs is provided
Preparation method, comprising the following steps:
S1: using metal precursor and organic ligand as raw material, metal-organic framework materials are prepared；
S2: preparation Ceramic gel: dispersing zirconates in solvent, be stirred generation clear gel, and one section of seal aging
After time, it is dried to obtain xerogel；The ceramic slurry prepared using gel method is not easy to reunite, and stability is more preferable.
S3: it prepares ceramic powder: by xerogel high-temperature calcination, obtaining ceramic powder after ball milling；
S4: in a solvent by ceramic powder and metal-organic framework materials dispersion, stirring is uniformly mixed it, and metal is organic
The additive amount of framework material is the 30wt%-70wt% of ceramic powder；Dispersing agent is added into mixture, is added after ball milling
Binder continues ball milling, obtains metal organic framework-Ceramic Composite slurry；
Dispersing agent, which is added, can be improved the stability of slurry, and particle is prevented to reunite again, and then improve the solid content of slurry；It is viscous
Knot agent can be improved the intensity of green body, and prevent powder segregation.
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, obtains ceramic idiosome after dry；High temperature is forged
The ceramic idiosome is burnt, the ceramic porous material based on MOFs is obtained.
Preferably, the molar ratio of above-mentioned preparation method, metal precursor and organic ligand is (1-10): (1-10) adds
Enter solvent dissolution, 4~12h is reacted at 25 DEG C~75 DEG C, metal-organic framework materials are prepared by coprecipitation.
Preferably, above-mentioned preparation method, metal precursor be zirconium, aluminium, magnesium, the sulfate of calcium, nitrate, acetate,
One or more of halide salt or its hydrate；Aluminium, magnesium, three kinds of metal cations of calcium radius and ceramics in zirconium metal ion
Radius differ less than 12%, can be as the crystal form of zirconium oxide formed after stabilizer stabilization ceramic post sintering；Using zirconium metal
The MOFs material of precursor preparation, the zirconium oxide formed after sintering is consistent with the ingredient of zirconium oxide in ceramics and crystal form, Neng Gouti
The adaptability of high composite material.
The organic ligand is aromatic carboxylic acids ligand, nitrogen-containing heterocycle class ligand is any one or more of.
Preferably, above-mentioned preparation method, zirconates are selected from basic zirconium chloride, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide, different
Any one of propyl alcohol zirconium, zirconium iso-octoate.
Preferably, above-mentioned preparation method, dispersing agent appointing in polyethylene glycol, polyvinylpyrrolidone, terpinol
One kind, additional amount are the 2wt%-3wt% of ceramic powder and metal-organic framework materials total amount.
Preferably, above-mentioned preparation method, binder are selected from polyethersulfone resin, trbasic zinc phosphate, polyvinyl butyral, poly- second
Any one of enol, starch, hydroxymethyl cellulose, waterglass, additive amount are ceramic powder and metal-organic framework materials
The 6wt%-10wt% of total amount.
Preferably, above-mentioned preparation method, in step S3, the calcination temperature is 500 DEG C -600 DEG C, and calcination time is
1.5-3h；
Preferably, above-mentioned preparation method, in step S5, the calcination temperature is 1200 DEG C -1600 DEG C, and calcination time is
15-30h。
Preferably, above-mentioned preparation method, in step S2, solvent is selected from water, methanol, ethyl alcohol, isopropanol, ethylene glycol, isobutyl
Any one or more of alcohol, glycerine.
Other side according to the invention provides a kind of ceramic porous material based on MOFs, uses above-mentioned
Preparation method described in one is prepared.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) ceramic porous material and preparation method thereof provided by the invention based on MOFs, with the more of compound with regular structure
The MOFs material of pore structure obtains metal organic framework-Ceramic Composite slurry as pore creating material；The ceramic embryo prepared with the slurry
Organic ligand of the body in high-temperature burning process in MOFs material volatilizees, and the metal in skeleton is in the form of the oxide and in ceramics
Zirconium oxide bond and inhibit the growth of the zirconia particles in ceramics, to form porous structure；In addition, MOFs material Central Plains
Some cellular structures are retained as the pore structure of ceramic material, therefore the ceramic porous material hole based on MOFs being prepared
Gap rate height, pore size and distribution of shapes are uniform, and the porous ceramic film material intensity of formation is higher.
(2) ceramic porous material and preparation method thereof provided by the invention based on MOFs is formed after the sintering of MOFs material
Oxide can also be used as sintering aid, for stablizing the crystal form of zirconium oxide in ceramics, and make ceramics burning during the sintering process
It ties technique and liquid-phase sintering is changed by solid-phase sintering, to reduce the sintering temperature of ceramics, save the cost.
(3) ceramic porous material and preparation method thereof provided by the invention based on MOFs, by adjusting in MOFs material
The organic ligand used can be designed and regulate and control to the size in duct, to adapt to porous ceramic film material to different pore size
Demand.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below each other it
Between do not constitute conflict and can be combined with each other.
Embodiment one
S1: the zirconium chloride of 9.4g and the trimesic acid of 6g are weighed respectively in the beaker of 50mL, 30mL is added thereto
N,N-Dimethylformamide, continue stirring until and be completely dissolved, react 4h at 50 DEG C；Pass through what is be centrifuged, be collected by filtration
Product is washed 3 times with n,N-Dimethylformamide, then product is transferred in vacuum oven, dry under 80 degrees Celsius
It is spare to finally obtain zirconium-based metallic organic framework material by 12h.
S2: the ZrOCl of 10g is weighed2·8H2O is dissolved in the ethyl alcohol of 15mL, adds the deionized water of 20vol%, is used
To promote the dissolution of solute；It is stirred generation clear gel, after seal aging 8h, dry 12h obtains xerogel at 40 DEG C；
S3: xerogel is calcined 1.5 hours at 600 DEG C, ball milling obtains zirconia ceramics powder afterwards for 24 hours；
S4: in ethanol by 8g zirconia ceramics powder and the dispersion of 2.4g (30%) metal-organic framework materials, 1h is stirred
It is uniformly mixed ceramic powder with metal-organic framework materials；0.2g (2%) polyethylene glycol (PEG400) is added into mixture
As dispersing agent, ball milling is for a period of time；1.04g (10%) polyethersulfone resin is added after ball milling as binder and continues ball
Mill, obtains metal organic framework-Ceramic Composite slurry；
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, and drying obtains ceramic embryo for 24 hours under room temperature
Body；The high-temperature calcination 15h at 1600 DEG C, obtains the ceramic porous material based on MOFs.
Using the porosity for impregnating ceramic porous material of the medium method test based on MOFs: first with vernier caliper measurement
The volume v of sample weighs up the aerial weight m of dry sample1, being then immersed in distilled water makes its saturation, i.e., using heating
Rouse the hole that such as method makes medium adequately fill up porous material.After being sufficiently saturated in sample immersion certain time, sample is removed, gently
Dab the medium of specimen surface, then electronic scale weighed amount aerial gross mass m at this time2, calculated by lower formula more
The porosity of Porous materials: f=(m2-m1)/vρWater；Root, which accordingly measures, to be obtained the porosity of the ceramic porous material based on MOFs and is
45%.
Specific surface area and the aperture of measurement composite porous material are tested by nitrogen adsorption desorption: by synthesis at 150 DEG C
Composite porous material Fruit storage 8h measures nitrogen Adsorption and desorption isotherms, measuring specific surface area is at 77K
1497m2.g-1, average pore size 0.9nm.
Using the method for three point bending test, the pottery based on MOFs is tested on ALJ-02B type hand power screw formula test machine
The flexural strength of porcelain porous material；It is 601MPa that test, which obtains its flexural strength,.
Embodiment two
S1: weighing 2,2'- bipyridyl -5,5'- dicarboxylic acids of 9.67 aluminum sulfate and 6.8g in the beaker of 50mL respectively, to
The dehydrated alcohol of 30mL is wherein added, continues stirring until and is completely dissolved, react 4h at 75 DEG C；By being centrifuged, being collected by filtration
The product arrived is washed 3 times with dehydrated alcohol, then product is transferred in vacuum oven, dry 12h under 80 degrees Celsius, most
It is spare that zirconium-based metallic organic framework material is obtained eventually.
S2: the zirconium-n-propylate for weighing 10g is dissolved in the glycerine of 15mL, is added the deionized water of 20vol%, is used to
Promote the dissolution of solute；It is stirred generation clear gel, after seal aging 10h, dry 12h obtains xerogel at 40 DEG C；
S3: xerogel is calcined 2 hours at 500 DEG C, ball milling obtains zirconia ceramics powder afterwards for 24 hours；
S4: in ethanol by 8g zirconia ceramics powder and the dispersion of 3.2g (40%) metal-organic framework materials, 1h is stirred
It is uniformly mixed ceramic powder with metal-organic framework materials；0.27g (2.4%) polyethylene glycol is added into mixture
(PEG400) it is used as dispersing agent, ball milling is for a period of time；1g (9%) waterglass is added after ball milling as binder and continues ball
Mill, obtains metal organic framework-Ceramic Composite slurry；
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, and drying obtains ceramic embryo for 24 hours under room temperature
Body；The high-temperature calcination 20h at 1450 DEG C, obtains the ceramic porous material based on MOFs.
Test obtains the porosity 58% of the composite porous material, average pore size 2.8nm, flexural strength 491MPa.
Embodiment three
S1: the calcium acetate of 3.76g and 4, the 4'- bipyridyl of 6.24g are weighed respectively in the beaker of 50mL, is added thereto
The tetrahydrofuran of 20mL, continues stirring until and is completely dissolved, and reacts 12h at 25 DEG C；Pass through the production for being centrifuged, being collected by filtration
Object is washed 3 times with tetrahydrofuran, then product is transferred in vacuum oven, and dry 12h, finally obtains under 80 degrees Celsius
Zirconium-based metallic organic framework material is spare.
S2: the zirconium-n-butylate for weighing 10g is dissolved in the isobutanol of 15mL, is added the deionized water of 20vol%, is used to
Promote the dissolution of solute；It is stirred generation clear gel, after seal aging 12h, dry 12h obtains xerogel at 40 DEG C；
S3: xerogel is calcined 6 hours at 500 DEG C, ball milling obtains zirconia ceramics powder afterwards for 24 hours；
S4: in ethanol by 8g zirconia ceramics powder and the dispersion of 4g (50%) metal-organic framework materials, stirring 1h makes
Ceramic powder is uniformly mixed with metal-organic framework materials；0.31g (2.6%) polyvinylpyrrolidone is added into mixture to make
For dispersing agent, ball milling is for a period of time；0.96g (8%) polyvinyl butyral is added after ball milling as binder and continues ball
Mill, obtains metal organic framework-Ceramic Composite slurry；
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, and drying obtains ceramic embryo for 24 hours under room temperature
Body；The high-temperature calcination 25h at 1400 DEG C, obtains the ceramic porous material based on MOFs.
Test obtains the porosity 67% of the composite porous material, average pore size 2.2nm, flexural strength 451MPa.
Example IV
S1: the magnesium nitrate of 4.07g and 2,4,6- tri- (4- carboxyl phenyl) -1,3,5- triazine of 60g are weighed respectively in 50mL
Beaker in, the N of 45mL is added thereto, N diethylformamide continues stirring until and be completely dissolved, and reacts 6h at 60 DEG C；It is logical
The product for being centrifuged, being collected by filtration is crossed, with N, N diethylformamide is washed 3 times, and product is then transferred to vacuum oven
In, dry 12h, it is spare to finally obtain zirconium-based metallic organic framework material under 80 degrees Celsius.
S2: the zirconium tert-butoxide for weighing 10g is dissolved in the isopropanol of 15mL, is added the deionized water of 20vol%, is used to
Promote the dissolution of solute；It is stirred generation clear gel, after seal aging 8h, dry 12h obtains xerogel at 40 DEG C；S3:
Xerogel is calcined 2.5 hours at 550 DEG C, ball milling obtains zirconia ceramics powder afterwards for 24 hours；
S4: in ethanol by 8g zirconia ceramics powder and the dispersion of 4.8g (60%) metal-organic framework materials, 1h is stirred
It is uniformly mixed ceramic powder with metal-organic framework materials；0.36g (2.8%) polyvinylpyrrolidone is added into mixture
As dispersing agent, ball milling is for a period of time；0.9g (7%) polyvinyl alcohol is added after ball milling as binder and continues ball milling, obtains
To metal organic framework-Ceramic Composite slurry；
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, and dry 12h obtains ceramic embryo at 40 DEG C
Body；The high-temperature calcination 20h at 1300 DEG C, obtains the ceramic porous material based on MOFs.
Test obtains the porosity 79% of the composite porous material, average pore size 5.9nm, flexural strength 372MPa.
Embodiment five
S1: porphines is in the beaker of 50mL for the zirconium chloride and four (the 4- carboxy phenyls) of 10.2g for weighing 15g respectively, thereto
The chloroform of 30mL is added, continues stirring until and is completely dissolved, react 8h at 45 DEG C；Pass through what is be centrifuged, be collected by filtration
Product is washed 3 times with chloroform, then product is transferred in vacuum oven, dry 12h under 80 degrees Celsius, final
It is spare to zirconium-based metallic organic framework material.
S2: the zirconium iso-propoxide for weighing 10g is dissolved in the methanol of 15mL, adds the deionized water of 20vol%, for promoting
Into the dissolution of solute；It is stirred generation clear gel, after seal aging 8h, dry 12h obtains xerogel at 40 DEG C；
S3: xerogel is calcined 2 hours at 600 DEG C, ball milling obtains zirconia ceramics powder afterwards for 24 hours；
S4: in ethanol by 8g zirconia ceramics powder and the dispersion of 5.6g (70%) metal-organic framework materials, 1h is stirred
It is uniformly mixed ceramic powder with metal-organic framework materials；0.4g (3%) terpinol is added into mixture as dispersing agent,
Ball milling is for a period of time；0.82g (6%) hydroxymethyl cellulose is added after ball milling as binder and continues ball milling, obtains metal
Organic backbone-Ceramic Composite slurry；
S5: metal organic framework-Ceramic Composite slurry is poured into molding die, and drying obtains ceramic embryo for 24 hours at 40 DEG C
Body；The high-temperature calcination 30h at 1200 DEG C, obtains the ceramic porous material based on MOFs.
Test obtains the porosity 85% of the composite porous material, average pore size 8.6nm, flexural strength 345MPa.
Ceramic porous material and preparation method thereof provided by the invention based on MOFs, with the porous knot with compound with regular structure
The MOFs material of structure obtains metal organic framework-Ceramic Composite slurry as pore creating material；Existed with ceramic idiosome prepared by the slurry
Organic ligand volatilization in high-temperature burning process in MOFs material, metal in skeleton in the form of the oxide with the oxygen in ceramics
Change zirconium to bond and inhibit the growth of the zirconia particles in ceramics, to form porous structure；In addition, original in MOFs material
The cellular structure ceramic porous material hole based on MOFs that is retained as the pore structure of ceramic material, therefore is prepared
Rate height, pore size and distribution of shapes are uniform, and the porous ceramic film material intensity of formation is higher.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the ceramic porous material based on MOFs, which comprises the following steps:
S1: using metal precursor and organic ligand as raw material, metal-organic framework materials are prepared；
S2: it preparation Ceramic gel: disperses zirconates in solvent, is stirred generation clear gel, seal aging is for a period of time
Afterwards, it is dried to obtain xerogel；
S3: it prepares ceramic powder: by xerogel high-temperature calcination, obtaining ceramic powder after ball milling；
S4: in a solvent by ceramic powder and metal-organic framework materials dispersion, stirring is uniformly mixed it, metal organic framework
The additive amount of material is the 30wt%-70wt% of ceramic powder；Dispersing agent is added into mixture, bonding is added after ball milling
Agent continues ball milling, obtains metal organic framework-Ceramic Composite slurry；
S5: after metal organic framework-Ceramic Composite sizing material forming and high-temperature calcination, the ceramic porous material based on MOFs is obtained
Material.
2. preparation method as described in claim 1, which is characterized in that the metal precursor and the molar ratio of organic ligand are
(1-10): (1-10) is added solvent dissolution, 4~12h is reacted at 25 DEG C~75 DEG C, it is organic to prepare metal by coprecipitation
Framework material.
3. preparation method as claimed in claim 2, which is characterized in that the metal precursor is the sulfuric acid of zirconium, aluminium, magnesium, calcium
One or more of salt, nitrate, acetate, halide salt or its hydrate；
The organic ligand is aromatic carboxylic acids ligand, nitrogen-containing heterocycle class ligand is any one or more of.
4. preparation method as described in claim 1, which is characterized in that the zirconates is selected from basic zirconium chloride, zirconium-n-propylate, positive fourth
Any one of alcohol zirconium, zirconium tert-butoxide, zirconium iso-propoxide, zirconium iso-octoate.
5. preparation method as described in claim 1 or 4, which is characterized in that the dispersing agent is selected from polyethylene glycol, polyethylene pyrrole
Any one of pyrrolidone, terpinol, additional amount are the 2wt%- of ceramic powder and metal-organic framework materials total amount
3wt%.
6. preparation method as described in claim 1 or 4, which is characterized in that the binder is selected from polyethersulfone resin, phosphoric acid
Any one of zinc, polyvinyl butyral, polyvinyl alcohol, starch, hydroxymethyl cellulose, waterglass, additive amount are ceramics
The 6wt%-10wt% of powder and metal-organic framework materials total amount.
7. preparation method as described in claim 1, which is characterized in that in step S3, the calcination temperature is 500 DEG C -600
DEG C, calcination time 1.5-3h.
8. preparation method as described in claim 1, which is characterized in that in step S5, the calcination temperature is 1200 DEG C -1600
DEG C, calcination time 15-30h.
9. preparation method as described in claim 1, which is characterized in that in step S2, solvent is selected from water, methanol, ethyl alcohol, isopropyl
Any one or more of alcohol, ethylene glycol, isobutanol, glycerine.
10. a kind of ceramic porous material based on MOFs, which is characterized in that described in any item using the claims 1-9
Preparation method is prepared.
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