CN106587077B - Three-dimensional ordered macroporous-mesopore oxide material of one kind and preparation method thereof - Google Patents
Three-dimensional ordered macroporous-mesopore oxide material of one kind and preparation method thereof Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
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Abstract
The present invention relates to a kind of preparation methods of three-dimensional ordered macroporous-mesoporous material.The present invention provides a kind of preparation methods of three-dimensional ordered macroporous-mesoporous material, first, the material is that have three-dimensional ordered macroporous and ordered mesopore structure oxide material, wherein, the oxide material is any one in silica, titanium dioxide, alundum (Al2O3) and transition metal oxide, the three-dimensional ordered macroporous average pore size is 50nm~1 μm, and order mesoporous average pore size is 2~30nm；Secondly, the method which is mainly combined using soft or hard template, wherein the hard template uses poly (methyl methacrylate) micro-sphere for template, and soft template uses P123, CTAB, F127 for soft template.The advantages of preparation method of three-dimensional ordered macroporous-mesoporous material according to the present invention has preparation method without special installation and harsh conditions, simple for process, controllability is strong, large-scale production highly practical, easy to implement, has practicability.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly to a kind of three-dimensional ordered macroporous-mesopore oxide material
Material and preparation method thereof.
Background technology
Porous material as a kind of emerging Porous materials, because it is low with relative density, specific strength is high, large specific surface area,
Permeability is good, strong adsorption, porosity are big, light-weight, sound insulation, it is heat-insulated many advantages, such as, cause the extensive concern of people with
Research.According to the standard of International Union of Pure and Applied Chemistry (IUPAC), porous material can be divided into three classes：Aperture ruler
It is very little to be known as poromerics in 2nm materials below；Material of the aperture size in 2-50nm is known as mesoporous material；Aperture size is more than
The material of 50nm is known as large pore material (Xu Ruren, Pang Wenqin molecular sieves and porous material chemistry;M]Beijing：Scientific publication
Society).As people go deep into porous material research, porous material oneself through obtaining the fields such as adsorbing, separate, analyze, be catalyzed
It is widely applied.In recent years, the getting worse of environmental pollution, research of the porous material in terms of environmental pollution improvement oneself through at
For current porous material application field one of research hotspot.With going deep into for research, people to the performance of porous material and
More stringent requirements are proposed for function, how to design and prepare the height that the porous material with special nature and function causes people
Degree is paid attention to.
Foramen magnum-mesoporous material (Hierarchical porous materials) refer to it is a kind of by macropore, mesoporous form
The porous material of compound pore passage structure has uniform sequential macropore duct (50nm or more) and uniform sequential meso-hole structure
(2-50nm), higher Kong Rong (theoretical porosities;74%) diversity (simple oxide, the composite oxides formed with skeleton
With solid solution etc.) the features such as (F.Li, Z.W.Nicholas, et al.Langmuir, 2007,23,3996.).Unique macropore
Duct (can reach several microns) and higher Kong Rong compensates for previous aperture and meso-porous molecular sieve material makes it difficult for macromolecular to enter
The shortcomings that duct, makes it have broad application prospects in catalysis, filtering and separation of macromolecular etc.；It is mesoporous simultaneously can be with
It works to small molecule, or passes through size distinction size selection or morphology selection property (filtering or centrifugation).In addition, hole
The diversity of wall skeleton composition, promotes the preparation of various foramen magnum-mesoporous oxides, to prepare the novel work(of more good characteristics
It can make contributions in terms of material.Foramen magnum-mesoporous oxide material because its unique pore passage structure and can modulation pore size etc.
Advantage has important application prospect in various fields, can be widely applied to agent carrier, photonic crystal, filtering and separation material
Material and electrode material etc., cause the extensive interest of people and concern.
Currently, the preparation of foramen magnum-mesoporous material is mainly or using multicomponent template.Utilize two or more soft templates
Presoma is immersed in multicomponent template by the mode that agent and hard mould agent are used in conjunction with, and is prepared with foramen magnum-mesoporous structure
Material (A.Stein, F.Li, et al.Chem.Mater., 2008,20,649.).Macropore-is prepared using multicomponent template
Mesoporous material, first, can directly presoma/mesoporous template be mixed with polymer microballoon and is co-deposited, second is that by forerunner
Impregnated polymer microsphere template after body/mesoporous template mixing.Wherein, the product degree of order of first method is not fine, and meeting
Make not to be connected to inside duct, the ordered arrangement of polymer microballoon can be influenced by being primarily due to mesoporous template.For example, using different grains
Foramen magnum-mesoporous material structure is complete made from diameter microballoon self assembly, and aperture is uniform, on hole wall it is mesoporous in three-dimensional order arrangement and
Aperture adjustability is good, duct connectivity it is strong (J.J.Wang, Q.L.W.Knoll, et al.J.Am.Chem.Soc., 2006,128,
15606).But this method, there is significant limitation, the different microballoon of two kinds of grain sizes will carry out in precursor solution
Efficient self assembly is a prodigious problem.Big ball is set to be formed tightly packed, bead is filled in big ball gap, not only difficult
Degree is big, and time-consuming.A variety of methods can be used to accelerate its assembling in single microballoon, and it is heavy such as to evaporate construction from part, centrifugal process, gravity
Drop method, electrophoresis etc..But the microballoon of two kinds of different-grain diameters assembles simultaneously, and above method is all not applicable.In addition, also there is document report
Prepare the other methods of foramen magnum-mesoporous material.In air-liquid hydrogen bubble template, pass through the bubble of bubbling process generation
As template generation macropore dimensional structure, supermolecular module is used to generate meso-hole structure.This method at a low price and can be prepared
With the macroporous structure reliably controlled while keeping the material of good meso-hole structure.But obtained blocky porous material exists
Random holes are showed on macropore dimension level.
In view of the foregoing, the method to prepare foramen magnum-mesoporous material more common at present is in polymeric colloid crystalline substance
Multistage template of one or two kinds of surfactants as soft template is introduced in body stencil apertures.This surfactant is main
It is block copolymer.Introduce block copolymer has very extensive application prospect as soft template, is because they are cheap easy
, it can be provided for material relatively regular mesoporous.Block copolymer is introduced there are mainly two types of scheme, a kind of scheme be introduce it is single
Colloid microballoon or microballoon cluster, suspension either powder, into surfactant and the mixed system of source metal.Another kind side
Case is that precursor solution is filled into colloidal crystal template, and this method has been widely used for preparing foramen magnum-mesoporous material.
Invention content
One of the objects of the present invention is to provide a kind of three-dimensional ordered macroporous-mesopore oxide material, the material be with
Three-dimensional ordered macroporous and ordered mesopore structure oxide material, wherein three-dimensional ordered macroporous average pore size is 50nm-1 μm,
Order mesoporous average pore size is 2-30nm.
The second object of the present invention is to provide a kind of polymethyl methacrylate (PMMA) microballoon and colloidal crystal mould
The microballoon of the preparation method of plate, this method synthesis has uniform particle diameter, the advantage that synthetic method is simple and success rate is high；
The third object of the present invention is to provide a kind of side simply preparing three-dimensional ordered macroporous-mesopore oxide material
Method, the preparation process is simple, at low cost, requirement that is environmentally safe, meeting Green Chemistry；
In order to achieve the above objectives, present invention firstly provides a kind of simple methods for preparing PMMA colloidal crystal templates.
This method comprises the following steps：
120-240mL distilled water is taken, is added in round-bottomed flask, after heating water bath to 60-90 DEG C of temperature, 60-120mL is added
The 0.3- weighed in advance is added under rotating speed appropriate after stirring 10-30min in refined monomers methyl methacrylate (MMA)
The initiator K of 1.2g2S2O8(being heated to 20-60mL water dissolutions mutually synthermal).Lasting stirring is lower to react 1-5h, obtains milky white
Color suspension.
Since the PMMA microsphere suspension liquid energy of preparation voluntarily precipitates, microballoon lotion is placed in Flat bottom container, with 40-80 DEG C
Temperature in drying box slow evaporation, depositing them obtain colloidal crystal template, but overlong time, be not suitable for experimental conditions.
Therefore, the colloidal crystal template of PMMA is formed by accelerating centrifugation in the present invention, the specific steps are：PMMA lotion microballoons are put
It sets in centrifuge tube, 1-10h is centrifuged with the rotating speed of 1000-10000rpm/min.After centrifugation, the clear liquid on test tube upper layer is removed,
It is left without water droplet until test tube is inverted a period of time.Then test tube is dried in 20-50 DEG C of drying box, the white chunks of gained
Substance is PMMA microsphere colloidal crystal template.
The present invention also provides a kind of methods for the oxide material simply preparing three-dimensional ordered macroporous-meso-hole structure.
Its step are as follows：
Weigh the presoma TEOS of 2.08~8.32g oxide materials, the HCl of 1~5mL2mol/L, 1~5mLH2O, 2~
8mL ethyl alcohol and the mixing of 2.3~5.6g soft templates are dissolved in reactor, and wherein the volume ratio of water and ethyl alcohol is 1:0.5~1:2；
The volume ratio of water and hydrochloric acid is 1:0.5~1:2；The presoma TEOS of oxide material and the mass ratio of soft template are 1:0.25
~1:2；Mixing is dissolved in reactor.By above-mentioned mixed liquor be placed under magnetic stirring 25-45 DEG C of stirring in water bath 1-6h obtain it is uniform
Transparent precursor solution, after the colloidal crystal template 1-3h for using it as maceration extract impregnation drying, filter removal it is extra before
Liquid solution is driven, constant temperature 12-48h is dried in 30-60 DEG C of baking oven by remaining residue solid matter, is obtained containing presoma Colloidal crystals
Body template.Sample after drying is fitted into glass tube, 400-1000 DEG C is warming up to using tube furnace in the case where being passed through air conditions,
Template agent removing is removed in the roasting of constant temperature certain time, the air velocity 60-100mL/min in roasting process, heating rate be 1-2 DEG C/
min.After dropping to room temperature, sample sieving separating is obtained into the oxide material of three-dimensional ordered macroporous-meso-hole structure.
Description of the drawings
Fig. 1 is the stereoscan photograph of PMMA microsphere prepared by embodiment 1；
Fig. 2 is the grain size distribution of PMMA microsphere prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of PMMA colloidal crystal templates prepared by embodiment 2；
Fig. 4 is 3DOM-m SiO prepared by embodiment 32Stereoscan photograph；
Fig. 5 is 3DOM-m SiO prepared by embodiment 32Transmission electron microscope photo；
Fig. 6 is 3DOM-m SiO prepared by embodiment 42Stereoscan photograph；
Fig. 7 is 3DOM-m SiO prepared by embodiment 42Transmission electron microscope photo；
Fig. 8 is 3DOM-m SiO prepared by embodiment 52Stereoscan photograph；
Fig. 9 is 3DOM-m SiO prepared by embodiment 52Transmission electron microscope photo；
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Embodiment 1
Specific embodiment according to the present invention, polymethyl methacrylate template and three-dimensional ordered macroporous-mesoporous oxidation
Method comprising the following steps progress may be used in the preparation of object：
Specific implementation 1
Monodisperse polymer micro-sphere is prepared using surfactant- free emulsion polymerization
240mL distilled water is taken, is added in round-bottomed flask, after heating water bath to 80 DEG C of temperature, the refined MMA of 120mL are added,
After stirring 20min under rotating speed appropriate, the initiator K of the 0.6g weighed in advance is added2S2O8It (is heated to 40mL water dissolutions
It is mutually synthermal).Lasting stirring is lower to react 2h, obtains milky suspension.Obtained microspherulite diameter is than more uniform, using this micro-
Ball can make the metal oxide finally obtained have preferable form and structure.As shown in Figure 1, synthesized PMMA microsphere
Uniform particle diameter, dispersibility is preferable, and particle diameter distribution is relatively narrow, and average grain diameter is at 449nm or so (shown in Fig. 2).
Specific implementation 2
Colloidal crystal template is prepared using centrifugal deposition method
Microballoon lotion is placed in centrifuge tube, closelypacked Colloidal crystals are obtained with the rotating speed centrifugal treating 10h of 3000rpm
Body template, or microballoon lotion is placed in Flat bottom container, with 60 DEG C of temperature, slow evaporation, depositing them obtain in drying box
To colloidal crystal template.The scanning electron microscope (SEM) photograph of synthesized colloidal crystal is as shown in figure 3, hexagonal row is presented in colloidal crystal template
Cloth forms the close-packed structure based on face-centered cubic (fcc).
Specific implementation 3
Three-dimensional ordered macroporous-meso-porous titanium dioxide silicon carrier (3DOM-m SiO are prepared using colloidal crystal template method2)
Stoichiometrically weigh 4.16~8.32g TEOS, the HCl of 1~2.5mL2mol/L, 1~2.5mL H2O, 2~
5mL ethyl alcohol and 3.7~4.6g polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) component, mixing
It is dissolved in reactor.Above-mentioned mixed liquor is placed in 45 DEG C of stirring in water bath 3h under magnetic stirring and obtains homogeneous and transparent SiO2Presoma
Solution is then allowed to stand 1h, using above-mentioned clear solution as the colloidal crystal template 2h of maceration extract impregnation drying after, filter removal
Extra precursor solution, by remaining residue solid matter, constant temperature 12h is dried in 50 DEG C of baking ovens, is obtained containing presoma Colloidal crystals
Body template.Sample after drying is fitted into glass tube, target temperature is warming up to using tube furnace in the case where being passed through air conditions, it is permanent
Template agent removing is removed in the roasting of warm certain time, 80~100mL/min of air velocity in roasting process, and heating rate is 1~2 DEG C/
min.After dropping to room temperature, sample sieving separating is obtained into the SiO of three-dimensional ordered macroporous-meso-hole structure2Oxide carrier material.Figure
4 be 3DOM-m SiO2Scanning electron microscope (SEM) photograph, as seen from Figure 4 colloidal crystal template method prepare SiO2Carrier forms regular
The perforation of three-dimensional ordered macroporous structure duct three-dimensional order, aperture is uniform, and pore wall thickness is uniform, and it is clear to have below each macropore
Visible aperture window is interconnected to form the topological structure of three-dimensional perforation between the window of hole.The diameter of macropore is about 310nm, small
The diameter of hole window is about 100nm；Pore wall thickness is about uniformly 50nm.Fig. 5 is 3DOM-m SiO2Transmission electron microscope picture, by scheming
It can be seen that the SiO of three-dimensional ordered macroporous structure2On hole wall there are regular its pore diameter range of orderly meso-hole structure be 2~
10nm。
Specific implementation 4
Three-dimensional ordered macroporous-meso-porous titanium dioxide silicon carrier 3DOM-m SiO are prepared using colloidal crystal template method2
Stoichiometrically weigh 4.16~8.32g TEOS, the HCl of 1~2.5mL 2mol/L, 1~2.5mL H2O, 2
~5mL ethyl alcohol and 3.7~4.6g P123 components, mixing are dissolved in reactor.Above-mentioned mixed liquor is placed in 45 under magnetic stirring
DEG C stirring in water bath 3h obtains homogeneous and transparent SiO2Precursor solution is then allowed to stand 2h, using above-mentioned clear solution as maceration extract
After the colloidal crystal template 2h of impregnation drying, filters and remove extra precursor solution, remaining residue solid matter is dried at 50 DEG C
Constant temperature 12h is dried in case, is obtained containing presoma colloidal crystal template.Sample after drying is fitted into glass tube, is being passed through
It is warming up to target temperature using tube furnace under air conditions, template agent removing is removed in the roasting of constant temperature certain time, hollow in roasting process
80~100mL/min of gas velocity, heating rate are 1~2 DEG C/min.After dropping to room temperature, sample sieving separating, which is obtained three-dimensional, to be had
The SiO of the foramen magnum-mesoporous structure of sequence2Oxide carrier material.Fig. 6 is 3DOM-m SiO2Scanning electron microscope (SEM) photograph, as seen from Figure 4
SiO prepared by colloidal crystal template method2Carrier forms regular three-dimensional ordered macroporous structure duct three-dimensional order perforation, aperture
Uniform, pore wall thickness is uniform, has high-visible aperture window below each macropore, and being interconnected to form three-dimensional between the window of hole passes through
Logical topological structure.The diameter of macropore is about 310nm, and the diameter of aperture window is about 100nm；Pore wall thickness is about uniformly
50nm.Fig. 7 is 3DOM-m SiO2Transmission electron microscope picture, deposited on the SiO2 hole walls of three-dimensional ordered macroporous structure as seen from the figure
It is 2-10nm in regular its pore diameter range of orderly meso-hole structure.
Specific implementation 5
Three-dimensional ordered macroporous-meso-porous titanium dioxide silicon carrier 3DOM-m SiO are prepared using colloidal crystal template method2
Stoichiometrically weigh 4.16~8.32g TEOS, the HCl of 1~2.5mL 2mol/L, 1~2.5mL H2O、2
~5mL ethyl alcohol and 3.7~4.6g P123 components, mixing are dissolved in reactor.Above-mentioned mixed liquor is placed in 35 under magnetic stirring
DEG C stirring in water bath 3h obtains homogeneous and transparent SiO2Precursor solution is then allowed to stand 1h, using above-mentioned clear solution as maceration extract
After the colloidal crystal template 2h of impregnation drying, filters and remove extra precursor solution, remaining residue solid matter is dried at 50 DEG C
Constant temperature 12h is dried in case, is obtained containing presoma colloidal crystal template.Sample after drying is fitted into glass tube, is being passed through
It is warming up to target temperature using tube furnace under air conditions, template agent removing is removed in the roasting of constant temperature certain time, hollow in roasting process
80~100mL/min of gas velocity, heating rate are 1~2 DEG C/min.After dropping to room temperature, sample sieving separating, which is obtained three-dimensional, to be had
The SiO of the foramen magnum-mesoporous structure of sequence2Oxide carrier material.Fig. 8 is 3DOM-m SiO2Scanning electron microscope (SEM) photograph, as seen from Figure 4
SiO prepared by colloidal crystal template method2Carrier forms regular three-dimensional ordered macroporous structure duct three-dimensional order perforation, aperture
Uniform, pore wall thickness is uniform, has high-visible aperture window below each macropore, and being interconnected to form three-dimensional between the window of hole passes through
Logical topological structure.The diameter of macropore is about 310nm, and the diameter of aperture window is about 100nm；Pore wall thickness is about uniformly
50nm.Fig. 9 is 3DOM-m SiO2Transmission electron microscope picture, the SiO of three-dimensional ordered macroporous structure as seen from the figure2Exist on hole wall
Regular its pore diameter range of orderly meso-hole structure is 2-10nm.
Claims (2)
1. a kind of preparation method of three-dimensional ordered macroporous-mesopore oxide material, which is characterized in that the material is that have with three-dimensional
The oxide material of sequence macropore and ordered mesopore structure has wherein the three-dimensional ordered macroporous average pore size is 50nm~1 μm
The mesoporous average pore size of sequence is 2~30nm, and the oxide material is silica, and the method for preparing the material is soft or hard template
The method being combined, the specific steps are：
(1) preparation of precursor solution：Weigh the presoma TEOS of 2.08~8.32g oxide materials, 1~5mL 2mol/L
HCl, 1~5mL H2O, 2~8mL ethyl alcohol and the mixing of 2.3~5.6g soft templates are dissolved in reactor, wherein the body of water and ethyl alcohol
Product is than being 1:0.5~1:2；The volume ratio of water and hydrochloric acid is 1:0.5~1:2；The presoma TEOS and soft template of oxide material
The mass ratio of agent is 1:0.25~1:2；Reactor is placed in water-bath, under magnetic stirring, set temperature is 25~45 DEG C,
Homogeneous and transparent precursor solution is obtained after stirring 1~6h；
(2) preparation of presoma colloidal crystal template：Using obtained precursor solution as maceration extract, polymethyl is added
1~3h of dipping is repeated in sour methyl esters colloidal crystal template, filters and removes extra precursor solution, by remaining residue solid matter
12~48h of constant temperature is dried in 30~60 DEG C of baking ovens, is obtained containing presoma colloidal crystal template；
(3) preparation of the oxide material of three-dimensional ordered macroporous-meso-hole structure：By the colloidal crystal containing silica precursor
Template is fitted into glass tube, and 400~1000 DEG C are warming up to using tube furnace in the case where being passed through air conditions, after 4~10h of constant temperature, roasting
Burning-off template agent removing, air velocity is set as 30~300mL/min in roasting process, and heating rate is 1~2 DEG C/min；Roasting
After dropping to room temperature after burning, sample sieving separating is obtained into the oxide material of three-dimensional ordered macroporous-meso-hole structure；
The soft template is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, cetyl trimethyl
Any one in ammonium bromide, polyoxyethylene poly-oxygen propylene aether block copolymer.
2. a kind of preparation method of three-dimensional ordered macroporous-mesopore oxide material as described in claim 1, which is characterized in that
The preparation method of polymethyl methacrylate colloidal crystal template includes the following steps in the step (2)：
The distilled water of the monomers methyl methacrylate and 120~240mL that take 60~120mL mixes in four mouthfuls of reactors, and
With heating water bath to 60~90 DEG C；Whole process carries out under stiring, wherein the rotating speed stirred is in 250~400rpm/min, with
Afterwards, under protection of argon gas, the potassium peroxydisulfate initiator aqueous solution of 0.3~1.2g is added, persistently stirs 1~5h, wherein stir
Rotating speed obtains monodisperse poly (methyl methacrylate) micro-sphere lotion in 250~400rpm/min；
Microballoon lotion is placed in centrifuge tube, 1~10h is centrifuged with the rotating speed of 1000~10000rpm/min, after centrifugation, removes examination
The clear liquid on pipe upper layer leaves without water droplet until test tube is inverted a period of time, then dries test tube in 20~50 DEG C of drying boxes,
The white chunks substance of gained is methyl methacrylate microballoon colloidal crystal template.
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| CN108452791A (en) * | 2018-02-07 | 2018-08-28 | 江南大学 | A kind of 3DOM TiO2- CaO materials, preparation method and applications |
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| CN109589968B (en) * | 2018-12-19 | 2021-11-05 | 沈阳师范大学 | K-OMS-2 catalyst supported by three-dimensional ordered macroporous-mesoporous titanium-silicon composite oxide carrier and preparation method thereof |
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