CN102887526A - Aluminosilicate mesoporous material and synthesis method thereof - Google Patents
Aluminosilicate mesoporous material and synthesis method thereof Download PDFInfo
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- CN102887526A CN102887526A CN201110204917XA CN201110204917A CN102887526A CN 102887526 A CN102887526 A CN 102887526A CN 201110204917X A CN201110204917X A CN 201110204917XA CN 201110204917 A CN201110204917 A CN 201110204917A CN 102887526 A CN102887526 A CN 102887526A
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- mesoporous material
- aluminate
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Abstract
The invention relates to a disk type aluminosilicate mesoporous material with an annular pore structure and a synthesis method of the disk type aluminosilicate mesoporous material. The disk type aluminosilicate mesoporous material has an annular pore structure, wherein the disk diameter of the disk type aluminosilicate mesoporous material is about 60-80nm, the diameter of an annular pore is about 3-5nm, the pore wall thickness is 4-6nm, and the disk type aluminosilicate mesoporous material has a specific surface area being about 500-1200m<2>.g<-1> and a pore volume being 0.70-1.30cm<3>.g<-1>. A dimeric cationic surfactant is used as a structure directing agent, under the condition of the existence of inorganic base, the disk type aluminosilicate mesoporous material with the annular pore structure is obtained through a hydro-thermal synthesis method. The disk type aluminosilicate mesoporous material with the annular pore structure has a wide application prospect in fields such as catalysis, absorption and separation, medicine controlled release, and electronic sensing and can be used as templates for synthesizing other materials.
Description
Technical field
The present invention relates to a kind of inorganic porous material and synthetic method thereof, particularly a kind of silico-aluminate mesoporous material and synthetic method thereof.
Background technology
Mesoporous material is owing to have larger specific surface area and characteristics such as pore volume, adjustable aperture and pore structure, controllable pattern and modifiable surface properties, thus catalysis, adsorb with separate, medicament slow release, electronic sensor and potential application prospect is arranged as the every field such as template of synthetic other materials.
In synthesize meso-porous material, all to use organic formwork agent as structure directing agent under the general condition.The structure directing agent that people often adopt mainly comprises cats product, anion surfactant and nonionogenic tenside.Document Nature 359,710-712 (1992) have reported that the use cats product has synthesized the irregular SiO 2 mesoporous materials of pattern.Document Science 273,768-771 (1996) have reported that guiding has synthesized the SiO 2 mesoporous materials of hollow sphere by the control oil-water interface.Document Science 282,1302-1305 (1998) have reported that having used neutral double type synthesis of surfactant has a SiO 2 mesoporous materials of imitated vesicle structure.Recently, document Adv.Funct.Mater., 14,507-512 (2004) have reported that having used asymmetric double subtype synthesis of surfactant has a stratiform SiO 2 mesoporous materials of striped pore passage structure.In addition, document J.Am.Chem.Soc., 132,15144-15147 (2010) has reported use segmented copolymer and cats product as double template, has synthesized the spherical material of the silicon-dioxide with two mesopore orbits, nucleocapsid structure.Yet up to now, the synthetic method with disc-shaped silico-aluminate mesoporous material of annulus structure there is no report in document and the patent at home and abroad.
Summary of the invention
The object of the invention is to propose a kind of synthetic method with disc-shaped silico-aluminate mesoporous material of annulus structure.
The feature of silico-aluminate mesoporous material of the present invention is as follows:
Its chemical constitution is: Si
XAlO
YWherein, X=1-500; Y=2X+1.5;
It is to have the annulus structure, is the silico-aluminate mesoporous material that disc-shaped or disc-shaped are assembled.Wherein, the diameter of the annulus of this material is about 3-5nm, and pore wall thickness is 4-6nm, and the diameter of disk is 60-80nm, and specific surface area is 500-1300m
2G
-1, pore volume is 0.70-1.30cm
3G
-1
Disc-shaped silico-aluminate mesoporous material with annulus structure of the present invention adopts the double type cats product as structure directing agent, under the existence condition of mineral alkali, by the method acquisition of Hydrothermal Synthesis.
Specifically comprise following process and step:
1) preparation of initial gel:
Silicon source and aluminium source are joined in a certain amount of water according to a certain percentage, after stirring, under 20～60 ℃ of continuous stirring conditions, add mineral alkali regulation system pH value to alkalescence, add again afterwards the double type cats product, continue to stir 1～8h, obtain initial gel; The silicon of reaction colloidal sol: aluminium: water: the molar ratio of double type positively charged ion template is 1: 0.002-1: 20-10000: 0.025-0.20.
2) hydrothermal crystallizing:
The reaction colloidal sol that step 1 is made is transferred in the Autoclaves for synthesis, and in 90～130 ℃, hydrothermal crystallizing is 1～6 day under the autogenous pressure.
3) drying and roasting:
The product that step 2 hydrothermal crystallizing is good is through washing and filtering, and in 100～120 ℃ of lower dry 12～48h, in retort furnace, under 500～650 ℃, calcine at last 4～12h, remove the double type cats product, namely get the disc-shaped silico-aluminate mesoporous material with annulus structure.
The pH value of reaction colloidal sol is 8-13 in the step 1 of the present invention.
The silicon of reaction colloidal sol in the step 1 of the present invention: aluminium: water: the preferred molar ratio example of double type positively charged ion template is 1: 0.01-0.1: 100-1000: 0.05-0.10.
Mineral alkali used in the present invention is sodium hydroxide and/or potassium hydroxide.
Silicon used in the present invention source is one or more the mixture in silicon sol, silicon gel, water glass, active silica or the positive silicon ester; The aluminium source is one or more the mixture in aluminium salt, aluminate, activated alumina or the aluminum alkoxide.
Double type cats product used herein is [C
mH
2m+1N (CH
3)
2-(CH
2)
s-N (CH
3)
2C
mH
2m+1] X
2, be abbreviated as [Cm-s-m] X
2, m=12 wherein, 14,16,18, s=2,3,4,5, X are Cl
-, Br
-Or OH
-
Disc-shaped silico-aluminate mesoporous material with annulus structure of the present invention can be applicable to catalysis, adsorbs and separates, medicament slow release, electronic sensor and as the fields such as template of synthetic other materials.
Description of drawings
Fig. 1 is the typical transmission electron microscope picture that the sample 8 that obtains in 1 among the embodiment has the silico-aluminate mesoporous material of annulus structure.
Fig. 2 is the typical scan Electronic Speculum figure that the sample 11 that obtains in 1 among the embodiment has the silico-aluminate mesoporous material of annulus structure.
Fig. 3 is the Small angle XRD diffracting spectrum that the sample 1-12 that obtains in 1 among the embodiment has the silico-aluminate mesoporous material of annulus structure.
Embodiment
Below by embodiment the present invention is further elaborated, but the present invention is not limited to these embodiment.
According to a certain percentage aluminium source, silicon source are joined in the deionized water, make it even under stirring, add afterwards a certain amount of mineral alkali, the pH value of conditioned reaction colloidal sol is to pH=8～13, add again afterwards a certain amount of double type cats product, continue to stir 1～8h, obtain initial gel.With make mix after reaction colloidal sol move in the stainless steel Autoclaves for synthesis and seal, in 90～130 ℃, hydrothermal crystallizing is 1～6 day under the autogenous pressure.The solid product centrifugation that hydrothermal crystallizing is good, extremely neutral with deionized water wash, at 100～120 ℃ of lower air drying 12～48h, and in retort furnace, calcining down 4～12h in 500～650 ℃ at last, remove the double type cats product, the disc-shaped silico-aluminate mesoporous material that namely obtains having the annulus structure.The corresponding relation of the pH value after the proportioning raw materials in sample number into spectrum and the initial gel, the sodium hydroxide that is used for adjusting initial pH of latex gel value and/or potassium hydroxide, the adjustment, crystallization temperature, crystallization time is as shown in table 1.
Table 1: the corresponding relation of sample number into spectrum and preparation condition
Embodiment 2
Sample prepared among the embodiment 1 is carried out transmission electron microscope to be characterized.Institute's employing instrument is the JEOLJEM-2000EX transmission electron microscope, and the instrument operating voltage is 120kV.Transmission electron microscope picture shows that all samples all has the annulus structure, and the diameter of annulus is 3-5nm, and pore wall thickness is 4-6nm, and the diameter of disk is 60-80nm.Typical case annular pore passage structure transmission electron microscope picture take sample 8 as representative, as shown in Figure 1.
Embodiment 3
Sample prepared among the embodiment 1 is carried out scanning electron microscope to be characterized.Institute's employing instrument is FEIQuanta 200F scanning electron microscope, and acceleration voltage is 200V-30kV.Scanning Electron Microscope photos reveal, all samples pattern all is the gathering of disc-shaped or disc-shaped.Typical scanning electron microscope (SEM) photograph take sample 11 as representative, as shown in Figure 2.
Embodiment 4
Sample 1-12 prepared among the embodiment 1 is carried out little angle XRD to be characterized.Institute's employing instrument is Philips X ' Pert PROX type X-ray diffractometer, and the instrument operating voltage is 40kv, and working current is 40mA.Resulting little angle XRD result as shown in Figure 3.Sample 1-12 in 2 θ=2 ° and 4 ° located all to occur the diffraction peak that intensity does not wait, can be attributed to the diffraction peak of annular mesopore orbit; Wherein first diffraction peak of sample 11 appears at the position of 2 θ=2.5, and the peak type is wider, the relative irregularity of the meso-hole structure of interpret sample 11; Sample 12 can be attributed to the layered mesoporous structure that the disc-shaped sample stacking forms in the diffraction peak of 2 θ=1.
Sample 1-12 prepared among the embodiment 1 is carried out nitrogen physisorption to be characterized.Institute's employing instrument is Micromeritics Tristar3000 type nitrogen physisorption instrument.Carry out before the nitrogen physisorption sign, resulting sample 1-12 need to carry out pre-treatment.Pretreatment condition is as follows: at normal temperatures sieve sample is vacuumized; After reaching vacuum condition, process 1h at 130 ℃; Process 2h at 350 ℃ afterwards.Specific surface is tried to achieve by the BET method, and pore volume is calculated by the adsorptive capacity of 0.99 correspondence of relative pressure on the nitrogen adsorption isotherm.Specific surface area and the pore volume of resulting sample are as shown in table 2.Data can be found out from table 2, and this mesoporous material has larger specific surface area and pore volume, can be used as adsorption separating agent and support of the catalyst.
Table 2: the specific surface area of gained sample and pore volume
| Sample number into spectrum | Specific surface area (m 2/g) | Pore volume (cm 3/g) |
| 1 | 576 | 0.73 |
| 2 | 724 | 0.83 |
| 3 | 900 | 1.10 |
| 4 | 1236 | 1.25 |
| 5 | 637 | 0.78 |
| 6 | 786 | 0.86 |
| 7 | 857 | 0.92 |
| 8 | 952 | 1.02 |
| 9 | 1.36 | 1.10 |
| 10 | 1064 | 1.17 |
| 11 | 1158 | 1.23 |
| 12 | 1276 | 1.28 |
Claims (10)
1. a silico-aluminate mesoporous material is characterized in that, has annular mesopore orbit structure, and its chemical constitution is:
Si
XAlO
YWherein, X=1-1000; Y=2X+1.5.
2. silico-aluminate mesoporous material according to claim 1 is characterized in that, the diameter of described annular mesopore orbit is about 3～5nm, and pore wall thickness is 4-6nm.
3. silico-aluminate mesoporous material according to claim 1 is characterized in that, pattern is the gathering of disc-shaped or disc-shaped, and described disk diameter is 60-80nm.
4. silico-aluminate mesoporous material according to claim 1 is characterized in that, specific surface area is 500-1300m
2G
-1, pore volume is 0.70-1.30cm
3G
-1
5. the preparation method of the described arbitrary silico-aluminate mesoporous material of claim 1-4 is characterized in that synthesis step is as follows:
(1) preparation of initial gel: silicon source and aluminium source are added in a certain amount of water according to a certain percentage, after stirring, under 20～60 ℃ of continuous stirring conditions, add mineral alkali regulation system pH value to alkalescence, add again afterwards the double type cats product, continue to stir 1～8h, obtain initial gel, silicon in the described initial gel: aluminium: water: the molar ratio of double type positively charged ion template is 1: 0.002-1: 20-10000: 0.025-0.2;
(2) hydrothermal crystallizing: the initial gel that step (1) is made is transferred in the Autoclaves for synthesis, and hydrothermal crystallizing is 1～6 day under 90～130 ℃ of autogenous pressures, obtains crystallization product;
(3) drying and roasting: with the crystallization product that obtains in the step (2) through washing, filter, behind 100～120 ℃ of lower dry 12～48h, in 500～650 ℃ of lower roasting 4～12h, namely get described mesoporous aluminoshilicate material.
6. the preparation method of silico-aluminate mesoporous material according to claim 5 is characterized in that, described mineral alkali is sodium hydroxide and/or potassium hydroxide.
7. the preparation method of silico-aluminate mesoporous material according to claim 5 is characterized in that, described silicon source is one or more the mixture in silicon sol, silicon gel, water glass, white carbon black, active silica or the positive silicon ester; Described aluminium source is one or more the mixture in aluminium salt, aluminate, aluminum oxyhydroxide, activated alumina or the aluminum alkoxide.
8. the preparation method of silico-aluminate mesoporous material according to claim 5 is characterized in that, described double type cats product molecular formula is:
[C
mH
2m+1N(CH
3)
2-(CH
2)
s-N(CH
3)
2C
mH
2m+1]·X
2，
Wherein, m=12,14,16,18; S=2,3,4,5; X is Cl
-, Br
-Or OH
-
9. the preparation method of silico-aluminate mesoporous material according to claim 5 is characterized in that, the pH value of described initial gel is 8-13.
10. the preparation method of silico-aluminate mesoporous material according to claim 5 is characterized in that, silicon in the described initial gel: aluminium: water: the molar ratio of double type positively charged ion template is 1: 0.01-0.1: 100-1000: 0.05-0.10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694846A (en) * | 2016-03-28 | 2016-06-22 | 华中科技大学 | Hybrid supermolecule room temperature phosphorescent material and preparation method thereof |
| CN109665542A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN101108736A (en) * | 2006-07-21 | 2008-01-23 | 中国石油天然气集团公司 | Method of manufacturing Y type molecular sieve having micropore and mesohole at the same time |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108736A (en) * | 2006-07-21 | 2008-01-23 | 中国石油天然气集团公司 | Method of manufacturing Y type molecular sieve having micropore and mesohole at the same time |
Non-Patent Citations (3)
| Title |
|---|
| OLIVIER COLLART ET AL.: "Aluminum In corporation into MCM-48 toward the Creation of Bronsted Acidity", 《JOURNAL OF PHYSICS CHEMISTRY B》 * |
| SEAN M.SOLBERG ET AL.: "synthesis and Reactivity of Al-MMM-2: A New Microporous/Mesoporous Catalyst for the Alkylation of Toluene", 《JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS》 * |
| YU HAN ET AL.: "Hydrothermally Stable Ordered Hexagonal Mesoporous Aluminosilicates Assembled from a Triblock Copolymer and Preformed Aluminosilicate Precursors in Strongly Acidic Media", 《CHEMISTRY OF MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694846A (en) * | 2016-03-28 | 2016-06-22 | 华中科技大学 | Hybrid supermolecule room temperature phosphorescent material and preparation method thereof |
| CN109665542A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method thereof |
| CN109665542B (en) * | 2017-10-17 | 2022-07-12 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
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