CN108862304B - Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof - Google Patents

Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof Download PDF

Info

Publication number
CN108862304B
CN108862304B CN201810865072.0A CN201810865072A CN108862304B CN 108862304 B CN108862304 B CN 108862304B CN 201810865072 A CN201810865072 A CN 201810865072A CN 108862304 B CN108862304 B CN 108862304B
Authority
CN
China
Prior art keywords
molecular sieve
silicon
aluminum
source
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810865072.0A
Other languages
Chinese (zh)
Other versions
CN108862304A (en
Inventor
阳晓宇
金成静
刘欢
安亚楠
高晨
白航
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201810865072.0A priority Critical patent/CN108862304B/en
Publication of CN108862304A publication Critical patent/CN108862304A/en
Application granted granted Critical
Publication of CN108862304B publication Critical patent/CN108862304B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention belongs to the field of inorganic materials, and discloses a hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure, wherein an organosilane bridge with methylene is introduced between two silicon atoms to be connected to replace a siloxane bridge so as to improve the hydrophobicity; in addition, the hydrophobic hybrid silicon-aluminum molecular sieve is formed by stacking nanoparticles, and the micro-nano structure of the molecular sieve can further enhance the hydrophobic property. According to the invention, organosilane with methylene groups is used as a silicon source, the organic-inorganic hybrid microcrystalline zeolite molecular sieve is synthesized under an alkaline condition and a template-free condition, a new function is added to an inorganic molecular sieve matrix, the product can be endowed with a unique micro-nano structure and morphology, and the molecular sieve can show unique oleophilic and hydrophobic surface properties by substituting methylene for lattice oxygen atoms. In addition, the preparation method provided by the invention is simple, the reaction conditions are mild, and the method can be widely applied to researches on novel catalysts, adsorbents, self-cleaning coatings and the like.

Description

Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic and organic materials, and particularly relates to a hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure and a preparation method thereof.
Background
The zeolite molecular sieve is an inorganic microporous material with regular pore channels and formed by connecting tetrahedral units through shared oxygen bridges, has a unique crystal structure and a plurality of excellent performances such as good ion exchange property, good catalytic property, good adsorptivity and the like, and is widely applied to the fields of detergent industry, petrochemical industry, fine chemical industry, environmental protection, development of new functional materials and the like. The organic-inorganic hybrid material has the characteristics of both organic material and inorganic material, and can realize the complementation and optimization of performance through the composition of material functions. The molecular sieve has excellent hydrophilic property endowed by abundant hydroxyl groups on the surface, and the introduction of organic groups can realize the functionalization of the porous material and the adjustment of the hydrophobicity of the pore wall of the porous material, realize the conversion of hydrophilicity and hydrophobicity and further expand the application of the molecular sieve. Therefore, introduction of organic groups into the framework structure of molecular sieves to increase the hydrophobicity thereof has been a major hot research direction of materials. At present, the general synthetic methods of the organic-inorganic hybrid molecular sieve comprise a copolycondensation method and a post-grafting method, and the related preparation process is complex and the reaction conditions are harsh; related researches on grafting organic groups directly into the framework structure of the molecular sieve are rarely reported.
It is known that two key factors of a super-hydrophobic material are the low surface energy of the material and the unique micro-nano structure thereof, and the roughness and the porosity of the surface of the material can greatly enhance the hydrophobic property. Particles with a layered surface topography and well-defined surface geometry have a rougher surface compared to particles with a smooth surface.
Disclosure of Invention
The invention mainly aims to provide a hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure, aiming at the defects in the prior art, the preparation method is simple, the reaction condition is mild, the shape and the size of nanoparticles on the surface of the molecular sieve are adjustable, and the molecular sieve film prepared by using the molecular sieve is compact in structure, prominent in hydrophobic and lipophilic properties, and suitable for popularization and application.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
the hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure is a hybrid silicon-aluminum molecular sieve microcrystalline sphere formed by stacking nanoparticles, and an organosilane bridge containing methylene is arranged in the hybrid silicon-aluminum molecular sieve microcrystalline sphere.
In the above embodiment, the organosilane bridge containing methylene group contains-Si-CH2-Si-bond.
In the scheme, the size of the nano particles is 25-200nm, and the diameter of the hybrid silicon-aluminum molecular sieve microcrystal ball is 200nm-5 mu m.
In the above scheme, the nanoparticles are spherical, flaky or amorphous.
In the above scheme, the organosilane bridge containing methylene is bridged by the organosilane bridge containing methylene, and the silicon source is used
The preparation method of the hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having the micro-nano hierarchical structure comprises the following steps:
1) putting a silicon source in an alkali liquor, and hydrolyzing at room temperature under the stirring condition to obtain a silicon source solution I;
2) adding an aluminum source into the alkali liquor, and uniformly stirring to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, and uniformly stirring and mixing to obtain a reaction solution III;
4) and carrying out low-temperature hydrothermal reaction on the reaction liquid III, and then centrifuging, washing and drying to obtain the hydrophobic hybrid silicon-aluminum molecular sieve.
In the above scheme, the silicon source may be bis-ethoxysilyl methane (BTESM) or the like.
In the scheme, the aluminum source can be sodium metaaluminate, potassium metaaluminate, aluminum chloride and the like, and the alkali source can be sodium hydroxide, potassium hydroxide and the like.
In the scheme, the molar ratio of the silicon source to the aluminum source is 1 (0.1-1).
In the scheme, the alkali liquor can be sodium hydroxide or potassium hydroxide aqueous solution and the like.
In the scheme, water and OH in the step 1)-The mass ratio of the silicon source is (2.5-4.5): 0.05-0.6): 1.
In the scheme, water and OH in the step 2)-The mass ratio of the aluminum source is (5-21): 0.4-1.6): 1.
In the scheme, the low-temperature hydrothermal reaction temperature is 90-180 ℃, and the time is 7-12 days.
In the scheme, the hydrolysis time in the step 1) is 6-12 h.
In the scheme, the stirring speed in the step 1) is 500-800 r/min.
In the scheme, the stirring time in the step 2) is 0.5-2 h.
The principle of the invention is as follows: under the conditions of alkaline environment and no template agent, organic groups are introduced into a molecular sieve framework by controlling synthesis conditions and adjusting the silicon-aluminum ratio of the molecular sieve, and the surface roughness of the material is designed to obtain the hydrophobic material with excellent performance.
Compared with the prior art, the invention has the beneficial effects that
1) According to the invention, bis-ethoxy silicon-based methane is used as a silicon source, sodium metaaluminate and the like are used as an aluminum source, the organic-inorganic hybrid microcrystalline zeolite molecular sieve is synthesized under an alkaline condition and a template-free condition, and methylene is connected between two silicon atoms to form a bridge so as to replace a siloxane bridge, so that the hydrophobic property of the obtained product is improved; the related synthesis method is simple, the reaction condition is mild, and the method is different from the traditional copolycondensation method and the post-grafting method;
2) according to the invention, the hydrophobic property of the material can be greatly improved by introducing organic groups into the silicon-aluminum molecular sieve; in addition, the obtained hybrid silicon-aluminum molecular sieve has a micro-nano structure formed by stacking nano particles with different shapes and sizes, so that the surface roughness can be effectively improved, and the hydrophobicity and lipophilicity of the obtained material are further improved; the shape and the size of the nano particles on the surface of the molecular sieve are easy to regulate and control, and the applicability is wide;
3) the methylene group in the molecule of the hybrid silicon-aluminum molecular sieve synthesized by the invention has higher chemical activity, and is beneficial to post-chemical modification and modulation treatment, so that the obtained material has good plasticity and adjustable denaturation, and other physical and chemical properties can be expected to be optimized;
4) the preparation process provided by the invention is simple, the reaction condition is mild, special processing equipment is not needed, the reaction condition is easy to control, and the large-scale popularization and production are facilitated.
Drawings
FIG. 1 is a schematic diagram of a process for the hydrothermal synthesis of an organic group-containing silicoaluminophosphate molecular sieve as described in example 1.
FIG. 2 is an SEM image of hybrid microspheres on the surface of the organic group-containing aluminosilicate molecular sieve obtained in example 1, wherein (b) is an enlarged view of the surface of the crystallites.
FIG. 3 is a graph of performance analysis of the organic group-containing aluminosilicate molecular sieve obtained in example 1, wherein (a) is an infrared spectrum, (b) is an XRD diffraction pattern, (c) is a BET absorption diagram, and (d) is a thermogravimetric analysis diagram.
Fig. 4 is an SEM image of the hybrid microspheres on the surface of the organic group-containing aluminosilicate molecular sieve obtained in example 2, wherein (b) is an enlarged view of the surface of the crystallites.
FIG. 5 is a graph of performance analysis of the organic group-containing aluminosilicate molecular sieve obtained in example 2, wherein (a) is an infrared spectrum, (b) is an XRD diffraction pattern, (c) is a BET absorption diagram, and (d) is a thermogravimetric analysis diagram.
FIG. 6 is an SEM image of an organic group-containing silicoaluminophosphate molecular sieve prepared under different temperature and time conditions in example 3, wherein (a) is an SEM image of oven-hydrothermal synthesis at 150 ℃ for 7d, and (b) is an enlarged view thereof; (c) is SEM picture of oven-hydrothermal synthesis 7d at 140 deg.C, and (d) is enlarged view thereof; (e) an SEM image of oven-hydrothermal synthesis at 140 deg.C for 9d, and (f) an enlarged image thereof; (g) SEM image of 120 ℃ oven-hydrothermal synthesis of 9d, and (h) enlarged image thereof.
FIG. 7 is a comparative IR and XRD analysis chart of the organic group-containing aluminosilicate molecular sieve synthesized in example 3 under different temperature and time conditions.
Fig. 8 is an SEM image of the organic group molecular sieve obtained in the comparative example, in which (b) is an enlarged view of the surface of the crystallite.
FIG. 9 is a graph showing the analysis of the performance test of the organic group-containing molecular sieve obtained in the comparative example, wherein (a) is an infrared spectrum, (b) is an XRD diffraction pattern, (c) is a BET absorption diagram, and (d) is a thermogravimetric analysis diagram.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure is shown in a schematic diagram of a synthetic route in figure 1, and the specific preparation method comprises the following steps:
1) 3.7375g H are weighed in turn2Placing O, 0.2763g NaOH and 1.0625g BTESM in a clean conical flask, and stirring for 8 hours at room temperature (the rotating speed is 700r/min) to completely hydrolyze the BTESM to obtain a silicon source solution I;
2) 3.7375g H are weighed in turn2O、0.2763g NaOH、0.3519g NaAlO2Placing the aluminum source solution in a clean conical flask, stirring for 10min at room temperature in an open atmosphere, and uniformly stirring to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, carrying out open stirring on the obtained mixed solution at room temperature for 20min, and fully mixing to obtain a reaction solution III;
4) carrying out reaction on the obtained reaction liquid III; and putting the mixture into a reaction kettle, placing the reaction kettle into a drying oven at 150 ℃, performing hydrothermal synthesis for 7d, taking the kettle, cooling, centrifuging, washing with deionized water, repeating the steps for 3 times, and drying overnight to obtain the hydrophobic hybrid silicon-aluminum molecular sieve.
The product obtained in this example is observed by a field emission scanning electron microscope for surface morphology, and as a result, as shown in fig. 2, it can be seen from fig. 2 that the surface of the molecular sieve thin film has microcrystalline spheres with non-uniform sizes and shapes, and after being amplified, the crystals can be observed to be in a stacked state, the structure is dense, and the CA of the crystal is 142.4 degrees, and the hydrophobicity is good.
The external spectrogram, XRD diffractogram, BET absorption diagram and thermogravimetric analysis diagram of the product obtained in this example are respectively shown in FIG. 3, and the obtained product is analyzed from 3a) infrared spectrogram, which shows the transmittance of each atomic group in the molecule at different wavelengths, and is 3725cm-1Has a distinct peak, is the vibration result of-Si-OH, and is 2789cm-1And 2890cm-1Has two peaks respectively attributed to-CH2Asymmetric and symmetric stretching vibration of the-group, these two peaks clearly indicate-CH2-the group is inserted into the inorganic framework; at 1650cm-1And 1485cm-1The existence of the first two peaks indicates that Si-CH conforming to the hybrid organic-inorganic structure is retained2-a Si bond. The results of the X-ray diffraction analysis are shown in FIG. 3b), which shows that the organic group-containing silico-aluminum molecular sieve is octahedral but has a weak crystallinity. N is a radical of2The specific surface area adsorption analysis results are shown in FIG. 3c), and FIG. 3c) is N2Adsorption/desorption isotherms, showing a large adsorption gradient near a P/P0 of 0.9, clearly indicating the presence of micropores in the molecular structure; and the volume of the micropores was found to be 0.21cm3The micropore volume estimated based on this plot of experimental data appears to be less than that of conventional zeolitic molecular sieves due to the presence of CH2The larger size of the group is mutually exclusive with the oxygen bridge. The thermogravimetric analysis result is shown in fig. 3d), fig. 3d) reflects the thermal stability of the organic group-containing silicon-aluminum molecular sieve in the air atmosphere under the high temperature condition, and a gradual weight loss of about 22.5% can be observed from 100 to 400 ℃, namely, the C element is evaporated and removed at the high temperature, and the result is very consistent with the IR research result, thereby proving the successful access of the organic group methylene.
Example 2
A hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure is prepared by the following steps:
1) 3.7375g H are weighed in turn2Placing O, 0.2763g NaOH and 1.0625g BTESM in a clean conical flask, and stirring for 12h at room temperature in an open manner (the rotating speed is 700r/min) to completely hydrolyze the BTESM to obtain a silicon source solution I;
2) 3.7375g H are weighed in turn2O、0.2763g NaOH、0.7038g NaAlO2Placing the aluminum source solution in a clean conical flask, stirring for 10min at room temperature in an open atmosphere, and uniformly stirring to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, carrying out open stirring on the obtained mixed solution at room temperature for 20min, and fully mixing to obtain a reaction solution III;
4) carrying out reaction on the obtained reaction liquid III; and (3) putting the mixture into a reaction kettle, placing the reaction kettle into a drying oven at 180 ℃, carrying out hydro-thermal synthesis for 12d, taking the kettle, cooling, centrifuging, washing with deionized water, repeating the steps for 3 times, and drying overnight to obtain the hydrophobic hybrid silicon-aluminum molecular sieve.
The product obtained in this embodiment is observed with a field emission scanning electron microscope, and the hydrophobicity of the surface is determined by surface contact angle test, the scanning electron microscope analysis result of the obtained product is shown in fig. 4, and fig. 4 shows that hybrid microcrystalline spheres with uneven shapes and sizes grow on the surface of the molecular sieve, and the hybrid microcrystalline spheres are in an irregular stacking state layer by layer, and when the CA of the hybrid microcrystalline spheres is 122.5 °, that is, the contact angle is relatively small, and the hydrophobicity is relatively good.
The external spectrogram, XRD diffractogram, BET absorption diagram and thermogravimetric analysis diagram of the product obtained in this example are respectively shown in FIG. 5, and are analyzed from 5a) infrared spectrogram at 3456cm-1The vibration absorption peak of-Si-OH is 2679cm-1And 2812cm-1Two peaks are formed, and-CH is proved2Successful access of the group. The X-ray diffraction analysis results are shown in fig. 5b), which shows that the lattice structure of the synthesized silicon-aluminum molecular sieve is consistent with the standard map. FIG. 5c) is N2Specific surface area adsorption analysis, N2The adsorption/desorption isotherm showed a large adsorption gradient around a P/P0 of 0.94, clearly indicating the presence of micropores in the molecular structure, and the micropore volume was measured to be 0.08cm3The volume of the micropores is smaller. The results of the thermogravimetric analysis are shown in fig. 5d), fig. 5d) reflects the thermal stability of the organic molecular sieve in an air atmosphere at high temperature, from 100 to 350 ℃, a progressive weight loss of about 17.5% is observed, the content of C element reaches about 21.3%, again demonstrating the presence of organic groups. The results show that when the content of the aluminum source is too high, the synthesis temperature is too high, and the crystallization time is too long, the obtained silicon-aluminum molecular sieve has small micropore volume and relatively poor hydrophobic property.
Example 3
A hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure is prepared by the following steps:
1) 3.7375g H are weighed in turn2Placing O, 0.2763g NaOH and 1.0625g BTESM in a clean conical flask, and stirring for 8h at room temperature in an open manner (the rotating speed is 700r/min, if the room temperature is lower, the stirring is carried out in a 25 ℃ water bath in an open manner), so that the BTESM is completely hydrolyzed to obtain a silicon source solution I;
2) 3.7375g H are weighed in turn2O、0.2763g NaOH、0.1760g NaAlO2Placing in a clean conical flask, and stirring at room temperature for 10min (if the room temperature is low, water bath at 25 deg.C is still used); stirring uniformly to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, carrying out open stirring on the obtained mixed solution at room temperature for 20min, and fully mixing to obtain a reaction solution III;
4) carrying out reaction on the obtained reaction liquid III; and (3) putting the mixture into a reaction kettle, putting the mixture into a 150 ℃ oven for hydrothermal synthesis for 7d, a 140 ℃ oven for hydrothermal synthesis for 9d, and a 120 ℃ oven for hydrothermal synthesis for 9d, respectively taking the kettle after the reaction is finished, cooling, centrifuging, washing with deionized water, repeating the steps for 3 times, and drying overnight to obtain the hydrophobic hybrid silicon-aluminum molecular sieve (corresponding to the products (a), (c), (e) and (g) respectively).
The product obtained in this example is observed by using a field emission scanning electron microscope for surface morphology, and the surface hydrophobicity is judged by surface contact angle test, the scanning electron microscope analysis results of the obtained product are respectively shown in fig. 6, and it can be seen from fig. 6(a), (c), (e) and (g) that a large amount of non-uniform nanoparticles are grown on the surface of the molecular sieve, a large-area surface covering and stacking structure is presented, and the structure is compact, corresponding enlarged views are shown in FIG. 6(b), (d), (f) and (h), wherein the surfaces of the two groups (a) and (c) are spherical structures formed by stacking particles, and (e) and (g) two groups of spherical structures with stacked platelets on the surfaces, the size and the shape of the molecular sieve surface hybrid microcrystal structure are different, which shows that the size and the shape of the surface microcrystal ball are changed along with the change of experimental conditions.
(a) The performance test analysis of the four groups of products (c), (e) and (g) is shown in figure 7, figure 7a) is an infrared spectrum contrast analysis figure, and figure 7b) is an XRD diffraction contrast analysis figure, and the synthesized sample is in a sodalite structure after being compared with a standard PDF card. And the higher the hydrothermal synthesis temperature and the longer the crystallization time are, the larger the crystallite structure size is, the larger the surface contact angle is, and the better the hydrophobic property is, but the hydrothermal synthesis temperature is generally not more than 180 ℃, and the crystallization time is generally not more than 12 d. The shape and size of the nano particles on the surface of the molecular sieve are controlled by regulating the hydrothermal synthesis temperature and the crystallization time.
Comparative example
A preparation method of a silicon-aluminum molecular sieve comprises the following steps:
1) 2.037g of BTESM and 5.65g (20 wt%) of TPAOH were weighed in succession into a clean Erlenmeyer flask and stirred open at room temperature for 8h at a rotational speed of 700 r/min.
2) Stirring the solution obtained in the step 1) for 20min in a water bath at 50 ℃ in an open manner to uniformly disperse the BTESM in the solution;
3) putting the solution obtained in the step 2) into a reaction kettle, putting the reaction kettle into a 90 ℃ oven, and carrying out hydro-thermal synthesis for 12d to obtain a final product.
The product obtained in the comparative example is observed by a field emission scanning electron microscope for surface morphology, the surface hydrophobicity is judged by a surface contact angle test, the scanning electron microscope analysis result of the obtained product is shown in fig. 8, fig. 8 shows that the surface of the molecular sieve grows with the microcrystalline spheres with non-uniform shapes and sizes, the enlarged image of (b) shows that the nano particles on the surface of the microspheres do not present a layer-by-layer stacking state but are dispersed on each part of the surface, the CA (measured) is 90.4 degrees, and the hydrophobicity is poor, which indicates that the molecular sieve prepared by using TPAOH and a silicon source can also form the surface microcrystalline spheres, but the nano particles are irregular in shape and have no hydrophobicity. The result of X-ray diffraction analysis is shown in FIG. 9b), and comparison with a standard card shows that the synthesized molecular sieve has an octahedral structure. FIG. 9c) is N2Specific surface area adsorption analysis, N2Adsorption/desorption isotherm at P/P0A large adsorption gradient was exhibited around 0.95, clearly indicating the presence of micropores in the molecular structure, and the micropore volume was measured to be 0.12cm3(ii)/g, which is less than the micropore volume of the hydrophobic molecular sieve prepared by the preparation method of the invention.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (6)

1. A hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having a micro-nano hierarchical structure is a hybrid silicon-aluminum molecular sieve microcrystalline sphere formed by stacking nanoparticles, and an organosilane bridge containing methylene is arranged in the hybrid silicon-aluminum molecular sieve microcrystalline sphere; the size of the nano particles is 25-200nm, and the diameter of the micro-crystal spheres of the hybrid silicon-aluminum molecular sieve is 200nm-5 mu m;
the preparation method comprises the following steps:
1) putting a silicon source in an alkali liquor, and hydrolyzing at room temperature under the stirring condition to obtain a silicon source solution I;
2) adding an aluminum source into the alkali liquor, and uniformly stirring to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, and uniformly stirring and mixing to obtain a reaction solution III;
4) carrying out low-temperature hydrothermal reaction on the reaction liquid III, and then centrifuging, washing and drying to obtain the hydrophobic hybrid silicon-aluminum molecular sieve;
the low-temperature hydrothermal reaction temperature is 120-150 ℃, and the time is 7-12 d;
the silicon source is bis-ethoxy silicon-based methane; the aluminum source is sodium metaaluminate, potassium metaaluminate or aluminum chloride;
the molar ratio of the silicon source to the aluminum source is 1 (0.1-1).
2. The hydrophobic hybrid aluminosilicate molecular sieve of claim 1, wherein the methylene group-containing organosilane bridge contains-Si-CH2-Si-bond.
3. The hydrophobic hybrid aluminosilicate molecular sieve of claim 1, wherein the nanoparticles are spherical, platelet-shaped, or amorphous.
4. The method for preparing the hydrophobic hybrid silicon-aluminum molecular sieve of any one of claims 1 to 3, which is characterized by comprising the following steps:
1) putting a silicon source in an alkali liquor, and hydrolyzing at room temperature under the stirring condition to obtain a silicon source solution I;
2) adding an aluminum source into the alkali liquor, and uniformly stirring to obtain an aluminum source solution II;
3) dropwise adding the silicon source solution I into the aluminum source solution II, and uniformly stirring and mixing to obtain a reaction solution III;
4) carrying out low-temperature hydrothermal reaction on the reaction liquid III, and then centrifuging, washing and drying to obtain the hydrophobic hybrid silicon-aluminum molecular sieve;
the low-temperature hydrothermal reaction temperature is 120-150 ℃, and the time is 7-12 d;
the silicon source is bis-ethoxy silicon-based methane; the aluminum source is sodium metaaluminate, potassium metaaluminate or aluminum chloride;
the molar ratio of the silicon source to the aluminum source is 1 (0.1-1).
5. The method according to claim 4, wherein the water and OH in step 1)-The mass ratio of the silicon source is (2.5-4.5): 0.05-0.6): 1; step 2) water and OH-The mass ratio of the aluminum source is (5-21): 0.4-1.6): 1.
6. The preparation method of claim 4, wherein the hydrolysis time in the step 1) is 6-12 h.
CN201810865072.0A 2018-08-01 2018-08-01 Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof Active CN108862304B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810865072.0A CN108862304B (en) 2018-08-01 2018-08-01 Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810865072.0A CN108862304B (en) 2018-08-01 2018-08-01 Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108862304A CN108862304A (en) 2018-11-23
CN108862304B true CN108862304B (en) 2022-02-18

Family

ID=64307387

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810865072.0A Active CN108862304B (en) 2018-08-01 2018-08-01 Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108862304B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477204A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Layered molecular sieve and synthesis method thereof
CN112850739B (en) * 2021-03-12 2023-07-25 许昌学院 Large-grain LTJ zeolite and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145141A (en) * 2013-03-07 2013-06-12 太原理工大学 Preparation method of organic-inorganic hybrid transparent mesoporous gel monolith
CN108264057A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 A kind of method of the controllable ZSM-5 zeolite of synthesis in solid state wellability

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145141A (en) * 2013-03-07 2013-06-12 太原理工大学 Preparation method of organic-inorganic hybrid transparent mesoporous gel monolith
CN108264057A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 A kind of method of the controllable ZSM-5 zeolite of synthesis in solid state wellability

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Organic-Inorganic Hybrid Zeolites Containing Organic Frameworks;Katsutoshi Yamamoto et al.;《Science》;20030418(第5618期);第470-472页及"Supporting Online Material"部分 *

Also Published As

Publication number Publication date
CN108862304A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
Peng et al. Fabrication of novel hierarchical ZSM-5 zeolite membranes with tunable mesopores for ultrafiltration
WO2012138418A1 (en) Zeolite ddr nanocrystals
CN108862304B (en) Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof
CN107512728B (en) Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores
KR101444939B1 (en) Single-phase GIS-NaP1 Zeolite And A Method Of Manufacturing The Same
CN114351126A (en) Preparation method of stainless steel fiber-loaded ZSM-5 molecular sieve, water-based damping coating and preparation method thereof
Servatan et al. Synthesis of cost-effective hierarchical MFI-type mesoporous zeolite: introducing diatomite as silica source
JP3274867B2 (en) Method for preparing mesoporous crystalline material
Naskar et al. Influence of PVP buffer layer on the formation of NaA zeolite membrane
CN113603110A (en) Template-free preparation method of porous LSX zeolite molecular sieve
CN107840349B (en) Preparation method of nano ZSM-5 hierarchical pore aggregate
CN109678176B (en) Synthesis method of needle-shaped ZSM-5 molecular sieve with controllable particle size
JP4512060B2 (en) Three-dimensional structure mesoporous silica and method for producing the same
Hu et al. Influence of alkalinity on the synthesis of hierarchical LTA zeolite by using bridged polysilsesquioxane
CN107381591B (en) Preparation method of petal-shaped sodalite at room temperature
CN114011390B (en) Preparation method and application of porous zeolite adsorbent
US9938637B2 (en) Production method of zeolite film in which one axis is completely vertically oriented, using steam under synthetic gel-free condition
Araujo Thermal analysis applied to template removal from siliceous MCM-48 nanoporous material
KR100941930B1 (en) Highly ordered organic-inorganic hybrid mesoporous molecular sieves without acid, manufacturing method of the materials
Li et al. Characterization of methylated nanoscale MCM-41 material
KR101074163B1 (en) Free-standing nanoporous silica/carbon hybrid film with crystalline silica in nanopore walls, manufacturing method of the materials
Padhi et al. Effect of modification of zeolite A using sodium carboxymethylcellulose (CMC)
CN115448324B (en) MFI structure molecular sieve hierarchical pore material and preparation method thereof
CN115028175B (en) Preparation method of lamellar ZSM-5 molecular sieve
CN113149029B (en) Preparation method of B @ HS hollow sphere molecular sieve

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant