CN108975345B - Two-dimensional ultrathin SAPO-34 molecular sieve sheet material and preparation method thereof - Google Patents
Two-dimensional ultrathin SAPO-34 molecular sieve sheet material and preparation method thereof Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 22
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- 238000004876 x-ray fluorescence Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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- 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
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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Abstract
A two-dimensional ultrathin SAPO-34 molecular sieve sheet material is 1-25 nanometers thick, has a crystal structure of an SAPO-34 molecular sieve, and has a silicon/aluminum atomic ratio of 0.05-0.3. The technical points of the invention are as follows: cheap and easily-obtained aluminum phosphate, a silicon source and organic amine are used as reactants, a layered precursor is stripped through a chemical method, and then gas phase crystallization is carried out to prepare the two-dimensional ultrathin SAPO-34 molecular sieve material. The two-dimensional ultrathin SAPO-34 molecular sieve material has huge external surface area, the content of silicon is adjustable in a certain range, and the method is universal. The material has many advantages and can be produced in large scale. The method has the advantages of less template agent consumption, low cost and no environmental pollution basically, and is suitable for industrial mass production. The invention discloses a preparation method of the compound.
Description
The technical field is as follows:
the invention relates to a two-dimensional ultrathin SAPO-34 molecular sieve sheet material and a preparation method thereof.
Background art:
SAPO-34 is the most attractive type of SAPO series molecular sieves (aluminophosphate silicon molecular sieves), and due to the special CHA type molecular sieve pore channel structure, the SAPO-type molecular sieves are suitable for adjusting acidity, have good thermal stability and hydrothermal stability, and show excellent catalytic activity in a plurality of reactions. Among them, the catalyst has higher selectivity to C2-C4 products in the reaction (MTO) for preparing low-carbon olefin by catalytic conversion of methanol, and is known to be the optimal catalyst for MTO reaction. In addition, the catalyst also shows excellent catalytic performance in aspects of catalytic selective reduction of NOx, automobile exhaust purification and the like. Meanwhile, SAPO-34 molecular sieves with different morphological structures have been found to have great differences in catalytic performance.
Therefore, the synthesis and performance research of SAPO-34 molecular sieves with different morphological structures attract extensive attention. Numerous literature reports and patent applications relating to the synthesis of SAPO-34 molecular sieves are continuously published and published. For example, the literature reports: in 2018, a paper published by Jilin university Tuhong topic group on Chemical Communications in UK reports the synthesis and application of SAPO-34 molecular sieves with a multi-stage pore channel structure on an MTO reaction, and a paper published by Dazonian university Tuhong topic group on Chemical Communications in UK reports the synthesis and application of SAPO-34 molecular sieves with a core-shell structure on an MTO reaction; in 2016, a report on SAPO-34 molecular sieve material formed by stacking of lamellar structures was published by Zhanglixiong topic group of university of Nanjing industry on Microporous and esophoour materials; patents for SAPO-34 molecular sieves with a sheet structure are: in 2013, a flaky nano SAPO-34 molecular sieve with low silicon content, a preparation method and application thereof (application number: 201310670278.5), in 2014, a synthesis method of a flaky nano SAPO-34 molecular sieve (application number: 201410557543.3), in 2015, a nanosheet self-assembled SAPO-34 molecular sieve and a preparation method thereof (application number: 201510061554.7), in 2016, a solid-phase synthesis method of a flaky and laminated SAPO-34 (application number: 201610371179.0), in 2016, a preparation method and application of a flaky SAPO-34 molecular sieve (application number: 201610874619.4), in 2017, a nanosheet vortex self-assembled SAPO-34 hierarchical molecular sieve and a preparation method thereof (application number: 201710111759.0). Among these reports, the research can be mainly attributed to: (1) a novel synthesis method of a multi-stage structure SAPO-34 molecular sieve, (2) synthesis of a sheet-shaped self-assembled SAPO-34 molecular sieve, and (3) application of the SAPO-34 molecular sieve.
Summarizing the literature results on SAPO-34 molecular sieve preparation for many years, it can be found that no method has been available for preparing a two-dimensional ultra-thin SAPO-34 molecular sieve sheet material with adjustable Si/Al ratio and thickness below 25 nm.
The invention content is as follows:
the technical scheme of the invention is as follows:
a two-dimensional ultrathin SAPO-34 molecular sieve sheet material is 1-25 nanometers thick, has a crystal structure of an SAPO-34 molecular sieve, and has a silicon/aluminum atomic ratio of 0.05-0.3.
A method for preparing the two-dimensional ultrathin SAPO-34 molecular sieve thin sheet material comprises the following steps:
step 1, preparing the aluminum phosphate nano-coil powder material with a laminated structure. The preparation method is based on the literature (chem. Commun.,2009, 3443-3445). The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
The synthesis method of the aluminum phosphate nanocolloid comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
And 2, adding an alcoholic solution of a silicon source into the aluminum phosphate nano coil powder material obtained in the step 1, wherein the adding amount of the silicon source is 10-50% of the mass of the aluminum phosphate nano coil, stirring at room temperature to form a paste, and then standing for 24 hours.
And 3, adding tetraethyl ammonium hydroxide solution into the paste obtained in the step 2, wherein the adding amount of tetraethyl ammonium hydroxide solution is 20-40% of the mass of the aluminum phosphate nanocolloid, stirring at room temperature to form a paste, and then standing for 24 hours.
And 4, adding water, tetraethyl ammonium hydroxide solution and triethylamine into the polytetrafluoroethylene lining of the hydrothermal kettle, wherein the adding amount of the tetraethyl ammonium hydroxide solution and the triethylamine is 20-40%, 40-80% and 80-200% of the mass of the aluminum phosphate nanocoil in sequence.
And 5, transferring the paste obtained in the step 3 into the polytetrafluoroethylene lining in the step 4, sealing, and performing hydrothermal treatment at 160-200 ℃ for 20-72 hours. Thereafter, it is naturally cooled to room temperature, filtered to obtain a precipitate, and the precipitate is washed with water and anhydrous ethanol several times, preferably dried at 60 ℃ for 24 hours to obtain a dry white powder.
And 6, putting the white powder obtained in the step 5 into a muffle furnace, and raising the temperature from room temperature to 550 ℃ in an air atmosphere, wherein the temperature is preferably kept for 5 hours. After that, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The above-mentioned preparation method, the silicon source described in step 2, is preferably tetraethyl orthosilicate, tetrapropyl orthosilicate or tetrabutyl orthosilicate.
In the above preparation method, the alcohol in step 2 includes methanol or ethanol.
In the above preparation method, the tetraethylammonium hydroxide solution is a 25% aqueous solution.
The technical points of the invention are as follows: cheap and easily-obtained aluminum phosphate, a silicon source and organic amine are used as reactants, a layered precursor is stripped through a chemical method, and then gas phase crystallization is carried out to prepare the two-dimensional ultrathin SAPO-34 molecular sieve material. The two-dimensional ultrathin SAPO-34 molecular sieve material has huge external surface area, the content of silicon is adjustable in a certain range, and the method is universal. The material has many advantages and can be produced in large scale. The method has the advantages of less template agent consumption, low cost and no environmental pollution basically, and is suitable for industrial mass production. The invention discloses a preparation method of the compound.
Description of the drawings:
FIG. 1 is an X-ray powder diffraction pattern of a flaky SAPO-34 molecular sieve material prepared according to example 1 of the invention.
FIG. 2 is a TEM transmission electron micrograph of the flaked SAP5-34 molecular sieve material prepared in example 1 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of a flaky SAPO-34 molecular sieve material prepared according to example 2 of the invention.
FIG. 4 is a TEM transmission electron micrograph of the flaky SAPO-34 molecular sieve material prepared in example 2 of the invention.
FIG. 5 is a TEM transmission electron micrograph of the flaky SAPO-34 molecular sieve material prepared in example 3 of the invention.
FIG. 6 is a TEM transmission electron micrograph of the flaky SAPO-34 molecular sieve material prepared in example 4 of the invention.
FIG. 7 is a TEM transmission electron micrograph of the flaky SAPO-34 molecular sieve material prepared in example 5 of the invention.
FIG. 8 is a TEM transmission electron micrograph of the flaky SAPO-34 molecular sieve material prepared in example 6 of the invention.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples.
Example 1:
taking 0.500 g of aluminum phosphate nanocoil powder, adding 0.050 g of tetraethyl orthosilicate and 0.550 g of methanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.100 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon inner liner of the hydrothermal kettle to which 0.100 g of water, 0.200 g of tetraethylammonium hydroxide (25%) solution and 0.400 g of triethylamine were added, and sealed; then, carrying out hydrothermal treatment at 160 ℃ for 72 hours; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction (see figure 1), the appearance of the product is detected as a sheet with the thickness of 1 nanometer by a TEM electron microscope (see figure 2), and the X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.05.
Example 2:
taking 1.000 g of aluminum phosphate nano-coil powder, adding 0.500 g of tetraethyl orthosilicate and 0.700 g of ethanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.400 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon inner liner of the hydrothermal kettle to which 0.400 g of water, 0.800 g of tetraethylammonium hydroxide (25%) solution and 2.000 g of triethylamine were added, and sealed; then, heating the mixture for 48 hours at 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction (see figure 3), the appearance of the product is detected as a sheet with the thickness of 4 nanometers by a TEM electron microscope (see figure 4), and the X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.30.
Example 3:
taking 2.000 g of aluminum phosphate nano-roll powder, adding 0.40 g of tetrapropyl orthosilicate and 2.000 g of methanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.500 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon inner liner of the hydrothermal kettle to which 0.600 g of water, 1.000 g of tetraethylammonium hydroxide (25%) solution and 2.400 g of triethylamine were added, and sealed; then, heating the mixture for 20 hours at 200 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction, the appearance of the product is detected as a sheet with the thickness of 10 nanometers by a TEM electron microscope (see figure 5), and the X-ray fluorescence spectrum analysis shows that the atomic ratio of silicon to aluminum of the sample is 0.1.
Example 4:
taking 3.000 g of aluminum phosphate nano-roll powder, adding 0.750 g of tetrabutyl orthosilicate and 2.850 g of ethanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.900 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon inner liner of the hydrothermal kettle to which 1.050 g of water, 1.800 g of tetraethylammonium hydroxide (25%) solution and 4.400 g of triethylamine were added, and sealed; then, heating the mixture for 48 hours at 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction, the appearance of the product is 20 nanometer thin slices (shown in figure 6) by TEM electron microscope detection, and the X-ray fluorescence spectrum analysis shows that the silicon/aluminum atom ratio of the sample is 0.14.
Example 5:
taking 4.000 g of aluminum phosphate nano-coil powder, adding 1.500 g of tetraethyl orthosilicate and 3.300 g of methanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 1.300 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon inner liner of the hydrothermal kettle to which 1.100 g of water, 2.200 g of tetraethylammonium hydroxide (25%) solution and 3.800 g of triethylamine were added, and sealed; then, heating the mixture for 48 hours at 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction, the appearance of the product is detected as a thin slice with the thickness of 25 nanometers by a TEM electron microscope (see figure 7), and the X-ray fluorescence spectrum analysis shows that the atomic ratio of silicon to aluminum of the sample is 0.2.
Example 6:
taking 5.000 g of aluminum phosphate nano-coil powder, adding 0.750 g of tetraethyl orthosilicate and 5.250 g of ethanol, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 1.400 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to the teflon liner of a hydrothermal kettle to which 1.500 g of water, 2.200 g of tetraethylammonium hydroxide (25%) solution and 5.500 g of triethylamine were added, and sealed; then, heating the mixture for 48 hours at 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dry white powder; thereafter, the obtained white powder was put into a muffle furnace, and was heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a white sample powder.
The product is identified as SAPO-34 molecular sieve by X-ray powder diffraction, the appearance of the product is detected as a sheet with the thickness of 15 nanometers by a TEM electron microscope (see figure 8), and the X-ray fluorescence spectrum analysis shows that the atomic ratio of silicon to aluminum of the sample is 0.22.
Claims (4)
1. A preparation method of a two-dimensional ultrathin SAPO-34 molecular sieve flake material is characterized by comprising the following steps of:
step 1, preparing an aluminum phosphate nano coil powder material with a laminated structure;
step 2, adding an alcoholic solution of a silicon source into the aluminum phosphate nano coil powder material obtained in the step 1, wherein the adding amount of the silicon source is 10-50% of the mass of the aluminum phosphate nano coil, stirring at room temperature to form a paste, and then standing for 24 hours;
step 3, adding tetraethyl ammonium hydroxide solution into the paste obtained in the step 2, wherein the adding amount of tetraethyl ammonium hydroxide solution is 20-40% of the mass of the aluminum phosphate nanocolloid, stirring at room temperature to form a paste, and then standing for 24 hours;
step 4, adding water, tetraethyl ammonium hydroxide solution and triethylamine into a polytetrafluoroethylene lining of the hydrothermal kettle, wherein the adding amount of the water, the tetraethyl ammonium hydroxide solution and the triethylamine is 20-40%, 40-80% and 80-200% of the mass of the aluminum phosphate nanocoil in sequence;
step 5, transferring the paste obtained in the step 3 into the polytetrafluoroethylene lining in the step 4, sealing, and performing hydrothermal treatment at 160-200 ℃ for 20-72 hours; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate by using water and absolute ethyl alcohol, and drying to obtain white powder;
step 6, putting the white powder obtained in the step 5 into a muffle furnace, heating the white powder to 550 ℃ from room temperature in an air atmosphere, keeping the temperature, and naturally cooling the white powder to room temperature to obtain white sample powder;
the silicon source in the step 2 is tetraethyl orthosilicate, tetrapropyl orthosilicate or tetrabutyl orthosilicate;
the crystal structure of the product obtained by the preparation method is an SAPO-34 molecular sieve, the thickness is 1-25 nanometers, and the atomic ratio of silicon to aluminum is 0.05-0.3.
2. The method for preparing the two-dimensional ultrathin SAPO-34 molecular sieve flake material as claimed in claim 1, wherein the method comprises the following steps: the alcohol in the step 2 is methanol or ethanol.
3. The method for preparing the two-dimensional ultrathin SAPO-34 molecular sieve flake material as claimed in claim 1, wherein the method comprises the following steps: the tetraethyl ammonium hydroxide solution is 25% aqueous solution.
4. The method for preparing the two-dimensional ultrathin SAPO-34 molecular sieve flake material as claimed in claim 1, wherein the method comprises the following steps: the drying temperature in the step 5 is 60 ℃, the drying time is 24 hours, and the temperature in the step 6 is increased from room temperature to 550 ℃ and then is kept for 5 hours.
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