CN116835620A - Method for preparing two-dimensional nano sheet by intercalation-stripping boehmite - Google Patents
Method for preparing two-dimensional nano sheet by intercalation-stripping boehmite Download PDFInfo
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- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 52
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims description 24
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004299 exfoliation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002064 nanoplatelet Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for preparing a two-dimensional nano sheet by intercalation-stripping boehmite, belongs to the technical field of two-dimensional boehmite with large pore volume and high specific surface area, and provides a method for synthesizing the two-dimensional boehmite nano sheet with large pore volume and high specific surface area at low cost. According to the invention, the boehmite is intercalated by inorganic small molecules, and interlayer acting force is weakened, so that the two-dimensional boehmite nano-sheet layer is peeled off. The obtained nano-sheets increase the specific surface area of boehmite, and pore channels formed by assembling the nano-sheets increase the pore volume of the boehmite. The preparation method provided by the invention has the advantages of low synthesis cost, simplicity in operation, synthesis by adopting industrial raw materials, no use of any organic template agent, suitability for industrial production and the like;the pore volume of the two-dimensional boehmite nano-sheet prepared by the method is up to 2.43cm 3 Per gram, specific surface area up to 542.3m 2 And/g, assembled by two-dimensional nano-sheets with the length exceeding 20nm and the thickness of about 2 nm. The pore structure is far higher than that of the same type of boehmite or alumina materials which have been reported and industrially used.
Description
Technical Field
The invention relates to the technical field of preparation of alumina or alumina precursor materials, and provides a method for preparing a two-dimensional nano sheet by intercalation-stripping boehmite.
Background
Meanwhile, the porous alumina with high specific surface area and large pore volume can be widely applied to the fields of catalysts, catalyst carriers, adsorbents and the like. In reactions such as Fischer-Tropsch synthesis and catalytic combustion, alumina with high specific surface area and large pore volume can increase the number of active sites, promote mass transfer and improve catalytic efficiency. In Fluid Catalytic Cracking (FCC) catalysts, alumina is an important substrate and pore volume has a large impact on the conversion of heavy oils. In the hydrogenation reaction, the alumina with hierarchical pores and high specific surface area is favorable for the dispersion of active metals, promotes the mass transfer of reactants/products, and thus improves the activity and stability of the catalyst. In ethylbenzene dehydrogenation, alumina with high specific surface area and large pore volume can promote the dispersion of VOx species, improve the accessibility of active points and improve the catalytic activity. In adsorption, specific surface area, pore volume and pore diameter are key factors affecting adsorption efficiency. High specific surface area can promote CO 2 Congo red and phosphate, while a large pore volume favors the formation of multiple layers of adsorption, increasing adsorption capacity. Thus, the development of alumina having both high specific surface area and large pore volume is critical for basic research and technical applications.
Although researchers have attempted to increase the specific surface area and pore volume of alumina using a templating agent, it is difficult to increase both the specific surface area and pore volume. Patent CN 106475023A discloses a synthetic method of peptizing pseudo-boehmite and adding surfactant, the specific surface area of alumina is up to 313m 2 /g, and pore volume of 0.71cm 3 And/g. Patent CN 105983446A discloses an alumina synthesized with an organic templating agent with a pore volume increased to 1.33cm 3 Per g, and a specific surface area of 192m 2 And/g. This is because most of the templating agent cannot act inside the alumina, and it is difficult to construct channels in the alumina crystal. And the use of the organic template agent/solvent increases the production cost and the environmental pollution.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing two-dimensional nanoplatelets from intercalated-exfoliated boehmite. Because most alumina is obtained by pyrolysis of boehmite, and the pore structure of alumina is determined by the nature of the boehmite precursor. The small molecules are used for intercalating boehmite to weaken acting force between boehmite layers, so that the boehmite sheet layer is peeled off. The specific surface area of boehmite is increased by the peeled two-dimensional nano-sheets, and the pore volume of boehmite is increased by pore channels formed by assembling the two-dimensional nano-sheets in synthesis. And boehmite with developed pore structure can obtain alumina with high specific surface and large pore volume after pyrolysis. The two-dimensional boehmite prepared by the method has the advantages of low synthesis cost, simplicity in operation, adoption of industrial raw materials, no limitation to raw material sources, no use of any organic template agent, suitability for industrial production and the like.
To achieve this, the following parameters need to be adjusted:
from the standpoint of boehmite production: both the concentration of the acidic aluminum source and the time of neutralization can affect boehmite formation. Higher aluminum source concentrations and longer neutralization times favor the formation of boehmite with better crystallinity, which is detrimental to subsequent intercalation-exfoliation. However, too low a concentration of the aluminum source and too short a neutralization time would result in an amorphous sample, again detrimental to subsequent intercalation-exfoliation. Therefore, the crystallinity of boehmite can be controlled by controlling the concentration of the acidic aluminum source and the neutralization time, thereby controlling the ease of intercalation-exfoliation.
From the standpoint of the intercalation of small inorganic molecules, it is necessary to select small inorganic molecules of suitable size to intercalate boehmite. This requires not only changing the type of modifier but also adjusting the pH of the gel prior to the addition of the modifier. Because the pH of the gel before the modifier is added determines the nature of the modifier in terms of mode of presence, degree of polymerization, charge, etc. This will determine whether the modifier reacts internally or whether the modifier acts on the boehmite. On the other hand, although the pH of the gel is regulated before the modifier is added, the acidity or alkalinity of the system is influenced by the acidity or alkalinity of the modifier, which determines whether the modifier reacts internally or the modifier acts on the boehmite. Therefore, it is necessary to ensure the addition of the modifier within a certain pH range by diluting the modifier to some extent and regulating the rate of addition of the modifier. This helps to maximize the promotion of the modifier into the boehmite interlayer and to achieve boehmite exfoliation.
From the viewpoint of stabilizing the two-dimensional nanoplatelets, although the two-dimensional nanoplatelets can be obtained using the above method, excessive aging will cause the nanoplatelets to dissolve under the promotion of high temperature and anions and cations. Therefore, the synthesis temperature needs to be gradually lowered after peeling. However, the proper temperature facilitates migration and assembly between the nanoplates to form new channels. Therefore, the cooling time and temperature of the system after peeling are required to be preferable.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing two-dimensional nano-sheets by intercalation-exfoliation of boehmite, comprising the steps of:
(1) Adding an alkaline aluminum source into an acidic aluminum source with a certain concentration at a certain temperature;
(2) After neutralization reaction for a period of time, regulating the pH value of the gel to a certain value;
(3) Diluting the modifier solution to a certain concentration and adding the modifier solution into the gel at a certain speed;
(4) Reducing the temperature of the synthesis system to a certain value within a certain time, aging for a period of time within a certain temperature range, filtering and washing to obtain boehmite which is formed by assembling two-dimensional nano sheets and has high specific surface area and large pore volume;
preferably, the concentration of the acidic aluminum source in step (1) is such that Al in solution 2 O 3 The content is 5-30mg/L;
preferably, the neutralization reaction time in the step (2) is 0.5-3h;
preferably, the pH of the gel in the step (2) is adjusted to 4-9;
preferably, the modifier in the step (3) is one or more of silicon-containing, boron-containing and phosphorus-containing compounds; wherein the silicon-containing compound is one or more of sodium silicate, silica sol and silicon tetrachloride; the boron-containing compound is one or more of ammonium borate and boric acid; the phosphorus-containing compound is one or more of phosphoric acid, pyrophosphoric acid and ammonium phosphate;
preferably, the concentration of the modifier in the step (3) is 10mg/L to 30mg/L in terms of oxide;
preferably, the rate of addition of the modifier in step (3) is from 6mL/min to 12mL/min;
preferably, the cooling time of the synthesis system in the step (4) is 1-6h;
preferably, the temperature of the synthesis system of step (4) is reduced to between 20 ℃ and 80 ℃;
the process according to any one of claims 1 to 9, wherein the specific surface area is 542.3m 2 Per g, pore volume of 2.43cm 3 And/g, a thickness of about 2nm, and a length of more than 20 nm.
The invention provides a method for preparing a two-dimensional nano sheet by intercalation-exfoliation of boehmite. The preparation method provided by the invention has the advantages of low synthesis cost, simplicity in operation, adoption of industrial raw materials, no limitation to raw material sources, no use of any organic template agent, suitability for industrial production and the like.
The invention also provides a two-dimensional nano sheet prepared by the preparation method according to the scheme, and the results of examples show that the boehmite prepared by the invention has a specific surface area of 542.3m 2 Per g, pore volume of 2.43cm 3 And/g, a two-dimensional material having a thickness of about 2nm and a length exceeding 20 nm.
Drawings
FIG. 1 shows N of two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5 2 Adsorption and desorption isotherm diagram;
FIG. 2 is a graph showing pore size distribution of two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5;
FIG. 3 is a graph showing the cumulative pore volume versus pore size distribution of the two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5;
FIG. 4 is an XRD pattern of two-dimensional boehmite obtained in examples 1, 2, 3, 4, 5;
FIG. 5 is an SEM image (a-b) and a TEM image (c-d) of the two-dimensional boehmite obtained in example 1. Wherein, the illustration in the c diagram is a statistical diagram of the length of the nano-sheet, and the illustration in the d diagram is a statistical diagram of the thickness of the nano-sheet.
Detailed Description
The following is a detailed description of the present invention with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Dropwise adding the sodium metaaluminate solution into 10mg/L aluminum sulfate solution at 75 ℃ to react into gel, wherein the neutralization time is 1h, adjusting the pH of the gel to 4, and adding 250mL of 12mg/L sodium silicate solution into the gel at a speed of 8 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 55℃over 5 hours. And then aging at 55 ℃ for 1 hour. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-1. The obtained A-1 has a specific surface area of 542.3m 2 Per g, pore volume of 2.43cm 3 /g。
Example 2
The sodium metaaluminate solution is dripped into 15mg/L aluminum sulfate solution at 75 ℃ to react into gel, the neutralization time is 2h, the pH of the gel is adjusted to 9, and 250mL of 18mg/L sodium silicate solution is added into the gel at the speed of 7 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 65℃over 4 hours. And then aging is continued for 1h at 65 ℃. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-2. The obtained A-2 has a specific surface area of 411.3m 2 Per g, pore volume of 2.11cm 3 /g。
Example 3
Dropwise adding the sodium metaaluminate solution into 25mg/L aluminum sulfate solution at 75 ℃ to react into gel, wherein the neutralization time is 2.5h, adjusting the pH of the gel to 7, and adding 250mL of 23mg/L sodium silicate solution into the gel at a speed of 8 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 45℃over 3 hours. And then aging is continued at 45 ℃ for 1 hour. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-3. The specific surface area of the obtained A-3 is 542.1m 2 Per g, pore volume of 2.07cm 3 /g。
Example 4
The sodium metaaluminate solution is dripped into 10mg/L aluminum sulfate solution at 75 ℃ to react into gel, the neutralization time is 1.5h, the pH of the gel is regulated to 7, and 250mL of 15mg/L sodium silicate solution is added into the gel at the speed of 11 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 25℃over 2 hours. And then aging at 25 ℃ for 1 hour. The two-dimensional nano-sheet is obtained after filtration and washing and is marked as A-4. The obtained A-4 has a specific surface area of 544.9m 2 Per g, pore volume of 1.94cm 3 /g。
Example 5
The sodium metaaluminate solution is dripped into 15mg/L aluminum sulfate solution at 75 ℃ to react into gel, the neutralization time is 0.5h, the pH of the gel is adjusted to 9, and 250mL of 18mg/L sodium silicate solution is added into the gel at the speed of 7 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 15℃over 1 hour. And then aging is continued for 1h at 20 ℃. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-5. The obtained A-5 has a specific surface area of 547.7m 2 Per g, pore volume of 2.10cm 3 /g。
Example 6
Dropwise adding the sodium metaaluminate solution into 10mg/L of aluminum nitrate solution at 75 ℃ to react into gel, wherein the neutralization time is 1h, adjusting the pH of the gel to 4, and adding 250mL of 12mg/L of pyrophosphoric acid solution into the gel at a speed of 8 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 55℃over 5 hours. And then aging at 55 ℃ for 1 hour. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-6. The specific surface area of the obtained A-6 is 505.8m 2 Per g, pore volume of 1.25cm 3 /g。
Example 7
Dropwise adding the sodium metaaluminate solution into 25mg/L of aluminum chloride solution at 75 ℃ to react into gel, wherein the neutralization time is 2.5h, adjusting the pH of the gel to 7, and adding 250mL of 23mg/L of ammonium borate solution into the gel at a speed of 8 mL/min. After the completion of the dropwise addition, the temperature of the system was lowered to 45℃over 3 hours. And then aging is continued at 45 ℃ for 1 hour. Filtering and washing to obtain the two-dimensional nano sheet which is marked as A-3. The specific surface area of the obtained A-3 is 449.5m 2 Per g, pore volume of 1.48cm 3 /g。
Characterization:
(1) Characterization of two-dimensional nanoplatelets
FIG. 1 shows N of two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5 2 Adsorption and desorption isotherm diagram; FIG. 2 is a graph showing pore size distribution of two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5; FIG. 3 is a graph showing the cumulative pore volume versus pore size distribution of the two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5; FIG. 4 is an XRD pattern of two-dimensional boehmite obtained in examples 1, 2, 3, 4, and 5. FIG. 5 shows the two obtainedSEM and TEM images of the vitamin boehmite.
As can be seen from fig. 1, all samples have type IV isotherms, indicating that the two-dimensional boehmite obtained in all examples is mesoporous; P/P 0 The adsorption capacity of the curve is obviously increased after 0.9, which shows that the two-dimensional boehmite shown by the invention has larger pore volume.
As can be seen from fig. 2, all samples had a porous distribution and the pore size was between 15-50 nm.
As can be seen from FIG. 3, the contribution of pores smaller than 20nm to pore volume was 1cm for all samples 3 The contribution degree of pores with the diameter of more than 20nm to the pore volume is also 1cm 3 /g, which indicates that all samples have both more mesopores and partially larger mesopores.
It can be seen from fig. 4 that boehmite loses the diffraction peak of the (020) crystal plane after intercalation-exfoliation, which indicates that boehmite loses periodicity in the [020] direction, which is related to intercalation-exfoliation.
From FIG. 5, it can be seen that boehmite is assembled from two-dimensional nano-sheets having an average length of 24.5nm and a thickness of 2-3nm.
Claims (9)
1. A method for preparing two-dimensional nano-sheets by intercalation-exfoliation of boehmite, comprising the steps of:
(1) Adding an alkaline aluminum source into an acidic aluminum source with a certain concentration at a certain temperature;
(2) After neutralization reaction for a period of time, regulating the pH value of the gel to a certain value;
(3) Diluting a modifier with a certain concentration to a certain concentration, and adding the modifier into gel at a certain speed;
(4) And (3) reducing the temperature of the synthesis system to a certain value within a certain time, aging for a period of time within a certain temperature range, and filtering and washing to obtain the two-dimensional boehmite nano-sheet with high specific surface area and large pore volume.
2. The method of claim 1, wherein the concentration of the acidic aluminum source in step (1) is at a concentration of Al in solution 2 O 3 Content ofCalculated as 5-30mg/L.
3. The method according to claim 1, wherein the neutralization reaction time in the step (2) is 0.5 to 3 hours.
4. The method of claim 1, wherein the gel in step (2) is pH-adjusted to 4-9.
5. The method of claim 1, wherein the modifier in step (3) is one or more of a silicon-containing, boron-containing, and phosphorus-containing compound; wherein the silicon-containing compound is one or more of sodium silicate, silica sol and silicon tetrachloride; the boron-containing compound is one or more of ammonium borate and boric acid; the phosphorus-containing compound is one or more of phosphoric acid, pyrophosphoric acid and ammonium phosphate.
6. The method according to claim 1, wherein the concentration of the modifier in the step (3) is 10mg/L to 30mg/L in terms of oxide.
7. The method of claim 1, wherein the modifier is added in step (3) at a rate of 6mL/min to 12mL/min.
8. The method according to claim 1, wherein the cooling time of the synthesis system in step (4) is 1 to 6 hours.
9. The method of claim 1, wherein the temperature of the synthesis system in step (4) is reduced to between 20 ℃ and 80 ℃.
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