CN114044538B - Core-shell structure M-phase VO with surface mesoporous structure 2 Is prepared by the preparation method of (2) - Google Patents
Core-shell structure M-phase VO with surface mesoporous structure 2 Is prepared by the preparation method of (2) Download PDFInfo
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- CN114044538B CN114044538B CN202111238872.8A CN202111238872A CN114044538B CN 114044538 B CN114044538 B CN 114044538B CN 202111238872 A CN202111238872 A CN 202111238872A CN 114044538 B CN114044538 B CN 114044538B
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 230000027311 M phase Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 132
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 50
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 6
- 239000010963 304 stainless steel Substances 0.000 description 5
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- 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
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a core-shell structure M-phase VO with a surface mesoporous structure 2 According to the preparation method, vanadium pentoxide is selected as a vanadium source, citric acid is used as a reducing agent, the vanadium pentoxide is induced to be reduced into a deep blue aqueous solution, the deep blue aqueous solution serves as a nucleation guiding template in the hydrothermal reaction process, nano particles are formed by self-assembly from inside to outside, cetyl trimethyl ammonium bromide is added, the cetyl trimethyl ammonium bromide on a shell can be removed by calcination to form a mesoporous surface, and the obtained inorganic material has an excellent mesoporous structure, a high specific surface area and a lower phase transition temperature, and is used as an adsorption, photocatalysis and electrode material, so that the inorganic material has a wide application prospect; the preparation method of the invention also has the advantages of simple equipment, easy control and low manufacturing cost.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a core-shell structure M-phase VO with a surface mesoporous structure 2 Is prepared by the preparation method of (1).
Background
In recent years, along with the continuous perfection of nano preparation technology, M-phase VO with various different morphologies 2 Has been developed by successive synthesis. Such as nanoparticles, nanorods, nanowires, solid microspheres, hollow microspheres, and the like. In general, different morphologies tend to have different physical and chemical properties. The core-shell structure has a special internal space structure, so that the core-shell structure has good optical and electrochemical characteristics, and is widely applied to gas storage separation, drug delivery and catalytic protection. In addition, the porous material has a specific surfaceThe advantages of high area, low relative density and the like, particularly the advantages of large specific surface area, adjustable pore diameter and the like of mesoporous materials are highlighted in the field of porous materials.
Most of the preparation methods of the prior prepared core-shell structure are selective corrosion and dissolution methods and soft template methods for synthesizing Pt@SiO 2 Mesoporous catalysts, and the like. These methods all have common disadvantages: the process is complex and generally requires 2-3 heat treatments. Finally, the inner spherical shell material or the outer spherical shell material is removed through calcination or solvent dissolution, so that the microsphere with the core-shell structure is formed, and insufficient carbon residue removal can exist.
Disclosure of Invention
The invention aims to provide a core-shell structure M-phase VO with a surface mesoporous structure 2 The preparation method of the (2) prepares the M-phase VO with the core-shell structure 2 The surface has a uniform mesoporous structure.
The technical scheme adopted by the invention is that the core-shell structure M-phase VO with the surface mesoporous structure 2 The preparation method of the catalyst is specifically implemented according to the following steps:
step 1, dissolving citric acid in deionized water to obtain a citric acid solution;
step 2, adding vanadium pentoxide into the citric acid solution, and stirring until a deep blue aqueous solution is formed;
step 3, adding hexadecyl trimethyl ammonium bromide into the deep blue aqueous solution, and continuously stirring;
step 4, transferring the mixed solution obtained in the step 3 into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a drying box, cooling to room temperature after the reaction is finished, centrifuging to take out a black product, washing with deionized water and ethanol, removing surface impurities, and vacuum drying to obtain VO 2 (M) a precursor;
step 5, VO is carried out 2 Placing the precursor in a vacuum tube furnace, heating at 500-600deg.C for 2-8 hr to obtain core-shell structure VO with surface mesoporous structure 2 (M)。
The invention is also characterized in that:
the specific process of the step 1 is as follows: adding 0-0.125mol/mL citric acid into deionized water in a water bath at a volume ratio of 1:2, and stirring for 20min after adding citric acid at 60-90 ℃ to obtain a citric acid solution.
And 2, mixing the vanadium pentoxide and the citric acid solution for 4-8 hours in a mass ratio of 1:1-5.
The mass ratio of hexadecyl trimethyl ammonium bromide in the step 3 to vanadium pentoxide in the step 2 is 1:50.
And in the step 4, placing the hydrothermal reaction kettle in a drying box, wherein the drying temperature is 180-220 ℃ and the drying time is 6-24 hours.
The vacuum drying specific process in the step 4 is as follows: and placing the black product with the surface impurities removed in a vacuum drying oven, and preserving the temperature at 80 ℃ for 10-16h.
VO is generated in step 5 2 After the precursor (M) is placed in a vacuum tube furnace, under the condition of argon atmosphere, the argon flow rate is 40-300sccm, and the heating rate is 10-20 ℃/min, and the temperature is 500-600 ℃.
The beneficial effects of the invention are as follows:
the invention relates to a core-shell structure M-phase VO with a surface mesoporous structure 2 In the preparation method of (2), vanadium pentoxide is selected as a vanadium source. Citric acid is used as a reducing agent to induce the reduction of vanadium pentoxide into a dark blue aqueous solution. During the hydrothermal reaction, it acts as a nucleation guiding template, forming nanoparticles by self-assembly from inside to outside. Cetyl trimethyl ammonium bromide is added, and the cetyl trimethyl ammonium bromide on the shell can be removed by calcination to form a mesoporous surface. The obtained inorganic material has excellent mesoporous structure, high specific surface area and lower phase transition temperature, and has wide application prospect when being used as an adsorption, photocatalysis and electrode material; the preparation method of the invention also has the advantages of simple equipment, easy control and low manufacturing cost.
Drawings
FIG. 1 is a core-shell structure VO prepared in example 1 2 (M) a transmission electron microscopy image of mesoporous material;
FIG. 2 is a core-shell structure VO prepared in example 2 2 (M) a transmission electron microscopy image of mesoporous material;
FIG. 3 is a core-shell structure VO prepared in example 3 2 (M) a transmission electron microscopy image of mesoporous material;
FIG. 4 is a core-shell structure VO prepared in comparative example 1 2 (M) scanning electron microscope pictures of mesoporous materials;
FIG. 5 is a core-shell structure VO prepared in comparative example 2 2 (M) transmission electron microscope image of mesoporous material.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention provides a core-shell structure M-phase VO with a surface mesoporous structure 2 The preparation method of the catalyst is specifically implemented according to the following steps:
step 1, adding 20 milliliters of citric acid with the concentration of 0-0.125mol/mL into 40 milliliters of deionized water in a water bath, wherein the volume ratio of the citric acid to the deionized water is 1:2, the temperature of the water bath is 60-90 ℃, and stirring for 20 minutes after adding the citric acid to obtain a citric acid solution;
step 2, adding vanadium pentoxide into the citric acid solution, wherein the mass ratio of the vanadium pentoxide to the citric acid solution is 1:1-5, and stirring for 4-8 hours until a dark blue aqueous solution is formed;
step 3, adding cetyl trimethyl ammonium bromide into the deep blue aqueous solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the vanadium pentoxide in the step 2 is 1:50, and continuously stirring;
transferring the mixed solution obtained in the step (3) into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a drying oven, drying at 180-220 ℃ for 6-24 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a black product, flushing with deionized water and ethanol to remove surface impurities, placing the black product with the surface impurities removed into a vacuum drying oven, and preserving the temperature at 80 ℃ for 10-16 hours to obtain VO 2 (M) a precursor;
step 5, VO is carried out 2 Placing the precursor in a vacuum tube furnace, under the condition of argon atmosphere, argon flow speed is 40-300sccm, heating rate is 10-20 ℃/min, heating temperature is 500-600 ℃, and holding temperature is 500-600 ℃ for 2-8h, so as to obtain the core-shell with mesoporous structureStructure VO 2 (M)。
The invention selects vanadium pentoxide as vanadium source. Citric acid is used as a reducing agent to induce the reduction of vanadium pentoxide into a dark blue aqueous solution. During the hydrothermal reaction, it acts as a nucleation guiding template, forming nanoparticles by self-assembly from inside to outside. Cetyl trimethyl ammonium bromide is added, and the cetyl trimethyl ammonium bromide on the shell can be removed by calcination to form a mesoporous surface. The obtained inorganic material has excellent mesoporous structure, high specific surface area and lower phase transition temperature, and has wide application prospect when being used as an adsorption, photocatalysis and electrode material 2 (M) is M-phase VO 2 。
Example 1
20 ml of 0.075mol/ml citric acid was added to 40ml deionized water and dissolved by stirring for 20min at 80℃in a water bath to form a citric acid solution. The mass ratio of the vanadium pentoxide to the citric acid is 1:3, then 2g of the vanadium pentoxide is weighed, added into the citric acid solution and stirred for 4 hours. Subsequently, 0.04g of cetyltrimethylammonium bromide was added and stirring was continued for 60min. The resulting mixed solution was transferred to a hydrothermal reaction vessel (304 stainless steel/100 ml high temperature resistant reaction vessel) and reacted at 180℃for 18 hours. Centrifuging the hydrothermal product with a high-speed centrifuge (rotation speed 9000rmp for 20 min), collecting black product, washing with ethanol and deionized water for 6 times, placing in a vacuum drying oven, and maintaining at 80deg.C for 12 hr to obtain VO 2 (M) a precursor. Then VO is carried out 2 The precursor (M) is placed in a vacuum tube furnace and annealed under the condition of argon atmosphere (flow rate 80 sccm), the heating rate is 10 ℃/min, the annealing temperature is 500 ℃, the heat preservation time is 2 hours, and finally the core-shell VO with the mesoporous structure is obtained 2 The specific surface area of the obtained unit mass material is 100M2/g, the mesoporous aperture is 5.02nm, and the pore volume is 0.14cm3/g. FIG. 1 shows a core-shell VO obtained in example 1 2 As can be seen from FIG. 1, the transmission electron microscope photograph of the (M) microsphere shows that the core-shell VO 2 The edges of the microspheres are not smooth, and the microspheres have an egg-shaped core-shell structure.
Example 2
Will be 20 milli0.1mol/ml of citric acid is added into 40ml of deionized water, and the mixture is stirred for 20min under the water bath condition of 80 ℃ to be dissolved to form a citric acid solution. Then 2g of vanadium pentoxide is weighed, the mass ratio of the vanadium pentoxide to the citric acid is 1:4, and the mixture is added into the citric acid solution and stirred for 6 hours. Subsequently, 0.04g of cetyltrimethylammonium bromide was added and stirring was continued for 60min. The resulting mixed solution was transferred to a hydrothermal reaction vessel (304 stainless steel/100 ml high temperature resistant reaction vessel) and reacted at 200℃for 18 hours. Centrifuging the hydrothermal product with a high-speed centrifuge (rotation speed 9000rmp for 20 min), collecting black product, washing with ethanol and deionized water for 6 times, placing in a vacuum drying oven, and maintaining at 80deg.C for 12 hr to obtain VO 2 (M) a precursor. Then VO is carried out 2 The precursor (M) is placed in a vacuum tube furnace and annealed under the condition of argon atmosphere (flow speed 110 sccm), the heating rate is 10 ℃/min, the annealing temperature is 550 ℃, the heat preservation time is 6h, and finally the core-shell VO with the mesoporous structure is obtained 2 (M) microspheres, the specific surface area of the obtained material per unit mass is 141M 2 The mesoporous pore diameter is 6.05nm, and the pore volume is 0.15cm3/g. FIG. 2 shows a core-shell VO obtained in example 2 2 As can be seen from FIG. 2, the core-shell structure with regular edges is clearly observed in the transmission electron micrograph of the (M) microspheres.
Example 3
20 ml of 0.125mol/ml citric acid was added to 40ml deionized water and dissolved by stirring for 20min at 80℃in a water bath to form a citric acid solution. Then 2g of vanadium pentoxide is weighed, the mass ratio of the vanadium pentoxide to the citric acid is 1:5, and the mixture is added into the citric acid solution and stirred for 8 hours. Subsequently, 0.04g of cetyltrimethylammonium bromide was added and stirring was continued for 60min. The resulting mixed solution was transferred to a hydrothermal reaction vessel (304 stainless steel/100 ml high temperature resistant reaction vessel) and reacted at 200℃for 24 hours. Centrifuging the hydrothermal product with a high-speed centrifuge (rotation speed 9000rmp for 20 min), collecting black product, washing with ethanol and deionized water for 6 times, placing in a vacuum drying oven, and maintaining at 80deg.C for 12 hr to obtain VO 2 (M) a precursor. Then VO is carried out 2 The precursor (M) is placed in a vacuum tube furnace, and annealed under the condition of argon atmosphere (flow rate 150 sccm)And the temperature rising rate is 10 ℃/min, the annealing temperature is 600 ℃, the heat preservation time is 8 hours, and finally the core-shell VO with the mesoporous structure is obtained 2 (M) microspheres, wherein the specific surface area of the obtained material per unit mass is 177M2/g, the mesoporous aperture is 7.04nm, and the pore volume is 0.16cm3/g. FIG. 3 shows a core-shell VO obtained in example 3 2 From the transmission electron micrograph of (M) microspheres, the core-shell structure and the multi-layer core-shell structure are clearly observed as shown in FIG. 3.
To facilitate further imaging of the microsphere characteristics produced by the method of the present invention, comparative examples 1, 2 were set up:
comparative example 1
20 ml of 0.05mol/ml citric acid was added to 40ml deionized water and dissolved by stirring for 20min at 80℃in a water bath to form a citric acid solution. Then 2g of vanadium pentoxide is weighed, the mass ratio of the vanadium pentoxide to the citric acid is 1:2, and the mixture is added into the citric acid solution and stirred for 6 hours. Subsequently, 0.04g of cetyltrimethylammonium bromide was added and stirring was continued for 60min. The resulting mixed solution was transferred to a hydrothermal reaction vessel (304 stainless steel/100 ml high temperature resistant reaction vessel) and reacted at 200℃for 18 hours. Centrifuging the hydrothermal product with a high-speed centrifuge (rotation speed 9000rmp for 20 min), collecting black product, washing with ethanol and deionized water for 6 times, placing in a vacuum drying oven, and maintaining at 80deg.C for 12 hr to obtain VO 2 (M) a precursor. Then VO is carried out 2 The precursor (M) is placed in a vacuum tube furnace and annealed under the condition of argon atmosphere (flow speed 150 sccm), the heating rate is 10 ℃/min, the annealing temperature is 550 ℃, the heat preservation time is 6h, and finally the flaky or rod-shaped VO is obtained 2 (M) flaky or rod-shaped VO 2 As shown in FIG. 4, the scanning electron microscope photograph of (M) shows that VO is shown in FIG. 4 2 (M) is a sheet structure.
Comparative example 2
20 ml of 0.15mol/ml citric acid was added to 40ml deionized water and dissolved by stirring for 20min at 80℃in a water bath to form a citric acid solution. Then 2g of vanadium pentoxide is weighed, the mass ratio of the vanadium pentoxide to the citric acid is 1:6, and the mixture is added into the citric acid solution and stirred for 8 hours. Followed by the addition of 0.04g of hexadecyl trimethyl bromideAmmonium, stirring was continued for 60min. The resulting mixed solution was transferred to a hydrothermal reaction vessel (304 stainless steel/100 ml high temperature resistant reaction vessel) and reacted at 200℃for 18 hours. Centrifuging the hydrothermal product with a high-speed centrifuge (rotation speed 9000rmp for 20 min), collecting black product, washing with ethanol and deionized water for 6 times, placing in a vacuum drying oven, and maintaining at 80deg.C for 12 hr to obtain VO 2 (M) a precursor. Then VO is carried out 2 The precursor (M) is placed in a vacuum tube furnace, and is annealed under the condition of argon atmosphere (flow speed 110 sccm), the heating rate is 10 ℃/min, the annealing temperature is 600 ℃, the heat preservation time is 8 hours, and finally the solid VO is obtained 2 (M) microspheres, solid VO 2 As shown in FIG. 5, the transmission electron micrograph of the (M) microspheres shows that VO is shown in FIG. 5 2 (M) is a solid microsphere structure.
VO obtained by examples 1-3 of the present invention 2 (M) microspheres, and the flaky or rod-shaped VO obtained in comparative example 1 2 (M), solid VO obtained in comparative example 2 2 VO obtained by examples 1-3 compared to (M) microspheres 2 As can be seen from the transmission electron microscope photograph of the (M) microsphere, the VO obtained by the method of the invention 2 (M) the specific surface area of the microsphere per unit mass material is 100-200cm 2 Per g, mesoporous pore diameter of 5.014-7.046nm and pore volume of 0.143-0.162cm 3 And/g, which is derived therefrom, the mesoporous core-shell structure VO obtained 2 The microsphere material (M) has an excellent mesoporous structure and a high specific surface area.
Through the mode, the core-shell structure VO with the surface mesoporous structure 2 The preparation method of (M) has simple preparation process, easy control and low manufacturing cost; the VO is 2 (M) high crystallinity, large specific surface area and abundant mesopores on the surface. The material has wide application prospect in the fields of photoelectric devices, adsorption separation, photocatalysis and the like.
Claims (1)
1. Core-shell structure M-phase VO with surface mesoporous structure 2 The preparation method is characterized by comprising the following steps:
step 1, dissolving citric acid in deionized water to obtain a citric acid solution; the specific process is as follows: adding citric acid with the concentration of 0.075-0.125mol/mL into deionized water in a water bath, wherein the volume ratio of the citric acid to the deionized water is 1:2, the water bath temperature is 60-90 ℃, and stirring for 20min after adding the citric acid to obtain a citric acid solution;
step 2, adding vanadium pentoxide into the citric acid solution, and stirring until a deep blue aqueous solution is formed;
the mass ratio of the vanadium pentoxide to the citric acid is 1:1-5, and the stirring time is 4-8h;
step 3, adding cetyl trimethyl ammonium bromide into the deep blue aqueous solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the vanadium pentoxide in the step 2 is 1:50, and continuously stirring;
step 4, transferring the mixed solution obtained in the step 3 into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a drying box, cooling to room temperature after the reaction is finished, centrifuging to take out a black product, washing with deionized water and ethanol to remove surface impurities, and then vacuum drying to obtain M-phase VO 2 A precursor;
the hydrothermal reaction kettle is placed in a drying oven, the drying temperature is 180-220 ℃, and the drying time is 6-24 hours;
the vacuum drying process comprises the following specific steps: placing the black product with the surface impurities removed in a vacuum drying oven, and preserving the temperature at 80 ℃ for 10-16h;
step 5, VO of M phase 2 The precursor is placed in a vacuum tube furnace, the heating temperature is 500-600 ℃, the heating time is 2-8h, and finally the core-shell structure M-phase VO with a mesoporous structure is obtained 2 ；
VO of M phase 2 After the precursor is placed in a vacuum tube furnace, under the condition of argon atmosphere, the argon flow rate is 40-300sccm, the heating rate is 10-20 ℃/min, and the temperature is 500-600 ℃.
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