CN110665464A - MIL-101 core-shell structure nano composite material and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 239000011258 core-shell material Substances 0.000 title claims abstract description 33
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910010342 TiF4 Inorganic materials 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 7
- 239000000725 suspension Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
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- 238000000108 ultra-filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000004729 solvothermal method Methods 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 2
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- 239000013110 organic ligand Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J35/19—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses an MIL-101 core-shell structure nano composite material and a preparation method thereof, which comprises the following steps of firstly, Cr (NO)3)3·9H2Mixing O, terephthalic acid, HF and deionized water, and performing ultrafiltration at room temperaturePouring the mixture into a reaction kettle, heating, separating, washing and drying to obtain MIL-101(Cr) powder; dissolving the MIL-101(Cr) powder in ethanol, stirring, and adding TiF4Stirring the aqueous solution, placing the suspension in a stainless steel tetrafluoroethylene lined hydrothermal autoclave for heating, separating, washing and drying to finally obtain MIL-101(Cr)/TiO2The core-shell structure nano composite material has mild preparation conditions and simple process; synthetic MIL-101(Cr)/TiO2The composite material has uniform size and good dispersibility, and is expected to be applied to photoelectric materials or photocatalytic materials and the like.
Description
Technical Field
The invention relates to the technical field of MILs (linear nano-scaled) nano composite materials, in particular to an MIL-101 core-shell structure nano composite material and a preparation method thereof.
Background
Metal-organic frameworks (MOFs) are a new type of highly porous material, and their structure is composed of Metal ions and organic ligands arranged periodically. MOFs have a wide range of structures, adjustable pore sizes, and ultra-high porosity. Some MILs have flexibility, and the channels expand and contract under different pressure and temperature influences. The MIL-101 material can be applied to the fields of gas separation, storage, adsorption, catalysis and the like.
At present, MIL-101 material is mostly applied to catalytic decomposition and adsorption by adopting a single component, and although the MIL-101 material also has the advantages of high catalytic activity, stable chemical property, strong thermal stability and the like compared with the existing common catalytic and adsorption material, the MIL-101 material is far from enough for the existing complex pollution source, especially for waste water containing organic pollutants and CO-containing waste water2The adsorption performance of the exhaust gas and the like is poor. And the current method for preparing the MIL-101 material is also complex.
Disclosure of Invention
In view of the above, the invention aims to provide an MIL-101 core-shell structure nanocomposite and a preparation method thereof, wherein the MIL-101 core-shell structure nanocomposite is prepared by adopting a solvothermal method and a hydrothermal reaction, and the method is simple and easy to implement.
The invention provides a MIL-101 core-shell structure nanocomposite material based on the above objects, which comprises a core formed by MIL-101(Cr) with an octahedral structure,TiO coated on the MIL-101(Cr) surface2And (4) a shell.
A preparation method of an MIL-101 core-shell structure nano composite material comprises the following steps,
(1) MIL-101(Cr) octahedron preparation: first Cr (NO)3)3·9H2Mixing O, terephthalic acid, HF and deionized water, performing ultrasonic treatment at room temperature for 20-40 min, performing hydrothermal reaction on the mixed solution, and performing centrifugal separation, washing and drying on the reactant to obtain octahedron MIL-101 (Cr);
(2)MIL-101(Cr)/TiO2preparing a core-shell structure nano composite material: adding the MIL-101(Cr) prepared in the step (1) into ethanol, stirring and mixing, and then adding TiF4The aqueous solution is continuously stirred, then the hydrothermal reaction is carried out, the reaction product is centrifugally separated, washed and dried, and MIL-101(Cr)/TiO is obtained2A core-shell structure nanocomposite material.
Optionally, the mass fraction of the HF in the step (1) is 30-50 wt%.
Optionally, the temperature of the hydrothermal reaction in the step (1) is 180-230 ℃, and the reaction time is 7-12 hours.
Optionally, the TiF in the step (2)4The molar concentration of the compound is 0.018-0.025 mol/L.
Optionally, the hydrothermal reaction temperature in the step (2) is 140-200 ℃, and the heating time is 10-16 h.
Optionally, the ethanol solution is added in the step (2) and the TiF is added4The stirring time of the aqueous solution is 15-25 min.
Optionally, in the step (2), the drying temperature is 55-70 ℃, and the drying time is 10-14 h.
Optionally, the washing in step (1) and step (2) is performed by using dimethylformamide and ethanol respectively.
From the above, the MIL-101 core-shell structure nanocomposite and the preparation method thereof provided by the invention have the advantages that the MIL-101(Cr) octahedron is prepared by adopting a solvothermal method, the MIL-101(Cr) octahedron is used as a matrix material, and the hydrothermal reaction is continued to prepare the MIL-101(Cr)/TiO2The method is simple and feasible, and the novel MIL-101(Cr)/TiO nano composite material obtained by the preparation method is novel2Core-shell structure nanocomposite material combining MIL-101(Cr) and TiO2The characteristics and advantages of the two materials form a novel multifunctional composite material, and the novel multifunctional composite material has great application potential in the fields of adsorption and catalytic decomposition of organic matters in gas or wastewater treatment and the like.
Drawings
FIG. 1 shows MIL-101(Cr) and TiO of an embodiment of the present invention2And MIL-101(Cr)/TiO2XRD pattern of (a);
FIG. 2 is an SEM image of MIL-101(Cr) prepared in example 1 of the present invention;
FIG. 3 shows MIL-101(Cr)/TiO prepared in example 1 of the present invention2An electron microscope image;
FIG. 4 shows MIL-101(Cr)/TiO prepared in example 1 of the present invention2Reduction of CO2Generating CH4A graph is shown schematically;
FIG. 5 shows MIL-101(Cr)/TiO prepared in example 2 of the present invention2SEM picture;
FIG. 6 shows MIL-101(Cr)/TiO prepared in example 3 of the present invention2SEM image.
Detailed Description
In the following description of the embodiments, the detailed description of the present invention, such as the manufacturing processes and the operation and use methods, will be further described in detail to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
In order to solve the defects of the performance of an MIL-101 material and the complex problems of the preparation method in the prior art, the MIL-101 core-shell structure nano composite material provided by the invention comprises a core formed by an octahedral MIL-101(Cr) structure and TiO coated on the surface of the MIL-101(Cr)2And (4) a shell.
Meanwhile, the preparation method of the MIL-101 core-shell structure nano composite material comprises the following steps,
(1) MIL-101(Cr) octahedron preparation: first Cr (NO)3)3·9H2O, p-benzeneMixing dicarboxylic acid, HF and deionized water, performing ultrasonic treatment at room temperature for 20-40 min, performing hydrothermal reaction on the mixed solution, and performing centrifugal separation, washing and drying on the reactant to obtain octahedron MIL-101 (Cr);
(2)MIL-101(Cr)/TiO2preparing a core-shell structure nano composite material: adding the MIL-101(Cr) prepared in the step (1) into ethanol, stirring and mixing, and then adding TiF4The aqueous solution is continuously stirred, then the hydrothermal reaction is carried out, the reaction product is centrifugally separated, washed and dried, and MIL-101(Cr)/TiO is obtained2A core-shell structure nanocomposite material.
Firstly preparing a nucleus consisting of MIL-101(Cr) with an octahedral structure by a solvothermal method, and then preparing TiO coated on the surface of the MIL-101(Cr) by using the solvothermal method2The shell forms the MIL-101 nano composite material with the core-shell structure, and the whole preparation process is simple and easy to operate.
Specifically, the preparation method of the MIL-101 core-shell structure nanocomposite provided in embodiment 1 of the present invention includes the following steps,
(1) 0.8004g of Cr (NO)3)3·9H2O, 0.3322g of terephthalic acid, 0.1mL of HF (40 wt%) and 14mL of deionized water were mixed and hydrated, and then the solution was uniformly dispersed by sonication at room temperature for 30 min. Placing the dispersed suspension in 25mL of hydrothermal solution of a stainless steel lining reaction kettle, and heating for 10h at 200 ℃; centrifuging to obtain reaction product, washing the centrifuged product with ethanol and (N, N-methylformamide) DMF for several times, and vacuum drying at 60 deg.C for 12 hr to obtain MIL-101 (Cr);
(2) 5.2mg MIL-101(Cr) was dissolved in 10mL ethanol and stirred for 20min, then 3mL TiF was added4(0.022M) and stirring the aqueous solution for 20 min; placing the mixed suspension in 25mL hydrothermal solution of stainless steel lined reaction kettle, heating at 180 deg.C for 14h, centrifuging, washing with ethanol and water for several times, and vacuum drying at 60 deg.C for 12h to obtain MIL-101(Cr)/TiO2。
The product was analyzed using X-ray light diffraction (XRD), Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM).
FIG. 1 shows example 1XRD pattern of the product. MIL-101(Cr) and TiO obtained in the preparation process of example 1 are given separately2Nanospheres and MIL-101(Cr)/TiO2The XRD pattern of the composite material shows that the product of the embodiment contains TiO2And MIL-101 (Cr).
FIG. 2 is an SEM photograph of MIL-101(Cr) obtained in the production process of the product of example 1. As can be seen from the figure, the MIL-101(Cr) prepared is an octahedral structure with uniform size.
FIG. 3 shows MIL-101(Cr)/TiO 2, a product obtained in example 1 of the present invention2The SEM image of (A) is a SEM image, and (b) (c) is a TEM image. As can be seen from the figure, a layer of TiO is uniformly grown on the surface of the MIL2. TEM picture further proves that the prepared composite material is of a core-shell structure, the inside is MIL-101(Cr), and the outside is wrapped by TiO2And (3) nanoparticles.
Meanwhile, the prepared MIL-101(Cr) and MIL-101(Cr)/TiO2And pure TiO2Is a photocatalyst and is at 300mW/cm-2CO in the presence of water under full-spectrum light irradiation2The results of the reduction study are shown in FIG. 4. 6h after irradiation, pure TiO2Shows a methane yield of 0.414. mu. mol/g-1. In contrast, sample MIL-101(Cr)/TiO2The highest activity was shown to be 1.2930.414. mu. mol/g-1Is pure TiO2Three times that of the original. The main reason for this is the MIL-101(Cr)/TiO preparation2The composite material has higher specific surface area and can provide more active sites. In order to further improve the MIL-101(Cr)/TiO2The photocatalytic activity of (B) is in MIL-101(Cr)/TiO2And a cocatalyst Pt is loaded on the surface of the composite material to be used as an electron trap. The rate of methanogenesis was 16.43. mu. mol/g-1This is due to the efficient separation of electron-hole pairs.
Furthermore, the preparation method of the MIL-101 core-shell structure nanocomposite material provided in embodiment 2 of the present invention includes the following steps,
(1) 0.8004g of Cr (NO)3)3·9H2O, 0.3322g terephthalic acid, 0.1mLHF (40 wt%) and 14mL deionized water are mixed and hydrated, and then ultrasonic treatment is carried out at room temperature for 30min evenly dispersing the solution; placing the suspension in 25mL of hydrothermal solution with a stainless steel lining, and heating at 200 ℃ for 10 h; centrifuging to obtain reaction product, washing the centrifuged product with ethanol and (N, N-methylformamide) DMF for several times, and vacuum drying at 60 deg.C for 12 hr to obtain MIL-101 (Cr);
(2) 5.2mg MIL-101(Cr) was dissolved in 10mL ethanol and stirred for 20min, then 5mL TiF was added4(0.022M) and stirring the aqueous solution for 20 min; placing the mixed suspension in 25mL hydrothermal solution of stainless steel lined reaction kettle, heating at 180 deg.C for 14h, centrifuging, washing with ethanol and water for several times, and vacuum drying at 60 deg.C for 12h to obtain MIL-101(Cr)/TiO2。
FIG. 5 shows MIL-101(Cr)/TiO prepared in example 2 of the present invention2SEM image of product, increase TiF4After the addition of (c), there is an excess of titanium dioxide dispersed around the product.
Furthermore, the preparation method of the MIL-101 core-shell structure nanocomposite material provided in embodiment 3 of the present invention includes the following steps,
(1) 0.8004g of Cr (NO)3)3·9H2Mixing and hydrating O, 0.3322g of terephthalic acid, 0.1mL of HF (40 wt%) and 14mL of deionized water, and performing ultrasonic treatment at room temperature for 30min to uniformly disperse the solution; placing the suspension in 25mL of hydrothermal solution with a stainless steel lining, and heating at 200 ℃ for 10 h; centrifuging to obtain reaction product, washing the centrifuged product with ethanol and (N, N-methylformamide) DMF for several times, and vacuum drying at 60 deg.C for 12 hr to obtain MIL-101 (Cr);
(2) 5.2mg MIL-101(Cr) was dissolved in 10mL ethanol and stirred for 20min, then 5mL TiF was added4(0.022M) and stirring the aqueous solution for 20 min; placing the mixed suspension in 25mL hydrothermal solution of stainless steel lined reaction kettle, heating at 140 deg.C for 14h, centrifuging, washing with ethanol and water for several times, and vacuum drying at 60 deg.C for 12h to obtain MIL-101(Cr)/TiO2。
FIG. 6 shows MIL-101(Cr)/TiO prepared in example 3 of the present invention2SEM image of the product, heating at 140 deg.C to obtain the product, and partially compounding and synthesizing due to low temperatureThe results were poor.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The MIL-101 core-shell structure nanocomposite is characterized by comprising a core formed by MIL-101(Cr) with an octahedral structure and TiO coated on the surface of the MIL-101(Cr)2And (4) a shell.
2. A preparation method of an MIL-101 core-shell structure nano composite material is characterized by comprising the following steps,
(1) MIL-101(Cr) octahedron preparation: first Cr (NO)3)3·9H2Mixing O, terephthalic acid, HF and deionized water, performing ultrasonic treatment at room temperature for 20-40 min, performing hydrothermal reaction on the mixed solution, and performing centrifugal separation, washing and drying on the reactant to obtain octahedron MIL-101 (Cr);
(2)MIL-101(Cr)/TiO2preparing a core-shell structure nano composite material: adding the MIL-101(Cr) prepared in the step (1) into ethanol, stirring and mixing, and then adding TiF4The aqueous solution is continuously stirred, then the hydrothermal reaction is carried out, the reaction product is centrifugally separated, washed and dried, and MIL-101(Cr)/TiO is obtained2A core-shell structure nanocomposite material.
3. The preparation method of the MIL-101 core-shell structure nanocomposite material according to claim 2, wherein the mass fraction of HF in the step (1) is 30-50 wt%.
4. The preparation method of the MIL-101 core-shell structure nanocomposite material according to claim 2, wherein the hydrothermal reaction in the step (1) is carried out at a temperature of 180-230 ℃ for 7-12 h.
5. The method for preparing MIL-101 core-shell nanocomposite according to claim 2, wherein the TiF in the step (2)4The molar concentration of the compound is 0.018-0.025 mol/L.
6. The preparation method of the MIL-101 core-shell structure nanocomposite material according to claim 2, wherein the hydrothermal reaction temperature in the step (2) is 140-200 ℃, and the heating time is 10-16 h.
7. The method for preparing MIL-101 core-shell nanocomposite material according to claim 2, wherein the step (2) comprises adding ethanol solution and adding TiF4The stirring time of the aqueous solution is 15-25 min.
8. The preparation method of the MIL-101 core-shell structure nanocomposite material according to claim 2, wherein the drying temperature in the step (2) is 55-70 ℃, and the drying time is 10-14 h.
9. The method for preparing the MIL-101 core-shell structure nanocomposite material according to claim 2, wherein the washing in the step (1) and the washing in the step (2) are performed by using dimethylformamide and ethanol, respectively.
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