CN108359105A - Metal organic framework/iron oxide composite material of core-shell structure preparation method - Google Patents
Metal organic framework/iron oxide composite material of core-shell structure preparation method Download PDFInfo
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- CN108359105A CN108359105A CN201810139329.4A CN201810139329A CN108359105A CN 108359105 A CN108359105 A CN 108359105A CN 201810139329 A CN201810139329 A CN 201810139329A CN 108359105 A CN108359105 A CN 108359105A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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Abstract
The invention discloses a kind of 101 (Fe)/Fe of MIL2O3The preparation method of nuclear-shell structured nano-composite material, concrete operations flow are as follows：First by terephthalic acid (TPA) (H2) and FeCl BDC3·6H2O is added to dimethylformamide（DMF）In solution, mixture is ultrasonically treated, is subsequently poured into reaction kettle and carries out heating reaction, is centrifuged after reaction, is dried again after washing precipitation, obtains MIL 101 (Fe) yellow powder；Then 25 DEG C synthetic of MIL 101 (Fe) powder is placed at room temperature for 3 months or more, MIL 101 (Fe)/Fe can be obtained2O3Nuclear-shell structured nano-composite material.
Description
Technical field
The invention belongs to field of new materials, more particularly to a kind of novel MIL-101 (Fe)/Fe2O3Nuclear shell structure nano is compound
The preparation method of material.
Background technology
MOFs（Metal-Organic Frameworks）The abbreviation of metal organic framework complex, it be by metal from
Son makees coordination center, and organic molecule makees the novel porous materials of co-ordinating backbone composition.It is broadly divided into following type：Netted gold
Category and organic framework material（Abbreviation IRMOFs）, class zeolite imidazole skeleton material（Abbreviation ZIFs）, Antoine Lavoisier framework material（Referred to as
MILs）, duct formula framework material referred to as（PCNs）.As porous material family newcomer its there are many unique performances,
For example specific surface area, good crystallinity, duct adjustability, the chemical constituent of superelevation are replaceable and surface is functionalisable etc..
MIL-101 is one of the representative the most classical of MILs series, it has the characteristic not available for other MOFs materials, not only there is Jie
Pore structure while also microporous pipeline (diameter<2 nm be micropore, 2-50 nm be it is mesoporous), therefore with great pore volume with
And specific surface area, and what can be stablized is present in air, but also high temperature resistant.MIL-101 (Fe) material is with Fe ions
Make coordination center, preparation process is simple and nontoxic and pollution-free.
Fe2O3It as important transition metal oxide, is widely present in nature, and is widely used in catalysis, pottery
The fields such as porcelain, pigment, ferromagnetic material, light gas sensitive.And in photocatalysis field, iron oxide has energy gap（Eg) small, property
Stable, nontoxic, the inexpensive advantage of energy, and have preferable response to ultraviolet light and visible light, to the utilization ratio of sunlight
It is higher, it can be used for the fields such as environmental contaminants processing and photolysis water hydrogen, oxygen processed, be a kind of very promising visible light
Catalyst.
Above two material is combined, the comprehensive respective characteristic of both materials is prepared a kind of novel multi-functional multiple
Condensation material.New material has both the characteristic of above two material, can effectively improve the efficiency of catalysis reaction, therefore will have very
Good application prospect.
Invention content
The object of the present invention is to provide a kind of MIL-101 (Fe)/Fe2O3The preparation method of nuclear-shell structured nano-composite material,
This method prepares MIL-101 (Fe) octahedrons using solvent-thermal method, and octahedra for basis material with MIL-101 (Fe), in sky
With 25 DEG C of temperature, slowly oxidation makes the octahedra surfaces MIL-101 (Fe) grow Fe in gas2O3MIL-101 is prepared in crystal
(Fe)/Fe2O3Nuclear-shell structured nano-composite material, the method are simple and easy to operate.
Technical scheme is as follows：
（1）MIL-101 (Fe) is octahedra to be prepared
First by terephthalic acid (TPA) and FeCl3·6H2O is added in dimethyl formamide solution, is carried out at ultrasound to mixture
Reason, is subsequently poured into reaction kettle and carries out heating reaction, centrifuged after reaction, is dried again after washing precipitation, obtains MIL-
101 (Fe) are octahedra.
（2）MIL-101(Fe)/TiO2It is prepared by nuclear-shell structured nano-composite material
By step（1）The MIL-101 (Fe) of preparation is octahedra to be placed in 25 DEG C of air environment 3 months or more, and MIL- is obtained
101(Fe)/Fe2O3Nuclear-shell structured nano-composite material.
Wherein, step（1）Described in terephthalic acid (TPA) in dimethyl formamide solution molar concentration be 0.07-0.08
mol/L；FeCl3·6H2Molar concentrations of the O in dimethyl formamide solution is 0.15-0.16 mol/L.
Step（1）Described in supersound process mixed solution be at 25 DEG C at room temperature, time of supersound process is 15-30
The frequency of min, ultrasonic wave are 90 HZ.
Step（1）Described in reaction temperature be 110-130 DEG C, the reaction time be 18-24 h.
Step（1）Described in the detailed process of centrifugation, washing and drying be：It is washed, is then centrifuged for ethyl alcohol, repeatedly 3
It is secondary, it places into baking oven, 8-12 h is placed at 60 DEG C.
Beneficial effects of the present invention：
1) solvent thermal process and air oxidation process is used to prepare nuclear-shell structured nano-composite material, it is simple for process easy to operate；
2) MIL-101 (Fe)/Fe prepared by the present invention2O3Nuclear-shell structured nano-composite material favorable dispersibility, ingredient are controllable；
3) preparation method of the present invention obtains MIL-101 (Fe)/Fe2O3Nuclear-shell structured nano-composite material, the material combine
MIL-101 (Fe) and Fe2O3Two kinds of respective characteristics of material, form a kind of novel composite material, have in fields such as photocatalysis
There is extraordinary application prospect.
Description of the drawings
Fig. 1 is the compound front and back XRD diagram of 1 product of embodiment, is the XRD diagram and MIL-101 of MIL-101 (Fe) respectively
(Fe)/Fe2O3XRD diagram；
Fig. 2 (a) (b) is the SEM figures of the MIL-101 (Fe) obtained in 1 preparation process of embodiment；
Fig. 2 (c) (d) is 1 product MIL-101 (Fe) of embodiment/Fe2O3The SEM of composite material schemes；
Fig. 3 is the SEM figures of embodiment 2；
Fig. 4 is the SEM figures of embodiment 3；
Fig. 5 is the SEM figures of embodiment 4；
Fig. 6 is the SEM figures of embodiment 5；
Fig. 7 is the SEM figures of embodiment 6；
Fig. 8 is the SEM figures of embodiment 7；
Fig. 9 is the SEM figures of embodiment 8；
Figure 10 is the SEM figures of embodiment 9.
Specific implementation mode
The present invention is done with reference to embodiment and is further explained, embodiment is merely to illustrate the present invention, and does not have to
To limit the practical range of the present invention.
Embodiment 1
By 0.14 g terephthalic acid (TPA)s and 0.5 g FeCl3·6H2O is added in 12 mL dimethylformamides, 90 rooms HZ
Lower 30 min of ultrasound of temperature, then solution is poured into reaction kettle, 24 h are reacted at 130 DEG C.After being cooled to room temperature, washed with ethyl alcohol
It washs, is then centrifuged for, 3 times repeatedly, finally solution is put into baking oven, placed 12 hours at 60 DEG C, obtain MIL-101 (Fe) octahedral
Body；Then the exposure of MIL-101 (Fe) powder is obtained into MIL-101 (Fe)/Fe in air and after being kept for 25 DEG C, 3 months2O3
Nuclear-shell structured nano-composite material.
X-ray optical diffraction is respectively adopted（XRD）And scanning electron microscope（SEM）Product is analyzed.Fig. 1 is that embodiment 1 is produced
The compound front and back XRD diagram of product, is the XRD diagram and MIL-101 (Fe)/Fe of MIL-101 (Fe) respectively2O3XRD diagram.The result shows that
Contain Fe in the product of embodiment 12O3, and Fe2O3Diffraction maximum it is more sharp, illustrate surface growth ferric oxide particles crystallization
Well.
Fig. 2 (a) (b) is the SEM figures for the MIL-101 (Fe) that embodiment 1 is prepared, it can be seen from the figure that MIL-101
(Fe) octahedral structure is complete；Fig. 2 (c) (d) is 1 product MIL-101 (Fe) of embodiment/Fe2O3The SEM of composite material schemes, in figure
It can be seen that composite material remains as shape of octahedron, one layer of Fe has been grown on MIL-101 (Fe) octahedrons2O3。
Embodiment 2
By 0.2 g terephthalic acid (TPA)s and 0.66 g FeCl3·6H2O is added in 15 mL dimethylformamides, 90 HZ room temperatures
Lower ultrasonic 30 min, then solution is poured into reaction kettle, 18 h are reacted at 110 DEG C.After being cooled to room temperature, washed with ethyl alcohol
It washs, is then centrifuged for, 3 times repeatedly, finally centrifugation product is put into baking oven, is placed 10 hours at 60 DEG C, obtains MIL-101 (Fe)
It is octahedra；Then MIL-101 (Fe) powder is exposed in air and keeps room temperature（25℃）, MIL-101 is obtained after 3 months
(Fe)/Fe2O3Nuclear-shell structured nano-composite material.
The SEM spectrum of the present embodiment product is as shown in figure 3, as can be seen from the figure in MIL-101 (Fe) octahedral table
Face has grown one layer of Fe2O3Crystal.
Embodiment 3
By 0.14 g terephthalic acid (TPA)s and 0.5 g FeCl3·6H2O is added in 12 mL dimethylformamides, 90 HZ room temperatures
Lower ultrasonic 15 min, then solution is poured into reaction kettle, 24 h are reacted at 120 DEG C.After being cooled to room temperature, washed with ethyl alcohol
It washs, is then centrifuged for, 3 times repeatedly, finally centrifugation product is put into baking oven, is placed 10 hours at 60 DEG C, obtains MIL-101 (Fe)
It is octahedra；Then MIL-101 (Fe) powder is exposed in air and keeps room temperature（25℃）, MIL-101 is obtained after 3 months
(Fe)/Fe2O3Nuclear-shell structured nano-composite material.
The SEM spectrum of the present embodiment product is as shown in figure 4, as can be seen from the figure in MIL-101 (Fe) octahedral table
Face has also grown one layer of Fe2O3Crystal, only no embodiment 1 and embodiment 2 is apparent.This may with ultrasonication when
Between it is too short related.
Embodiment 4
The difference of the present embodiment and embodiment 1：MIL-101 (Fe) powder made from 1 condition of embodiment is positioned over 60 DEG C
Baking oven in, 24 h.
The SEM spectrum of the present embodiment product is as shown in figure 5, as can be seen from the figure MIL-101 (Fe) most of quilts
Oxidation.
Embodiment 5
The difference of the present embodiment and embodiment 1：It will be positioned over 60 by MIL-101 (Fe) powder made from 1 condition of case
DEG C baking oven in, 18 h.
The SEM spectrum of the present embodiment product is as shown in fig. 6, as can be seen from the figure MIL-101 (Fe) is also most of quilt
Oxidation, compared with Example 4 without too big difference.
Embodiment 6
The difference of the present embodiment and embodiment 2：It will be positioned over by MIL-101 (Fe) powder made from 2 condition of embodiment
In 60 DEG C of baking oven, 14 h.
The SEM spectrum of the present embodiment product is as shown in fig. 7, the as can be seen from the figure degree of oxidation phase of MIL-101 (Fe)
There is apparent reduction than embodiment 4 and embodiment 5.
Embodiment 7
The difference of the present embodiment and embodiment 2：It will be positioned over by MIL-101 (Fe) powder made from 2 condition of embodiment
In 70 DEG C of baking oven, 8 h.
The SEM spectrum of the present embodiment product is as shown in figure 8, as can be seen from the figure with the raising MIL-101 of temperature
(Fe) apparent variation has occurred in degree of oxidation.
Embodiment 8
The difference of the present embodiment and embodiment 1：It will be positioned over by MIL-101 (Fe) powder made from 1 condition of embodiment
In 80 DEG C of baking oven, 8 h.
The SEM spectrum of the present embodiment product is unable to get corresponding as shown in figure 9, MIL-101 (Fe) is almost aoxidized
Nanocomposite.
Embodiment 9
The difference of the present embodiment and embodiment 1：It will be exposed to by MIL-101 (Fe) powder made from 1 condition of embodiment
In air and temperature is maintained at 25 DEG C, 2 months.
The SEM spectrum of the present embodiment product is as shown in Figure 10, and the octahedral surface MIL-101 (Fe) is not completely by oxygen
Change, this example demonstrates that the oxidation on the surface MIL-101 (Fe) is related with the time of exposure.
Claims (5)
1. a kind of MIL-101 (Fe)/Fe2O3The preparation method of nuclear-shell structured nano-composite material, it is characterised in that：
（1）MIL-101 (Fe) is octahedra to be prepared
First by terephthalic acid (TPA) and FeCl3·6H2O is added in dimethyl formamide solution, is carried out at ultrasound to mixture
Reason, is subsequently poured into reaction kettle and carries out heating reaction, centrifuged after reaction, is dried again after washing precipitation, obtains MIL-
101 (Fe) are octahedra；
（2）MIL-101(Fe)/Fe2O3It is prepared by nuclear-shell structured nano-composite material
By step（1）The MIL-101 (Fe) of preparation is octahedra to be placed in 25 DEG C of air environment 3 months or more, and MIL- is obtained
101(Fe)/Fe2O3Nuclear-shell structured nano-composite material.
2. MIL-101 (Fe)/Fe as described in claim 12O3The preparation method of nuclear-shell structured nano-composite material, feature
It is：Step（1）Described in terephthalic acid (TPA) in dimethyl formamide solution molar concentration be 0.07-0.08 mol/L；
FeCl3·6H2Molar concentrations of the O in dimethyl formamide solution is 0.15-0.16 mol/L.
3. MIL-101 (Fe)/Fe as described in claim 12O3The preparation method of nuclear-shell structured nano-composite material, feature
It is：Step（1）Described in supersound process be mixed solution 25 DEG C at room temperature be ultrasonically treated 15-30 min, ultrasonic wave
Frequency is 90 HZ.
4. MIL-101 (Fe)/Fe as described in claim 12O3The preparation method of nuclear-shell structured nano-composite material, feature
It is：Step（1）Described in the temperature reacted be 110-130 DEG C, the reaction time is 18-24 h.
5. MIL-101 (Fe)/Fe as described in claim 12O3The preparation method of nuclear-shell structured nano-composite material, feature
It is：Step（1）Described in centrifugation, washing and drying detailed process be washed with ethyl alcohol, be then centrifuged for, 3 times repeatedly, then
It is put into baking oven, is placed 8-12 hours at 60 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113477253A (en) * | 2021-07-21 | 2021-10-08 | 电子科技大学 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
| CN114100686A (en) * | 2021-11-17 | 2022-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterojunction metal organic framework material, product and application thereof |
| CN115724473A (en) * | 2022-10-09 | 2023-03-03 | 安徽信息工程学院 | Method for preparing ferric oxide nano-rod by MOF room temperature conversion |
| CN115770619A (en) * | 2022-11-08 | 2023-03-10 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Process for preparing nano composite material |
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| CN106770496A (en) * | 2017-01-04 | 2017-05-31 | 福州大学 | A kind of preparation method of the di-iron trioxide composite construction gas sensor of zinc doping |
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| CN106770496A (en) * | 2017-01-04 | 2017-05-31 | 福州大学 | A kind of preparation method of the di-iron trioxide composite construction gas sensor of zinc doping |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113477253A (en) * | 2021-07-21 | 2021-10-08 | 电子科技大学 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
| CN114100686A (en) * | 2021-11-17 | 2022-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterojunction metal organic framework material, product and application thereof |
| CN115724473A (en) * | 2022-10-09 | 2023-03-03 | 安徽信息工程学院 | Method for preparing ferric oxide nano-rod by MOF room temperature conversion |
| CN115770619A (en) * | 2022-11-08 | 2023-03-10 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Process for preparing nano composite material |
| CN115770619B (en) * | 2022-11-08 | 2024-03-12 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Method for preparing nanocomposite |
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