CN109939742A - A kind of preparation method of modified MIL-53 (Fe) material of manganese - Google Patents
A kind of preparation method of modified MIL-53 (Fe) material of manganese Download PDFInfo
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- CN109939742A CN109939742A CN201910313197.7A CN201910313197A CN109939742A CN 109939742 A CN109939742 A CN 109939742A CN 201910313197 A CN201910313197 A CN 201910313197A CN 109939742 A CN109939742 A CN 109939742A
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Abstract
The present invention relates to metal-organic framework materials preparation technical fields, provide a kind of preparation method of modified MIL-53 (Fe) material of manganese, it is placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE) the following steps are included: ferric chloride hexahydrate, four water manganese acetates and reaction dissolvent are mixed, it is sealed against being put into electric drying oven with forced convection again and carries out solvent thermal reaction, obtain modified MIL-53 (Fe) material of manganese.Characteristic of the present invention according to MILs material structure and function, it selects that MILs material is made using solvent heat or hydrothermal synthesis to be research object, its equipment is simple, preparation energy consumption is low, and the reaction time is shorter, and the catalytic performance of modified MIL-53 (Fe) material of preparation-obtained manganese can be significantly improved, and conversion ratio degradable to the catalysis oxidation of toluene is high, and the complexity due to dimethylbenzene structure compared to toluene, conversion ratio is opposite to be lower, but may finally reach about 70% conversion.
Description
Technical field
The present invention relates to metal-organic framework materials preparation technical fields, and in particular to a kind of manganese is modified MIL-53 (Fe)
The preparation method of material.
Background technique
The continuous improvement of economic rapid development, living standards of the people, pushes advancing for science.Green wood as a result,
The development of material is also taken advantage of a situation and goes, and increasingly important role is played in our life.Due to life in green wood
The requirement of material is increasingly stringenter, therefore we also become more and more deep for the research of new material, the class of new catalytic material
Type and function also tend to diversification.Catalysis material can be all used in most of industrial process, such as petrochemical industry, biochemistry, coal chemical industry
And environmental protection etc., it can be seen that can all be applied to catalysis material at many aspects that we live.However, since we are once big
Amount be used as catalysis material conventional porous materials its own there are drawbacks and deficiency, be not able to satisfy the growing need of industrial production
It wants.Therefore, there are the Main Topics that are developed into of the porous material of more application values, and with wide before
Scape.
Metal-organic framework materials (MOFs), it is that one kind is assembled by multiple tooth organic ligand and inorganic metal ion newly
Type porous material.After this material is developed, because its excellent catalytic performance is just developed rapidly, and absorption,
Catalysis, ion exchange, sensor, luminous and luminescent material etc. are widely applied.Show excellent catalytic performance
With considerable application prospect.In consideration of it, the synthesis and application of this polyporous materials have obtained the height of all kinds of subjects of region of chemistry
Degree concern, and one of the Main way for rapidly becoming interdisciplinary research.
MIL (Materials of Institut Lavoisier) series is that MOFs series material has critical role
It is a kind of.At high operating temperatures, MILs material can lose the BDC molecule in hole, make aperture increases, and after temperature lowers,
Aperture can reduce again, reuptake hydrone into duct, just as can breathe.Due to its unique respiration and greatly
Aperture is widely used as the absorption of hydrogen, carbon dioxide, methane and some chain alkane.MIL series material is most noticeable
A feature be material the great flexibility of skeleton, extraneous factor stimulation under, material structure can be in macropore and two kinds of aperture
Change between form.
In recent years, metal framework structure material becomes one of the research hotspot of researchers.But the MOFs material of early stage
Expect that structure function is simple, aperture is larger.At the same time, various different series and with different characteristics MOFs material meet the tendency of and
It is raw.MOFs is formed by connecting by organic acid and metal ion, and earliest MOFs material is proposed by Benard F Hoskins, but is worked as
When the obtained stability of MOFs material of scientists it is not high, and aperture larger porosity is also smaller.Finally study
Persons pass through the proportion for changing metal center element, organic ligand and reactant, so that the stability of material is improved, simultaneously
Specific surface area also becomes much larger.Compared with conventional porous materials, MOFs material has bigger specific surface area and more flourishing
Cellular structure, structure composition designability are higher.Can by change synthesis condition or to the channel surfaces of synthetic material into
The modification of row later period obtains the different MOFs material of functional characteristic.The metallic element of research discovery later is as node, hinged node
Organic ligand with node, the ligancy of usual metallic element be it is changeable, can be with shape when causing organic ligand coupled
It is different at aperture.The MOFs of functional diversities, there are many embody in the connection of metallic element and organic ligand for diversity feature.
Meanwhile MILs material made from distinct methods catalytic oxidation activity and in terms of there is difference, exploration is ground
Study carefully that material energy consumption is lower, and reaction time shorter preparation method has great importance.
Summary of the invention
Based on the above background, characteristic of the present invention according to MILs material structure and function, selection use solvent heat or hydro-thermal
Synthesizing and MILs material is made is research object, provides a kind of preparation method of modified MIL-53 (Fe) material of manganese, preparation consumption
Can be low, the reaction time is shorter.
The following technical solution is employed by the present invention:
A kind of preparation method of modified MIL-53 (Fe) material of manganese, comprising the following steps: by ferric chloride hexahydrate, four water
Manganese acetate and reaction dissolvent mixing are placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then to be sealed against being put into electric heating air blast dry
Solvent thermal reaction is carried out in dry case, obtains modified MIL-53 (Fe) material of manganese.
Further, the ferric chloride hexahydrate and the molar ratio of four water manganese acetates are 1:4~4:1.
Further, the ferric chloride hexahydrate and the molar ratio of four water manganese acetates are 2:3~3:2.
Further, the solvent thermal reaction carries out at 120~150 DEG C of temperature；Reaction time is 24~48h.
Further, the reaction dissolvent is N, N- dimethylformamide, methanol, ethyl alcohol and/or water.
Further, the reaction dissolvent is N, N- dimethylformamide.
Further, further comprising the steps of: to the reaction product obtained after the completion of solvent thermal reaction carry out distilled water and/
Or dehydrated alcohol washing, then be centrifuged, then the product after centrifuge separation is placed in electric drying oven with forced convection and is carried out
It is dry.
Further, the drying temperature is 105~120 DEG C；Drying time is 4~8h.
The invention has the advantages that:
Equipment is simple, solves the insoluble problem of part presoma, preparation energy consumption is low, and the reaction time is shorter；When it
After loading manganese ion, catalytic performance can be significantly improved, the promotion of Fe-Mn being combined with conducive to catalytic efficiency and performance,
A series of synthesized MILs compounds are degradable to the catalysis oxidation of toluene and conversion ratio is high, and due to dimethylbenzene structure
Compared to the complexity of toluene, conversion ratio is opposite to be lower, but may finally reach about 70% conversion, the conversion of paraxylene
With preferable effect.
Detailed description of the invention
Fig. 1 is the XRD analysis figure of modified MIL-53 (Fe) material of manganese obtained by embodiment 1-4；
Fig. 2 is catalytic result figure of modified MIL-53 (Fe) material of manganese obtained by embodiment 1-4 to toluene；
Fig. 3 is the catalytic result of modified MIL-53 (Fe) the material paraxylene of manganese obtained by embodiment 1-4.
Specific embodiment
The present invention is specifically described with reference to the accompanying drawing:
Embodiment 1
By the ferric chloride hexahydrate of 0.38656g, four water manganese acetates (ferric chloride hexahydrate and four water of 0.08763g
Manganese acetate molar ratio is 4:1) it is placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then 10mL DMF is put into reaction kettle
In (100ml), sealing, which is placed in 150 DEG C of electric drying oven with forced convection, stands 48h；Three times through distillation water washing by obtained product
Again through dehydrated alcohol washing two to three times, then centrifuge separation is done the electric heating air blast that the product after centrifuge separation is placed in 105 DEG C
Dry 4h in dry case.
Embodiment 2
By the ferric chloride hexahydrate of 0.2899g, four water manganese acetates (ferric chloride hexahydrate and the four water second of 0.1753g
Sour manganese molar ratio is 3:2) it is placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then 10mL DMF is put into reaction kettle (100ml)
In, sealing, which is placed in 150 DEG C of electric drying oven with forced convection, stands 48h；By obtained product through distillation water washing three times again through nothing
To three times, then the product after centrifuge separation is placed in 105 DEG C of electric drying oven with forced convection by centrifuge separation for water-ethanol washing two
Dry 4h.
Embodiment 3
By the ferric chloride hexahydrate of 0.1933g, four water manganese acetates (ferric chloride hexahydrate and the four water second of 0.2829g
Sour manganese molar ratio is 2:3) it is placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then 10mL DMF is put into reaction kettle (100ml)
In, sealing, which is placed in 150 DEG C of electric drying oven with forced convection, stands 48h；By obtained product through distillation water washing three times again through nothing
To three times, then the product after centrifuge separation is placed in 105 DEG C of electric drying oven with forced convection by centrifuge separation for water-ethanol washing two
Dry 4h.
Embodiment 4
By the ferric chloride hexahydrate of 0.0966g, four water manganese acetates (ferric chloride hexahydrate and the four water second of 0.4382g
Sour manganese molar ratio is 1:4) it is placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then 10mL DMF is put into reaction kettle (100ml)
In, sealing, which is placed in 150 DEG C of electric drying oven with forced convection, stands 48h；By obtained product through distillation water washing three times again through nothing
To three times, then the product after centrifuge separation is placed in 105 DEG C of electric drying oven with forced convection by centrifuge separation for water-ethanol washing two
Dry 4h.
The product that embodiment 1-4 is reacted carries out XRD analysis, and it is shown that the result is shown in Figure 1.
Using toluene, dimethylbenzene as research object, modified MIL-53 (Fe) material of analysis manganese as efficient catalyst with
The concentration of toluene, dimethylbenzene is observed in the variation of time and temperature, analyzes the catalytic degradation performance and change of this kind of material
Change reason, and load base metal manganese to it, the conversion ratio of toluene, dimethylbenzene is analyzed by gas-chromatography.
Modified MIL-53 (Fe) material of manganese obtained by embodiment 1-4 is carried out to the catalytic of toluene, dimethylbenzene,
Catalysis degeneration experiment is carried out at different temperature, analyzes its degradation property to volatile organic compound.Manganese is modified MIL-53
(Fe) material to the catalytic result of toluene as shown in Figure 2.The results show that the toluene conversion of Fe2-Mn3 finally may be used
To reach 97% or so, and its fire box temperature is 340 DEG C when toluene conversion is up to 90%；To first after MILs material load manganese ion
The catalytic degradation of benzene is closer to when toluene conversion is up to 90%.
The catalytic result of modified MIL-53 (Fe) the material paraxylene of manganese obtained by embodiment 1-4 is shown in into figure
Shown in 3.The results show that the degradation property tool of paraxylene has a certain impact after load manganese ion, wherein the two of Fe2-Mn3
Toluene conversion may finally reach 68%；And when xylene conversion rate is up to 60%, actual temperature is 419 DEG C in burner hearth.
Embodiment 5
Ferric chloride hexahydrate, four water manganese acetates (ferric chloride hexahydrate and four water manganese acetate molar ratios be 2:1) are set
It is put into reaction kettle (100ml) in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then by 20mL methanol, sealing is placed in 120 DEG C
It is stood for 24 hours in electric drying oven with forced convection；By obtained product through distillation water washing three times again through dehydrated alcohol washing two to three times,
Then product after centrifuge separation is placed in 120 DEG C of electric drying oven with forced convection dry 4h, it is modified to obtain manganese by centrifuge separation
MIL-53 (Fe) material.
Embodiment 6
Ferric chloride hexahydrate, four water manganese acetates (ferric chloride hexahydrate and four water manganese acetate molar ratios be 1:1) are set
It is put into reaction kettle (100ml) in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then by 15mL water, sealing is placed in 130 DEG C of electricity
36h is stood in hot blast drying box；By obtained product through distillation water washing three times again through dehydrated alcohol washing two to three times, from
Then product after centrifuge separation is placed in 105 DEG C of electric drying oven with forced convection dry 8h by heart separation, obtain the modified MIL- of manganese
53 (Fe) materials.
Embodiment 7
Ferric chloride hexahydrate, four water manganese acetates (ferric chloride hexahydrate and four water manganese acetate molar ratios be 3:1) are set
It is put into reaction kettle (100ml) in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then by 30mL ethyl alcohol, sealing is placed in 130 DEG C
36h is stood in electric drying oven with forced convection；By obtained product through distillation water washing three times again through dehydrated alcohol washing two to three times,
Then product after centrifuge separation is placed in 110 DEG C of electric drying oven with forced convection dry 6h, it is modified to obtain manganese by centrifuge separation
MIL-53 (Fe) material.
Due to the distinctive skeleton structure of MILs material, either regular pentagon or cage structure, the gold of frame center
Belonging to site all has catalytic activity, so that the degradation to compound provides possibility.Its distinctive active inorganic metallic site
Center and functional group with catalytic performance make the conversion ratio of the volatile organic compounds such as toluene high.And when its load
After manganese ion, catalytic performance can be significantly improved, and illustrate the promotion of Fe-Mn being combined with conducive to catalytic efficiency and performance.
A series of synthesized MILs compounds are degradable to the catalysis oxidation of toluene and conversion ratio is high.And due to dimethylbenzene structure
Compared to the complexity of toluene, conversion ratio is opposite to be lower, but may finally reach about 70% conversion, the conversion of paraxylene
Also it can be achieved on.
The complexity of compound structure is to degradation property to be also illustrated to the comparison of toluene and dimethylbenzene by Fe3-Mn2
Having centainly influences, but it requires not improve substantially to degradation temperature, therefore, the volatility of same type under same temperature
Catalytic oxidation can be carried out simultaneously by closing object.
Certainly, the above description is not a limitation of the present invention, and the present invention is also not limited to the example above, this technology neck
The variations, modifications, additions or substitutions that the technical staff in domain is made within the essential scope of the present invention also should belong to of the invention
Protection scope.
Claims (8)
1. a kind of preparation method of modified MIL-53 (Fe) material of manganese, which comprises the following steps: by six water of iron chloride
It closes object, four water manganese acetates and reaction dissolvent mixing to be placed in the reaction kettle that liner is polytetrafluoroethylene (PTFE), then is sealed against being put into
Solvent thermal reaction is carried out in electric drying oven with forced convection, obtains modified MIL-53 (Fe) material of manganese.
2. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 1, which is characterized in that the chlorine
The molar ratio for changing iron hexahydrate and four water manganese acetates is 1:4~4:1.
3. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 2, which is characterized in that the chlorine
The molar ratio for changing iron hexahydrate and four water manganese acetates is 2:3~3:2.
4. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 1, which is characterized in that described molten
Agent thermal response carries out at 120~150 DEG C of temperature；Reaction time is 24~48h.
5. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 1, which is characterized in that described anti-
Answering solvent is N, N- dimethylformamide, methanol, ethyl alcohol and/or water.
6. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 5, which is characterized in that described anti-
Answering solvent is N, N- dimethylformamide.
7. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 1, which is characterized in that further include
Following steps: carrying out distilled water to the reaction product obtained after the completion of solvent thermal reaction and/or dehydrated alcohol wash, then carry out from
Product after centrifuge separation, is then placed in electric drying oven with forced convection and is dried by heart separation.
8. a kind of preparation method of modified MIL-53 (Fe) material of manganese according to claim 7, which is characterized in that described dry
Dry temperature is 105~120 DEG C；Drying time is 4~8h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569944A (en) * | 2020-05-20 | 2020-08-25 | 湖南垚恒环境科技有限公司 | Manganese ion doped metal organic framework material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032408A (en) * | 2017-04-26 | 2017-08-11 | 浙江大学 | A kind of ferroso-ferric oxide/C classifying nano spherical structure composites of MnO doping and preparation method thereof |
| CN109293930A (en) * | 2018-07-03 | 2019-02-01 | 东莞理工学院 | One kind is based on+divalent metal MIL-53 poromerics and preparation method thereof |
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- 2019-04-18 CN CN201910313197.7A patent/CN109939742A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032408A (en) * | 2017-04-26 | 2017-08-11 | 浙江大学 | A kind of ferroso-ferric oxide/C classifying nano spherical structure composites of MnO doping and preparation method thereof |
| CN109293930A (en) * | 2018-07-03 | 2019-02-01 | 东莞理工学院 | One kind is based on+divalent metal MIL-53 poromerics and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111569944A (en) * | 2020-05-20 | 2020-08-25 | 湖南垚恒环境科技有限公司 | Manganese ion doped metal organic framework material and preparation method thereof |
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