CN105536708B - A kind of advanced composite material (ACM) and preparation method thereof based on metal-organic framework materials and carbon nanotube - Google Patents
A kind of advanced composite material (ACM) and preparation method thereof based on metal-organic framework materials and carbon nanotube Download PDFInfo
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- CN105536708B CN105536708B CN201510995702.2A CN201510995702A CN105536708B CN 105536708 B CN105536708 B CN 105536708B CN 201510995702 A CN201510995702 A CN 201510995702A CN 105536708 B CN105536708 B CN 105536708B
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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]
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention discloses a kind of advanced composite material (ACM) and preparation method thereof based on metal-organic framework materials and carbon nanotube.The carbon nanotube makes pipe outer wall be connected with organic ligand functional groups by chemical modification, allow modified carbon nanotube and metal-organic framework materials by metal ion and organic ligand functional group pass through coordination bonding act on it is compound, to obtain a kind of novel porous composite material.Carbon nanotube obtains the carbon nanotube for being connected to binary organic acid by carboxylated, chloride and amidation three-step reaction, is mixed with binary organic acid monomer and metal salt monomer, and the composite material is prepared by solvent-thermal process method.The material combines the characteristic of two polyporous materials, shows more preferably adsorption separation performance.
Description
Technical field
The present invention relates to a kind of advanced composite material (ACM) based on metal-organic framework materials and carbon nanotube and its preparation sides
Method；The material combines the characteristic of two polyporous materials, shows more preferably adsorption separation performance.
Background technology
Metal-organic framework materials are that a kind of have that bigger serface, high porosity, chemistry can modify and structure composition is more
The novel porous materials of sample.Such material is the multiple tooth organic ligand by oxygen-containing or nitrogen etc.（It is fragrant polyacid and polybase mostly)
With porous material made of transition metal ions self assembly, possess in fields such as gas storage, adsorbing separation and catalysis wide
Application prospect.In recent years, the extensive concern that advanced composite material (ACM) causes people is prepared based on metal-organic framework materials.Utilize gold
Belong to organic framework material architectural characteristic and combine other materials functionality, can two class material of effective integration obtaining property of advantage
It can more preferably composite material.Have been reported that metal-organic framework materials can be with carbon nanotube, graphene or high molecular material knot
It closes and improves gas absorption performance.
Carbon nanotube is a kind of micropore nanophase materials, has the advantages that large specific surface area, adsorption capacity are big and excellent
Mechanics, electromagnetism, calorifics and optical property.It can adsorb heavy metal ion and organic contamination as sorbing material effectively from water
Object.Surface is carried out to carbon nanotube and is modified the dispersibility that can improve it in a liquid, to improve its absorption property.In addition, table
Face, which is modified, can also make carbon nanotube outer wall connect different functionalities group, and functional composite wood is further prepared with other materials
Material.The present invention is by taking MIL-101 type metal-organic framework materials as an example, by the carbon nanotube of chemical modification and MIL-101 type metals
The ligand self assembly of organic framework material prepares a kind of advanced composite material (ACM).
MIL-101 type metal-organic framework materials are one kind in MIL type metal-organic framework materials, and organic ligand is
Terephthalic acid (TPA) and metal ligand are trivalent transition metal ion, are matched from group with metal ion by the symmetrical carboxyl in organic ligand
Dress forms position.MIL-101 has octahedral crystal structure, three ducts, shows high-specific surface area, macropore holds, high fever is steady
The advantages that qualitative.NH containing amino2_ MIL-101 and MIL-101 crystal structures having the same and similar structural behaviour,
But organic ligand used is 2- amino terephthalic acid (TPA)s, because carrying amido functional group NH2_ MIL-101 have better hydrophily and
It can be modified utilization based on amino.Compared with other porous materials, NH2_ MIL-101 and MIL-101 is as catalyst, absorption
Separation material, optical material and magnetic material etc. have wide practical use.
Carbon nanotube/metal organic framework material can be prepared with metallic ion coordination by having been reported carboxylic carbon nano-tube
Expect composite material.But carboxyl functional group contained by carboxylic carbon nano-tube is relatively low, and symmetry is poor, make its with metallic ion coordination not
Fully, the stability of formed self-assembled structures is poor.The organic ligand for synthesizing metal-organic framework materials is grafted by the present invention
In carbon nanotube outer wall, the carbon nanotube with organic ligand functional group is connect with organic ligand and metal ligand self assembly,
Prepare a kind of advanced composite material (ACM).The composite material not only has the characteristic there are two types of poromerics, and can form additional micropore
Structure, to have excellent adsorption separation performance.
Invention content
The present invention provides a kind of advanced composite material (ACM) based on metal-organic framework materials and carbon nanotube and its preparation side
Method.Carbon nanotube is first made pipe outer wall be connected with organic ligand functional groups by the preparation method by chemical modification, then will be modified
Carbon nanotube can be acted on by coordination bonding by metal ion and organic ligand functional group with metal-organic framework materials it is multiple
It closes, to obtain a kind of novel porous composite material.
The preparation method of carbon nanotube proposed by the present invention/metal-organic framework materials composite material includes the following steps：
1）Chemical modification carbon nanotube.Unmodified carbon nanotube is placed in concentrated acid and is ultrasonically treated certain time at a certain temperature,
Rinse and use the miillpore filter that aperture is 0.2 micron to depressurize collected by suction carbon nanotube with a large amount of deionized waters afterwards；Make repeatedly again
It is rinsed after filtrate is in neutrality with deionized water, vacuum drying obtains acidification carbon nanotube.Acidification carbon nanotube is set
It is kept stirring back flow reaction certain time at a certain temperature in thionyl chloride, rear decompression filters or be collected by centrifugation carbon nanometer
Pipe；Reusability anhydrous tetrahydro furan cleaning gained carbon nanotube, vacuum drying obtain acyl chlorides carbon nano tube again.By 2- amino
Terephthalic acid (TPA) is dissolved in anhydrous organic solvent by a certain percentage, and appropriate acyl chlorides carbon nano tube, room are added in the solution
Temperature lower supersound process certain time makes the amide between acyl chlorides carbon nano tube and 2- amino terephthalic acid (TPA)s, and the reaction was complete, rear to centrifuge
It collects carbon nanotube and cleans carbon nanotube with water or organic solvent repeatedly, then be dried in vacuo to obtain the carbon nanometer after chemical modification
Pipe.2）Prepare carbon nanotube/metal-organic framework materials composite material.By the carbon nanotube after chemical modification, dicarboxylic acid monomer
It is added in solvent by a certain percentage with trivalent metal salt, reflection suspension is obtained after ultrasonic dissolution/dispersion.Suspension is placed in
Certain time is reacted by solvent-thermal process method in closed reactor, or is placed in flask and certain time is reacted by microwave process for synthesizing.
After reaction, gained reaction product is centrifuged collection solid, then solid, gained is collected by centrifugation after soaked in solvent repeatedly
The vacuum dried activation of solid obtains carbon nanotube/metal-organic framework materials composite material.
As preferred：The step 1）Middle carbon nanotube is single-walled carbon nanotube, double-walled carbon nano-tube or multi-wall carbon nano-tube
One kind in pipe.
The step 1）Middle concentrated acid is the mixture in the concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2:
1-3:1, sour treatment temperature is 70-80 °C, processing time is 5-6 h.
The step 1）Middle acyl chloride reaction temperature is 70-75 °C, the reaction time is 8-16 h, acidification carbon nanotube is two
A concentration of 6-10 g/L in chlorine sulfoxide.
The step 1）Organic solvent is one in methanol, ethyl alcohol, tetrahydrofuran, dimethylformamide in middle amide reaction
Kind or mixture, a concentration of 5-10 g/L of 2- amino terephthalic acid solutions, acyl chlorides carbon nano tube and 2- amino terephthaldehydes
The mass ratio of acid is 1:5~1:10.
The step 2）Middle solvent be water, ethyl alcohol, dimethylformamide, trivalent metal salt be aluminium salt, molysite or chromic salts, two
First acid monomers are 2- amino terephthalic acid (TPA) or terephthalic acid (TPA).
The step 2）A concentration of 0.05-0.10 mol/L of middle binary acid in a solvent, binary acid and trivalent metal salt
Molar ratio be 1:1, the mass ratio of carbon nanotube and 2- amino terephthalic acid (TPA)s after chemical modification is 4:100-6:100.
The step 2）Middle solvent-thermal process reaction temperature is 105-155 °C, the reaction time is 4 ~ 6 h, microwave process for synthesizing
Reaction power be 400-600 W, temperature is 60 ~ 80 °C, the reaction time be 20 ~ 30 min.
The step 1）With step 2）Middle drying temperature is 80 ~ 110 °C, drying time is 12-24 h.
Advantageous effect：Composite material prepared by the present invention is made by the Coordinate self-assembly between binary acid and ionizable metal salt
It is linked together with by carbon nanotube and metal-organic framework materials, the composite material is made not only to be provided simultaneously with two class poromerics
Pore structure and architectural characteristic, new microcellular structure is also formed in junction.Such composite material can be applied to adsorbing separation neck
More preferably absorption property is put on display in domain.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of carbon nanotube/MIL-101 (Fe) composite material prepared by embodiment 1.
Fig. 2 is carbon nanotube/NH prepared by embodiment 22The transmission electron microscope picture of _ MIL-101 (Fe) composite material.
Specific implementation mode
Comparative example 1
By the FeCl of the terephthalic acid (TPA) of 1 mmol and 1 mmol3·6H2O is incorporated in 20 ml dimethylformamides, room
It is poured into polytetrafluoroethylene (PTFE) closed reactor after 20 min of the lower stirring of temperature.It is naturally cold after reaction kettle is reacted 4 h under 150 °C
But it to room temperature, is centrifuged and collects yellow solid product MIL-101 (Fe).Collected MIL-101 (Fe) is soaked in repeatedly
To dissolve unreacted monomer in water and ethyl alcohol, solid product is collected by centrifugation again, immersion and centrifugation step is repeated several times.Finally
Collected product obtains MIL-101 (Fe) metal-organic framework materials after being dried in vacuo 24 h under 80 °C.
Prepared MIL-101 (Fe) and original carbon nanotubes are respectively used to Static Adsorption experiment, evaluate and test it and adsorb desulfurization
Performance.The n-heptane solution that thiophene concentration is 800 mg/L is configured, thiophene-positive heptan that 50 mL are added in 0.10 g adsorbents is weighed
Alkane solution, it is 150 r/min to be placed in constant temperature oscillator and keep frequency of oscillation.After adsorbing 12 h under 30 °C, centrifuge
Adsorbent and solution take upper solution microcoulomb sulphur meter to measure the thiophene concentration after absorption, are calculated and are inhaled by formula defined below
The attached dose of thiophene adsorbance under the adsorption conditions.This is surveyed, and absorption result is shown in Table 1.
q=(C 0 -C t )V/m
In formula,qFor adsorbance, mg/g；C 0 WithC t Solution concentration respectively before absorption and after absorption, mg/L；VSuction used
Attached liquor capacity, L；mFor sorbent used quality, g.
Comparative example 2
By the FeCl of the 2 amino terephthalic acid (TPA)s and 1 mmol of 1 mmol3·6H2O is incorporated in 25 ml water, at room temperature
20 min are stirred to be placed in microwave reactor.Reaction power reacts 30 min when being 400 W under 60 °C, is centrifuged receipts
Collect brown solid NH2_MIL-101(Fe).Collected NH2_ MIL-101 (Fe) is soaked in water and ethyl alcohol repeatedly with molten
Unreacted monomer is solved, solid product is collected by centrifugation again, immersion and centrifugation step is repeated several times.Final collected product exists
NH is obtained after being dried in vacuo 24 h under 80 °C2_ MIL-101 (Fe) metal-organic framework materials.
Prepared NH2_ MIL-101 (Fe) and original carbon nanotubes are respectively used to Static Adsorption experiment, evaluate and test its absorption
De- phenol performance.The aqueous solution that phenol concentration is 1000 mg/L is configured, phenol-water that 50 mL are added in 0.1 g adsorbents is weighed
Solution, it is 150 r/min to be placed in constant temperature oscillator and keep frequency of oscillation.After adsorbing 12 h under 30 °C, centrifuges and inhale
Attached dose and solution take upper solution high performance liquid chromatography to measure the phenol concentration after absorption, by the definition meter in comparative example 1
Calculate Adsorption of Phenol amount of the adsorbent under the adsorption conditions.This is surveyed, and absorption result is shown in Table 2.
Embodiment 1
The unmodified carbon nanotubes of 0.5g are placed in the concentrated sulfuric acid and concentrated nitric acid mixture（Volume ratio is 3:1）In, at 80 °C
8 h of lower supersound process rinse with a large amount of deionized waters and use the polytetrafluoroethylene (PTFE) miillpore filter decompression that aperture is 0.2 micron to take out afterwards
Carbon nanotube is collected in filter；Reusability deionized water is rinsed after filtrate is in neutrality again, and 80 °C of 24 h of vacuum drying are obtained
To acidification carbon nanotube.Acidification carbon nanotube is placed in thionyl chloride under 80 °C and is kept stirring 12 h of back flow reaction, after subtract
Pressure filters or is collected by centrifugation carbon nanotube；Reusability anhydrous tetrahydro furan cleaning gained carbon nanotube again, 90 °C of vacuum drying
24 h obtain acyl chlorides carbon nano tube.The 2- amino terephthalic acid (TPA)s of 1 g are dissolved in 100 ml anhydrous dimethyl formamides,
Acyl chlorides carbon nano tube is added in the solution, being ultrasonically treated 12 h at room temperature makes acyl chlorides carbon nano tube and 2- amino terephthaldehydes
The reaction was complete for amide between acid, after carbon nanotube be collected by centrifugation and clean carbon nanotube, then 105 °C with water or organic solvent repeatedly
24 h are dried in vacuo to be dried in vacuo to obtain the carbon nanotube after chemical modification.
It prepares that embodiment used in composite material is identical as comparative example 1, but is added in the synthetic system of MIL-101 (Fe)
Carbon nanotube after the chemical modification of 0.01 g.Prepared by solvent-thermal process method, through isolate and purify and etc. obtain carbon nanotube/
MIL-101(Fe).Fig. 1 is the transmission electron microscope picture of carbon nanotube/MIL-101 (Fe) nano-particle prepared by the example, this institute
It surveys absorption result and is shown in Table 1.
Embodiment 2
The chemical modification embodiment of carbon nanotube is same as Example 1.Prepare embodiment used in composite material with it is right
Ratio 2 is identical, but in NH2The carbon nanotube after the chemical modification of 0.01 g is added in the synthetic system of _ MIL-101 (Fe).By
Microwave process for synthesizing prepare, through isolate and purify and etc. obtain carbon nanotube/NH2_MIL-101(Fe).Fig. 1 is prepared by the example
Carbon nanotube/NH2The transmission electron microscope picture of _ MIL-101 (Fe) nano-particle, this is surveyed, and absorption result is shown in Table 1.
It is the linear carbon nanotube series connection organic bone of metal that Fig. 1 and Fig. 2, which can see synthesized composite material its pattern,
The cubic crystal of frame material.The absorption property of Tables 1 and 2 is compared, prepared carbon nanotube/metal-organic framework materials are multiple
Its adsorbance of condensation material is apparently higher than carbon nanotube and metal-organic framework materials.
The thiophene adsorbance of different adsorbents used in 1 comparative example 1 of table and embodiment 1.
| Adsorbent | q (mg/g) |
| Carbon nanotube | 13.7 |
| MIL-101(Fe) | 20.8 |
| Carbon nanotube/MIL-101 (Fe) | 34.2 |
The Adsorption of Phenol amount of different adsorbents used in 2 comparative example 2 of table and embodiment 2.
| Adsorbent | q (mg/g) |
| Carbon nanotube | 208.7 |
| NH2_MIL-101(Fe) | 239.1 |
| Carbon nanotube/NH2_MIL-101(Fe) | 346.9 |
Claims (3)
1. a kind of preparation method of carbon nanotube/metal-organic framework materials composite material, includes the following steps：It will be unmodified
It is 3 that carbon nanotube, which is placed in volume ratio,:It in 1 concentrated sulfuric acid and concentrated nitric acid mixture, is ultrasonically treated 8 hours at 80 DEG C, collects carbon and receive
Mitron and being rinsed repeatedly to filtrate with deionized water is in neutrality, and is dried in vacuo at 80 DEG C and is obtained within 24 hours acidification carbon nanotube；It will
Acidification carbon nanotube, which is placed in thionyl chloride at 80 DEG C, is kept stirring back flow reaction 12 hours, collects carbon nanotube and makes repeatedly
Gained carbon nanotube is cleaned with anhydrous tetrahydro furan, is dried in vacuo 24 hours at 90 DEG C and obtains acyl chlorides carbon nano tube；By 1g's
2- amino terephthalic acid (TPA)s are dissolved in 100ml anhydrous dimethyl formamides, and acyl chlorides carbon nano tube, acyl chlorides are added in the solution
The mass ratio of carbon nano tube and 2- amino terephthalic acid (TPA)s is 1:2~1:16, the 2- amino of gained carbon nano tube containing acyl chlorides
Terephthalic acid solution is ultrasonically treated 12h at room temperature, and carbon nanotube is collected by centrifugation and cleans acyl with water or organic solvent repeatedly
Amination carbon nanotube is dried in vacuo the carbon nanotube for obtaining the modification of 2- amino terephthalic acid (TPA)s for 24 hours at 105 DEG C；By 1mmol
Terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)s, the ferric trichloride of 1mmol, 0.01g 2- amino terephthalic acid (TPA)s be modified carbon
Nanotube is incorporated in 20ml dimethylformamides, passes through solvent-thermal process method or microwave process for synthesizing after stirring 20min at room temperature
It reacts certain time, is cooled to room temperature after reaction at a certain temperature, be centrifuged repeatedly collection and impregnate solid product to going
Except unreacted monomer, final collected solid product obtains carbon nanotube/MIL- after being dried in vacuo 24 hours at 80 DEG C
101 (Fe) composite materials or carbon nanotube/NH2_ MIL-101 (Fe) composite material.
2. preparation method according to claim 1, which is characterized in that carbon nanotube/MIL-101 (Fe) composite material
Solvent structure condition be to be reacted 4 hours at 150 DEG C in closed reactor.
3. preparation method according to claim 1, which is characterized in that the carbon nanotube/NH2_ MIL-101 (Fe) is compound
The microwave method synthesis condition of material is to be reacted 30 minutes at 400W reaction powers, 60 DEG C.
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