CN105536708A - Novel composite material based on metal-organic framework material and carbon nanotube and preparation method of novel composite material - Google Patents
Novel composite material based on metal-organic framework material and carbon nanotube and preparation method of novel composite material Download PDFInfo
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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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Abstract
The invention discloses a novel composite material based on a metal-organic framework material and a carbon nanotube and a preparation method of the novel composite material. The carbon nanotube is chemically modified, so that the outer wall of the carbon nanotube is connected with an organic ligand functional group, and the modified carbon nanotube can be combined with the metal-organic framework material through a ligand bonding effect between metal ions and the organic ligand functional group, therefore a novel porous composite material is obtained. A carbon nanotube connected with dicarboxylic acid is obtained by means of performing three reactions of carboxylation, acylating chlorination and amidation on the carbon nanotube; the carbon nanotube connected with the dicarboxylic acid is mixed with dicarboxylic acid monomers and metal salt monomers; the composite material is prepared through a solvent thermal synthesis method. The novel composite material disclosed by the invention has the advantages that the characteristics of two types of porous materials are combined, so that better adsorption and separation performances are obtained.
Description
Technical field
The present invention relates to a kind of advanced composite material (ACM) based on metal-organic framework materials and CNT and preparation method thereof; This material, in conjunction with the characteristic of two polyporous materials, shows more excellent adsorption separation performance.
Background technology
Metal-organic framework materials be a kind of there is bigger serface, high porosity, chemistry can modify and the novel porous materials of structure Diversity.Such material is by containing the multiple tooth organic ligand (being fragrant polyacid and polybase mostly) of oxygen or nitrogen etc. and the porous material of transition metal ions self assembly, gathers around have broad application prospects in fields such as atmosphere storage, adsorbing separation and catalysis.In recent years, prepare based on metal-organic framework materials the extensive concern that advanced composite material (ACM) causes people.Utilize the architectural characteristic of metal-organic framework materials and functional in conjunction with other material, the advantage of effective integration two class material can obtain the more excellent composite of performance.Now have been reported metal-organic framework materials to be combined with CNT, Graphene or macromolecular material and to improve gas absorption performance.
CNT is a class micropore nanophase materials, has the advantage that specific area is large, adsorption capacity is large, and the mechanics of excellence, electromagnetism, calorifics and optical property.It can effectively Adsorption of Heavy Metal Ions and organic pollution from water as sorbing material.Surface modification is carried out to CNT and can improve its dispersiveness in a liquid, thus improve its absorption property.In addition, surface modification also can make CNT outer wall connect different functionalities group, prepares functional composite material further with other material.The part self assembly of the CNT of chemical modification and MIL-101 type metal-organic framework materials, for MIL-101 type metal-organic framework materials, is prepared a kind of advanced composite material (ACM) by the present invention.
MIL-101 type metal-organic framework materials is the one in MIL type metal-organic framework materials, and its organic ligand is terephthalic acid (TPA) and metal ligand is trivalent transition metal ion, joins self assembly form position by the symmetrical carboxyl in organic ligand and metal ion.MIL-101 has octahedral crystal structure, three ducts, shows the advantages such as high-specific surface area, large pore volume, high thermal stability.Containing amino NH
2_ MIL-101 and MIL-101 has identical crystal structure and similar structural behaviour, but the organic ligand used amino terephthalic acid (TPA) that is 2-, because of with amido functional group NH
2_ MIL-101 has better hydrophily and can carry out modification utilization based on amino.Compared with other porous material, NH
2_ MIL-101 and MIL-101 has wide practical use as catalyst, adsorption and separation material, optical material and magnetic material etc.
Have been reported carboxylic carbon nano-tube and can prepare CNT/metal-organic framework materials composite with metallic ion coordination.But carboxyl functional group is lower contained by carboxylic carbon nano-tube, and symmetry is poor, makes itself and metallic ion coordination insufficient, form the less stable of self-assembled structures.The organic ligand of synthetic metals organic framework material is grafted on CNT outer wall by the present invention, is connected by the CNT with organic ligand functional group, prepares a kind of advanced composite material (ACM) with organic ligand and metal ligand self assembly.This composite not only has the characteristic of two kinds of poromerics, and can form extra microcellular structure, thus possesses excellent adsorption separation performance.
Summary of the invention
The invention provides a kind of advanced composite material (ACM) based on metal-organic framework materials and CNT and preparation method thereof.CNT first makes pipe outer wall be connected with organic ligand functional group by chemical modification by this preparation method, again modified CNT can be passed through cooperate and bond function compound with metal-organic framework materials by metal ion and organic ligand functional group, thus obtain a kind of novel porous composite.
The preparation method of CNT/metal-organic framework materials composite that the present invention proposes comprises the steps: 1) chemical modification CNT.Unmodified CNT is placed in concentrated acid ultrasonic process certain hour at a certain temperature, a large amount of deionized water rinsing of rear use also collects CNT with the miillpore filter decompress filter that aperture is 0.2 micron; Reusability deionized water carries out rinsing until filtrate is after neutrality again, and vacuum drying obtains acidifying CNT.Acidifying CNT being placed in thionyl chloride keeps stirring and refluxing to react certain hour, rear decompress filter or collected by centrifugation CNT at a certain temperature; Reusability anhydrous tetrahydro furan cleaning gained CNT again, vacuum drying obtains chloride CNT.Amino for 2-terephthalic acid (TPA) is dissolved in anhydrous organic solvent by a certain percentage, appropriate chloride CNT is added in this solution, under room temperature, ultrasonic process certain hour makes the acid amides between chloride CNT and the amino terephthalic acid (TPA) of 2-react completely, rear collected by centrifugation CNT repeatedly with water or organic solvent cleaning CNT, then vacuum drying obtains the CNT after chemical modification.2) CNT/metal-organic framework materials composite is prepared.CNT after chemical modification, dicarboxylic acid monomer and trivalent metal salt are added in solvent by a certain percentage, obtains reflecting suspension after ultrasonic dissolution/dispersion.Suspension is placed in closed reactor and reacts certain hour by solvent-thermal process method, or be placed in flask and react certain hour by microwave process for synthesizing.After reaction terminates, gained product collects solid through centrifugation, then collected by centrifugation solid after soaked in solvent repeatedly, and gained solid obtains CNT/metal-organic framework materials composite through vacuum drying activation.
As preferably: in described step 1), CNT is the one in SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
In described step 1), concentrated acid is the mixture in the concentrated sulfuric acid and red fuming nitric acid (RFNA), and the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 2:1-3:1, and acid treatment temperature is 70-80 ° of C, the processing time is 5-6h.
In described step 1), acyl chloride reaction temperature is 70-75 ° of C, the reaction time is 8-16h, the concentration of acidifying CNT in thionyl chloride is 6-10g/L.
In described step 1), in acid amides reaction, organic solvent is one in methyl alcohol, ethanol, oxolane, dimethyl formamide or mixture, the amino terephthalic acid solution's concentration of 2-is 5-10g/L, and the mass ratio of chloride CNT and the amino terephthalic acid (TPA) of 2-is 1:5 ~ 1:10.
Described step 2) in solvent be water, ethanol, dimethyl formamide, trivalent metal salt is aluminium salt, molysite or chromic salts, and dicarboxylic acid monomer is the amino terephthalic acid (TPA) of 2-or terephthalic acid (TPA).
Described step 2) in binary acid concentration be in a solvent 0.05-0.10mol/L, the mol ratio of binary acid and trivalent metal salt is 1:1, the CNT after chemical modification and 2-amino terephthalic acid (TPA) mass ratio be 4:100-6:100.
Described step 2) in solvent-thermal process reaction temperature be 105-155 ° of C, the reaction time is 4 ~ 6h, the reaction power of microwave process for synthesizing is 400-600W, temperature is 60 ~ 80 ° of C, the reaction time is 20 ~ 30min.
Described step 1) and step 2) in baking temperature be 80 ~ 110 ° of C, drying time is 12-24h.
Beneficial effect: CNT and metal-organic framework materials are linked together by the Coordinate self-assembly effect between binary acid and ionizable metal salt by the composite prepared by the present invention, make this composite not only possess pore structure and the architectural characteristic of two class poromerics simultaneously, also form new microcellular structure in junction.This kind of composite can be applicable to adsorbing separation field, puts on display better absorption property.
Accompanying drawing explanation.
Fig. 1 is the transmission electron microscope picture of CNT/MIL-101 (Fe) composite prepared by embodiment 1.
Fig. 2 is CNT/NH prepared by embodiment 2
2the transmission electron microscope picture of _ MIL-101 (Fe) composite.
Detailed description of the invention.
Comparative example 1.
By the terephthalic acid (TPA) of 1mmol and the FeCl of 1mmol
36H
2o is incorporated in 20ml dimethyl formamide, pours in polytetrafluoroethylene (PTFE) closed reactor after stirred at ambient temperature 20min.After reactor is reacted 4h under 150 ° of C, naturally cool to room temperature, collect yellow solid product MIL-101 (Fe) through centrifugation.Collected MIL-101 (Fe) is soaked in dissolve unreacted monomer in water and ethanol repeatedly, collected by centrifugation solid product again, repeatedly repeats to soak and centrifugation step.Final collected product obtains MIL-101 (Fe) metal-organic framework materials under 80 ° of C after vacuum drying 24h.
Prepared MIL-101 (Fe) and original carbon nanotubes are respectively used to Static Adsorption test, evaluate and test its adsorption desulfurize performance.Configuration thiophene concentration is the n-heptane solution of 800mg/L, takes thiophene-n-heptane solution that 0.10g adsorbent adds 50mL, is placed in constant temperature oscillator and keeps frequency of oscillation to be 150r/min.Adsorb 12h under 30 ° of C after, centrifugation adsorbent and solution, get upper solution microcoulomb sulphur meter and measure the thiophene concentration after adsorbing, calculate the thiophene adsorbance of adsorbent under this adsorption conditions by following definition.This example survey absorption result in table 1.
Q=(C
0-C
t) V/m, in formula: q is adsorbance, mg/g; C
0with C
tsolution concentration before being respectively absorption and after absorption, mg/L; V adsorbent solution volume used, L; M is sorbent used quality, g.
Comparative example 2.
By the FeCl of 2 of 1mmol amino terephthalic acid (TPA)s and 1mmol
36H
2o is incorporated in 25ml water, and stirred at ambient temperature 20min is placed in microwave reactor.Under 60 ° of C, react 30min when reaction power is 400W, collect brown solid NH through centrifugation
2_ MIL-101 (Fe).Collected NH
2_ MIL-101 (Fe) is soaked in dissolve unreacted monomer in water and ethanol repeatedly, collected by centrifugation solid product again, repeatedly repeats to soak and centrifugation step.Final collected product obtains NH after vacuum drying 24h under 80 ° of C
2_ MIL-101 (Fe) metal-organic framework materials.
Prepared NH
2_ MIL-101 (Fe) and original carbon nanotubes are respectively used to Static Adsorption test, evaluate and test the de-phenol performance of its absorption.Configuration phenol concentration is the aqueous solution of 1000mg/L, takes phenol-aqueous solution that 0.1g adsorbent adds 50mL, is placed in constant temperature oscillator and keeps frequency of oscillation to be 150r/min.Adsorb 12h under 30 ° of C after, centrifugation adsorbent and solution, get the phenol concentration after the absorption of upper solution high-performance liquid chromatogram determination, calculate the Adsorption of Phenol amount of adsorbent under this adsorption conditions by the definition in comparative example 1.This example survey absorption result in table 2.
Embodiment 1.
Unmodified for 0.5g CNT is placed in the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixture (volume ratio is 3:1), ultrasonic process 8h under 80 ° of C, a large amount of deionized water rinsing of rear use also collects CNT with the polytetrafluoroethylene (PTFE) miillpore filter decompress filter that aperture is 0.2 micron; Reusability deionized water is carried out rinsing until filtrate is after neutrality again, and 80 ° of C vacuum drying 24h obtain acidifying CNT.Acidifying CNT is placed in thionyl chloride keeps stirring and refluxing to react 12h, rear decompress filter or collected by centrifugation CNT under 80 ° of C; Reusability anhydrous tetrahydro furan cleaning gained CNT again, 90 ° of C vacuum drying 24h obtain chloride CNT.Amino for the 2-of 1g terephthalic acid (TPA) is dissolved in 100ml anhydrous dimethyl formamide, chloride CNT is added in this solution, under room temperature, ultrasonic process 12h makes the acid amides between chloride CNT and the amino terephthalic acid (TPA) of 2-react completely, rear collected by centrifugation CNT repeatedly with water or organic solvent cleaning CNT, then 105 ° of C vacuum drying 24h vacuum drying obtains the CNT after chemical modification.
Prepare composite embodiment used identical with comparative example 1, but in the synthetic system of MIL-101 (Fe), add the CNT after the chemical modification of 0.01g.Standby by solvent-thermal process legal system, obtain CNT/MIL-101 (Fe) through steps such as separation and purification.Fig. 1 is the transmission electron microscope picture of CNT/MIL-101 (Fe) nano particle prepared by this example, this example survey absorption result in table 1.
Embodiment 2.
The chemical modification embodiment of CNT is identical with embodiment 1.Prepare composite embodiment used identical with comparative example 2, but at NH
2the CNT after the chemical modification of 0.01g is added in the synthetic system of _ MIL-101 (Fe).Prepared by microwave process for synthesizing, obtain CNT/NH through steps such as separation and purification
2_ MIL-101 (Fe).Fig. 1 is CNT/NH prepared by this example
2the transmission electron microscope picture of _ MIL-101 (Fe) nano particle, this example survey absorption result in table 1.
Fig. 1 and Fig. 2 can see that its pattern of synthesized composite is the cubic crystal of wire CNT series connection metal-organic framework materials.The absorption property of contrast table 1 and table 2, prepared CNT/its adsorbance of metal-organic framework materials composite is apparently higher than CNT and metal-organic framework materials.
The thiophene adsorbance of table 1 comparative example 1 and embodiment 1 different adsorbent used.
| Adsorbent | q (mg/g) |
| CNT | 13.7 |
| MIL-101(Fe) | 20.8 |
| CNT/MIL-101 (Fe) | 34.2 |
The Adsorption of Phenol amount of table 2 comparative example 2 and embodiment 2 different adsorbent used.
| Adsorbent | q (mg/g) |
| CNT | 208.7 |
| NH 2_MIL-101(Fe) | 239.1 |
| CNT/NH 2_MIL-101(Fe) | 346.9 |
Claims (8)
1. the preparation method of CNT/metal-organic framework materials composite, comprise the steps: that unmodified CNT is placed in concentrated acid and reacts by (1), acidifying CNT is obtained with dry process through collecting, gained acidifying CNT and thionyl chloride are fully reacted, chloride CNT is obtained with dry process through collecting, amino for 2-terephthalic acid (TPA) and chloride CNT are placed in anhydrous organic solvent by a certain percentage and react certain hour, reacted by the acid chloride functional groups of CNT and the amino generation acid amides of the amino terephthalic acid (TPA) of 2-, obtain the CNT being connected to binary acid, the CNT after chemical modification is obtained after collecting and processing with drying, 2) amino to the CNT after chemical modification, terephthalic acid (TPA) or 2-terephthalic acid monomers and trivalent metal salt are added in solvent by a certain percentage, obtain reflecting suspension after ultrasonic dissolution/dispersion, by solvent-thermal process method or microwave process for synthesizing, suspension is reacted certain hour under certain reaction temperature, reaction terminates rear centrifugation and collects gained solid reaction product, collected by centrifugation solid product after soaked in solvent repeatedly again, gained solid obtains CNT/metal-organic framework materials composite through vacuum drying activation.
2. preparation method according to claim 1, is characterized in that, described CNT is the one in SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described trivalent metal salt is aluminium salt, molysite or chromic salts.
3. preparation method according to claim 1, is characterized in that, described concentrated acid is one in the concentrated sulfuric acid and red fuming nitric acid (RFNA) or both mixtures, and acid treatment temperature is 60-90 degree, and the processing time is 4-8h.
4. preparation method according to claim 1, is characterized in that, described acyl chloride reaction temperature is 60-8 degree, and the reaction time is 6-24h, and the concentration of acidifying CNT in thionyl chloride is 2-20g/L.
5. preparation method according to claim 1, is characterized in that, in the reaction of described acid amides, organic solvent is one in methyl alcohol, ethanol, oxolane, dimethyl formamide or mixture; The amino terephthalic acid solution's concentration of described 2-is 2-15g/L, and the mass ratio of chloride CNT and the amino terephthalic acid (TPA) of 2-is 1:2 ~ 1:16.
6. preparation method according to claim 1, it is characterized in that, it is described that to prepare composite dicarboxylic acid monomer used concentration be in a solvent 0.02-0.15mol/L, the mol ratio of binary acid and trivalent metal salt is 1:0.5-1:2, and the mass ratio of the CNT after chemical modification and the amino terephthalic acid (TPA) of 2-is 2:100 ~ 10:100.
7. preparation method according to claim 1, is characterized in that, described solvent-thermal process reaction temperature is 100-200 ° of C, and the reaction time is 2 ~ 12h; The reaction power of described microwave process for synthesizing is 300-800W, and temperature is 50 ~ 90 ° of C, and the reaction time is 10 ~ 60min.
8. preparation method according to claim 1, is characterized in that, described baking temperature is 80 ~ 120 ° of C, and drying time is 12-24h.
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| CN106925226A (en) * | 2017-03-17 | 2017-07-07 | 沈阳工业大学 | A kind of preparation method based on Organometallic framework material high-performance adsorbent |
| CN107722294A (en) * | 2017-11-17 | 2018-02-23 | 北京林业大学 | Microwave reaction method Fast back-projection algorithm MIL 88A type metal-organic framework materials |
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