CN107670640B - Carbon nano tube immobilized quaternary ammonium salt magnetic functional material and preparation method and application thereof - Google Patents
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a carbon nano tube immobilized quaternary ammonium salt magnetic functional material and a preparation method and application thereof, and is characterized in that: the carbon nano tube immobilized quaternary ammonium salt magnetic functional material comprises a carboxylated carbon nano tube, a nano magnetic material coated on the surface of the carboxylated carbon nano tube, an amination reagent immobilized on the surface of the carboxylated carbon nano tube, and a quaternary ammonium salt functional reagent grafted on the amination reagent. Compared with the prior art, the invention has the advantages that: the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material can be applied to removing perchlorate in water, and has stronger magnetism, higher adsorption capacity and better adsorption selectivity; and the preparation method is simple.
Description
Technical Field
The invention belongs to the field of functional materials for preventing and treating water pollution, and particularly relates to a carbon nano tube immobilized quaternary ammonium salt magnetic functional material as well as a preparation method and application thereof
Background
Perchlorate is taken as a persistent emerging pollutant with high diffusivity, and can compete with iodide ions to enter thyroid after being taken into a human body to induce thyroid cancer, so that the perchlorate is also called as powerful thyrotoxin. In the production process of solid propellants such as fireworks and explosives, ammonium perchlorate is used as an oxidant in a large quantity, and a small amount of ammonium perchlorate can permeate and migrate to surface water and underground water through medium water, so that the current pollution situation of the ammonium perchlorate to water bodies is widely concerned at home and abroad. Since 1997, the USEPA detected perchlorate in groundwater, surface water and drinking water in 42 states, california, etc. Therefore, the control research on the perchlorate in the water body becomes a research hotspot in the fields of water treatment and water pollution prevention and control.
In recent years, researchers have used carbon nanotubes as adsorbents to remove residual perchlorate in water (q.fang, b.chen, Adsorption of perchlorate on raw and oxidized carbon nanotubes Adsorption. carbon,2012,50, 2209). Although the carbon nano tube can efficiently adsorb residual perchlorate in water, the defects of difficult solid-liquid separation, poor regeneration capability and the like exist. In addition, carbon nanotubes can adsorb inorganic anions such as bromate, nitrate, nitrite and iodate while adsorbing perchlorate, and have poor selectivity for adsorbing perchlorate (f. metzelder, t.c. schmidt, Environmental conditions of organic reactions to multi-walled carbon nanotubes by column Science Technology,2017,51, 4928). The scholars adopt quaternary ammonium salt as an adsorption functional group to modify bamboo reeds and activated carbon, so that the adsorption selectivity of the adsorbent to perchlorate is greatly improved. In view of the strong adsorption capacity of the carbon nano tube to the perchlorate and the high selectivity of the quaternary ammonium salt functional group to the perchlorate, the development of the functional material combining the carbon nano tube and the quaternary ammonium salt to adsorb the perchlorate in the water body has wide application prospect, but the material does not appear in the prior art.
Disclosure of Invention
The invention aims to solve the first technical problem and provide a carbon nano tube immobilized quaternary ammonium salt magnetic functional material which has large adsorption capacity and strong selective adsorption capacity and can realize solid-liquid separation aiming at the current situation of the prior art.
The second technical problem to be solved by the present invention is to provide a method for preparing the carbon nanotube-supported quaternary ammonium salt magnetic functional material, aiming at the current situation of the prior art.
The third technical problem to be solved by the invention is to provide an application of the carbon nanotube-supported quaternary ammonium salt magnetic functional material for removing perchlorate in water, aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a carbon nano tube immobilized quaternary ammonium salt magnetic functional material is characterized in that: the nano-magnetic material is coated on the surface of the carboxylated carbon nanotube, an amination reagent immobilized on the surface of the carboxylated carbon nanotube and a quaternary ammonium salt functional reagent grafted on the amination reagent.
In the scheme, the nano magnetic material is nano ferroferric oxide.
As an improvement, the amination reagent is diethylenetriamine.
The improvement is that the quaternary ammonium salt functional reagent is at least one of 2, 3-epoxypropyltrimethyl ammonium chloride and 2, 3-epoxypropyltriethyl ammonium chloride.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the carbon nanotube immobilized quaternary ammonium salt magnetic functional material is characterized by comprising the following steps of:
(1) preparing the carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method: 0.5-3.0 g FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then adding 3.0g of anhydrous sodium acetate, 0.5-5 mL of ammonia water solution, 5-20 mL of amination reagent and 20-100 mg of carboxylated carbon nano tube, carrying out ultrasonic dispersion for 5-10 min, then adding the mixed solution into a polytetrafluoroethylene high-pressure kettle, reacting for 5-12 h at 160-250 ℃, cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is neutral, washing with ethanol for several times, and carrying out vacuum drying for 6-12 h at 30-90 ℃ to obtain the carbon nano tube immobilized amino magnetic functional material.
(2) Preparing the carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting a ring-opening reaction: adding 0.5-2.5 g of the carbon nanotube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, ultrasonically dispersing for 5-10 min until the material is uniformly dispersed, heating to 60-90 ℃, dropwise adding 2-10 mL of quaternary ammonium salt functional reagent, and carrying out reflux reaction for 6-12 h. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is neutral, washing with ethanol for several times, and carrying out vacuum drying at 30-90 ℃ for 6-12 h to obtain the carbon nanotube-supported quaternary ammonium salt magnetic functional material.
Preferably, the ammonia water solution in the step (1) is at least one of ammonia water with the content of 10% (V/V) and ammonia water with the content of 25% (V/V).
The technical scheme adopted by the invention for solving the third technical problem is as follows: the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material is characterized in that: adding 20-100 mg of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of 5.0-500 mg/L perchlorate solution, adjusting the pH to 2-9, and then oscillating at a constant temperature of 15-50 ℃ for 1-120 min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water.
Compared with the prior art, the invention has the advantages that:
(1) the magnetic functional material of the carbon nano tube immobilized quaternary ammonium salt has strong magnetism, can be stably dispersed in a solution, and can realize rapid solid-liquid separation and enrichment by adopting the action of a simple magnetic field.
(2) The preparation method is simple, the carbon nano tube immobilized quaternary ammonium salt magnetic functional material is obtained by adopting a solvothermal method and an open-loop reaction, a strong alkaline reaction environment is provided through ammonia water, nano ferroferric oxide generated in situ is uniformly coated on the surface of the carbon nano tube, and an amination reagent is immobilized on the surface of the carbon nano tube through an acylation reaction; then grafting the quaternary ammonium salt active functional group to an acylated amination reagent through ring opening reaction; the carbon nano tube immobilized quaternary ammonium salt magnetic functional material prepared by the invention has stronger binding force and stable property due to the chemical bonding action between carboxyl on the surface of the carboxylated carbon nano tube and amino in the amination reagent and between the amino of the amination reagent and epoxy in the quaternary ammonium salt functional reagent, and the nano ferroferric oxide in the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material has uniform granularity and spherical appearance.
(3) According to the invention, through controllable preparation of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material and optimization of conditions such as adsorption pH, adsorption temperature, adsorption time, perchlorate concentration and the like, the carbon nano tube immobilized quaternary ammonium salt magnetic functional material has strong removal capability on perchlorate in water, so that the carbon nano tube immobilized quaternary ammonium salt magnetic functional material is suitable for removing perchlorate in water environment; meanwhile, the treatment time and cost are saved, and compared with the existing adsorbing materials such as carbon nanotubes, quaternary ammonium salt modified activated carbon, quaternary ammonium salt modified bamboo reeds and the like, the material has higher adsorption capacity and better adsorption selectivity in the aspect of perchlorate removal.
Drawings
Fig. 1 is a projection electron microscope image of a carbon nanotube-supported quaternary ammonium salt magnetic functional material according to a first embodiment of the present invention;
fig. 2 is a hysteresis loop diagram of the carbon nanotube-supported quaternary ammonium salt magnetic functional material according to the first embodiment of the present invention;
fig. 3 is an X-ray photoelectron spectrum of the carbon nanotube supported quaternary ammonium salt magnetic functional material according to the first embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The first embodiment is as follows:
a preparation method of a carbon nano tube immobilized quaternary ammonium salt magnetic functional material comprises the following steps:
(1) preparing carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method, and adding 2.0g of FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then 3.0g of anhydrous sodium acetate is added, 0.5mL of 10% (V/V) ammonia water solution, 20mL of diethylenetriamine and 50mg of carboxylated carbon nanotubes are added, ultrasonic dispersion is carried out for 10min, and then the mixed solution is added into a polytetrafluoroethylene autoclave to react for 10h at 200 ℃. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, then washing with ethanol for several times, and carrying out vacuum drying at 60 ℃ for 6h to obtain the carbon nanotube immobilized amino magnetic functional material.
(2) Preparing a carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting an open-loop reaction, adding 1.0g of the carbon nano tube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, performing ultrasonic dispersion for 10min until the material is uniformly dispersed, heating to 80 ℃, dropwise adding 2mL of 2, 3-epoxypropyltrimethylammonium chloride, performing reflux reaction for 8h, cooling to room temperature, performing magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, washing with ethanol for several times, and performing vacuum drying at 60 ℃ for 6h to obtain the carbon nano tube immobilized quaternary ammonium salt magnetic functional material.
The transmission electron microscope image of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material is shown in figure 1, and Fe in the carbon nano tube immobilized quaternary ammonium salt magnetic functional material3O4The particle size is 50nm, the morphology is regular, the particle size is uniform, and the particles are uniformly distributed on the surface of the carbon nano tube. As can be seen from FIG. 2, the prepared carbon nanotube-supported quaternary ammonium salt magnetic functional material has strong saturation magnetization (72.2emu/g), so that the material can realize efficient directional movement under the action of an external magnetic field, and the material can be recycled. As shown in FIG. 3, the bonding energies of the carbon spectrum (C1 s), the oxygen spectrum (O1 s) and the nitrogen spectrum (N1 s) in the quaternary ammonium salt magnetic functional material carried by the carbon nanotube are 284.0eV, 530.2eV and 399.8eV respectively, which indicates that the quaternary ammonium salt active functional group is successfully carried on the surface of the magnetic carbon nanotube.
And adding 50mg of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of perchlorate solution with the concentration of 100mg/L, adjusting the pH value to 3, and then oscillating at the constant temperature of 30 ℃ for 10min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water. The adsorption amount of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material for adsorbing perchlorate in water is 70 mg/g.
Example two:
a preparation method of a carbon nano tube immobilized quaternary ammonium salt magnetic functional material comprises the following steps:
(1) preparing carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method, and adding 2.0g of FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then 3.0g of anhydrous sodium acetate is added, 2.0mL of 25% (V/V) ammonia water solution with the concentration, 10mL of diethylenetriamine and 100mg of carboxylated carbon nanotubes are added, ultrasonic dispersion is carried out for 8min, and then the mixed solution is added into a polytetrafluoroethylene autoclave for reaction for 12h at 200 ℃. Cooling to room temperature, magnetically separating, washing with ultrapure water for several times until pH is 7.0, and washing with ethanolAnd then, drying for 12 hours in vacuum at 30 ℃ to prepare the carbon nano tube immobilized amino magnetic functional material.
(2) Preparing a carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting a ring-opening reaction, adding 2.5g of the carbon nano tube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, ultrasonically dispersing for 5min until the material is uniformly dispersed, heating to 80 ℃, dropwise adding 10mL of 2, 3-epoxypropyltriethylammonium chloride, and carrying out reflux reaction for 12 h. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, then washing with ethanol for several times, and carrying out vacuum drying at 30 ℃ for 12h to obtain the carbon nanotube-supported quaternary ammonium salt magnetic functional material.
And (3) adding 100mg of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of perchlorate solution with the concentration of 400mg/L, adjusting the pH to 9, and then oscillating at the constant temperature of 50 ℃ for 100min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water. The adsorption amount of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material for adsorbing perchlorate in water is 152 mg/g.
Example three:
a preparation method of a carbon nano tube immobilized quaternary ammonium salt magnetic functional material comprises the following steps:
(1) preparing carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method, and adding 2.0g of FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then 3.0g of anhydrous sodium acetate is added, 5mL of 10% (V/V) ammonia water solution, 5mL of diethylenetriamine and 20mg of carboxylated carbon nanotubes are added, ultrasonic dispersion is carried out for 5min, and then the mixed solution is added into a polytetrafluoroethylene autoclave for reaction for 5h at 200 ℃. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, then washing with ethanol for several times, and carrying out vacuum drying at 90 ℃ for 8h to obtain the carbon nanotube immobilized amino magnetic functional material.
(2) Preparing a carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting an open-loop reaction, adding 0.5g of the carbon nano tube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, performing ultrasonic dispersion for 8min until the dispersion is uniform, heating to 80 ℃, dropwise adding 5mL of 2, 3-epoxypropyltrimethylammonium chloride, performing reflux reaction for 6h, cooling to room temperature, performing magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, washing with ethanol for several times, and performing vacuum drying at 90 ℃ for 8h to obtain the carbon nano tube immobilized quaternary ammonium salt magnetic functional material.
And (3) adding 20mg of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of 5mg/L perchlorate solution, adjusting the pH value to 6, and then oscillating at the constant temperature of 15 ℃ for 1min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water. The adsorption amount of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material for adsorbing perchlorate in water is 122 mg/g.
Example four:
(1) preparing carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method, and adding 0.5g of FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then 3.0g of anhydrous sodium acetate is added, 0.5mL of 10% (V/V) ammonia water solution, 20mL of diethylenetriamine and 50mg of carboxylated carbon nanotubes are added, ultrasonic dispersion is carried out for 10min, and then the mixed solution is added into a polytetrafluoroethylene autoclave to react for 10h at 160 ℃. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, then washing with ethanol for several times, and carrying out vacuum drying at 60 ℃ for 6h to obtain the carbon nanotube immobilized amino magnetic functional material.
(2) Preparing a carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting an open-loop reaction, adding 1.0g of the carbon nano tube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, performing ultrasonic dispersion for 10min until the material is uniformly dispersed, heating to 60 ℃, dropwise adding 2mL of 2, 3-epoxypropyltrimethylammonium chloride, performing reflux reaction for 8h, cooling to room temperature, performing magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, washing with ethanol for several times, and performing vacuum drying at 60 ℃ for 6h to obtain the carbon nano tube immobilized quaternary ammonium salt magnetic functional material.
And adding 50mg of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of perchlorate solution with the concentration of 100mg/L, adjusting the pH value to 3, and then oscillating at the constant temperature of 30 ℃ for 10min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water. The adsorption amount of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material for adsorbing perchlorate in water is 86.2 mg/g.
Example five:
(1) preparing carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method, and adding 3.0g of FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then 3.0g of anhydrous sodium acetate is added, 0.5mL of 10% (V/V) ammonia water solution, 20mL of diethylenetriamine and 50mg of carboxylated carbon nanotubes are added, ultrasonic dispersion is carried out for 10min, and then the mixed solution is added into a polytetrafluoroethylene autoclave to react for 10h at 250 ℃. Cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, then washing with ethanol for several times, and carrying out vacuum drying at 60 ℃ for 6h to obtain the carbon nanotube immobilized amino magnetic functional material.
(2) Preparing a carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting an open-loop reaction, adding 1.0g of the carbon nano tube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, performing ultrasonic dispersion for 10min until the material is uniformly dispersed, heating to 90 ℃, dropwise adding 2mL of 2, 3-epoxypropyltrimethylammonium chloride, performing reflux reaction for 8h, cooling to room temperature, performing magnetic separation, washing with ultrapure water for several times until the pH value is 7.0, washing with ethanol for several times, and performing vacuum drying at 60 ℃ for 6h to obtain the carbon nano tube immobilized quaternary ammonium salt magnetic functional material.
And adding 50mg of the prepared carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of perchlorate solution with the concentration of 100mg/L, adjusting the pH value to 3, and then oscillating at the constant temperature of 30 ℃ for 10min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water. The adsorption amount of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material for adsorbing perchlorate in water is 52.8 mg/g.
Claims (6)
1. A carbon nano tube immobilized quaternary ammonium salt magnetic functional material is characterized in that: the device comprises a carboxylated carbon nanotube, a nano magnetic material coated on the surface of the carboxylated carbon nanotube, an amination reagent immobilized on the surface of the carboxylated carbon nanotube and a quaternary ammonium salt functional reagent grafted on the amination reagent;
the preparation method of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material comprises the following steps:
(1) preparing the carbon nano tube immobilized amino magnetic functional material by adopting a solvothermal method: 0.5-3.0 g FeCl3·6H2Adding O into 20mL of glycol, and performing ultrasonic dispersion until the solution is clear; then adding 3.0g of anhydrous sodium acetate, 0.5-5 mL of ammonia water solution, 5-20 mL of amination reagent and 20-100 mg of carboxylated carbon nano tube, carrying out ultrasonic dispersion for 5-10 min, then adding the mixed solution into a polytetrafluoroethylene high-pressure kettle, reacting for 5-12 h at 160-250 ℃, cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is neutral, washing with ethanol for several times, and carrying out vacuum drying for 6-12 h at 30-90 ℃ to obtain the carbon nano tube immobilized amino magnetic functional material;
(2) preparing the carbon nano tube immobilized quaternary ammonium salt magnetic functional material by adopting a ring-opening reaction: adding 0.5-2.5 g of the carbon nanotube immobilized amino magnetic functional material prepared in the step (1) into 50mL of methanol, ultrasonically dispersing for 5-10 min until the material is uniformly dispersed, heating to 60-90 ℃, dropwise adding 2-10 mL of quaternary ammonium salt functional reagent, and carrying out reflux reaction for 6-12 h; cooling to room temperature, carrying out magnetic separation, washing with ultrapure water for several times until the pH value is neutral, washing with ethanol for several times, and carrying out vacuum drying at 30-90 ℃ for 6-12 h to obtain the carbon nanotube-supported quaternary ammonium salt magnetic functional material.
2. The carbon nanotube-supported quaternary ammonium salt magnetic functional material according to claim 1, characterized in that: the nano magnetic material is nano ferroferric oxide.
3. The carbon nanotube-supported quaternary ammonium salt magnetic functional material according to claim 1, characterized in that: the amination reagent is diethylenetriamine.
4. The carbon nanotube-supported quaternary ammonium salt magnetic functional material according to claim 1, characterized in that: the quaternary ammonium salt functional reagent is at least one of 2, 3-epoxypropyltrimethylammonium chloride and 2, 3-epoxypropyltriethylammonium chloride.
5. The carbon nanotube-supported quaternary ammonium salt magnetic functional material according to claim 1, characterized in that: the ammonia water solution in the step (1) is at least one of ammonia water with the content of 10% (V/V) and ammonia water with the content of 25% (V/V).
6. The application of the carbon nanotube-supported quaternary ammonium salt magnetic functional material according to any one of claims 1 to 5, wherein the quaternary ammonium salt-supported magnetic functional material comprises: adding 20-100 mg of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material into 100mL of 5.0-500 mg/L perchlorate solution, adjusting the pH to 2-9, and then oscillating at a constant temperature of 15-50 ℃ for 1-120 min to finish the application of the carbon nano tube immobilized quaternary ammonium salt magnetic functional material in removing perchlorate in water.
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| CN102274714A (en) * | 2011-08-03 | 2011-12-14 | 上海理工大学 | Absorbing material for removing anion in water and preparation method thereof |
| CN102583315A (en) * | 2012-02-15 | 2012-07-18 | 西北工业大学 | Method for preparing ferroferric oxide/ carbon nano tube composite material |
| CN105129898A (en) * | 2015-08-26 | 2015-12-09 | 宁波大学 | Renewable amino functionalized magnetic carbon nano composite material, and preparation method therefor and application thereof |
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| CN102274714A (en) * | 2011-08-03 | 2011-12-14 | 上海理工大学 | Absorbing material for removing anion in water and preparation method thereof |
| CN102583315A (en) * | 2012-02-15 | 2012-07-18 | 西北工业大学 | Method for preparing ferroferric oxide/ carbon nano tube composite material |
| CN105129898A (en) * | 2015-08-26 | 2015-12-09 | 宁波大学 | Renewable amino functionalized magnetic carbon nano composite material, and preparation method therefor and application thereof |
Non-Patent Citations (3)
| Title |
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| Adsorption of perchlorate onto raw and oxidized carbon nanotubes in aqueous solution;Qile Fang等;《CARBON》;20120120;第50卷;2209-2219页 * |
| Biosorption and Bioreduction of Perchlorate Using the Nano-;Yanan Shang等;《ACS Sustainable Chem. Eng.》;20170216;第5卷;2741-2748页 * |
| Enrichment of Polychlorinated Biphenyls from Aqueous Solutions Using Fe3O4 Grafted Multiwalled Carbon Nanotubes with Poly Dimethyl Diallyl Ammonium Chloride;Shaolin Zeng等;《Int. J. Mol. Sci.》;20120523;第13卷;6382-6398页 * |
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