CN112076750A - Preparation of ferroferric oxide modified carbon nanotube reduced graphene oxide compound and application of ferroferric oxide modified carbon nanotube reduced graphene oxide compound in removal of tetrabromobisphenol A in water - Google Patents

Preparation of ferroferric oxide modified carbon nanotube reduced graphene oxide compound and application of ferroferric oxide modified carbon nanotube reduced graphene oxide compound in removal of tetrabromobisphenol A in water Download PDF

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Publication number
CN112076750A
CN112076750A CN201910510219.9A CN201910510219A CN112076750A CN 112076750 A CN112076750 A CN 112076750A CN 201910510219 A CN201910510219 A CN 201910510219A CN 112076750 A CN112076750 A CN 112076750A
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graphene oxide
reduced graphene
modified carbon
carbon nanotube
oxide compound
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CN201910510219.9A
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Chinese (zh)
Inventor
周林成
张一梅
武盼盼
段亚晓
陈庄
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SUZHOU INSTITUTE OF NORTH CHINA ELECTRIC POWER UNIVERSITY
North China Electric Power University
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SUZHOU INSTITUTE OF NORTH CHINA ELECTRIC POWER UNIVERSITY
North China Electric Power University
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Priority to CN201910510219.9A priority Critical patent/CN112076750A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • B01J21/185Carbon nanotubes
    • B01J35/33
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

Abstract

The invention discloses a method for preparing a ferroferric oxide modified carbon nano tube/reduced graphene oxide compound and application of the ferroferric oxide modified carbon nano tube/reduced graphene oxide compound in removing tetrabromobisphenol A in water, which comprises the following steps: dispersing 20 mg of graphene oxide and 20 mg of carbon nano tubes in 60 ml of ethylene glycol, treating for 3 hours by using an ultrasonic cell disruptor to form uniform dispersion liquid, and then adding 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate,adding 0.45 g polyethylene glycol into the dispersion, and magnetically stirring for 30 min; transferring the mixed dispersion liquid into a reaction kettle, and reacting for 10 hours at 200 ℃; repeatedly cleaning the obtained precipitate deionized water and ethanol, and vacuum drying at 60 deg.C for 12 hr; and grinding the final product for later use. The catalyst prepared by the invention can rapidly degrade tetrabromobisphenol A, and the degradation rate constant is more than 0.5min‑1And is expected to be used for removing pollutants difficult to degrade.

Description

Preparation of ferroferric oxide modified carbon nanotube reduced graphene oxide compound and application of ferroferric oxide modified carbon nanotube reduced graphene oxide compound in removal of tetrabromobisphenol A in water
Technical Field
The invention relates to a method for preparing a ferroferric oxide modified carbon nanotube/reduced graphene oxide compound and application of the ferroferric oxide modified carbon nanotube/reduced graphene oxide compound in treatment of tetrabromobisphenol A (TBBPA) in wastewater.
Background
Along with the development of economic globalization, various waste gases, waste water and waste liquid are continuously discharged, so that the ecological environment is destroyed, and serious pollution is caused to water resources. Therefore, it is of great significance to explore efficient and economic sewage treatment technology.
The existing biological treatment method is difficult to treat substances with poor biodegradability and relative molecular mass from thousands to tens of thousands, and advanced oxidation methods (AOPs) can directly mineralize the substances or improve the biodegradability of pollutants through oxidation, have great advantages in the treatment aspect of trace harmful chemical substances such as environmental hormones and the like, can completely mineralize or decompose most organic substances, and have good application prospects. The Fenton technology is a commonly used advanced oxidation technology, has the advantages of simple operation process, easy reaction, low operation cost, low equipment investment, environmental friendliness and the like, and is commonly used for removing organic pollutants. However, the amount of the reagent used during the operation is large, and Fe is excessively contained2+The COD in the treated wastewater is increased and secondary pollution is generated; the mineralization of organic matters is insufficient, and the formed intermediate product is often more toxic; the pH range is 2.0-4.0, and the range is too narrow, so that the range of organic pollutant treatment is limited. In view of the disadvantages of the conventional Fenton technique in practical application, many Fenton-like techniques based on the conventional Fenton technique have been developed in recent yearsHas better application prospect.
In fenton-like technology, the choice of catalyst is very critical. Ferroferric oxide (Fe)3O4) Has strong magnetism, and can be used in medicine, metallurgy, electronics, textile, etc., and used as catalyst, polishing agent, pigment of paint and ceramics, glass colorant, etc. Therefore, in order to obtain a more efficient fenton-like catalyst, the ferroferric oxide needs to be modified.
Carbon Nanotubes (CNTs) as one-dimensional nanomaterials have light weight, perfect hexagonal structural connection, and many unusual mechanical, electrical, and chemical properties, and their broad application prospects have been continuously shown in recent years as the research on CNTs and nanomaterials proceeds. Reduced graphene oxide (rGO) is widely used due to its high specific surface area, excellent mechanical strength, abundant surface functional groups, high electrical conductivity and certain hydrophobic characteristics.
Thus, CNT and rGO co-modify Fe3O4The ternary composite material is expected to realize the synergistic enhancement of the catalytic performance of the catalyst, so that the organic pollutants can be rapidly and efficiently degraded.
Disclosure of Invention
The invention aims to provide a method for preparing CNT/rGO modified Fe3O4The method of the compound and the application thereof in water treatment can realize the high-efficiency degradation of endocrine disrupters in an aquatic system in a shorter time and in a wider pH range.
The invention provides a method for preparing CNT/rGO modified Fe3O4A method of compounding comprising the steps of:
(1) and dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruptor for later use.
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate, 0.45 g of polyethylene glycol were added to the dispersion in step (1), and the mixture was magnetically stirred for 30 min to be used.
(3) Transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃.
(4) And (4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol, and then drying the sample in vacuum at 60 ℃ for 12 hours.
(5) And (4) magnetically recovering the sample obtained in the step (4) and grinding the sample for standby.
The graphene oxide used in the step (1) is prepared by a Hummers method, and the ethylene glycol is either industrially pure or analytically pure.
FeCl used in the step (2)3·6H2O, sodium acetate and polyethylene glycol are either industrially pure or analytically pure.
And (5) sealing and storing the finally obtained catalyst at normal temperature.
The novel catalyst prepared by the method of the invention is characterized in that: the carbon nano tube plays a role of a carrier in the compound and can effectively inhibit Fe3O4The agglomeration of the magnetic particles ensures that the active microspheres are fully dispersed, and the strong crosslinking performance of the active microspheres and the pollutants promotes the mass transfer of the pollutants to the surface of the catalyst. The reduced graphene oxide has a certain hydrophobic effect, and the utilization rate of free radicals can be improved.
The invention has the advantages that: the carbon nano tube with large specific surface area fixes the ferroferric oxide magnetic particles, prevents the particles from agglomerating, greatly enhances the enrichment of the material on pollutants in a water body and accelerates the mass transfer speed of the pollutants to the catalyst. The addition of the reduced graphene oxide improves the utilization rate of free radicals. The catalyst prepared by the invention has high-efficiency catalytic performance, can adapt to a wider pH range, is easy to separate from a reaction system after being degraded, and is suitable for removing various pollutants.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
Example 1:
(1) and dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruptor for later use.
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate, 0.45 g of polyethylene glycol were added to the dispersion in step (1), and the mixture was magnetically stirred for 30 min to be used.
(3) Transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃.
(4) And (4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol, and then drying the sample in vacuum at 60 ℃ for 12 hours.
(5) And (4) magnetically recovering the sample obtained in the step (4) and grinding the sample for standby.
Modifying the prepared CNT/rGO with Fe3O4The compound is placed under a Transmission Electron Microscope (TEM) to observe the morphology of the material, and Fe is found3O4The magnetic microspheres are attached to the rGO and CNTs without significant agglomeration. The magnetic microsphere diameter was about 250-300 nm, indicating CNT/rGO @ Fe3O4The complex of (a) is synthesized.
Example 2:
(1) and dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruptor for later use.
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate, 0.45 g of polyethylene glycol were added to the dispersion in step (1), and the mixture was magnetically stirred for 30 min to be used.
(3) Transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃.
(4) And (4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol, and then drying the sample in vacuum at 60 ℃ for 12 hours.
(5) And (4) magnetically recovering the sample obtained in the step (4) and grinding the sample for standby.
The prepared catalyst is used for the research of degrading tetrabromobisphenol A (TBBPA), and the catalytic performance of the catalyst is verified. 20 mg L-1TBBPA (b: (20 mL) of the solution was placed in a 50 mL Erlenmeyer flask, to which 10.0 mg of the prepared catalyst was added. By adding 0.1M of H2SO4Or NaOH to adjust the pH of the solution to a range of 3.00-9.00, and adding 4.0 mM NH2OH to regulate the reaction rate, and H is added2O2(5.0-10.0 mM) to initiate the Fenton reaction. During the whole reaction process, the reaction solution is placed in a shaking table for 250 r min-1All tests were performed at room temperature. At given time intervals, 1.0 mL of sample was collected, 0.5 mL of methanol was immediately added to quench the active free radicals, and the remaining solid particles were then removed by filtration through a 0.22 micron filter and the final sample obtained was analyzed for changes in TBBPA concentration. The change of TBBPA concentration is tested by high performance liquid chromatography, and the degradation rate constant is more than 0.5min-1。,
Example 3:
(1) and dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruptor for later use.
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate, 0.45 g of polyethylene glycol were added to the dispersion in step (1), and the mixture was magnetically stirred for 30 min to be used.
(3) Transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃.
(4) And (4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol, and then drying the sample in vacuum at 60 ℃ for 12 hours.
(5) And (4) magnetically recovering the sample obtained in the step (4) and grinding the sample for standby.
The catalysts are respectively selected from Fe3O4、CNT/Fe3O4、rGO/Fe3O4And a final composite catalyst, the BPA in the example 2 is subjected to catalytic degradation under the same conditions, and the degradation is found to accord with a quasi first-order kinetic equation, wherein kinetic constants are 0.1634, 0.22073, 0.29635 and 0.51333 min-1The reaction rate of the composite catalyst is obviously superior to that of other catalysts, and the modified composite catalyst is provedThe composite catalyst has excellent catalytic performance.
Example 4:
(1) and dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruptor for later use.
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate, 0.45 g of polyethylene glycol were added to the dispersion in step (1), and the mixture was magnetically stirred for 30 min to be used.
(3) Transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃.
(4) And (4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol, and then drying the sample in vacuum at 60 ℃ for 12 hours.
(5) And (4) magnetically recovering the sample obtained in the step (4) and grinding the sample for standby.
The catalyst used in example 2 was repeatedly washed three times with deionized water and ethanol, dried under vacuum at 60 ℃ and used again to degrade TBBPA, and it was found that the removal efficiency remained at a very high level (94%) after 30 min. The above process is repeated to find that the TBBPA removal rate of the catalyst is still more than 85 percent after the catalyst is repeatedly used for 5 times, which indicates that the composite catalyst has good reusability.

Claims (3)

1. A method for preparing a heterogeneous Fenton catalyst of a ferroferric oxide modified carbon nanotube/reduced graphene oxide compound is characterized by comprising the following steps:
(1) dispersing 20 mg of graphene oxide and 20 mg of carbon nanotubes in 60 ml of ethylene glycol, and carrying out ultrasonic treatment for 3 hours by using an ultrasonic cell disruption instrument for later use;
(2) 0.46 g of FeCl3·6H2O, 1.7 g of sodium acetate and 0.45 g of polyethylene glycol are added to the dispersion in the step (1), and the mixture is magnetically stirred for 30 min for standby;
(3) transferring the dispersion liquid in the step (2) into a 100 mL polytetrafluoroethylene reaction kettle, and reacting for 10h at 200 ℃;
(4) after the reaction solution in the step (3) is cooled to room temperature, repeatedly washing the generated precipitate with deionized water and ethanol to remove residual reagent, and then drying the sample in vacuum at 60 ℃ for 12 hours;
(5) and (5) magnetically recovering the sample obtained in the step (4) to obtain the ferroferric oxide modified carbon nanotube/reduced graphene oxide compound.
2. The preparation method according to claim 1, wherein reduced graphene oxide is wound around the carbon nanotubes in the sample generated in the step (5), and ferroferric oxide is uniformly dispersed on the walls of the nanotubes and the surfaces of the reduced graphene oxide.
3. The catalyst obtained by the preparation method according to claim 1 is applied to Fenton-like fields, and is characterized in that the catalyst can rapidly degrade tetrabromobisphenol A, and the degradation rate constant is more than 0.5min-1
CN201910510219.9A 2019-06-13 2019-06-13 Preparation of ferroferric oxide modified carbon nanotube reduced graphene oxide compound and application of ferroferric oxide modified carbon nanotube reduced graphene oxide compound in removal of tetrabromobisphenol A in water Pending CN112076750A (en)

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Application publication date: 20201215