CN107537445A - Application of the carboxylated graphene oxide as adsorbent in adsorption of metal ions - Google Patents
Application of the carboxylated graphene oxide as adsorbent in adsorption of metal ions Download PDFInfo
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- CN107537445A CN107537445A CN201711019756.0A CN201711019756A CN107537445A CN 107537445 A CN107537445 A CN 107537445A CN 201711019756 A CN201711019756 A CN 201711019756A CN 107537445 A CN107537445 A CN 107537445A
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Abstract
The present invention provides a kind of application of carboxylated graphene oxide as adsorbent in adsorption of metal ions, belongs to technical field of waste water processing.This method is to prepare graphene oxide using the Hummers methods of classics, then mixes graphene oxide with monoxone in the basic conditions, is stirred in 25 DEG C of waters bath with thermostatic control, centrifuge washing, and drying prepares carboxylated graphene oxide.The preparation method of carboxylated graphene oxide is simple, and raw material is easy to get, and reaction condition is gentle, and handling process is simple, and good performance is shown in terms of wastewater treatment.
Description
Technical field
The present invention relates to a kind of application of carboxylated graphene oxide as adsorbent in adsorption of metal ions, especially
To the adsorption applications of metal ion in industrial wastewater, belong to technical field of sewage.
Background technology
Heavy metal is generally present in nature with simple substance or compound form, ecology and human health is threatened smaller；
But recently as the excessive exploitation to metalliferous mineral, generate the industrial wastewater containing a large amount of metal ions.
By taking heavy metal copper as an example, copper is the indispensable micronutrient of health, and industrial circle is strategic
One of element.In nature, copper mainly exists in the form of Copper Ores, and it is widely used in electric, light industry, machinery system
Make, building industry, the field such as national defense industry.However, the exploitation and smelting of copper zinc ore, intermetallic composite coating, machine-building, steel production
The Cu-W ore deposit in serious environmental pollution, such as water body is caused etc. industrial production.If with copper-containing wastewater irrigated farmland and sulphur
The administration of sour copper agrochemical agricultural chemicals can make a part of copper enter soil and plant in, can cause crops particularly rice and
Barley growth is bad, and can pollute grain seed.Crops can absorb the copper in soil by root, and a portion can be through food
Into human body.After copper is accumulated to a certain extent in vivo harm can be produced to health.In addition to Cu-W ore deposit, lead is dirty
The events such as dye, mercury pollution, cadmium pollution are also occurring again and again, therefore, effectively removed from industrial wastewater copper, lead, mercury, cadmium etc. from
Son has become a serious urgent problem.
In recent years, researchers have done many researchs to the removing method of metal ion in waste water, main to include changing
Learn the precipitation method, ion-exchange, electrolysis and absorption method etc..Wherein, absorption method is easy to get due to raw material, easy to operate, cost
Low, the advantages that metal ion removal rate is high, is widely used.However, conventional adsorbent such as activated carbon, biological adsorption agent, corn
Stalk, polymeric adsorbent, zeolite adsorption, clay adsorption and silica absorption etc., but these adsorbents are in terms of chromium ion removal
A definite limitation all be present.At present, graphene is because its big specific surface area is widely used field of waste water treatment and is achieved
Good effect.However, the research that adsorbent is made using carboxylated graphene oxide has no report.
In view of this, present invention generally provides a kind of carboxylated graphene oxide material as adsorbent in industrial wastewater
The absorption property application study of copper [Cu (II)] and lead [Pb (II)] ion.
The content of the invention
It is an object of the invention to provide a kind of carboxylated graphene oxide as adsorbent in adsorption of metal ions
Using.
To reach above-mentioned purpose, the present invention provides following technical scheme：A kind of preparation method of carboxylated graphene oxide,
Comprise the following steps：S1：Add graphene oxide into deionized water, it is scattered to obtain graphene oxide water solution；S2：To oxygen
Sodium hydroxide and monoxone are added in graphite aqueous solution, 24h is stirred under normal temperature；S3：It is washed with deionized several times, does
Carboxylated graphene oxide is obtained after dry.
As a further improvement on the present invention, in the aqueous solution of graphene oxide, the concentration of graphene oxide is 1mg/mL.
As a further improvement on the present invention, step S1 is specially：The ultrasonic disperse in 200W ultrasonic cleaners
30min, obtain the aqueous solution of graphene oxide.
As a further improvement on the present invention, in step S2, each component additional proportion is：Graphene oxide：Sodium hydroxide：
Monoxone is：50mg:3g:2g.
As a further improvement on the present invention, in step S3, drying process is specially that product vacuum under the conditions of 60 DEG C is done
Dry 12h.
To reach above-mentioned purpose, the present invention is also provided by the carboxyl of the preparation method preparation of above-mentioned carboxylated graphene oxide
Change graphene oxide composite material.
To reach above-mentioned purpose, the present invention also provide a kind of carboxylated graphene oxide material to Cu in solution (II) and
The application that Pb (II) ion is adsorbed.
As a further improvement on the present invention, carboxylated graphene oxide material carries out absorption tool to metal ion in solution
Body is：The accurate carboxylated graphene oxide material for weighing 3mg is added to 10mLs of the pH between 1 ~ 6 as adsorbent,
In the solution of 0.5mmol/L ~ 2mmol/L metal ion [Cu (II) or Pb (II)], 15 DEG C ~ 30 DEG C constant temperature stirring reaction 0h ~
24h, the solution of clarification is filtrated to get, the metal ion content of settled solution is then detected using atomic absorption spectrophotometer,
Finally calculate removal rate of the carboxylated graphene oxide material to metal ion.
As a further improvement on the present invention, filter process is specially：Adsorbent is filtered out using 220nm miillpore filters to obtain
The solution of clarification.
The beneficial effects of the present invention are：The preparation method of carboxylated graphene oxide material is simple used in the present invention, former
Material is easy to get, and reaction condition is gentle, and handling process is simple, and good performance is shown in terms of adsorption of metal ions.
Brief description of the drawings
Fig. 1 is the reaction scheme figure of the preparation method of carboxylated graphene oxide of the present invention.
Fig. 2 is the infrared spectrogram of the carboxylated graphene oxide shown in Fig. 1.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Fig. 1 is referred to, for the preparation method of the carboxylated graphene oxide of the present invention.This method is using graphene oxide as base
Plinth, monoxone is grafted on graphene oxide, forms the carboxylated graphene oxide material with adsorbing metal ions effect.Profit
There is big specific surface area in itself with graphene, big pi-conjugated Structure and stability can provide network as matrix, selection
Cooperation is modifying agent with the monoxone of carboxyl, and material can adsorb the metal ion under the conditions of acidity by electrostatic adsorption.
Wherein, graphene oxide can use classical Hummer methods to prepare, and freeze-drying obtains；Can also directly it purchase
Buy acquisition.Monoxone is by directly buying acquisition.
Embodiment 1：
The preparation method of carboxylated graphene oxide material comprises the following steps that：
S1：Add graphene oxide into deionized water, it is scattered to obtain the aqueous solution liquid of graphene oxide；S2：To oxidation stone
Sodium hydroxide and monoxone are added in the aqueous solution of black alkene, 24h is stirred under normal temperature；S3：It is washed with deionized several times, dries
After obtain carboxylated graphene oxide material.
Step S1 is specially：The ultrasonic disperse 30min in 200W ultrasonic cleaners, obtains the water-soluble of graphene oxide
Liquid；In addition, the concentration of its graphene oxide is 1mg/mL.
In step S2, each component addition is：Graphene oxide：Sodium hydroxide：Monoxone is：50mg:3g:2g.
In step S3, drying process is specially that product is dried in vacuo 12h under the conditions of 60 DEG C.
The carboxylated graphene oxide material obtained by above-mentioned preparation method, passes through FFIR（FT-
IR）The structure of determination sample.Test condition is：Wave-length coverage is 4000 ~ 400cm-1, resolution ratio 4, scanning times 32；Carboxylic
Base graphene oxide composite material, graphene oxide raw material are tested using the method for pressing potassium bromide troche.Test result such as Fig. 2 institutes
Show, illustrate that we are successfully prepared for carboxylated graphene oxide material.
The application that the carboxylated graphene oxide of the present invention is adsorbed to metal ion in solution, it is specially：It is accurate to claim
3mg carboxylated graphene oxide material is taken to be added to 10mLs of the pH between 1 ~ 6 as adsorbent, 0.5mmol/L ~
In the solution of 2mmol/L metal ion [Cu (II) or Pb (II)], 15 DEG C ~ 30 DEG C constant temperature stirring reaction 0h ~ 24h, filter
To the solution of clarification, the metal ion content of settled solution is then detected using atomic absorption spectrophotometer, is finally calculated
Removal rate of the carboxylated graphene oxide material to metal ion.
Filter process is specially：The solution that adsorbent clarified is filtered out using 220nm miillpore filters, then utilizes atom
Absorption spectrophotometer detects the metal ion content of settled solution.
Below by the Application Example of the carboxylated graphene oxide material obtained with embodiment 1, illustrate carboxylic of the invention
The purposes of base graphene oxide composite material adsorbing metal ions.
Embodiment 2：
Adsorption capacity of the atomic absorption spectroscopy determination carboxylated graphene oxide to Cu (II) or Pb (II) metal ion
The accurate carboxylated graphene oxide material for weighing 3mg is added to the 10mL of pH=4.00,1.5mmol/L Cu (II) or
In the solution of Pb (II) ion, 25 DEG C of constant temperature stirring reaction 45min, filter out adsorbent using 220nm miillpore filters and clarified
Solution, the metal ion content of settled solution is then detected using atomic absorption spectrophotometer, and metal ion is calculated and contains
Changes of contents after measuring before treatment, so as to calculate adsorbance of the carboxylated graphene oxide to bivalent metal ion.Meanwhile
The graphene oxide modified is could be used without as a comparison case, using same method to being handled with a industrial wastewater.
Adsorbance of the carboxylated graphene oxide to metal ion is calculated as follows：
Q：Adsorbance（mg/g）；C1：Concentration of metal ions before absorption（mmol/L）；C2：Concentration of metal ions after absorption（mmol/
L）；V：The volume of adsorption liquid（L）；m：The quality of carboxylated graphene oxide（g）；M：The atomic weight of metal ion（g/mol）.
As a result it is as shown in the table：
From above table, carboxylated graphene oxide is good to the adsorption effect of metal ion.Containing Cu (II) or Pb (II)
After the carboxylated graphene oxide material process using the present invention, the removal rate of metal ion in solution is metal ion waste water
More than 80%.
By experimental results demonstrate carboxylated graphene oxide opposing metallic ion concentration ratio is higher, Adsorption metal
The efficiency of ion is higher.
In summary：The preparation method of the carboxylated graphene oxide of the present invention is simple, and raw material is easy to get, reaction condition temperature
With, handling process is simple, and prepare carboxylated graphene oxide materials show come out good bivalent metal ion adsorptivity
Energy.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (1)
- A kind of 1. application of carboxylated graphene oxide as adsorbent in bivalent cupric ion and lead (II) ion absorption.
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Cited By (11)
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| CN109078621A (en) * | 2018-09-07 | 2018-12-25 | 南阳理工学院 | A kind of preparation of magnetic nano adsorption material and its application in contaminated wastewater improvement |
| CN109248639A (en) * | 2018-09-30 | 2019-01-22 | 浙江工业大学上虞研究院有限公司 | A kind of micro passage reaction and preparation method thereof of sulfonated graphene modification |
| CN110152631A (en) * | 2018-03-28 | 2019-08-23 | 山东联星能源集团有限公司 | A kind of preparation method of adsorptivity graphene oxide hydrogel |
| CN110280224A (en) * | 2019-08-08 | 2019-09-27 | 西南科技大学 | The preparation method and application of functionalization graphene base aeroge |
| CN110668612A (en) * | 2019-11-27 | 2020-01-10 | 衡阳丰联精细化工有限公司 | Wastewater treatment method |
| CN110743503A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工程大学 | PCN metal organic framework and graphene oxide composite adsorption material and preparation method thereof |
| CN112547023A (en) * | 2020-12-02 | 2021-03-26 | 萝北瑞喆烯碳新材料有限公司 | Wastewater treatment agent and preparation method and application thereof |
| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN115646511A (en) * | 2022-11-29 | 2023-01-31 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
| CN117923907A (en) * | 2024-03-25 | 2024-04-26 | 山东华信工业科技有限公司 | Preparation method of silicon carbide ceramic |
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| CN110152631A (en) * | 2018-03-28 | 2019-08-23 | 山东联星能源集团有限公司 | A kind of preparation method of adsorptivity graphene oxide hydrogel |
| CN109078621A (en) * | 2018-09-07 | 2018-12-25 | 南阳理工学院 | A kind of preparation of magnetic nano adsorption material and its application in contaminated wastewater improvement |
| CN109248639B (en) * | 2018-09-30 | 2021-03-02 | 浙江工业大学上虞研究院有限公司 | Sulfonated graphene modified microchannel reactor and preparation method thereof |
| CN109248639A (en) * | 2018-09-30 | 2019-01-22 | 浙江工业大学上虞研究院有限公司 | A kind of micro passage reaction and preparation method thereof of sulfonated graphene modification |
| CN110280224A (en) * | 2019-08-08 | 2019-09-27 | 西南科技大学 | The preparation method and application of functionalization graphene base aeroge |
| CN110743503A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工程大学 | PCN metal organic framework and graphene oxide composite adsorption material and preparation method thereof |
| CN110743503B (en) * | 2019-10-25 | 2023-04-18 | 哈尔滨工程大学 | PCN metal organic framework and graphene oxide composite adsorption material and preparation method thereof |
| CN110668612A (en) * | 2019-11-27 | 2020-01-10 | 衡阳丰联精细化工有限公司 | Wastewater treatment method |
| CN112547023A (en) * | 2020-12-02 | 2021-03-26 | 萝北瑞喆烯碳新材料有限公司 | Wastewater treatment agent and preparation method and application thereof |
| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN112871145B (en) * | 2021-01-13 | 2022-05-13 | 北京大学 | Graphene material and preparation method and application thereof |
| CN115646511A (en) * | 2022-11-29 | 2023-01-31 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
| CN115646511B (en) * | 2022-11-29 | 2024-04-05 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
| CN117923907A (en) * | 2024-03-25 | 2024-04-26 | 山东华信工业科技有限公司 | Preparation method of silicon carbide ceramic |
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