CN107537445B - 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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- CN107537445B CN107537445B CN201711019756.0A CN201711019756A CN107537445B CN 107537445 B CN107537445 B CN 107537445B CN 201711019756 A CN201711019756 A CN 201711019756A CN 107537445 B CN107537445 B CN 107537445B
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- graphene oxide
- carboxylated graphene
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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 classical Hummers method, then mixes graphene oxide with monoxone under alkaline condition, stirs in 25 DEG C of waters bath with thermostatic control, centrifuge washing, drying preparation carboxylated graphene oxide.The preparation method of carboxylated graphene oxide is simple, and raw material is easy to get, and reaction condition is mild, and treatment process is simple, and good performance is shown in terms of wastewater treatment.
Description
Technical field
A kind of application the present invention relates to 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 technique
Heavy metal is usually present in nature with simple substance or compound form, is threatened ecology and human health smaller;
But recently as the excessive exploitation to metalliferous mineral, produce the industrial wastewater containing a large amount of metal ions.
By taking heavy metal copper as an example, copper is the strategic of the indispensable micronutrient of human health and industrial circle
One of element.In nature, copper mainly exists in the form of Copper Ores, is widely used in electrical, light industry, mechanical system
It makes, building industry, the fields such as national defense industry.However, the exploitation and smelting of copper zinc ore, intermetallic composite coating, machine-building, steel production
Etc. industrial productions cause serious environmental pollution, such as the Cu-W ore deposit in water body.If with copper-containing wastewater irrigated farmland and sulphur
The application of sour copper agrochemical pesticide can be such that a part of copper enters in soil and plant, will cause crops especially 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 generated to human health.Other than 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, and main includes changing
Learn the precipitation method, ion-exchange, electrolysis method 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, common adsorbent such as active carbon, biological adsorption agent, corn
Stalk, absorption resin, zeolite absorption, clay adsorption and silica absorption etc., but these adsorbents are in terms of chromium ion removal
All there is certain restrictions.Currently, graphene is since its big specific surface area is widely used field of waste water treatment and is achieved
Good effect.However, being had not been reported using the research that carboxylated graphene oxide makees adsorbent.
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.
Summary of the invention
The purpose of the present invention is to provide a kind of carboxylated graphene oxides as adsorbent in adsorption of metal ions
Using.
In order to achieve the above objectives, the invention provides the following technical scheme: a kind of preparation method of carboxylated graphene oxide,
Include the following steps: S1: adding graphene oxide into deionized water, dispersion obtains graphene oxide water solution;S2: to oxygen
Sodium hydroxide and monoxone are added in graphite aqueous solution, is stirred for 24 hours under room temperature;S3: it is washed with deionized several times, does
Carboxylated graphene oxide is obtained after dry.
As a further improvement of the present invention, in the aqueous solution of graphene oxide, the concentration of graphene oxide is 1mg/mL.
As a further improvement of the present invention, step S1 specifically: the ultrasonic disperse in 200W ultrasonic cleaner
30min obtains the aqueous solution of graphene oxide.
As a further improvement of the present invention, in step S2, each component additional proportion are as follows: graphene oxide: sodium hydroxide:
Monoxone are as follows: 50mg:3g:2g.
As a further improvement of the present invention, in step S3, drying process is specially that product vacuum under the conditions of 60 DEG C is dry
Dry 12h.
In order to achieve the above objectives, the present invention also provides the carboxyls of the preparation method preparation by above-mentioned carboxylated graphene oxide
Change graphene oxide composite material.
In order to achieve the above objectives, the present invention also provides a kind of carboxylated graphene oxide materials to Cu in solution (II) and
The application that Pb (II) ion is adsorbed.
As a further improvement of the present invention, carboxylated graphene oxide material carries out absorption tool to metal ion in solution
Body are as follows: the carboxylated graphene oxide material for accurately weighing 3mg is added to 10mL of the pH between 1 ~ 6 as adsorbent,
In the solution of the metal ion [Cu (II) or Pb (II)] of 0.5mmol/L ~ 2mmol/L, 15 DEG C ~ 30 DEG C constant temperature be stirred to react 0h ~
For 24 hours, clear solution is obtained by filtration, the metal ion content of clear solution is then detected using atomic absorption spectrophotometer,
Carboxylated graphene oxide material is finally calculated to the removal rate of metal ion.
As a further improvement of the present invention, filter process specifically: filter out adsorbent using 220nm miillpore filter and obtain
Clear solution.
The beneficial effects of the present invention are: the preparation method of carboxylated graphene oxide material used in the present invention is simple, former
Material is easy to get, and reaction condition is mild, and treatment process is simple, and good performance is shown in terms of adsorption of metal ions.
Detailed description of the invention
Fig. 1 is the reaction route figure of the preparation method of carboxylated graphene oxide of the present invention.
Fig. 2 is the infrared spectrogram of carboxylated graphene oxide shown in FIG. 1.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
It referring to Figure 1, is the preparation method of carboxylated graphene oxide of the invention.This method is using graphene oxide as base
Plinth is grafted monoxone on graphene oxide, forms the carboxylated graphene oxide material with adsorbing metal ions effect.Benefit
There is big specific surface area with graphene itself, for big pi-conjugated Structure and stability as matrix, selection can provide network
The monoxone of cooperation carboxyl is modifying agent, and material can adsorb the metal ion under the conditions of acidity by electrostatic adsorption.
Wherein, graphene oxide can be obtained using classical Hummer method preparation, freeze-drying;It can also directly purchase
Buy acquisition.Monoxone is obtained by directly purchase.
Embodiment 1:
Specific step is as follows for the preparation method of carboxylated graphene oxide material:
S1: adding graphene oxide into deionized water, and dispersion obtains the aqueous solution liquid of graphene oxide;S2: to oxygen
Sodium hydroxide and monoxone are added in the aqueous solution of graphite alkene, is stirred for 24 hours under room temperature;S3: being washed with deionized several times,
Carboxylated graphene oxide material is obtained after drying.
Step S1 specifically: the ultrasonic disperse 30min in 200W ultrasonic cleaner obtains the water-soluble of graphene oxide
Liquid;In addition, the concentration of its graphene oxide is 1mg/mL.
In step S2, each component additional amount are as follows: graphene oxide: sodium hydroxide: monoxone are as follows: 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 Fourier Transform Infrared Spectroscopy (FT-
IR the structure of sample) is measured.Test condition are as follows: wave-length coverage is 4000 ~ 400cm-1, resolution ratio 4, scanning times 32;Carboxylic
Base graphene oxide composite material, graphene oxide raw material are all made of the method test of pressing potassium bromide troche.Test result such as Fig. 2 institute
Show, illustrates that we are successfully prepared for carboxylated graphene oxide material.
The application that carboxylated graphene oxide of the invention adsorbs metal ion in solution, specifically: it is accurate to claim
The carboxylated graphene oxide material of 3mg is taken to be added to 10mL of the pH between 1 ~ 6 as adsorbent, 0.5mmol/L ~
In the solution of the metal ion [Cu (II) or Pb (II)] of 2mmol/L, 15 DEG C ~ 30 DEG C constant temperature are stirred to react 0h ~ for 24 hours, filter
To clear solution, then using the metal ion content of atomic absorption spectrophotometer detection clear solution, finally calculate
Removal rate of the carboxylated graphene oxide material to metal ion.
Filter process specifically: filter out adsorbent using 220nm miillpore filter and obtain clear solution, then utilize atom
The metal ion content of absorption spectrophotometer detection clear 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:
Absorption of the atomic absorption spectroscopy determination carboxylated graphene oxide to Cu (II) or Pb (II) metal ion
Ability
The carboxylated graphene oxide material for accurately weighing 3mg is added to the 10mL of pH=4.00, the Cu of 1.5mmol/L
(II) or in the solution of Pb (II) ion, 25 DEG C of constant temperature are stirred to react 45min, filter out adsorbent using 220nm miillpore filter and obtain
To clear solution, then using the metal ion content of atomic absorption spectrophotometer detection clear solution, and metal is calculated
Ion concentration before treatment after changes of contents, to calculate absorption of the carboxylated graphene oxide to bivalent metal ion
Amount.Meanwhile the graphene oxide that could be used without modification is as a comparison case, is carried out using same method to same a industrial wastewater
Processing.
Carboxylated graphene oxide is calculated as follows to the adsorbance of metal ion:
Q: adsorbance (mg/g);C1: concentration of metal ions (mmol/L) before adsorbing;C2: concentration of metal ions after absorption
(mmol/L);V: the volume (L) of adsorption liquid;M: the quality (g) of carboxylated graphene oxide;M: the atomic weight (g/ of metal ion
Mol).
As a result as shown in the table:
By above table it is found that carboxylated graphene oxide is good to the adsorption effect of metal ion.Containing Cu (II) or Pb
(II) metal ion waste water is after using carboxylated graphene oxide material processing of the invention, the removing of metal ion in solution
Rate is 80% or more.
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 carboxylated graphene oxide of the invention is simple, and raw material is easy to get, reaction condition temperature
With, treatment 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, for simplicity of description, not to above-mentioned reality
It applies 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, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (1)
1. a kind of application of carboxylated graphene oxide as adsorbent in bivalent cupric ion absorption, the application include:
Accurately weigh 3mg carboxylated graphene oxide material be added to pH=4.00 10mL, 1.5mmol/L cupric from
In the solution of son, 25 DEG C of constant temperature are stirred to react 45min;
The preparation method of the carboxylated graphene oxide includes:
S1: adding graphene oxide into deionized water, and dispersion obtains the aqueous solution of graphene oxide;S2: to graphite oxide
Sodium hydroxide and monoxone are added in the aqueous solution of alkene, is stirred for 24 hours under room temperature;S3: being washed with deionized several times, after dry
Obtain carboxylated graphene oxide material;
In the step S2, graphene oxide used: sodium hydroxide: monoxone=50mg:3g:2g;
Adsorbance of the application to bivalent cupric ion are as follows: every gram of carboxylated graphene oxide material can adsorb 259.03 milligrams
Bivalent cupric ion.
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