KR20160139462A - Graphene Oxide Having Excellent Adsorption Property Toward Heavy Metal Ions and Preparing Method Thereof - Google Patents
Graphene Oxide Having Excellent Adsorption Property Toward Heavy Metal Ions and Preparing Method Thereof Download PDFInfo
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Abstract
Description
The present invention relates to an oxide graphene excellent in heavy metal adsorption performance and a method for producing the same.
Fullerene, carbon nanotube, graphene, and graphite are examples of materials composed of carbon atoms. Among them, graphene is an atom in which carbon atoms are arranged in a hexagonal shape And is a material having a plate-like structure composed of one layer. Due to its unique structure and the electrons inside it, graphene is not only very stable and excellent in electrical, mechanical and chemical properties, but also an excellent conductive material that moves electrons much faster than silicon, have. Graphene has not only electrical, mechanical and chemical stability, but also has excellent conductivity properties, so it is attracting attention as a basic material for electronic circuits.
In addition, since graphenes generally have electrical characteristics that vary depending on the crystal orientation of graphene of a given thickness, the user can express the electrical characteristics in the selected direction and thus design the device easily. Therefore, graphene can be effectively used for carbon-based electric or electromagnetic devices.
Graphene is thin, flexible and transparent because it consists of layers of atomic thickness. Graphene is a form in which graphite is separated by a sheet and it is very difficult to strip off a sheet. Before the Scotch tape method, which was awarded the Nobel Prize for physics, chemical synthesis by oxidation and reduction of graphite was the most used.
Oxidative graphene is an oxidation product of graphene. Many methods have been developed by Staudenmaier, Hummer and Dffeman et al., Starting with Brodie and Schfhaeutl in the nineteenth century. Among them, Hummer ' I use it a lot. Oxidized graphite oxide, which is oxidized by strong acid and oxidizing agent, is strongly hydrophilic and water molecules are inserted between the layers and easily peeled off. The graphene oxide thus obtained is reduced again, If removed, a structure similar to graphene is generated again.
Since the graphene oxide exists in a form in which the hydroxyl group and the epoxy group are bonded to the surface and the carboxyl group is bonded to the edge, the graphene grains have properties different from those inherent to graphene and have a wide specific surface area and strong mechanical strength. There are many studies in the field. Graphene has a property of not being easily dispersed in water, but oxidized graphene has a large number of functional groups including oxygen, so that it is well dispersed in water and exhibits good performance for cation adsorption.
On the other hand, at the time of water treatment and industrial wastewater treatment, the treatment cost is gradually increasing due to the heavy metals contained in the treated water. Therefore, it is necessary to develop a technique for improving the removal efficiency of heavy metals of the adsorbent. Particularly, it is required to develop a material to replace the existing heavy metal adsorption efficiency of activated carbon and zeolite.
Heavy metals are mostly rare metals. Rare metals imports and consumption are gradually increasing, but the ratio of rare metals recycled is small. Therefore, industrial effects are expected to be great when recycling rare metals through adsorption of heavy metals.
Numerous references are referenced throughout the specification and are cited therein. The disclosure of the cited document is incorporated herein by reference in its entirety to more clearly describe the state of the art to which the present invention pertains and the content of the present invention.
The present inventors have made efforts to provide a technology for developing oxidized graphene as an alternative to the conventional adsorbent, which improves the adsorption amount of heavy metals. As a result, the present invention has been completed by producing graphene oxide having an excellent heavy metal adsorption ability by controlling the structure and size of oxidized graphene and carboxyl group.
Accordingly, an object of the present invention is to provide a technique of manufacturing an oxide graphene containing a carboxyl group as an oxygen-containing functional group at a specific ratio or more.
It is another object of the present invention to provide a composition and a product for adsorbing a heavy metal containing the graphene oxide.
It is still another object of the present invention to provide a method for producing the graphene oxide.
Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.
One aspect of the present invention is an oxide graphene comprising oxygen functional groups, wherein the ratio of carboxyl groups in the total oxygen-containing functional groups is at least 5.0%.
Although the excellent metal ion adsorption performance of the graphene oxide is mainly attributed to the carboxyl group in the oxygen-containing functional group, there is no known technique for increasing only the carboxyl group specifically over a certain ratio.
It is known that when the amount of oxidizing agent is increased in the production of graphene oxide graphene to produce oxidized graphene having a high degree of oxidation, the ratio of epoxide group is increased (Krishnamoorthy et al., The chemical and structural analysis of graphene oxide with different degrees of oxidation, CARBON, 53: 38-49 (2013)).
It has also been found that the ratio of carbonyl groups (C = O) increases when oxidizing graphene oxide (Tang et al., Highly Oxidized Graphene Anchored Ni (OH) 2 Nanoflakes as Pseudocapacitor Materials for Ultrahigh Loading Electrode High Areal Specific Capacitance, J. Phys . Chem . C , 118 (43): 24866-24876 (2014)).
As described above, when the graphene oxide graphene is produced using the conventional method, the amount of oxidizing agent is quantitatively controlled to prepare oxide graphenes having different degrees of oxidation, or a method of further oxidizing the graphene oxide With such a strategy, it is impossible to specifically increase only the carboxyl group among the various oxygen-containing functional groups.
In the case of conventional graphene grains, the proportion of the carboxyl groups in the graphene oxide of the present invention is about 5.0% or more of the total number of oxygen-containing functional groups, while the proportion of the carboxyl groups in the total oxygen-containing functional groups is about 2.0% Or more, preferably 6.0% or more, more preferably 8.0% or more.
In one embodiment, the proportion of carboxyl groups contained in the oxidized graphene of the present invention may be 2.0 to 10.0% of the total oxygen containing functional groups.
The oxygen-containing functional groups contained in the graphene oxide mean mainly hydroxy, epoxide and carboxyl groups when oxidized graphene is produced and oxidized by the Hummer method. However, depending on the preparation and oxidation conditions, the hydroxy-, epoxide-, May be one or more substituents selected from the group consisting of hydrogen, hydroxyl, carboxyl, carboxyl, carboxyl, carboxyl, carbonyl, aldehyde, ester, alkoxy, peroxy, ether, acetal and ketal.
In other embodiments, the graphene oxide of the present invention may exhibit its structure and size as an aspect ratio.
The aspect ratio is the ratio (L / D) of the length of the graphene stack divided by the diameter, where the selected units of length and diameter are the same, and therefore the aspect ratio is an indefinite number because the unit is deleted when expressed in proportions.
In general, when graphene oxide is split into small pieces in the course of dispersion and stirring, the surface area increases but the aspect ratio decreases. The inventors of the present invention have found the surprising fact that although the surface area of the graphene graphene is increased as the aspect ratio is increased, the graphene grains are more advantageous for heavy metal adsorption.
Thus, the graphene oxide of the present invention has an aspect ratio of at least 250 or more and is characterized by having an excellent heavy metal adsorption performance.
Specifically, in one embodiment of the present invention, the aspect ratio value of the graphene oxide may be at least 250, preferably at least 500, more preferably at least 1000.
In other embodiments, the aspect ratio ratio of the oxidized graphene of the present invention may be between 250 and 1000. [
Another aspect of the present invention is to provide a heavy metal adsorbent composition containing the graphene oxide of the present invention and a product having heavy metal adsorption performance including the graphene oxide.
The heavy metal adsorbed by the composition and the product of the present invention refers to a set of elements having an atomic mass of 63.546 to 200.590 and a specific gravity of 4.5 or more between copper and lead in the periodic table and may exhibit toxicity to an organism and may exhibit strong coordination with a ligand Formed and can not be excreted out of the organism, and tend to accumulate in the body. It has been reported that cadmium, lead, and mercury, which are representative harmful heavy metals, show high affinity to the phosphoric acid, protein, and nucleic acid in the cells and change the action of the enzyme and inhibit the oxidation-phosphorylation process necessary for the structural change and energy metabolism of the nucleic acid There is a bar.
The heavy metal adsorbed by the composition and the product of the present invention may include Cr, Pb, Cd, Hg, Cu, Zn, Co, Ni, Mg, Fe, Mn, Lu, Cs and Ca.
The product having the heavy metal adsorption capability of the present invention includes, for example, an adsorption filter, a water purifier, a water treatment device, an air purifier, an air conditioner, and an air mask.
The heavy metal adsorption filter of the present invention may be used in a filtration apparatus having a reaction chamber and a treatment water or gas circulation apparatus in which one or several filters are continuously installed and the treatment water or the treatment gas component Introducing the purified water into the reaction chamber, passing the filtered gas through one or several installed filters to adsorb and remove heavy metal components, and receiving clean water or clean gas.
The adsorption filter for removing heavy metals according to the present invention may be used as a pretreatment filter, either individually or in combination with a carbon filter such as a micro-precipitate filter made of a metal or plastic, a granular activated carbon filter, a powder activated carbon filter, As the treatment filtration filter, an ultraviolet disinfecting device, an activated carbon filter, a ceramic filter, an active carbon filter containing silver (Ag), an ultrafiltration filter, a magnetization filter, etc. may be used respectively or in combination.
The heavy metal removal purifier according to the present invention may be a direct water type domestic water purifier including the oxidation graphene of the present invention in the main filter portion filter and capable of taking and drinking purified water as it is without a storage tank. In the existing water purification method using the reverse osmosis membrane, the water quality of the purified water is good but the flow rate is small and a separate storage tank must be employed. Therefore, there is a fear of secondary contamination due to microorganisms and storage capacity of the water purifier. The water purifier of the present invention can be characterized by rapidly adsorbing and removing heavy metals by including the graphene oxide of the present invention in the main filter part filter.
The water treatment apparatus having the heavy metal removal performance of the present invention can be used in various water treatment processes, water treatment systems and water treatment methods, and can be applied to household products, industrial products, medicines and other organic or inorganic substances And may be used in combination with other water treatment methods other than heavy metal removal such as ozone treatment, advanced oxidation treatment, membrane separation treatment, ultraviolet ray penetration, activated carbon treatment, and the like.
The air purifier having the heavy metal removal capability of the present invention purifies contaminated air and converts it into fresh air. Air may be passed through a filter to remove dust, germs and odors, and to adsorb and remove heavy metal components. A mechanical filter for collecting dust using a malt-peen or glass fiber, a high-performance filter for collecting particulates using glass fibers and cellulose fibers, and a deodorizing filter using activated carbon, Or a separate filter including an oxide graphene may be adopted. In addition, air purifiers which conventionally artificially generate ozone to deodorize, sterilize and purify air owing to the action of ozone, or an air purifier that sucks contaminated air through a fan, collects fine dust or bacterium by a microfilter, It can also be used in cleaners.
The air-conditioner having the heavy metal removal performance of the present invention is used for cooling a specific space such as a room, a car interior or the like in hot weather, season, or the like. The refrigerant compressed by the compressor is introduced into a condenser condenser and then evaporated by an evaporator through an expension valve to cool the room by the heat of vaporization. In the main filter located in the circulation area of the air, It is also possible to apply a pin to give a remarkably excellent heavy metal removal performance.
The air mask of the present invention is a disposable lotion mask for preventing the penetration of yellow dust, which is able to filter yellow dust particles contained in the air by being worn on the user's face when yellow dust is generated, .
In one embodiment, an air mask having heavy metal adsorption capability according to the present invention comprises a mask body formed by overlapping a surface and a lining, a hook band provided on both sides of the mask body, and a plurality of voids existing in the mask body And a filter member for filtering harmful substances contained in the air during respiration through each of the openings is provided, and a structure in which the filter member is applied with the oxidation graphene of the present invention may be employed.
Yet another aspect of the present invention is a method of preparing a coating composition comprising: (i) preparing an aqueous solution of a graphene oxide; (ii) adding a carboxylic acid or a salt thereof to the aqueous solution; And (iii) stirring the aqueous solution to which the carboxylic acid has been added. The present invention also provides a method for producing the graphene oxide according to the present invention, wherein the proportion of the carboxyl group is specifically increased.
In the process of the present invention, the carboxylic acid may be acetic acid, preferably bromoacetic acid, iodoacetic acid. When chloroacetic acid is used, the proportion of carboxyl groups in the graphene grains is slightly increased, but there is a disadvantage that the carboxyl group can not be increased to at least 5.0% or more because of insufficient reactivity.
Examples of the carboxylic acid having sufficient reactivity and capable of increasing the carboxyl group to not less than 5.0% include bromoacetic acid, iodoacetic acid, chloromalonic acid, 4- (chloromethyl) benzoic acid, 2 - (chloromethyl) oxazole-4-carboxylic acid, 5- (chloromethyl) furan-2-carboxylic acid and the like.
In the method of the present invention, in step (ii), the carboxylic acid or its salt is added in an amount of about 10 to 100 times, preferably 30 to 70 times, more preferably about 50 times .
In addition, in step (ii), a basic component which releases hydroxide ions in the aqueous solution or absorbs hydrogen ions, such as sodium hydroxide, together with the carboxylic acid may be added together in the same amount as the carboxylic acid.
The implementation of the stirring in the step (iii) is not limited to the specific method. After step (iii), the step of washing with an appropriate solvent, drying and filtering may be added to prepare the graft oxide of the present invention having a carboxyl group content of at least 5.0% of the total oxygen-containing functional groups.
Another aspect of the present invention is to provide a method for producing the graft oxide of the present invention having a carboxyl group content of at least 5.0% of the total oxygen-containing functional groups by introducing a carboxyl group by using a catalyst. Such a catalytic method includes a method using a palladium catalyst or a cobalt catalyst.
A method using a palladium catalyst includes (i) preparing a graphene oxide solution in a carboxylic acid solvent; And (ii) adding a palladium catalyst to the solution to introduce a carboxyl group into the oxidized graphene through a catalytic reaction.
The carboxylic acid used as a solvent in step (i) includes carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, (S) selected from the group consisting of capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, margaric acid, Stearic acid, arachidic acid, and the like.
When the oxidized graphene of the present invention is produced by the palladium catalyst method as described above, the carboxyl group is further introduced into the benzene ring of the oxidized graphene without changing the existing oxygen-containing functional groups of the graphene oxide in the step (ii) .
The method using a cobalt catalyst comprises the steps of: (i) preparing a graphene oxide solution in a ketone solvent; And (ii) adding a cobalt catalyst to the solution to introduce a carboxyl group into the oxidized graphene through a catalytic reaction.
In this case, in the step (ii), the epoxide group in the oxidized graphene is substituted with a carboxyl group to introduce a carboxyl group.
The graphene oxide of the present invention specifically increases the ratio of carboxyl groups forming strong bonds with heavy metal ions, and exhibits an excellent adsorption improvement effect on various heavy metals.
FIG. 1 shows a process of preparing graphene grains in which carboxyl groups are introduced at a specific ratio or more using a Pd catalyst or a Co catalyst.
Fig. 2 shows X-ray photoelectron spectroscopy (XPS) analysis and the results before and after the modification.
Fig. 3 shows the results of measurement of surface zeta potential at
4 (4a and 4b) show the results of evaluating the amount of adsorbed ions increased before and after the modification.
Fig. 5 shows the results of evaluating the adsorption rate of heavy metals before and after the reforming.
FIG. 6 shows the results of heavy metal adsorption evaluation on Cu ions using respective oxide grains having three kinds of
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention more specifically and that the scope of the present invention is not limited by these embodiments.
Example
< Carboxy Oxidized graphene synthesis >
(One) Example One ( Carboxy group Method of bonding with a substance having
Preliminarily synthesized graphene oxide was prepared and dispersed in water to prepare a 1 mg / ml aqueous solution of oxidized graphene. To the aqueous solution, NaOH was added 50 times as much as the weight of the oxidized graphene, and sodium bromoacetate was added at 50 times the weight of the oxidized graphene. The reaction mixture was stirred for 2 hours to carry out the carboxylation reaction. The reaction mixture was washed 5 times with 5 wt% HCl and H 2 SO 4 , and then washed three times with Acetone. Then, the resultant was filtered and then dried at 40 DEG C to prepare carboxygallized graphene.
(2) Example 2 ( Pd Catalyst Carboxy group Introduction)
1 mg / ml of a graphene oxide solution in an acetic acid solvent was prepared, and palladium (II) acetate was added to the solvent in an amount of 0.1 wt% relative to the graphene oxide. This was reacted in an autoclave at CO 15 bar and 90 ° C for 24 hours. Then, it was washed 5 times with acetone, filtered and dried at 40 캜 to prepare carboxylated oxidized graphene.
(3) Example 3 ( Co Catalyst Carboxy group Introduction)
1 mg / ml of a graphene oxide solution in an acetone solvent was prepared, and dicobalt octacarbonyl was added to the solvent in an amount of 0.1 wt% based on the graphene oxide. The autoclave was reacted at
(4) Example 4 (having various aspect ratios Oxidized graphene synthesis)
The graphene oxide was prepared using the method of coupling with a substance having a carboxyl group as described in Example 1, and graphene oxide having various aspect ratios was synthesized by controlling the ultrasonic treatment time in the dispersion of the oxidized graphene. Specifically, ultrasonic waves were treated for 1 minute, 3 minutes, and 5 minutes, respectively, to prepare graphene grains having aspect ratios of 100, 140, and 150, respectively.
< Carboxy Oxidized graphene Physical property experiment >
(1) Confirmation of increase of heavy metal adsorption site
XPS (X-ray photoelectron spectroscopy) analysis was performed to measure the kinetic energy obtained by irradiating the X-ray beam onto the carboxy-containing oxidized graphene prepared in Example 1 and the number of electrons escaped from the specimen, The results after that are shown in Fig.
As a result of the experiment, it was confirmed that the ratio of carboxy group in the total oxygen-containing functional groups of the graphene oxide before reforming was 2.4%, while that of the carboxy group after modification was increased to 8.0%.
In addition, since the surface charge becomes higher as the carboxyl group of the graphene oxide increases, the surface zeta potential at
(2) Oxidized graphene Heavy metal adsorption evaluation
Heavy metal adsorption tests were performed on representative heavy metals such as Co, Ni, Cu, Cd, Cr and Fe using the oxidized graphene prepared in Example 1 and compared with the results of cation adsorption before reforming, . The amount of ion adsorption after the modification was evaluated through data analysis and the results are shown in FIG. 4 (a and b).
As a result of the experiment, it was confirmed that the graphene oxide of the present invention, in which the proportion of carboxyl groups was specifically increased due to the modification, exhibited an adsorption improvement effect of 20 to 330% on various heavy metals.
The adsorption rate of heavy metals before and after the reforming was evaluated, and the results are shown in Fig.
As a result of the experiment, it was found that the adsorption amount of 90% was shown within about 5 minutes before the modification, but 90% of the adsorption amount was found within about 3 minutes after the modification, and it was confirmed that the increase of the heavy metal adsorption rate by the increase of the carboxyl group .
(3) Oxidized graphene Evaluation of Impact of Aspect Ratio on Heavy Metal Adsorption
The heavy metal adsorption evaluation on Cu ions was carried out using the respective graphene grains (
Experimental results show that when the aspect ratio of graphene oxide is reduced by ultrasonic treatment, the graphene oxide is disadvantageous to the heavy metal adsorption despite the increase of the surface area. The larger the aspect ratio, the more favorable the adsorption of heavy metals.
Claims (12)
(ii) adding a carboxylic acid or a salt thereof to the aqueous solution; And
(iii) stirring the carboxylic acid-added aqueous solution
The method according to claim 1,
(ii) adding a palladium catalyst to the solution to introduce a carboxyl group into the oxidized graphene through a catalytic reaction
The method according to claim 1,
(ii) adding a cobalt catalyst to the solution to introduce a carboxyl group into the oxidized graphene through a catalytic reaction
The method according to claim 1,
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| 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 |
| KR20200065784A (en) * | 2018-11-30 | 2020-06-09 | 한국과학기술연구원 | Cesium ion adsorbent, method for producing the same, and method for removing cesium ion using the same |
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| CN114314576A (en) * | 2021-11-30 | 2022-04-12 | 西安近代化学研究所 | Method for modifying carboxyl functionalization of graphene oxide |
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| KR20140028666A (en) | 2012-08-30 | 2014-03-10 | 엘지전자 주식회사 | Method for manufacturing graphene oxide and the graphene oxide manufactured by the same |
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| 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 |
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| CN114314576A (en) * | 2021-11-30 | 2022-04-12 | 西安近代化学研究所 | Method for modifying carboxyl functionalization of graphene oxide |
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| CN114601753A (en) * | 2022-05-13 | 2022-06-10 | 汕头市特丝多丽化妆品有限公司 | Cosmetic containing graphene for adsorbing heavy metals and preparation method thereof |
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