KR101640545B1 - Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same - Google Patents
Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same Download PDFInfo
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- KR101640545B1 KR101640545B1 KR1020150043552A KR20150043552A KR101640545B1 KR 101640545 B1 KR101640545 B1 KR 101640545B1 KR 1020150043552 A KR1020150043552 A KR 1020150043552A KR 20150043552 A KR20150043552 A KR 20150043552A KR 101640545 B1 KR101640545 B1 KR 101640545B1
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- carbon nitride
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- rgo
- graphene oxide
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- C01B31/043—
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- C01B31/0438—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Power Engineering (AREA)
- Composite Materials (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for producing a catalyst-graphitic carbon nitride-reduced graphene oxide complex, a composite produced thereby, and electrodes using the same. More specifically, the present invention relates to: 1) Thereby preparing a graphene oxide suspension; 2) preparing a graphite-type carbon nitride-reduced graphene oxide complex (gC 3 N 4 @RGO) by hydrothermal synthesis after adding a carbon nitride precursor to the suspension; And 3) carrying the transition metal catalyst by dispersing the complex in a polyol solvent, adding a transition metal salt, mixing, and stirring the mixture to form a catalyst-graphitic carbon nitride-reduced graphene A process for preparing an oxide complex is disclosed.
Description
The present invention relates to a method for producing a catalyst-graphitic carbon nitride-reduced graphene oxide composite, a catalyst-graphitic carbon nitride-reduced graphene oxide composite produced thereby, an electrode manufactured using the same, a fuel cell and a capacitor .
Graphene, which is a two-dimensional isoform of carbon with a hexagonal grid of carbon atoms, has a quantum Hall effect, high carrier mobility (~ 10,000 cm 2 / Vs) at room temperature, large specific surface area (2630 cm 2 / g) It has excellent properties such as excellent light transmittance (~ 97.7%), high mechanical properties (~ 1 TPa) and excellent thermal conductivity (3000-5000 W / mK). Methods for producing such graphenes include a method of separating a graphene layer from a graphite crystal and a chemical vapor deposition method of synthesizing graphene using a transition metal that absorbs carbon well at a high temperature as a catalyst layer, An epitaxial growth method has been studied in which the contained carbon grows along the surface texture. Particularly, the chemical peeling method which oxidizes graphite and separates it in a solution state and then reduces the graphite has a lot of researches because of the possibility of mass production and easy chemical modification and hybridization with other materials. Research is being conducted to prepare graphene oxide by expanding the interlayer distance by inserting a material between layers and applying it as an electrode active material of a secondary battery or a super capacitor.
In addition, graphene has attracted attention as an energy storage material and a catalyst carrier especially because it has a large specific surface area with unique electrical, thermal, optical and mechanical properties as described above. However, when applied to a catalyst carrier of graphene, severe aggregation due to strong π-electron interaction (π-π stacking interaction) between graphene nanosheets and redeposition of graphene nanosheets, Due to the weak interaction between the nanocatalysts, low stability of the catalyst using the support and high surface energy of the catalyst itself are problematic.
On the other hand, as an analogue of graphite, graphitic carbon nitride has a two-dimensional laminated structure which can be regarded as N-substituted graphite. The graphitic carbon nitride has attracted much attention due to the functionalization of nitrogen in the carbon structure and physical properties such as high hardness, low friction coefficient and catalytic activity. In particular, it has been reported that nano-sized metal particles are well adsorbed by nitrogen, and electron transfer of substances is higher than that of pure carbon, thereby increasing catalytic activity such as benzene activity, trimerization reactions, carbon dioxide activity, and photocatalyst .
However, conventional processes for producing graphite-type carbon nitride can be synthesized by carbonization of a CN-rich nitrogen precursor or condensation by fine thermal decomposition. However, the graphite-type carbon nitride thus formed has a disadvantage in that not only expensive equipment is used but also the synthesis yield is low and the manufacturing cost is high. Further, when the graphitic carbon nitride is used singly, there is a limit in that it can not exhibit electrical conductivity so as to be used industrially.
Therefore, the present inventors have studied graphene as an energy storage material and a catalyst support, and have found that by chemically modifying graphene oxide by preparing graphene-type carbon nitride-reduced graphene oxide complex using chemically peeled graphene oxide The present invention solves the problem of strong π electron interaction acting between graphene nanosheets and interaction between relatively weak graphene and catalyst so as to be applied as a catalyst carrier, The nitride-reduced graphene oxide complex was prepared and the present invention was completed.
Accordingly, it is a technical object of the present invention to provide a process for producing a catalyst-graphitic carbon nitride-reduced graphene oxide composite.
Another object of the present invention is to provide a catalyst-graphitic carbon nitride-reduced graphene oxide composite produced by the above method.
Another object of the present invention is to provide an electrode comprising the catalyst-graphitic carbon nitride-reduced graphene oxide complex.
Another object of the present invention is to provide a fuel cell and a capacitor which are manufactured using the electrode including the catalyst-graphitic carbon nitride-reduced graphene oxide composite.
According to an aspect of the present invention,
1) dispersing the lyophilized graphite oxide in distilled water to prepare a graphene oxide suspension;
2) preparing a graphite-type carbon nitride-reduced graphene oxide complex (gC 3 N 4 @RGO) by hydrothermal synthesis after adding a carbon nitride precursor to the suspension; And
3) a step of dispersing the composite in a polyol solvent, followed by adding a transition metal salt, mixing, and stirring to transfer the transition metal catalyst, and then, carrying the catalyst-graphitic carbon nitride-reduced graphene oxide A method of making a composite is provided.
In the present invention, the suspension prepared in the step 1) comprises graphite oxide containing at least one functional group selected from a hydroxyl group, a carboxyl group and an epoxy group; The carbon nitride precursor in the step 2) is selected from the group consisting of cyanuric chloride (C 3 Cl 3 N 3 ), melamine (C 3 H 6 N 6 ), melem (C 3 H 6 N 10 ), and melam (C 6 H 9 N 11 ) And the like.
More preferably, the carbon nitride precursor in step 2) is melamine; The weight ratio of melamine to graphite oxide may be 1: 5 to 20.
In the present invention, it is preferable that the gC 3 N 4 @RGO composite is prepared by hydrothermal synthesis and then heat-treated to stabilize the gC 3 N 4 @RGO composite. More preferably, the hydrothermal synthesis is carried out at a temperature of 90 to 110 DEG C for 48 to 120 hours; The heat treatment is performed at a temperature of 100 to 300 DEG C for 5 to 30 minutes.
Preferably, in the present invention, the step 3)
a) modifying the surface of the gC 3 N 4 @RGO composite prepared in the step 2);
b) dispersing the surface-modified composite in a polyol solvent, and further adding and mixing a transition metal salt; And
and c) carrying the transition metal catalyst on the surface-modified composite by adjusting the pH of the mixed solution of step b) to 9 to 11, followed by stirring and dispersing.
More preferably, the surface modification is performed using at least one oxidizing agent selected from H 2 SO 4 , HNO 3 and P 2 O 5 .
In the present invention, the polyol solvent in step 2) may be selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. It can be more than a species.
In the present invention, the transition metal salt may be at least one selected from the group consisting of Pt, Pd, Au, Ag, Ni, Co, Fe, Sn, , At least one metal selected from the group consisting of rhodium (Rh), osmium (Os), iridium (Ir), tungsten (W), ruthenium (Ru), titanium (Ti) and vanadium .
According to another aspect of the present invention, there is provided a catalyst-graphitic carbon nitride-reduced graphene oxide composite produced by the above method.
According to another aspect of the present invention, there is provided an electrode manufactured using the catalyst-graphitic carbon nitride-reduced graphene oxide composite, a fuel cell manufactured using the electrode, A capacitor is provided.
According to another aspect of the present invention, there is provided a fuel cell comprising: a fuel cell comprising a catalyst-graphitic carbon nitride-reduced graphene oxide complex; do.
According to another aspect of the present invention, there is provided a capacitor manufactured using an electrode manufactured using the catalyst-graphitic carbon nitride-reduced graphene oxide composite.
According to the method of the present invention, it is possible to produce reduced graphene oxide from which an oxygen functional group is removed without using an expensive reducing agent, and it is possible to prevent restacking of graphene oxide, As shown in Fig. Further, graphite-type carbon nitride is uniformly distributed on graphene oxide without carbonization or thermal treatment at a high temperature in a conventional process for producing graphite-type carbon nitride, and a high yield of graphite-type carbon nitride-reduced graphene oxide (gC 3 N 4 @ RGO) complexes can be produced.
Also, according to the method for producing a catalyst-graphitic carbon nitride-reduced graphene oxide composite according to the present invention, the material mobility and the surface area are maximized, and the catalyst metal particles are formed into a smaller form It can be applied to various fields as a catalyst body supported with a metal catalyst as well as an energy storage material.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of a flow diagram and complex of a process for preparing a catalyst-graphitic carbon nitride-reduced graphene oxide (M / gC 3 N 4 @ RGO) complex according to the present invention.
Figure 2 is a schematic representation of the reaction to produce gC 3 N 4 @RGO using melamine in accordance with one embodiment of the present invention.
FIG. 3 shows SEM analysis results of the gC 3 N 4 @RGO complex and RGO according to an embodiment of the present invention.
FIG. 4 shows the EDAX analysis results of the gC 3 N 4 @RGO complex and RGO according to an embodiment of the present invention.
FIG. 5 shows FT-IR analysis results of gC 3 N 4 @RGO complex and RGO according to an embodiment of the present invention.
FIG. 6 shows TEM analysis results and particle size distribution of Pt / gC 3 N 4 @RGO composite and Pt / RGO according to an embodiment of the present invention.
FIGS. 7 and 8 show the results of capacitance measurement of gC 3 N 4 @RGO composite and RGO according to an embodiment of the present invention.
FIG. 9 shows the results of the noncontact capacity analysis of gC 3 N 4 @RGO complex and RGO according to an embodiment of the present invention.
FIG. 10 shows the results of ECSA measurement of Pt / gC 3 N 4 @RGO composite, Pt / RGO, Pt / G and Pt / C according to an embodiment of the present invention.
Hereinafter, the present invention will be described in detail.
The method for producing a catalyst-graphitic carbon nitride-reduced graphene oxide composite according to the present invention comprises:
1) dispersing the lyophilized graphite oxide in distilled water to prepare a graphene oxide suspension;
2) preparing a graphite-type carbon nitride-reduced graphene oxide complex (gC 3 N 4 @RGO) by hydrothermal synthesis after adding a carbon nitride precursor to the suspension; And
3) dispersing the composite in a polyol solvent, and then adding a transition metal salt, mixing, and stirring to carry the transition metal catalyst.
In the method for producing the catalyst-graphitic carbon nitride-reduced graphene oxide complex according to the present invention, the step 1) is a step of preparing a graphene oxide suspension.
Specifically, the freeze-dried graphite oxide is dispersed by ultrasonication under distilled water to prepare a graphene oxide suspension uniformly dispersed in distilled water. At this time, the degree of ultrasonic dispersion assists the solvent to be inserted between the layer of the graphite oxide and induces the separation of the graphene oxide, so that the graphene oxide acts as a template of the graphitic carbon nitride.
The graphite oxide may be prepared by a variety of known methods including Hummers method. In the production of the graphite oxide, by controlling the oxidation method or the treatment time, the interlayer distance and oxidation degree of graphite oxide, the degree of defect, Size, and so on. At this time, the graphite oxide may be formed using at least one oxidizing agent selected from the group consisting of H 2 SO 4 , K 2 S 2 O 8 , KNO 3 , and KMnO 4 , and a graphite oxide having a functional group such as a hydroxyl group, a carboxyl group, Can be used. The graphite oxide to which the functional group is attached and the surface-modified graphite oxide can physically bond with the carbon nitride, thereby helping to produce graphitic carbon nitride.
In addition, the use of the freeze-dried graphite oxide prevents the phenomenon that the interlayer spacing between graphene sheets is narrowed and re-deposited again.
Also, in the method for producing the catalyst-graphitic carbon nitride-reduced graphene oxide composite according to the present invention, the step 2) is a step of preparing a graphite-type carbon nitride-reduced graphene oxide complex (gC 3 N 4 @RGO) .
Specifically, a carbon nitride precursor was added to the graphene oxide suspension prepared in the step 1), and then a graphite-type carbon nitride-reduced graphene oxide having a C 3 N 4 network structure (gC 3 N 4 @ RGO) complexes are prepared.
The carbon nitride precursors include cyanuric chloride (C 3 Cl 3 N 3 ), melamine (C 3 H 6 N 6 ), melem (C 3 H 6 N 10 ), and melam (C 6 H 9 N 11 ) May be used.
Specifically, in the case of melamine, the reaction is modeled and as shown in FIG. 2, the melamine is replicated by reaction and condensation with the aid of the functional group of graphene oxide in the step 1), and graphite having a C 3 N 4 network structure Type carbon nitride is formed.
The melamine may be added in a weight ratio of 1: 5 to 20 with respect to graphite oxide. When melamine is added in an amount less than the above-mentioned weight range, reduction of graphene oxide is difficult to occur effectively, and in addition, formation of an improved graphite-type carbon nitride is limited, and if it exceeds the weight range, by- Can be reduced.
The hydrothermal synthesis of step 2) is preferably performed at a temperature of 90 ° C to 110 ° C for 48 hours to 120 hours. When the temperature is less than 90 ° C, the conversion efficiency decreases to graphite-type carbon nitride, and when the temperature exceeds the above range, the oxygen functional groups of graphene oxide are decomposed due to heat to reduce synthesis efficiency. When the hydrothermal synthesis time in the temperature range is less than 48 hours, the proportion of the melon structure, which is a basic unit of carbon nitride, is high and it is difficult to have a highly ordered structure. When the hydrothermal synthesis time exceeds 120 hours, Is lowered.
Also, in the hydrothermal synthesis process in the step 2), reduced graphene oxide having oxygen functional groups removed without using any reducing agent, a gC 3 N 4 @RGO complex having a uniformly distributed graphite type carbon nitride is formed , Preventing graphene oxide from being deposited again.
At this time, the gC 3 N 4 @RGO complex may be prepared by the hydrothermal synthesis, followed by filtration, washing, drying, and then annealing to stabilize the gC 3 N 4 @RGO complex. At this time, the heat treatment may be performed at a temperature of 100 to 300 ° C for 5 to 30 minutes under an inert gas atmosphere.
Also, in the method for preparing a catalyst-graphitic carbon nitride-reduced graphene oxide composite according to the present invention, the step 3) is a step of supporting a transition metal catalyst.
Specifically, the gC 3 N 4 @RGO complex is dispersed in a polyol solvent, and then a transition metal (M) salt is added thereto, followed by mixing and stirring to disperse the catalyst. The transition metal catalyst is supported on the gC 3 N 4 @RGO complex. A graphite-type carbon nitride-reduced graphene oxide complex (M / g C 3 N 4 @ RGO) is prepared.
In the present invention, since the gC 3 N 4 @RGO complex is hydrophobic, it is preferable to further activate the catalyst so that the catalyst can be supported. Therefore, in the step 3)
a) modifying the surface of the gC 3 N 4 @RGO composite prepared in the step 2);
b) dispersing the surface-modified composite in a polyol solvent, and further adding and mixing a transition metal salt; And
c) carrying the transition metal catalyst on the surface-modified composite by controlling the pH of the mixed solution of step b) to 9 to 11, followed by stirring and dispersing.
At this time, the surface modification in step a) can be performed by a chemical treatment method or a physical bonding method.
In the case of chemical treatment, surface modification can be performed by acid treatment using at least one oxidizing agent selected from H 2 SO 4 , HNO 3, and P 2 O 5 , and the surface modification is not limited thereto, It is possible to modify it.
For example, a hydroxy group can be introduced into gC 3 N 4 @RGO by stirring in a hot acidic solution for 1 to 8 hours. If the agitation time is less than 1 hour, the surface of the gC 3 N 4 @RGO composite is not sufficiently modified, and if the agitation time is more than 8 hours, the structure of gC 3 N 4 @RGO composed of a carbon material is destroyed and excellent properties are lost There is a concern.
Further, in the case of physical bonding, it is possible to modify the surface by bonding polymers or the like, and preferably a conductive polymer having N-alkyl or N, N-dialkyl amide groups can be used. The conductive polymer may be at least one selected from the group consisting of a polyaniline-based polymer, a polypyrrole-based polymer, a polythiophene-based polymer, and a polyparaphenylene-based polymer.
For example, the conductive polymer may be dissolved in a solvent, and then the gC 3 N 4 @RGO complex may be added and stirred to physically couple the conductive polymer to the surface of the conductive polymer. The solvent may be ethanol, alcohol, water, tetrahydrofuran, methyl ethyl ketone, etc. Preferably, the solvent is used in a weight ratio of 1: 1 to 50 with respect to the gC 3 N 4 @RGO complex Use. If it is less than the above range, dispersion of the complex itself may be difficult, and when the above range is exceeded, the concentration may be too low to cause a problem that the conductive polymer is not bonded to the complex. In addition, it is preferable to dissolve the conductive polymer in the solvent, add the complex, and stir the mixture for 15 minutes or more to physically bind the conductive polymer completely.
In the step b), the surface-modified gC 3 N 4 @RGO complex is dispersed in a polyol solvent. The polyol solvent may be selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol (Triethylene Glycol) and tetraethylene glycol (Tetraethylene Glycol). Preferably, the gC 3 N 4 @RGO complex is used in an amount of from 0.001 to 0.5% by weight based on 100% by weight of the polyol solvent. When the content is less than 0.001 wt%, it is difficult to expect the improvement of the electrical conductivity by adding the gC 3 N 4 @RGO complex in the M / g C 3 N 4 @RGO complex after the reaction, and when it exceeds 0.5 wt% gC 3 N 4 @RGO composite powder is difficult to disperse.
Next, a transition metal (M) salt is added to and mixed with a solution in which the gC 3 N 4 @RGO composite powder is dispersed in a polyol solvent. In step c), the pH of the mixed solution is adjusted to control the size distribution of the catalyst Then, it is stirred and dispersed so that the transition metal catalyst is supported on the gC 3 N 4 @RGO complex.
At this time, the pH of the mixed solution can be adjusted to 9 to 11 to facilitate the reduction reaction, and potassium hydroxide (KOH) or sodium hydroxide (NaOH) having a strong alkaline property can be used as the pH adjusting solvent good. By adjusting the pH range, it is possible to more uniformly control the size distribution of the supported transition metal catalyst. In this case, it is preferable that the pH adjusting solvent is added after adding the transition metal salt to completely dissolve and mix.
Also, in the step c), the transition metal catalyst is supported on the gC 3 N 4 @RGO composite by stirring and dispersion, wherein the dispersion can be performed by ultrasonic dispersion.
The transition metal salt may be at least one selected from the group consisting of Pt, Pd, Au, Ag, Ni, Co, Fe, Sn, And may include at least one metal selected from rhodium (Rh), osmium (Os), iridium (Ir), tungsten (W), ruthenium (Ru), titanium (Ti), and vanadium (V) Or an atomic group, and it is not limited to the above-mentioned metal salt, but may be selected from metal salts which can have appropriate activity depending on the environment in which the catalyst is used.
As described above, according to the method of the present invention, the reduced graphene oxide is produced using a chemical stripping method related to the production of graphene, and by forming a complex with carbon nitride, by chemical modification and physical bonding, And the catalytic activity by the carbon nitride is improved, and the electrical characteristics and the like can be improved by graphene. Accordingly, the catalyst-graphitic carbon nitride-reduced graphene oxide composite of the present invention can exhibit excellent properties as an energy storage material.
Therefore, the catalyst-graphitic carbon nitride-reduced graphene oxide composite of the present invention manufactured by the above method can be utilized as an electrode material.
When the catalyst-graphitic carbon nitride-reduced graphene oxide composite of the present invention is used as a capacitor electrode, it is possible to provide an electrode having excellent electrical conductivity and durability. In this case, the non-storage capacity of the capacitor electrode is 10 to 350 F / g, preferably 200 to 350 F / g. That is, the capacitor electrode using the composite according to the present invention can be used as a supercapacitor electrode and can provide an electrode having superior electrical conductivity and durability than reduced graphene produced by using NaBH 4 as a reducing agent by a conventional chemical stripping method do.
Also, the catalyst-graphitic carbon nitride-reduced graphene oxide complex of the present invention can be usefully utilized as an electrode catalyst for fuel cells.
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
< Example 1> Platinum-graphite type Carbon nitride - Reduced Grapina Oxide (Pt / g-C 3 N 4 @RGO) composite
1-1 graphite Oxide Produce
First, a 500 ml Erlenmeyer flask was prepared, and graphite (SP-1, Bay carbon), NaNO 3 (1 g) and H 2 SO 4 (46 ml) were added at 0 to 5 ° C and stirred. KMnO 4 was slowly added to the solution, and the temperature was slowly raised by using a hot plate to conduct a water bath (30 ° C to 40 ° C). Thereafter, a mixed solution of hot distilled water (DI water) and H 2 O 2 (5.2 ml) was further added. Then, after vacuum filtration, it was washed with distilled water (DI water). The washed solution was sufficiently subjected to ultra sonication treatment and then lyophilized to obtain graphite oxide.
1-2 graphite type Carbon nitride - Reduced Grapina Oxide (g-C 3 N 4 @RGO) composite
0.2 g of the lyophilized graphite oxide in Example 1-1 was added with 1.6 g of melamine (2-amino-4,6-dichlorotriazine) in a solvent, and the mixture was ultrasonicated for 1 hour. GC 3 N 4 @RGO complex was prepared by hydrothermal synthesis at 100 ° C for 96 hours using a reflux condenser. Next, the thus-prepared gC 3 N 4 @RGO composite was annealed at 200 ° C for 30 minutes using a quartz tube furnace to stabilize the composite.
1-3 Platinum - Graphite Type Carbon nitride - Reduced Grapina Oxide (Pt / g-C 3 N 4 @RGO) composite
The gC 3 N 4 @RGO complex (0.1 g) prepared in Example 1-2 was added to a mixed solution of sulfuric acid (H 2 SO 4 ) and nitric acid (HNO 3 ) and stirred. The filtrate was washed with distilled water several times, and gC 3 N 4 @RGO complex and H 2 PtCl 6 6H 2 O, a platinum precursor, were ultrasonically dispersed in distilled water. Ethylene glycol solution was then added to the gC 3 N 4 @RGO complex, the pH was adjusted to 11 by adding NaOH, and the solution was refluxed for 4 hours and 30 minutes at about 135 ° C. Lt; / RTI > Thereafter, the sample was cooled to about 60 ° C, washed with vacuum filtration, and lyophilized to obtain a sample. The finally obtained catalyst was named Pt / gC 3 N 4 @RGO.
< Comparative Example 1> Reduced Grapina Oxide (RGO) Produce
First, graphite oxide was prepared by the same method as described in Example 1-1 above. 1.87 g of sodium borohydride (NaBH 4 ) and 30 ml of distilled water (DI-water) were added to the graphite oxide (0.1 g) using a dropping funnel and stirred at 90 ° C for 2 hours Reduced graphene oxide (RGO) was prepared.
< Comparative Example 2> Platinum Supported Reduced Grapina Oxide Manufacturing (Pt / RGO )
The procedure of Example 1-3 was repeated except that the gC 3 N 4 @RGO composite was replaced with the graphene oxide prepared by the method of Comparative Example 1, Pin oxide (Pt / RGO).
< Comparative Example 3> Platinum Supported Graphite Manufacturing (Pt / Gr )
Graphite (SP-1) purchased from Bay carbon was prepared without any treatment. Next, platinum-supported graphite (Pt / Gr) was prepared in the same manner as in Example 1-3, except that the prepared graphite was used in place of the gC 3 N 4 @RGO composite.
< Analysis example > Evaluation and Analysis
Structural and electrochemical performances of the materials prepared by the above Examples and Comparative Examples were evaluated and analyzed.
1-1 SEM analysis
The surface of the gC 3 N 4 @RGO composite prepared in Example 1-2 and the surface of RGO prepared in Comparative Example 1 was measured by a scanning electron microscope (SEM). The results are shown in FIG. 3 Respectively. The equipment used for the analysis was Hitachi's S-3500N model.
Referring to FIG. 3, it can be seen that the gC 3 N 4 @RGO composite unlike the RGO of the sheet-like structure has a structure in which graphite-type carbon nitride is attached to the graphene sheet.
1-2 EDAX analysis
The components of the gC 3 N 4 @RGO composite specimen prepared in Example 1-2 were analyzed by Energy Dispersive X-ray microanalysis (EDAX). The results are shown in FIG. 4 Respectively. The equipment used for the analysis was Hitachi's S-4700 model equipped with EDAX.
Referring to FIG. 4, graphite-type carbon nitride is uniformly distributed on the surface of the gC 3 N 4 @RGO composite prepared in Example 1-2 through the presence of nitrogen.
1-3 FT-IR analysis
The structure of the gC 3 N 4 @RGO composite specimen prepared in Example 1-2 and the structure of the RGO specimen prepared in Comparative Example 1 were measured by Fourier Transform Infrared Spectroscopy (FT-IR) The results are shown in Fig. The instrument used for the analysis was a NEW FT-IR Spectrum Two model from perkinElmer.
Referring to FIG. 5, on the surface of the gC 3 N 4 @RGO composite prepared in Example 1-2, peaks of hydroxyl group (hydroxyl, broad peak 2600 to 3468 cm -1 , -OH) group of graphite oxide ) disappears, C = N (1571,1630 cm -1 ), CN (1255,1323,1428 cm -1), CN-heterocycle (809 cm -1), NH 2 (broad peak 3150 ~ 3500 cm -1 ) group was generated.
On the surface of the RGO prepared in Comparative Example 1, a hydroxyl group (hydroxyl, broad 2600 to 3468 cm -1 , -OH), an alkyl group (alkyl, 2860, 2922 cm -1 , -CH 2 ) 1548 or 1623 cm -1) and a carboxyl group (carboxyl, 1720cm -1 (C = O), 1370cm -1 (CO), 1225cm -1 (-OH), COOH) can be confirmed that the group is present.
In addition, the melamine has an amine group (broad peak 3150-3500 cm -1 , -NH 2 or = NH), C = N (1571, 1630 cm -1 ), CN (1255, 1323, 1428 cm -1 ) CN Heterocycle (809 cm -1 ) can be confirmed.
1-4 TEM analysis
In order to analyze the structure of the Pt / gC 3 N 4 @RGO composite specimen prepared in Example 1-3 and the Pt / RGO specimen prepared in Comparative Example 2 and the distribution and size of the supported Pt particles, a transmission electron microscope (Transmission electron microscopy, TEM). The results are shown in Fig. The equipment used for the analysis was Jeol's JEM-2100F model.
6, it can be seen that the Pt / gC 3 N 4 @RGO composite prepared in Example 1-3 had smaller Pt particles distributed more uniformly than Pt / RGO prepared in Comparative Example 2 . The average particle size was found to be 1.5 to 2.5 nm in the case of Pt / gC 3 N 4 @RGO prepared in Example 1-3, and 2.5 to 4.0 nm in the case of Pt / RGO prepared in Comparative Example 2 Distribution. Thus, it can be seen that the method of the present invention can control the particle size because it can have a smaller particle size than the case of the embodiment of the present invention.
1-5 Measuring Capacitance
The capacitance of the gC 3 N 4 @RGO composite specimen prepared in Example 1-2 and the RGO specimen prepared in Comparative Example 1 were measured using a cyclic voltammetry (CV) 8. For analysis, IVIUMSTAT from Potentiostat was used and measured by a three-electrode method.
Specifically, a working electrode was prepared by mixing the specimen, the conductive material (Super-P) and the binder polyvinylidene difluoride (PVDF, Aldrich) prepared in Example 1-2 and Comparative Example 1, (85: 10: 5) and dissolved in N-methyl pyrrolidinone (NMP). The viscosity of the slurry was adjusted with NMP and uniformly coated on a nickel foam with a plastic spatula. The coated nickel foam was dried in an oven at 100 ° C. for 12 hours and then compressed using a roll press. The counter electrode was a platinum wire and the reference electrode was 10 and 20 volts in a voltage range of -0.8 to 0.2 V using a saturated calomel electrode (SCE) , And scan rates of 50, 100, 200, and 300 mV / s. At this time, 6 M of potassium hydroxide (KOH) was used as the electrolyte.
Referring to FIGS. 7 and 8, a CV characteristic according to a change in scan rate is evaluated. As a result, a capacitive behavior having a rectangular curved line characteristic of electric double layer capacitors (EDLCs) Respectively. Also, Specific Current [A / g] increased in proportion to the scanning speed . However, in the case of gC 3 N 4 @RGO, not only the capacitive behavior with rectangular curves characteristic of electric double layer capacitors (EDLCs), but also the capacitance is high even if the scanning speed is higher than RGO .
The value of the specific capacitance [F / g] can be confirmed through the CV test result, which is measured according to the following equation. V is the voltage range, m is the amount of the active material (g cm -2 ), and V is the current density (A cm -2 ), where V is the potential scan rate (V s -1 )
9, the specific capacitance [F / g]) was found to be proportional to the current density and inversely proportional to the scanning speed. In the case of the gC 3 N 4 @RGO composite prepared in Example 1-2, It can be confirmed that the RGO according to Comparative Example 1 has remarkably improved non-storage capacity as compared with the non-storage capacity.
1-6 Electrochemical properties and Specific surface area Measure
The Pt / gC 3 N 4 @RGO composite specimen prepared in Example 1-3 and the Pt / RGO, Pt / G specimen and commercially available Pt / C specimen prepared in Comparative Examples 2 and 3 were subjected to cyclic voltammetry (CV) The electrochemical surface area (ECSA) was measured by using an electrochemical cell. The electrochemical surface area (ECSA) was calculated from the equilibrium cyclic voltammograms of the supported electrolyte (1.0 MH 2 SO 4 ), based on the adsorption charge (0.21 mC / cm 2 ) Can be calculated from the total amount of charge in the hydrogen adsorption region. For analysis, IVIUMSTAT from Potentiostat was used and a three-electrode method was used. In addition, the electrochemical surface area (ECSA) is an important factor for measuring the intrinsic electrochemical activity of a catalyst based on platinum. The catalytic ink is prepared using the catalyst, 0.07 cm) to prepare a working electrode. Using a platinum wire as a counter electrode, Ag / AgCl as a reference electrode, and 1 M aqueous solution of sulfuric acid (H 2 SO 4 ) as an electrolyte, a scanning speed of 50 mV s -1 (cyclic voltammetry) measurement was performed at a scan rate. The results are shown in FIG. A strong peak appears at +0.1 to -0.25 V in the negative directional potential scan, indicating bound adsorbed hydrogen. The electrochemical surface area (ECSA) for each sample was Pt / gC 3 N 4 @RGO (81.5 m 2 g -1 ), Pt / RGO (51.1 m 2 g -1 ), Pt / C 2 g -1 ) and Pt / Gr (35.2 m 2 g -1 ), indicating the highest electrochemical surface area in Pt / gC 3 N 4 @RGO.
As described above, the Pt / gC 3 N 4 @RGO composite according to the present invention forms a complex by allowing carbon nitride to form a C3N4 network while using graphene oxide as a template to support a transition metal catalyst Thereby improving the activity of the catalyst and, at the same time, improving the mechanical and electrical properties of the catalyst.
Claims (13)
2) preparing a graphite-type carbon nitride-reduced graphene oxide complex (gC 3 N 4 @RGO) by hydrothermal synthesis after adding a carbon nitride precursor to the suspension; And
3) dispersing the composite in a polyol solvent, adding a transition metal salt, mixing and stirring, and carrying the transition metal catalyst,
The suspension prepared in the step 1) comprises graphite oxide containing at least one functional group selected from a hydroxyl group, a carboxyl group and an epoxy group; The carbon nitride precursor in the step 2) is selected from the group consisting of cyanuric chloride (C 3 Cl 3 N 3 ), melamine (C 3 H 6 N 6 ), melem (C 3 H 6 N 10 ), and melam (C 6 H 9 N 11 ) ≪ / RTI >
The step (3)
a) modifying the surface of the gC 3 N 4 @RGO composite prepared in step 2), b) dispersing the surface modified complex in a polyol solvent, further adding a transition metal salt and mixing, and c) The method comprising: controlling the pH of the mixed solution of the step b) to 9 to 11, and then carrying the transition metal catalyst on the surface-modified composite by stirring and dispersing the catalyst. The catalyst-graphitic carbon nitride- / RTI > oxide.
The carbon nitride precursor in step 2) is melamine; Wherein the weight ratio of the melamine to the graphite oxide is 1: 5 to 20. The method of claim 1, wherein the weight ratio of the graphite oxide to the graphite oxide is 1: 5 to 20.
In the step 2), the gC 3 N 4 @RGO composite is prepared by hydrothermal synthesis, and then the gC 3 N 4 @RGO composite is heat treated to stabilize the gC 3 N 4 @RGO composite. Oxide complex.
The hydrothermal synthesis is carried out at a temperature of 90 to 110 캜 for 48 to 120 hours; Wherein the heat treatment is performed at a temperature of 100 to 300 DEG C for 5 to 30 minutes.
Wherein the surface modification is performed using at least one oxidizing agent selected from H 2 SO 4 , HNO 3 and P 2 O 5 .
The polyol solvent in the step 3) is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , A process for producing a catalyst-graphitic carbon nitride-reduced graphene oxide complex.
The transition metal salt may be at least one selected from the group consisting of Pt, Pd, Au, Ag, Ni, Co, Fe, Sn, Rh, Characterized in that it comprises at least one metal selected from the group consisting of osmium (Os), iridium (Ir), tungsten (W), ruthenium (Ru), titanium (Ti) and vanadium Lt; RTI ID = 0.0 > of a nitride-reduced graphene oxide complex.
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