KR20130094560A - Synthesis method for metal nanoparticles-reduced graphene oxide hybrid material by atomic hydrogen - Google Patents
Synthesis method for metal nanoparticles-reduced graphene oxide hybrid material by atomic hydrogen Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0038—Manufacturing processes for forming specific nanostructures not provided for in groups B82B3/0014 - B82B3/0033
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
The present invention relates to a method for producing a hybrid material of metal nanoparticles and reduced graphene oxide using hydrogen reduction, and a hybrid material of metal nanoparticles and reduced oxidized graphene produced by such a method.
Generally, graphite is a structure in which a plate-like two-dimensional graphene sheet in which carbon atoms are connected in a hexagonal shape is laminated. Recently, graphene sheets were peeled off from graphite sheets and their properties were investigated. The most notable feature is that when an electron moves in the graphene sheet, it flows as if the mass of the electron is zero, which means that the electron flows at the speed of light movement in the vacuum, that is, the speed of light. The graphene sheet also has an unusual half-integer quantum Hall effect on electrons and holes.
The mobility of the graphene sheet known to date is known to have a high value of about 20,000 to 50,000 cm 2 / Vs. Above all, carbon nanotubes similar to the graphene sheet have a very low yield when they are subjected to purification after synthesis, so that even when synthesized using cheap materials, the final product is expensive, while graphite is very cheap In the case of single-walled carbon nanotubes, the characteristics of metals and semiconductors are different according to their chirality and diameters, and they have different band gaps even though they have the same semiconductor characteristics. Therefore, given single-walled carbon nanotubes, Or metallic properties, it is necessary to separate all the single-walled carbon nanotubes, which is known to be very difficult.
On the other hand, in the case of the graphene sheet, since the electrical characteristics are changed according to the crystal orientation of the graphene sheet of a given thickness, the user can express the electrical characteristics in the selected direction, so that the device can be designed easily. The characteristics of such a graphene sheet can be very effectively used for a carbon-based electric device or a carbon-based electromagnetic device in the future.
However, although such graphene sheets have very useful properties, no method for economical, large-area, and reproducible production has been developed to date. The method developed so far can be classified into two kinds, micromechanical method and SiC crystal pyrolysis method. The micro-mechanical method is a method of attaching a scotch tape to a graphite sample, and then removing the scotch tape. In this case, the number of the graphen sheets peeled out is not constant, and the shape is not uniform in the shape of the paper. In addition, when the SiC single crystal is heated, the SiC is decomposed to remove Si and the graphene sheet is formed by the remaining carbon (C).
In recent years, attempts have been made to manufacture graphene using a chemical method. A method of peeling the graphite by treating a chemical substance has been attempted. However, there are still difficulties in perfect control. Another method is to form and distribute graphene oxide. When the graphite is in an oxide form, it is easy to form a thin film since it is easily dispersed. Attempts have been made to form such graphene oxide (GO) using graphene using a reducing agent. Korean Patent Laid-Open Publication No. 2009-0059871 discloses a technique of dipping oxidized graphene in a solution containing a reducing agent to reduce and then doping an organic / inorganic dopant.
In addition, prior art related to the present invention discloses techniques for producing a hybrid of graphene with various metal nanoparticles.
Ruoff et al. Disclosed a method of using a modified polyol as a reducing agent at 120 ° C with NaBH 4 ( Ha HW, Kim IY , Hwang SJ, Ruoff RS . One - Pot Synthesis of Platinum Nanoparticles Embedded on Reduced Graphene Oxide for Oxygen Reduction in Methanol Fuel Cells . Electrochemical and Solid-State Letters . 2011; 14 (7): B70 ).
Erkang Wang et al. Disclose a technique using ethylene glycol (EG) as a reducing agent to reduce both GO and Pt precursors (Guo S, Wen D, Zhai Y, Dong S, Wang E. Platinum Nanoparticle Ensemble - on -Graphene Hybrid Nanosheet : One - Pot , Rapid Synthesis , and Used as New Electrode Material for Electrochemical Sensing . ACS Nano . 20104 (7): 3959-68.).
According to Sen Liu report, GO and H 2 PtCl 6 were prepared by microwave-mediated reduction using EG as reducing agent and solvent ( Liu S, Wang L, Tian J, Lu W, Zhang Y, Wang X, et al . Microwave- assisted rapid synthesis of Pt / graphene nanosheet composites and their application for methanol oxidation. Journal of Nanoparticle Research . 1-7 ).
As another method, there is disclosed a technique for producing Pt-RGO using thermal reduction in a high pH atmosphere. Hui Yang et al. Have performed thermal reduction at pH 12 and 140 ° C, where the pH value was controlled using NaOH solution ( He W, Jiang H, Zhou Y, Yang S, Xue X, Zou Z, et al . An efficient reduction route for the production of PdPt nanoparticles anchored on graphene nanosheets for use as durable oxygen reduction electrocatalysts . Carbon . (0) ).
These methods use highly toxic reducing agents and produce many byproducts. Also, the reduced graphene graphenes do not reproduce excellent quality due to the low reducing level of the reducing agent.
Accordingly, an object of the present invention is to provide a method for producing a hybrid material of reduced graphene grains and metal nanoparticles having excellent quality in a simple and rapid process.
It is also an object of the present invention to provide a hybrid material of graphene oxide and metal nanoparticles in which metal nanoparticles are uniformly distributed on a reduced oxidized graphene sheet.
It is also an object of the present invention to provide a reaction catalyst comprising the hybrid material.
According to an aspect of the present invention, there is provided a method for fabricating a metal nanoparticle, comprising: a first step of decorating metal nanoparticles on an oxidized graphene sheet by a hydrogen reduction action of a metal precursor; And a second step of reducing the oxidized graphene by hydrogen atoms dissociated on the metal nanoparticles and hydrogen atoms spread on the oxidized graphene sheet, and a method for producing a hybrid product of reduced metal oxide nanoparticles and reduced graphene oxide .
In one embodiment of the present invention, the first step includes: (a) mixing an oxidized graphite and a metal precursor in a reaction tank and obtaining an oxidized graphene suspension through ultrasonic dispersion; And (b) agitating the oxidized graphene suspension while injecting hydrogen gas from the bottom of the reaction tank to decorate the reduced metal nanoparticles on the oxidized graphene.
In one embodiment of the present invention, the step (b) may be performed by supplying hydrogen gas at a rate of 10 to 200 scc / min, stirring the suspension and hydrogen gas at a rate of 100 to 1000 rpm, Lt; 0 > C for 3 to 48 hours.
In one embodiment of the present invention, the method further comprises washing and drying the graphene grains after the step (b), wherein the drying may be performed in an oven at 60 to 100 ° C.
In one embodiment of the present invention, the second reducing step comprises the steps of: (c) increasing the degree of reactivity while supplying hydrogen to the reactant in the first stage while introducing hydrogen gas from the lower part of the reactor; and (d) Drying step.
In one embodiment of the present invention, the reaction of step (c) may be carried out at 50 to 150 ° C for 3 to 48 hours.
In one embodiment of the present invention, the metal nanoparticles may include a noble metal group, such as Pt, Pd, Rh, Ru, Ir, Os, Or a transition metal group, that is, any one or more metals selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), molybdenum (Mo), copper (Cu), silver (Ag) Can be used.
The present invention also provides a hybrid of metal nanoparticles and reduced graphene oxide prepared by the above method.
In one embodiment of the present invention, the size of the metal nanoparticles may be 1 to 100 nm.
In one embodiment of the present invention, the atomic ratio of carbon to oxygen (C / O) of the reduced graphene grains may be 10 to 30.
The present invention also provides a reaction catalyst comprising a mixture of the metal nanoparticles and reduced graphene oxide.
In an embodiment of the present invention, the reaction catalyst may be used for a fuel cell, a gas sensor, an electrochemical sensing device, and other chemical reactions. In addition, it can be widely used for various applications where various display elements, transparent electrodes of solar cells, and reduced oxide graphenes such as TFT semiconductor layers are used.
The method for producing a hybrid of the metal nanoparticles and the reduced graphene oxide according to the present invention is simple, clean, and quick in reaction steps. According to the method of the present invention, it is possible to produce a large amount of mixed materials uniformly distributing metal nanoparticles on oxidized graphene, which is very well-reduced, so that the processability and economical efficiency are excellent.
1 is a graph showing TGA and DTG thermal analysis results of oxidized graphene (GO) and platinum-reduced graphene oxide grains (hRGO-Pt)
2 is a SEM image of the morphology of platinum-reduced graphene oxide (hRGO-Pt)
Figure 3 is an HRTEM image of a platinum-reduced oxidized graphene hybrid (hRGO-Pt)
4 is a graph showing XRD spectra of oxidized graphene (GO), platinum-reduced oxidized graphene hybrid (hRGO-Pt) and graphite
5 is a graph showing the d-spacing of oxidized graphene (GO), reduced oxidized graphene (HRG), platinum-reduced oxidized graphene hybrid (hRGO-Pt) and graphite
6 is a graph showing the C1s XPS spectrum of graphene oxide (GO) and platinum-reduced graphene oxide grains (hRGO-Pt)
FIG. 7 shows the results of Raman spectroscopic analysis of oxidized graphene (GO) and platinum-reduced graphene oxide grains (hRGO-Pt).
The present invention provides a method for producing a hybrid in which metal nanoparticles (hereinafter also referred to as NP) and reduced graphene oxide (hereinafter also referred to as RGO) are hybridized by hydrogen reduction by active hydrogen.
In the past, graphene was reduced by using an organic solvent having high toxicity and then again using a high temperature or a strong chemical. However, the production method of the present invention achieves reduction of the metal and reduction of the oxidized graphene simply through a series of continuous reactions in which the metal precursor and the oxidized graphene are hydrogen-reduced together. Specifically, the production method of the present invention includes the following two-step continuous reaction.
(1) a first step of decorating the metal nanoparticles on the oxidized graphene sheet by the hydrogen reducing action of the metal precursor; And
(2) a second step of adsorbing on the metal nano-particles to reduce the oxidized graphene by dissociated hydrogen atoms.
In the above, the first step and the second step are both performed through a hydrogen reduction process using active hydrogen, which can be regarded as one substantially continuous process. In addition, the hydrogen reduction process is a wet process for providing hydrogen bubbles in an aqueous solution, and is free from toxic substances, and is excellent in handling and processability.
The first step is a step of simultaneously reducing the hydrogen graphene and the metal precursor and decorating the metal nanoparticles on the oxidized graphene. Here, the oxidized graphene can be obtained by ultrasonic dispersion of the oxidized graphite. When hydrogen is added after mixing the oxidized graphene and the metal precursor, the reduction of the oxidized graphene and the reduction of the metal precursor to the metal proceed simultaneously.
In one preferred example, the first step may include the following steps.
(a) mixing an oxidized graphite and a metal precursor in a reaction tank and obtaining an oxidized graphene suspension through ultrasonic dispersion; And
(b) a step of decorating the reduced metal nanoparticles on the oxidized graphene by stirring with the oxidized graphene suspension while introducing hydrogen gas from the bottom of the reaction tank
In the step (a), the graphene grains are formed by a known Staudenmaier L. Verfahren zurdarstellung der graphitsaure (Ber Dtsch Chem Ges 1898, 31, 1481-99), Hummers w. Offeman r. (J. Am. Chem. Soc. 1958, 80, 1339), Brody's method (Sur le poids atomique graphite. Ann Chim Phys 1860, 59, 466-72), and incorporated herein by reference have.
In the step (b), hydrogen gas is injected from the bottom of the reactor to simultaneously reduce the oxidized graphene and the metal precursor. The two reduction reactions proceed at the same time, so that the metal nanoparticles are decocted on the oxidized graphene or the reduced oxidized graphene together with the reduction. Particularly, metal particles such as platinum adsorb hydrogen very well, so they act effectively to reduce graphene by removing oxygen groups on the surface of graphene.
The hydrogen reduction of the present invention can achieve a uniform size and distribution of the metal nanoparticles and increase the reduction ratio of the oxidized graphene by using a wet hydrogen reduction reaction which provides hydrogen bubbles while stirring in an aqueous solution. In addition, since the reaction is carried out in a non-toxic aqueous solution, handling is easy.
If necessary, the step (b) may further include washing and drying the reactant. The drying can be preferably carried out in an oven at a temperature in the range of 60 to 100 캜, more preferably in the range of 80 to 100 캜.
Although the metal particles and the oxidized graphene are simultaneously reduced through the first step as described above, it is preferable to increase the reduction ratio of the oxidized graphene through an additional reduction reaction. Accordingly, in the present invention, a second step is performed in which hydrogen gas is introduced again into a reaction tank containing a mixture of metal particles produced through the first step and reduced graphene oxide to perform hydrogen reduction.
In the second step, the metal nanoparticles adsorb active hydrogen to more effectively remove the oxygen group on the surface of the oxidized graphene. That is, the hydrogen gas introduced into the reaction tank exists in two forms, adsorbed on the metal nanoparticles, dissociated active hydrogen, and active hydrogen spread on the oxide graphene sheet, all of which can be used to reduce oxidized graphene.
In one preferred example, the second step may include the following two steps.
(c) preparing a hybrid material of oxidized graphene, in which the metal nanoparticles as the reactant in the first step are decorated, and a reduced graphene graphene, through hydrogen reduction, while introducing hydrogen gas from the lower portion of the reaction tank; And
(d) drying the crude material.
On the other hand, the metal nanoparticles used in the present invention include noble metal groups such as platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium One or more selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), molybdenum (Mo), copper (Cu), silver (Ag) have.
Unless defined otherwise, all technical terms used in the present invention have the following definitions and are consistent with the meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Also, preferred methods or samples are described in this specification, but similar or equivalent ones are also included in the scope of the present invention. The contents of all publications referred to herein are incorporated herein by reference.
The term "Graphene" refers to a polycyclic aromatic molecule formed by covalent bonding of a plurality of carbon atoms to each other. The carbon atoms connected by the covalent bond form a 6-membered ring as a basic repeating unit, It is also possible to further include a 7-membered ring. The graphene thus appears as a single layer of covalently bonded carbon atoms (usually sp2 bonds). The graphene may have various structures, and such a structure may vary depending on the content of the 5-membered ring and / or the 7-membered ring which may be contained in the graphene. The graphene may be formed of a single layer, but they may be stacked to form a plurality of layers, and a thickness of up to 100 nm may be formed. Typically, the side ends of the graphene are saturated with hydrogen atoms.
The "Graphene Oxide (GO)" is an oxide formed by oxidizing graphite. Since such a graphene graphene can produce a dispersion solution unlike graphite, it can be thinned. Therefore, when the oxide graphene is thinned using a dispersion solution of the graphene oxide and then reduced, the sheet-like graphene can be formed.
The "Reduced Graphene Oxide (RGO)" refers to a reduction product obtained by reducing such graphene oxide. Such reduced graphene grains do not have the complete form of graphene (C = C / C-C conjugate structure) and contain less C = C than graphene. In other words, various band gaps exist between oxidized graphenes in which oxygen atoms or nitrogen atoms are partially mixed as elements other than carbon.
The term " about " is used in reference to an amount, a level, a value, a number, a frequency, a percentage, a dimension, a size, a quantity, a weight or a length of 30, 25, 20, 25, 10, 9, 8, 7, Level, value, number, frequency, percent, dimension, size, quantity, weight or length of a variable, such as 4, 3, 2 or 1%.
Throughout this specification, the words "comprises" and "comprising ", unless the context requires otherwise, include the steps or components, or groups of steps or elements, Steps, or groups of elements are not excluded.
Metal nanoparticles and reduced Graphene oxide Hybrid
The present invention provides a hybrid of metal nano-particles and reduced graphene oxide prepared by the above-described method. The hybrid material produced by the method according to the present invention has a uniform distribution of metal nanoparticles and a very high degree of reduction of graphene, thereby providing excellent conductivity and high quality.
In the reduced graphene graphene hybrid, metal nanoparticles are hybridized, thereby depriving electrons from the reduced graphene grains and lowering the bandgap barrier between the reduced graphene grains having various band gaps. As a result, Which compensates for the electrical properties of the pin. Therefore, when a thin film is formed using reduced oxidized graphene according to the present invention, it has high transmittance and conductivity.
The size of the nanoparticles is not particularly limited, but may be 1 to 100 nm. When the size of the metal particles exceeds 1000 nm, the effective surface area is decreased and the amount of metal used is too large, which causes unnecessary cost increase.
In the reduced oxidized graphene of the present invention, the atomic ratio of carbon to oxygen (C / O) is 10 to 30, and the ratio of oxygen is very low and the degree of reduction is very excellent. As the degree of reduction increases, the conductivity increases.
Therefore, the reduced graphene grains in which the metal nanoparticles of the present invention are hybridized have improved conductivity and can be used for fuel cells, gas sensors, electrochemical sensing devices, and other chemical reactions, and can be used for various display devices or transparent electrodes of solar cells And can be used in various fields such as a TFT semiconductor layer.
Hereinafter, the present invention will be further described through examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples. In particular, platinum is exemplified in the following examples, but it is also obvious to those skilled in the art that other types of metal nanoparticles are used.
< Example 1>
<1-1> Oxidized graphite And Graphene oxide Produce
According to the modified Hummers method, the graphite is oxidized with H 2 SO 4 and KMnO 4 to produce oxidized graphite. The prepared oxidized graphite was dried at 80 캜 under vacuum for 24 hours, and the concentration was 1.2 wt%. The oxidized graphite was dispersed in deionized water to a desired concentration of 1 mg / mL.
<1-2>
Thereafter, chloroplatinic acid hexahydrate (H 2 PtCl 6 .6H 2 O, 37%) was added into the beaker so that the platinum concentration in the oxidized graphite became 1 wt%, and the resulting suspension was stirred for 1 hour. Oxidized graphene (GO) was obtained by dispersing the exfoliation of oxidized graphite in a water bath for 1 hour by using ultrasonic waves.
Hydrogen gas was introduced from the bottom into the reactor containing the oxidized graphene (GO) suspension at a rate of 25 scc / min. The suspension was mixed with hydrogen gas (450 rpm) using a stirrer during reduction. The reaction was carried out at 80 DEG C for 24 hours. The prepared Pt-RGO was washed three times with water. After washing, the reaction was dried in an oven at 100 DEG C to remove any residual solvent.
<
1-3>
The reduction reaction of Pt-RGO powder was carried out in the reactor by adding hydrogen gas at a rate of 25 scc / min from the bottom to the reactor containing platinum-reduced graphene oxide (Pt-RGO) prepared in the first step, Respectively. The reduction process was carried out at 80 DEG C for 24 hours. The finally prepared Pt-RGO hybrid material in powder form was dried in an oven at 100 < 0 > C.
< Example 2 >
Screening of other metal nanoparticles
In the present invention, the metal nanoparticles may be selected from the group consisting of palladium (Pd), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium , That is, titanium (Ti), zirconium (Zr), vanadium (V), molybdenum (Mo), copper (Cu), silver (Ag), gold (Au) Particularly, when palladium is used as metal particles, it is advantageous for commercialization because it has a similar effect to platinum and is remarkably inexpensive in terms of cost.
< Example 3>
Review of reaction conditions
The reaction conditions are variable within a wide range depending on the metal precursor, which is the starting material, and are not particularly limited. However, in the present embodiment, the hydrogen gas can be introduced into the saturated state in the first or second step, and the charging rate is preferably in the range of 10_ to 200_scc / min, and more preferably in the range of 50_to 100_scc / min. In addition, the stirring speed of the suspension and the hydrogen gas is for preventing agglomeration of the oxidized graphene, and is preferably in the range of 100 to 1000 rpm, more preferably in the range of 200 to 500 rpm.
The reaction time is from several minutes to several days, preferably from 3 to 48 hours, more preferably from 6 to 24 hours, and still more preferably from 12 to 24 hours, depending on the conditions used. The reaction temperature is in the range of 50 to 150 占 폚, more preferably in the range of 50 占 폚 to 100 占 폚, and still more preferably in the range of 80 占 폚 to 100 占 폚. At a temperature lower than the above temperature range, the reaction is not unnecessarily slowed or reacted, while at high temperatures, the crystal grains of the metal nanoparticles become large and unnecessary energy wastes may be caused.
The graphite, the oxidized graphite and the metal precursor used in the present invention can be produced by using commercially available products, or by a known method, which is suitable for the above method and under known reaction conditions. Modifications of known methods may also be used, but are not described in detail herein.
< Experimental Example 1>
<Manufactured Pt - RGO hybrid Properties of Substances>
Elemental analysis (EA), thermogravimetric analysis (TGA) and electronic scanning (Raman spectroscopy) were performed to measure the physical properties of the Pt-RGO hybrid material (abbreviated as' hRGO- Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscope (HRTEM), X-ray diffraction (XRD), and Raman spectroscopy. The results are shown in Table 1 and Figs. 1 to 7.
As a result of the EA of the oxidized graphene and the platinum-reduced oxidized graphene, Table 1 shows that the composite of Example 1 had a very high carbon content and a very low oxygen content, resulting in a C / O ratio of 22 It can be seen that the reduction rate is very excellent.
Next, the thermal analysis results shown in FIG. 1 reveal that the content of oxygen-containing functional groups is greatly reduced. FIG. 2 also shows the shape of the platinum-reduced oxide graphene produced by SEM photographs.
Next, referring to the HRTEM image of FIG. 3, it can be seen that very small platinum nanoparticles are uniformly distributed on the surface of the oxidized graphene sheet (FIG. 3A). Platinum nanoparticles on this HRTEM image exhibited varying sizes from 2.3 nm to 5 nm, with most nanoparticle sizes being about 4 nm (FIG. 3b). The d-spacing of the platinum crystal lattice was measured to be 0.23 nm (Fig. 3c & 3d).
It can be seen that platinum is present on the platinum-reduced oxide grains prepared through the XRD spectrum of FIG. 4, and the d-spacing measurement result of FIG. 5 and the Scherrer equation show that the size of the metal particles is about 4.9 nm .
6, the relative intensities of the C1s / O1s peaks after the GO and Pt-RGO show that after active hydrogen reduction were markedly increased, and a new peak (Pt4f) for platinum was exhibited (FIG. 6A ). In XPS Pt4f spectrum (Fig. 6b), Pt 4f 7/2 with a binding energy of Pt f4 5/2 respectively were 71.37 eV and 74.58 eV, which is a result of 0 corresponds to the state of the platinum (Pt (0)). This C1s XPS result shows that the oxygen functional group is removed from the oxidized graphene during active hydrogen reduction (FIG. 6C). The intensity of peaks corresponding to oxygen functional groups such as hydroxyl group, epoxy group, peroxide group, and carbonyl group in the graphene oxide was markedly decreased, indicating that most of the oxygen functional groups were removed.
Referring to FIG. Raman spectroscopic analysis results of seven, in G- band peak of GO and hRGO-Pt, respectively 1595 cm -1, 1579 cm - 1. Similarly, the Pt-RGO peak at the D peak showed a significant increase in strength compared to the graphene oxide. The I D / I G ratio of HRGs increased significantly (from 1.0 for GO to 1.6 for hRGO-Pt), indicating that the structure of the GO was changed during the reduction step to compensate for structural deficiencies and to be of superior quality. Red shift of the G peak and increase in the I D / I G ratio in Pt-RGO compared to GO is small, but contributes to the recovery of sp 2 upon formation of many new graphite domains.
So far I looked at the center of the preferred embodiment for the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (11)
A second step of reducing the graphene oxide by hydrogen atoms adsorbed on the metal nanoparticles and dissociated on the graphene oxide sheet;
Method of producing a mixture of metal nanoparticles and reduced graphene oxide comprising a.
In the first step,
(a) mixing an oxidized graphite and a metal precursor in a reaction tank and obtaining an oxidized graphene suspension through ultrasonic dispersion; And
(b) decorating the reduced metal nanoparticles on the graphene oxide by stirring with the graphene oxide suspension while introducing hydrogen gas from the bottom of the reactor;
Method for producing a mixture of metal nanoparticles and reduced graphene oxide comprising a.
In step (b), hydrogen gas is introduced at a rate of 10 to 200 scc / min, the suspension and hydrogen gas are stirred at a rate of 100 to 1000 rpm, and the reaction is performed at 50 to 100 ° C. for 3 to 24 hours. Method for producing a mixture of metal nanoparticles and reduced graphene oxide, characterized in that.
Wherein the second reducing step comprises:
(c) preparing a hybrid material of oxidized graphene, in which the metal nanoparticles as the reactant in the first step are decorated, and a reduced graphene graphene, through hydrogen reduction, while introducing hydrogen gas from the lower portion of the reaction tank; And
and (d) drying the prepared material. The method for producing a hybrid of metal nanoparticles and reduced graphene oxide.
Wherein the reaction of step (c) is carried out at 50 to 150 ° C for 3 to 24 hours.
The metal nano-particles may be at least one selected from the group consisting of Pt, Pd, Rh, Ru, Ir, Os, Ti, Zr, Wherein at least one selected from the group consisting of molybdenum (Mo), copper (Cu), silver (Ag) and gold (Au) is selected.
The size of the metal nanoparticles is a mixture of metal nanoparticles and reduced graphene oxide, characterized in that 1 to 100nm.
A mixture of metal nanoparticles and reduced graphene oxide, characterized in that the atomic ratio of carbon to oxygen (C / O) of the reduced graphene oxide is 10 to 30.
The reaction catalyst is used for a fuel cell, a gas sensor, an electrochemical sensing device, a chemical reaction, or used in various display devices, transparent electrodes of a solar cell, or a TFT semiconductor layer.
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| CN104148061A (en) * | 2014-07-07 | 2014-11-19 | 上海应用技术学院 | Catalyst for waste water treatment and preparation method thereof |
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