CN109103467B - Preparation method and application of electrochemical stripping graphene-based metal catalyst - Google Patents
Preparation method and application of electrochemical stripping graphene-based metal catalyst Download PDFInfo
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Abstract
The embodiment of the invention discloses an electrochemical stripping graphene-based metal catalyst, and a preparation method and application thereof, wherein the graphene-based metal catalyst consists of electrochemical stripping graphene and metal nanoparticles distributed on the surface of the graphene. According to the electrochemical stripping graphene-based metal catalyst provided by the invention, the surface defects and oxygen-containing functional groups of the electrochemical stripping graphene are few, so that the mechanical property and the conductivity of the material are greatly improved. Thus, a graphene-based metal catalyst having excellent catalytic performance is obtained.
Description
Technical Field
The invention relates to the field of electrocatalysis, and particularly relates to an electrochemical stripping graphene-based metal catalyst, and a preparation method and application thereof.
Background
The catalyst material can improve the reaction rate, determine the reaction path, reduce the activation energy of the reaction, reduce the consumption of external energy, and enable a plurality of energy materials to be industrialized and commercialized, thereby enabling a plurality of new energy sources to be popularized and applied.
The fuel cell has the advantages of small volume, high energy conversion efficiency, high theoretical energy ratio, cleanness, environmental protection and the like, is widely applied to the fields of motor vehicles, mobile equipment and residents in families, and can be used as a power supply of portable electronic products such as notebook computers, video recorders, cameras and the like. However, the improvement of the performance of the electrode catalyst material and the reduction of the cost determine the improvement of the performance of the fuel cell and the widening of the application range to a large extent. Therefore, the development of a catalyst material with excellent electrocatalytic properties is a hot spot and focus of current fuel cell research.
Graphene is an ultra-thin two-dimensional carbon material with only one atom thickness. Research shows that graphene has excellent conductivity and high theoretical specific surface area (2630 m)2g-1). Compared with the traditional graphene oxide, the electrochemically stripped graphene has the advantages of few oxygen-containing functional groups and small defects, so that the electrochemically stripped graphene has the advantages of good mechanical property and high conductivity, and the great potential of the electrochemically stripped graphene in the field of fuel cells is determined. Introduction of electrochemically exfoliated graphene into electrode materials for fuel cells is expected to improve the performance of the cells. However, electrochemically exfoliated graphene is easy to agglomerate in water, and meanwhile, the surface of the electrochemically exfoliated graphene lacks functional groups, so that a metal catalyst is not easy to load. Therefore, it is very important to find a method for solving the problem of graphene agglomeration and loading a metal catalyst on the surface of the graphene agglomeration.
Disclosure of Invention
The embodiment of the invention discloses an electrochemical stripping graphene-based metal catalyst, and a preparation method and application thereof, which are used for improving the catalytic performance of the catalyst. The technical scheme is as follows:
the invention firstly provides an electrochemical stripping graphene-based metal catalyst, which consists of electrochemical stripping graphene and metal nanoparticles distributed on the surface of the graphene.
In a preferred embodiment of the present invention, the metal nanoparticles have a particle size of 5 to 10 nm.
The invention also provides a preparation method of the electrochemical stripping graphene-based metal catalyst, which comprises the following steps:
ultrasonically dispersing electrochemically stripped graphene in a polar aprotic solvent, adding a corresponding metal precursor into the solution, and stirring for 2 hours at room temperature;
the solution is heated to 70-90 ℃ under nitrogen flow, then sodium borohydride is added into the solution, and the solution is rapidly stirred for 0.5-1 hour. And then centrifugally washing and drying to obtain the electrochemical stripping graphene-based metal catalyst.
In a preferred embodiment of the invention, the polar solvent is selected from N, N-dimethylformamide.
In a preferred embodiment of the present invention, the metal precursor is selected from chloroplatinic acid, palladium chloride, and chloroauric acid.
In a preferred embodiment of the present invention, the mass ratio of the electrochemically exfoliated graphene to the metal precursor is 1: 1.
In a preferred embodiment of the invention, the oil bath temperature is 70 ℃ and the reaction time is 30 minutes.
The invention also provides an electrode material of a fuel cell, which takes the electrochemical stripping graphene-based metal catalyst as an anode active substance.
According to the technical scheme, the electrochemical stripping graphene-based metal catalyst is composed of electrochemical stripping graphene and metal nanoparticles distributed on the surface of the graphene, the electrochemical stripping graphene can be dispersed in a polar aprotic solvent, and preparation of the electrochemical stripping graphene-based metal catalyst is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of electrochemically exfoliated platinum graphene metals prepared in example 1;
FIG. 2 is a transmission electron microscope photograph of electrochemically exfoliated graphene-based metal platinum prepared in example 1;
FIG. 3 is an illustration of the electrocatalytic performance of the electrochemically exfoliated graphene-based metallic platinum prepared in example 1;
fig. 4 is an electrocatalytic stability of the electrochemically exfoliated graphene-based metal platinum prepared in example 1.
Detailed Description
The invention provides an electrochemical stripping graphene-based metal catalyst, which consists of electrochemical stripping graphene and metal nano-particles distributed on the surface of the graphene, wherein the particle size of the metal particles is 5-10 nm. The electrochemical stripping graphene-based metal catalyst can be prepared by the following method:
weighing 0.5-1.5 g of ammonium sulfate, dissolving in 100mL of water to serve as electrolyte, using a platinum wire as a negative electrode and a graphite foil as a positive electrode, connecting a direct-current power supply to electrolyze, carrying out suction filtration on the obtained suspension, washing with deionized water and ethanol for more than 3 times, mixing the dried product with N, N-dimethylformamide, carrying out ultrasonic treatment, standing, removing bottom precipitate, carrying out suction filtration on the upper-layer dispersion liquid with a polytetrafluoroethylene filter membrane, and drying to obtain the electrochemical stripping graphene;
ultrasonically dispersing electrochemically stripped graphene in a polar aprotic solvent, adding a metal precursor into the solution, stirring for 2 hours at room temperature, adding a reducing agent into the solution, protecting by nitrogen flow, heating at 70 ℃, quickly stirring for 0.5 hour, centrifugally washing, and drying to obtain the electrochemically stripped graphene-based metal catalyst.
In a preferred embodiment of the invention, the polar aprotic solvent is selected from the group consisting of N, N-dimethylformamide; the polar solvent is only required to be capable of dispersing the electrochemical stripping graphene, and preferably, the ratio of the polar aprotic solvent to the electrochemical stripping graphene is 1000-2000:1 mL/g; the metal precursor is selected from chloroplatinic acid, palladium chloride and chloroauric acid; the mass ratio of the electrochemical stripping graphene to the metal precursor is 3: 1-5, preferably 3: 2; the inert gas can be common gases such as argon, nitrogen and the like, and is preferably nitrogen; the reducing agent can be sodium citrate, sodium borohydride, ascorbic acid and other common reducing agents, and sodium borohydride is preferred.
The present invention also provides a fuel cell using the electrochemically exfoliated graphene-based metal catalyst as an anode catalyst, and the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The intrinsic graphene used in the invention is prepared by an electrochemical stripping method, called electrochemical stripping graphene (EEG) for short, and the specific method is as follows:
1.32g of ammonium sulfate was dissolved in 100ml of deionized water, and the solution was used as an electrolyte. Platinum (Pt) wire was used as the negative electrode, graphite foil was used as the positive electrode, and a dc power supply was connected to perform electrolysis. In the electrolysis process, the voltage is increased to 3V, the electrolysis is carried out for 5min, then is increased to 5V, the electrolysis is carried out for 5min, and finally is increased to 10V until the electrolysis is finished. The resulting suspension mixture was suction filtered and washed several times with deionized water and ethanol. Drying to obtain stripped graphene, mixing the dried product with N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment for 3h, standing for 8h, removing bottom precipitate to obtain high-quality electrochemical stripping graphene (EEG) dispersion, carrying out suction filtration on the dispersion with a polytetrafluoroethylene filter membrane (PTFE), and drying to obtain electrochemical stripping graphene (EEG).
Example 1:
0.03g of EEG was ultrasonically dispersed in 60ml of DMF and 0.02g of chloroplatinic acid (H) was added to the solution2PtCl6·6H2O), stirring for 2h at room temperature until uniform dispersion. The mixture was transferred to a 100mL round bottom flask in N2The stream was heated to 70 ℃ and then 0.1g of NaBH4Adding into the mixture, and rapidly stirring for 30 min. Then cooling to room temperature, centrifuging (10000 r/min), washing with ethanol for three times, pouring out the upper layer liquid, and drying at 60 ℃ in vacuum overnight to obtain the electrochemical stripping graphene-based metal platinum.
Example 2:
0.02g of EEG was ultrasonically dispersed in 60ml of DMF and 0.02g of palladium chloride (PdCl) was added to the solution2) And stirred at room temperature for 2h until uniformly dispersed. The mixture was transferred to a 100mL round bottom flask in N2The stream is heated to 70 ℃ and then 0.1g of KBH4Adding into the mixture, and rapidly stirring for 30 min. Then cooling to room temperature, centrifuging (10000 r/min), separating, washing with ethanol for three times, pouring out the upper layer liquid, and drying at 60 ℃ in vacuum overnight to obtain the electrochemical stripping graphene-based metal palladium.
Example 3:
0.02g of GO (graphene oxide) was ultrasonically dispersed in 60ml of DMF, and 0.02g of chloroplatinic acid (H) was added to the solution2PtCl6·6H2O), stirring for 2h at room temperature until uniform dispersion. The mixture was transferred to a 100mL round bottom flask in N2The stream was heated to 70 ℃ and then 0.1g of NaBH4Adding into the mixture, and rapidly stirring for 30 min. Then cooling to room temperature, centrifuging (10000 r/min), washing with ethanol for three times, pouring out the upper liquid, and drying at 60 ℃ in vacuum overnight to obtain the reduced graphene oxide-based metal platinum.
Performance and testing
1. X-ray diffraction (XRD) analysis
X-ray diffraction analysis was performed on the electrochemically exfoliated graphene-based metal platinum prepared in example 1 of the present invention using an X-ray powder diffractometer (model: X Pert PRO MPD) manufactured by Pasacaceae, Netherlands, and the analysis results are shown in FIG. 1; the radioactive source in the analysis process is Cu-Ka, the measuring step length is 0.017 degrees, and the scanning time is 10 seconds per step.
As can be seen from the comparison of XRD of the sample in fig. 1 with the standard card of Pt, the diffraction peak of electrochemically exfoliated graphene-based metal platinum is very matched with the standard peak of platinum in the standard PDF card, demonstrating that the metal platinum nanoparticles have been successfully loaded on the graphene surface.
2. Transmission Electron Microscope (TEM) analysis
Scanning analysis is performed on the electrochemically exfoliated graphene-based metal platinum prepared in example 1 by using a transmission electron microscope (JEOL JEM-2010), and as shown in fig. 2, it can be clearly seen in fig. 2 that metal platinum nanoparticles are dispersed on the surface of the electrochemically exfoliated graphene, and the particle size of the particles is about 3-8 nm.
Example 4
Treating glassy carbon electrodes
Grinding a glassy carbon electrode with a diameter of 3mm on a piece of lens wiping paper wetted by isopropanol for 0.5min in a circular manner, washing away surface dirt by deionized water, and sequentially carrying out HNO (high-purity oxygen) treatment on the cleaned lens wiping paper3、CH3CH2OH、H2And performing ultrasonic treatment in the O for 2-3 min respectively, and finally washing the surface of the electrode by using deionized water. Then using 1.0 μm and 0.3 μm Al in sequence for glassy carbon electrode2O3Polishing the slurry on the deer skin to a mirror surface, firstly washing off surface dirt after each polishing, then carrying out ultrasonic treatment according to the sequence, and washing with deionized water again after the ultrasonic treatment is finished. After thorough washing, the mixture was washed with 0.20mol/L KNO3 Middle record 1X 10-3mol/L of K3Fe(CN)6And (3) testing the performance of the electrode by using a cyclic voltammetry curve of the solution at a scanning speed of 50mV/s and in a scanning range of-0.6-0.8V. The peak potential difference in the cyclic voltammogram obtained under laboratory conditions is below 80mV and is connected as far as possibleApproximately 64mV is needed, the electrode can be used, otherwise the electrode is reprocessed until the requirement is met. And then, washing the electrode meeting the requirements with deionized water for later use.
Example 5
Working electrode preparation from glassy carbon electrode coating prepared in example 4
The prepared sample is as follows3OH is 3mg, 3 muL and 500 muL, and is prepared into a sample required by CV test, the sample is added into a 5ml sample tube, ultrasonic treatment is carried out for 30min, and a micro syringe is used for coating the mirror surface part of the processed glassy carbon electrode, the sample amount of each time is 1 muL, and the total amount is 5 muL. And airing the prepared working electrode for later use.
Comparative example 1
The sample prepared in example 1 was sampled according to the sample (EEG-Pt): Nafion: CH3OH is 3mg, 3 muL and 500 muL, and is prepared into a sample required by CV test, and the sample is added into a 5ml sample tube, is ultrasonically treated for 30min, and is coated on the mirror surface of the processed glassy carbon electrode by a micro-syringe, wherein the sample amount is 1 muL per time, and the total amount is 5 muL. And airing the prepared working electrode for later use. This electrode is referred to as electrode No. 1.
Comparative example 2
A working electrode was prepared with the reduced graphene oxide-based metal platinum (rGO-Pt) prepared in example 3 as the catalyst. The preparation process of comparative example 2 differed from comparative example 1 only in that the catalyst (EEG-Pt) in comparative example 1 was replaced with rGO-Pt, and the rest was the same as in comparative example 1. This electrode is referred to as electrode No. 2.
Fuel cell Performance testing
The electrode No. 1 and the electrode No. 2 are respectively tested on an electrochemical workstation, the test results are respectively shown in fig. 3 and fig. 4, the experiment is to carry out cyclic voltammetry test at a sweep rate of 0.05V/S, the sampling interval is 0.001V, and the voltage range is 0-1.0V.
FIG. 3 shows the results of the electrocatalytic performance tests of electrode No. 1 and electrode No. 2, from which it can be seen that the peak current density of platinum supported on electrochemically exfoliated graphene is 1.50mA/cm2And alsoThe peak current density of the original graphene oxide-supported platinum is 1.16mA/cm2(ii) a Therefore, compared with the electrode No. 2, the electrocatalytic performance of the electrode No. 1 is greatly improved. FIG. 4 shows the stability test results of electrode No. 1 and electrode No. 2, and it can be seen that the peak current density of the electrochemically exfoliated graphene loaded platinum is 1.28mA/cm after 200 CV cycles2Kept at 85% of the initial current density; after 200 CV cycle tests are carried out on the No. 2 electrode, the peak current density of the reduced graphene oxide loaded platinum is 0.77mA/cm2Held at 66% of the initial current density; it can be seen that the stability of the electrode No. 1 is greatly improved compared with that of the electrode No. 2.
The tests show that the electrochemical stripping graphene-based metal catalyst provided by the invention is used as a fuel cell anode catalyst, compared with a metal catalyst loaded by reduced graphene oxide, the electrochemical stripping graphene-based metal catalyst has obviously high electrocatalytic performance and obviously improved cycle stability.
The electrochemical stripping graphene-based metal catalyst, the preparation method and the application thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its central concept. It should be noted that it would be apparent to those skilled in the art that various changes and modifications can be made in the invention without departing from the principles of the invention, and such changes and modifications are intended to be covered by the appended claims.
Claims (11)
1. A graphene-based metal catalyst is characterized by consisting of electrochemically stripped graphene and metal nanoparticles distributed on the surface of the graphene;
the preparation method of the graphene-based metal catalyst comprises the following steps:
weighing 0.5-1.5 g of ammonium sulfate, dissolving in 100mL of water to serve as electrolyte, using a platinum wire as a negative electrode and a graphite foil as a positive electrode, connecting a direct-current power supply to electrolyze, carrying out suction filtration on the obtained suspension, washing with deionized water and ethanol for more than 3 times, mixing the dried product with N, N-dimethylformamide, carrying out ultrasonic treatment, standing, removing bottom precipitate, carrying out suction filtration on the upper-layer dispersion liquid with a polytetrafluoroethylene filter membrane, and drying to obtain the electrochemical stripping graphene;
ultrasonically dispersing electrochemically stripped graphene in a polar aprotic solvent, adding a metal precursor into the solution, stirring for 2 hours at room temperature, adding a reducing agent into the solution, protecting by nitrogen flow, heating at 70-90 ℃, quickly stirring for 0.5-1 hour, centrifugally washing, and drying to obtain a graphene-based metal catalyst;
the mass ratio of the electrochemical stripping graphene to the metal precursor is 3: 1-5.
2. The graphene-based metal catalyst according to claim 1, wherein the metal nanoparticles are selected from one of platinum, palladium, gold, silver, iron, cobalt, nickel, copper, tin, and zinc, and an alloy of any two of the foregoing metals.
3. The graphene-based metal catalyst according to claim 1, wherein the metal nanoparticles have a size of 2 to 20 nm.
4. The method for preparing a graphene-based metal catalyst according to claim 1, comprising the steps of:
weighing 0.5-1.5 g of ammonium sulfate, dissolving in 100mL of water to serve as electrolyte, using a platinum wire as a negative electrode and a graphite foil as a positive electrode, connecting a direct-current power supply to electrolyze, carrying out suction filtration on the obtained suspension, washing with deionized water and ethanol for more than 3 times, mixing the dried product with N, N-dimethylformamide, carrying out ultrasonic treatment, standing, removing bottom precipitate, carrying out suction filtration on the upper-layer dispersion liquid with a polytetrafluoroethylene filter membrane, and drying to obtain the electrochemical stripping graphene;
ultrasonically dispersing electrochemically stripped graphene in a polar aprotic solvent, adding a metal precursor into the solution, stirring for 2 hours at room temperature, adding a reducing agent into the solution, protecting by nitrogen flow, heating at 70-90 ℃, quickly stirring for 0.5-1 hour, centrifugally washing, and drying to obtain a graphene-based metal catalyst;
the mass ratio of the electrochemical stripping graphene to the metal precursor is 3: 1-5.
5. The method of claim 4, wherein the voltage of the DC power source is in the range of 3-15V.
6. The method of claim 4, wherein the metal precursor is selected from a chloride, nitrate, sulfate, acetate, or alkoxide of the metal.
7. The method of claim 4, wherein the polar aprotic solvent is selected from acetonitrile, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, or 1, 3-dimethyl-2-imidazolidinone.
8. The method of claim 4, wherein the reducing agent is selected from the group consisting of sodium citrate, sodium borohydride, potassium borohydride, lithium aluminum hydride, hydrazine hydrate, vitamin C, and ascorbic acid.
9. The method of claim 4, wherein the mass ratio of the electrochemically exfoliated graphene to the metal precursor is 1: 1.
10. Use of the graphene-based metal catalyst according to claim 1 as an electrode material for a fuel cell, having a peak current density of 1.5mA/cm2The activity retention after 200 cycles is 85% or more.
11. Use of the graphene-based metal catalyst according to claim 1 as a catalyst for hydrogenation reactions, dehydrogenation reactions or carbon dioxide conversion reactions.
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