CN109994745B - Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof - Google Patents
Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof Download PDFInfo
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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Abstract
The invention relates to a fullerene grafted graphene material supported palladium catalyst and preparation and application thereof. The catalyst takes an amino-functionalized fullerene pyrrolidine derivative and a graphene composite material as a carrier. The preparation method comprises the following steps: preparing a nitro-functionalized fullerene pyrrolidine derivative, preparing an amino-functionalized fullerene pyrrolidine derivative, preparing a fullerene grafted graphene material, and preparing a fullerene grafted graphene material supported palladium catalyst. The catalyst has good catalytic activity and stability, and has potential application prospect in fuel cells.
Description
Technical Field
The invention belongs to the field of fuel cell catalysts and preparation and application thereof, and particularly relates to a fullerene grafted graphene material supported palladium catalyst and a preparation method and application thereof.
Background
Fuel cells are one of the clean energy sources that have been rapidly developed in recent years. The high cost has been a major bottleneck limiting the wide-scale commercialization of fuel cells due to the noble metal catalysts involved therein. In order to reduce the cost and improve the effective utilization of the noble metal catalyst, a method of supporting the noble metal catalyst on the surface of a carbon material is currently commonly used. Among many carbon materials, emerging nanocarbon materials such as carbon nanotubes, graphene and fullerene materials have shown great potential in fuel cell catalyst support applications. Generally, a single nanocarbon material is used as a carrier to improve the performance of a catalyst and reduce the cost, and research on using a composite nanocarbon material as a carrier is still less. The application No. 201710409807.4 patent discloses a fullerene-graphene three-dimensional composite material supported palladium catalyst obtained by non-covalent bond self-assembly, which shows superior catalytic performance to a single-support catalyst. Therefore, the development of the composite nano carbon carrier is one of effective ways for improving the catalytic performance. However, the stability of the carrier material combined by weak non-covalent bond action between fullerene and graphene is poor, and the strong accumulation tendency of graphene is difficult to overcome effectively, so that the further exploration of grafting fullerene on the surface of graphene through a covalent bond is undoubtedly beneficial to the dispersion of graphene, and the catalytic performance of the catalyst is further improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fullerene grafted graphene material supported palladium catalyst, and a preparation method and application thereof, so as to overcome the defect of insufficient activity of a palladium catalyst in catalyzing methanol oxidation reaction in the prior art.
The invention provides a fullerene grafted graphene material supported palladium catalyst, which takes an amino functionalized fullerene pyrrolidine derivative and a graphene composite material as a carrier, wherein the structural formula of the amino functionalized fullerene pyrrolidine derivative is as follows:
wherein n is 1 to 5.
The carrier is obtained by heating and reacting an amino-functionalized fullerene pyrrolidine derivative with graphene oxide in a solvent and then reducing the reaction product.
The invention also provides a preparation method of the fullerene grafted graphene material supported palladium catalyst, which comprises the following steps:
(1) reacting fullerene C under nitrogen60Reacting p-nitrobenzaldehyde and sarcosine in a solvent according to the mass ratio of 0.8-1.2:1.8-2.2:1.8-2.2, cooling, separating and purifying to obtain the nitro-functionalized fullerene pyrrolidine derivative, wherein the fullerene C is60The proportion of the solvent is 60-80mg to 40-50 mL;
(2) dissolving the nitro-functionalized fullerene pyrrolidine derivative obtained in the step (1) in a solvent, adding a reducing agent for reaction, adjusting the pH of a lower layer solution obtained by liquid separation to be neutral, filtering, washing and drying to obtain an amino-functionalized fullerene pyrrolidine derivative, wherein the ratio of the nitro-functionalized fullerene pyrrolidine derivative to the reducing agent to the solvent is 95-105mg:250 mg: 300mg:95-105 mL;
(3) dispersing the amino-functionalized fullerene pyrrolidine derivative and graphene oxide in the solvent in the mass ratio of 1:6-10 in the step (2), reacting at 80-100 ℃ for 36-48h under the condition of nitrogen, cooling, and performing centrifugal separation to obtain a fullerene grafted graphene material, wherein the ratio of the graphene oxide to the solvent is 15-25mg:15-25 mL;
(4) and (3) dispersing the fullerene grafted graphene material in the step (3) in water, adding a palladium chloride aqueous solution, carrying out ultrasonic oscillation, adding a reducing agent solution, stirring for reaction, carrying out centrifugal separation, and washing to obtain the fullerene grafted graphene material supported palladium catalyst, wherein the mass ratio of a carrier to palladium in the catalyst is 4-6:1, and the ratio of the fullerene grafted graphene material to water is 15-25mg:30 mL.
The solvent in the step (1) is toluene.
The reaction temperature in the step (1) is 100-120 ℃, and the reaction time is 12-16 h.
The structural formula of the nitro-functionalized fullerene pyrrolidine derivative in the step (1) is as follows:
wherein n is 1 to 5.
The separation and purification in the step (1) adopt a silica gel column chromatography, wherein an eluent is toluene/ethanol (5: 1).
The solvent in the step (2) is a mixed solvent of toluene and ethanol with the volume ratio of 1.8-2.2:1.
And (3) the reducing agent in the step (2) is stannous chloride.
In the step (2), the reaction temperature is room temperature, and the reaction time is 10-15 h.
The solvent in the step (3) is dimethyl sulfoxide; the graphene oxide is prepared by using a Hummers method.
And (4) reducing the reducing agent in the step (4) by sodium borohydride, and reducing the graphene oxide and the palladium ions simultaneously.
And (4) the ultrasonic oscillation time in the step (4) is 25-35 min.
And (4) stirring and reacting for 10-15h at room temperature in the step (4).
The invention also provides an application of the fullerene grafted graphene material loaded palladium catalyst in a methanol fuel cell.
The electrochemical workstation used for testing the electro-catalysis performance in the application is CHI 660D, the potential scanning speed is 50mV/s, and the potential scanning range is-1-0.2V; the working electrode is a glassy carbon electrode, the counter electrode is a platinum wire electrode, the reference electrode is a Saturated Calomel Electrode (SCE), and the electrolyte is 1.0M CH3OH +1.0M NaOH solution.
Advantageous effects
(1) Compared with the patent with the application number of 201710409807.4, the method has the advantages that the defect of poor dispersion of graphene in the graphene is overcome by grafting the fullerene on the surface of the graphene through the strong covalent bond effect, and the catalytic performance of the catalyst is improved;
(2) the preparation method is simple and convenient, and the novel fullerene grafted graphene material palladium-loaded fuel cell catalyst is prepared by a room-temperature chemical reduction method;
(3) compared with a palladium catalyst taking pure graphene as a carrier, the fullerene grafted graphene material prepared by the invention has better catalytic performance and has potential application prospect in fuel cells.
Drawings
Fig. 1 is a transmission electron microscope image of the fullerene-grafted graphene material supported palladium catalyst in example 4.
FIG. 2 shows Pd catalyst (Pd/RGO-NH) with fullerene grafted graphene material as a carrier in example 52-C60) And a palladium catalyst (Pd/RGO) taking pure graphene as a carrier has a cyclic voltammetry curve for the electrocatalytic oxidation of methanol.
FIG. 3 is a chronoamperometric curve of the palladium catalyst on different supports for the electrocatalytic oxidation of methanol in example 5.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
And (3) synthesizing the nitro-functionalized fullerene pyrrolidine derivative.
Under nitrogenUnder these conditions, 70mg of C were added to a 100ml round bottom flask60140mg of p-nitrobenzaldehyde, 140mg of sarcosine and 45ml of toluene are reacted at 115 ℃ under reflux for 12 hours, cooled and filtered, and the filtrate is concentrated and purified by silica gel column chromatography, and the eluent is toluene/ethanol (5: 1). The obtained product is characterized by MALDI-TOF-MS, and a series of mass spectrum peaks are observed at molecular weights of 897, 1077, 1255, 1431 and 1610, and respectively correspond to nitro-functionalized fullerene pyrrolidine derivatives with 1-5 substituents.
Example 2
And (3) synthesizing an amino-functionalized fullerene pyrrolidine derivative.
Under the protection of nitrogen, dissolving the nitro-functionalized fullerene pyrrolidine derivative (100mg) in 100ml of a toluene-ethanol (2:1) mixed solvent, adding 280mg of stannous chloride, reacting at room temperature for 15h, standing for layering, obtaining a lower layer solution through liquid separation, adjusting the pH value to be neutral through sodium hydroxide, filtering and separating precipitated solids, washing with deionized water, and drying at 40 ℃ for 24 h to obtain an amino-functionalized fullerene pyrrolidine derivative; the obtained product is characterized by MALDI-TOF-MS, and a series of mass spectrum peaks are observed at molecular weights of 867, 1015, 1164, 1312 and 1461, and respectively correspond to amino-functionalized fullerene pyrrolidine derivatives with 1-5 substituents.
Example 3
And (3) preparing a fullerene grafted graphene material.
Ultrasonically dispersing the amino-functionalized fullerene pyrrolidine derivative (2.5mg) and graphene oxide (20mg) in dimethyl sulfoxide (20ml), heating to react for 48 hours at 90 ℃ under the protection of nitrogen, cooling to room temperature, centrifugally separating, washing with ethanol, and drying for 24 hours at 40 ℃ to obtain the fullerene grafted graphene material.
Example 4
And (3) preparing a palladium catalyst loaded by the fullerene grafted graphene material.
Ultrasonically dispersing 20mg of the fullerene-grafted graphene material in 30ml of deionized water, adding 2ml of palladium chloride aqueous solution (2mg/ml), ultrasonically treating for 30 minutes, slowly dropwise adding 10ml of newly-prepared sodium borohydride aqueous solution (10mg/ml), and adding the sodium borohydride aqueous solution into the mixtureThe reaction was stirred at room temperature for 12 hours. Centrifugally separating, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and then placing the precipitate in a vacuum drying oven to be dried for 24 hours at 40 ℃ to obtain the fullerene grafted graphene material supported palladium catalyst (Pd/RGO-NH)2-C60). The catalyst nanoparticles are uniformly dispersed on the surface of the fullerene-grafted graphene material (fig. 1) by TEM characterization. The palladium catalyst (Pd/RGO) with the pure graphene material as the carrier is prepared by the same process, except that graphene oxide is used for replacing the fullerene grafted graphene material.
Example 5
And (4) testing the performance of the electrocatalytic methanol oxidation reaction.
The fullerene-grafted graphene material prepared in example 4 was loaded with a palladium catalyst (Pd/RGO-NH)2-C60) Dispersing in ethanol (2mg/ml) by ultrasonic oscillation, transferring 5 μ l to the surface of a glassy carbon electrode, drying by an infrared lamp, and then dropwise adding 5 μ l Nafion solution (0.5%) to obtain the working electrode. Placing the prepared working electrode into 1.0M CH3In the OH +1.0M NaOH mixed solution, a platinum wire electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a cyclic voltammetry curve and a timing current curve of the methanol electrocatalytic oxidation are tested. A control was also run with a palladium catalyst (Pd/RGO) supported on a graphene-only material. It can be seen that the fullerene grafted graphene material supports the palladium catalyst (Pd/RGO-NH)2-C60) Compared with a palladium catalyst (Pd/RGO) taking a pure graphene material as a carrier, the catalyst has higher catalytic activity (figure 2) and stability (figure 3), wherein the current intensity of the former catalyst is improved by about 2 times compared with the latter catalyst, and the higher current intensity is still maintained after the continuous discharge for 2500 seconds. Therefore, the palladium catalyst taking the fullerene grafted graphene material as the carrier can obviously improve the performance of catalyzing the methanol oxidation reaction, and has potential application prospect in fuel cells.
Compared with the catalyst in patent application No. 201710409807.4, the catalyst performance of the catalyst in the invention is improved by more than 2 times, and the current density of the catalyst in the invention for catalyzing methanol oxidation reaches 730mA/mgPd(as shown in FIG. 2), whereas the latter is only 350mA/mgPdThe results show that the catalyst of the fullerene-graphene carrier material grafted by the covalent bond has remarkably improved catalytic performance.
Claims (9)
1. The fullerene-grafted graphene material supported palladium catalyst is characterized in that an amino-functionalized fullerene pyrrolidine derivative and a graphene composite material are used as a carrier, and the structural formula of the amino-functionalized fullerene pyrrolidine derivative is as follows:
wherein n is 1-5;
the preparation method of the fullerene grafted graphene material supported palladium catalyst comprises the following steps:
(1) reacting fullerene C under nitrogen60Reacting p-nitrobenzaldehyde and sarcosine in a solvent according to the mass ratio of 0.8-1.2:1.8-2.2:1.8-2.2, cooling, separating and purifying to obtain the nitro-functionalized fullerene pyrrolidine derivative, wherein the fullerene C is60The proportion of the solvent is 60-80mg to 40-50 mL;
(2) dissolving the nitro-functionalized fullerene pyrrolidine derivative obtained in the step (1) in a solvent, adding a reducing agent for reaction, adjusting the pH of a lower layer solution obtained by liquid separation to be neutral, filtering, washing and drying to obtain an amino-functionalized fullerene pyrrolidine derivative, wherein the ratio of the nitro-functionalized fullerene pyrrolidine derivative to the reducing agent to the solvent is 95-105mg:250 mg: 300mg:95-105 mL;
(3) dispersing the amino-functionalized fullerene pyrrolidine derivative and graphene oxide in the solvent in the mass ratio of 1:6-10 in the step (2), reacting at 80-100 ℃ for 36-48h under the condition of nitrogen, cooling, and performing centrifugal separation to obtain a fullerene grafted graphene material, wherein the ratio of the graphene oxide to the solvent is 15-25mg:15-25 mL;
(4) and (3) dispersing the fullerene grafted graphene material in the step (3) in water, adding a palladium chloride aqueous solution, carrying out ultrasonic oscillation, adding a reducing agent solution, stirring for reaction, carrying out centrifugal separation, and washing to obtain the fullerene grafted graphene material supported palladium catalyst, wherein the mass ratio of a carrier to palladium in the catalyst is 4-6:1, and the ratio of the fullerene grafted graphene material to water is 15-25mg:30 mL.
2. A preparation method of a fullerene grafted graphene material supported palladium catalyst comprises the following steps:
(1) reacting fullerene C under nitrogen60Reacting p-nitrobenzaldehyde and sarcosine in a solvent according to the mass ratio of 0.8-1.2:1.8-2.2:1.8-2.2, cooling, separating and purifying to obtain the nitro-functionalized fullerene pyrrolidine derivative, wherein the fullerene C is60The proportion of the solvent is 60-80mg to 40-50 mL;
(2) dissolving the nitro-functionalized fullerene pyrrolidine derivative obtained in the step (1) in a solvent, adding a reducing agent for reaction, adjusting the pH of a lower layer solution obtained by liquid separation to be neutral, filtering, washing and drying to obtain an amino-functionalized fullerene pyrrolidine derivative, wherein the ratio of the nitro-functionalized fullerene pyrrolidine derivative to the reducing agent to the solvent is 95-105mg:250 mg: 300mg:95-105 mL;
(3) dispersing the amino-functionalized fullerene pyrrolidine derivative and graphene oxide in the solvent in the mass ratio of 1:6-10 in the step (2), reacting at 80-100 ℃ for 36-48h under the condition of nitrogen, cooling, and performing centrifugal separation to obtain a fullerene grafted graphene material, wherein the ratio of the graphene oxide to the solvent is 15-25mg:15-25 mL;
(4) and (3) dispersing the fullerene grafted graphene material in the step (3) in water, adding a palladium chloride aqueous solution, carrying out ultrasonic oscillation, adding a reducing agent solution, stirring for reaction, carrying out centrifugal separation, and washing to obtain the fullerene grafted graphene material supported palladium catalyst, wherein the mass ratio of a carrier to palladium in the catalyst is 4-6:1, and the ratio of the fullerene grafted graphene material to water is 15-25mg:30 mL.
3. The method according to claim 2, wherein the solvent in step (1) is toluene; the reaction temperature is 100-120 ℃, and the reaction time is 12-16 h.
4. The method of claim 2, wherein the nitro work in step (1)The structural formula of the functionalized fullerene pyrrolidine derivative is as follows:
wherein n is 1 to 5.
5. The method according to claim 2, wherein the solvent in the step (2) is a mixed solvent of toluene and ethanol in a volume ratio of 1.8-2.2: 1; the reducing agent is stannous chloride.
6. The method according to claim 2, wherein the reaction temperature in the step (2) is room temperature, and the reaction time is 10-15 h.
7. The method according to claim 2, wherein the solvent in the step (3) is dimethyl sulfoxide; the graphene oxide is prepared by using a Hummers method.
8. The method according to claim 2, wherein the reducing agent in the step (4) is sodium borohydride; the ultrasonic oscillation time is 25-35 min; the stirring reaction temperature is room temperature, and the stirring reaction time is 10-15 h.
9. Use of the catalyst of claim 1 in a methanol fuel cell.
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| US20060115712A1 (en) * | 2004-11-26 | 2006-06-01 | Hee-Tak Kim | Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same. |
| CN103242217A (en) * | 2013-05-10 | 2013-08-14 | 黄山学院 | Fullerene derivative micron sheet and preparation method thereof |
| CN103951606A (en) * | 2014-05-07 | 2014-07-30 | 黄山学院 | Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure |
| CN105860957A (en) * | 2014-09-26 | 2016-08-17 | 重庆文理学院 | Preparation method of oxidized graphene composite for drug carrier |
| CN107195918A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier |
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| US20060115712A1 (en) * | 2004-11-26 | 2006-06-01 | Hee-Tak Kim | Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same. |
| CN103242217A (en) * | 2013-05-10 | 2013-08-14 | 黄山学院 | Fullerene derivative micron sheet and preparation method thereof |
| CN103951606A (en) * | 2014-05-07 | 2014-07-30 | 黄山学院 | Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure |
| CN105860957A (en) * | 2014-09-26 | 2016-08-17 | 重庆文理学院 | Preparation method of oxidized graphene composite for drug carrier |
| CN107195918A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier |
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