CN105024086A - Palladium/nitrogen-doped graphene composite electrode catalyst and preparation method thereof - Google Patents
Palladium/nitrogen-doped graphene composite electrode catalyst and preparation method thereof Download PDFInfo
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- CN105024086A CN105024086A CN201510317305.XA CN201510317305A CN105024086A CN 105024086 A CN105024086 A CN 105024086A CN 201510317305 A CN201510317305 A CN 201510317305A CN 105024086 A CN105024086 A CN 105024086A
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- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
- B01J23/44—Palladium
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a palladium/nitrogen-doped graphene composite electrode catalyst and a preparation method thereof. The preparation method comprises the following steps: carrying out ultrasonic dispersion on oxidized graphene in water, adding tripolycyanamide, heating and stirring the mixture, freezing and drying the mixed system and carrying out high-temperature heat treatment, so as to obtain nitrogen-doped graphene; carrying out ultrasonic dispersion again on the nitrogen-doped graphene in an ethylene glycol solution, adding a palladium nitrate solution to the ethylene glycol solution and mixing the mixture evenly; reducing palladium nitrate by virtue of a mild reduction method, and depositing palladium nanoparticles in-situ on the surface of the nitrogen-doped graphene; and after reaction is ended, carrying out centrifugal separation to obtain a solid product, and washing and drying the product to obtain the catalyst. By virtue of the mild reduction method, the palladium nanoparticles are deposited in-situ on the surface of the nitrogen-doped graphene; and high temperature or high pressure is not needed, so that the preparation method is simple and controllable, and the repeatability is relatively good. The prepared palladium/nitrogen-doped graphene composite electrode catalyst has excellent electrochemical properties as a direct methanol/formic acid fuel cell cathode material.
Description
Technical field
The present invention relates to a kind of palladium/nitrogen-doped graphene combination electrode Catalysts and its preparation method, belong to field of nano material preparation.
Background technology
Direct methanol/aminic acid fuel battery is as the proton membrane fuel battery of a new generation, have that operating temperature is low, energy efficiency is high, few and fuel is convenient to the advantages such as transport without electrolyte corrosion, disposal of pollutants, have broad application prospects in field of portable electronic apparatus.The major obstacle that govern direct methanol/aminic acid fuel battery commercialization process is at present its high preparation cost and liquid fuel (methyl alcohol and formic acid) oxidation kinetics reaction rate slowly, and the key addressed these problems is to find suitable anode catalyst material.
In recent years, the rise of nano-carbon material (as fullerene, carbon nano-tube, Graphene etc.) is that Design & preparation high performance direct methanol/aminic acid fuel battery anode catalyst provides new thinking.Wherein, Graphene becomes the focus of this area research at present because of the two-dimensional nanostructure of its uniqueness and the physical and chemical performance of excellence.Large result shows, the existence of Graphene can not only significantly improve the catalytic activity of reacting methyl alcohol and Oxidation of Formic Acid of noble metal catalyst, the desorption of toxicity species on its surface can also be accelerated, strengthen anti-poisoning capability (Sahoo N G, Pan Y, Li L, Chan S H.Graphene-Based Materials for Energy Conversion.Advanced Materials, 2012,24:4203-4210).On the other hand, by atom doped mode, every character (as electronic structure, chemism, thermal stability etc.) of Graphene can also be regulated further, thus widen its range of application.Many theories and experimental result prove all, and the nitrogen-atoms that electron affinity energy is larger can affect spin density and the CHARGE DISTRIBUTION of neighbouring carbon atom, promotes its chemism.When the Graphene of N doping is as carrier material supported precious metal nano-particle, the carbon atom that these activity are higher can produce strong interaction with precious metal atom, then distribution (the Lv R of nano particle is obviously improved, Cui T, JunM S, et al.Open-ended, N-doped carbon nanotube-graphene hybrid nanostructures ashigh-performance catalyst support.Advanced Functional Materials, 2011,21:999-1006).At present, the main method realizing nitrogen-doped graphene has: chemical vapour deposition (CVD), graphite electrode heat-treatment oxidation graphite, plasma sputtering etc. under arc discharge, ammonia atmosphere under pyridine atmosphere.But, these preparation method's complex process, preparation cost is higher and yield is low, be not suitable for large-scale industrial production, as document Sheng Z H, Shao L, Chen J J, etal.Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxidewith melamine and its excellent electrocatalysis.ACS Nano, preparation method disclosed in 2011,5:4350-4358.
Summary of the invention
The object of the present invention is to provide the palladium/nitrogen-doped graphene combination electrode Catalysts and its preparation method of a kind of high catalytic activity, high mithridatism and long circulation life.
The technical solution realizing the object of the invention is: a kind of palladium/nitrogen-doped graphene combination electrode Catalysts and its preparation method, comprises the following steps:
The first step, obtains graphite oxide dispersion by graphite oxide ultrasonic disperse in water;
Second step, in the system of the first step, add melamine and at 60-100 DEG C heating reflux reaction;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, heat treatment 1-2 hour at 500-600 DEG C, then raised temperature is to heat treatment 1-2 hour at 700-900 DEG C, the Graphene of obtained N doping;
5th step, is placed in ethylene glycol solution ultrasonic disperse by the Graphene of the N doping obtained in the 4th step;
6th step, adds palladium nitrate solution and ultrasonicly to mix in the system of the 5th step;
7th step, adds hydrazine hydrate solution and stirring reaction in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the first step, described graphite oxide adopts Hummer legal system standby, and the ultrasonic disperse time is 1-3 hour, and temperature is 20-40 DEG C, and the concentration of described graphite oxide dispersion is 1-4g/L.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in second step, described melamine and the mass ratio of graphite oxide are 1:2-4:1, and heating return time is 1-2 hour.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the 3rd step, cryodesiccated temperature is-40 DEG C ~-50 DEG C.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the 4th step, at 500-600 DEG C, heat treated heating rate is 2.3 DEG C/min, and at 700-800 DEG C, heat treated heating rate is 5 DEG C/min.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the 5th step, the Graphene of N doping and the mass ratio of ethylene glycol are 1:10-1:30, and described ultrasonic time is 1-3 hour.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the 6th step, the mass ratio of described Metal Palladium and nitrogen-doped graphene compound is 1:49-1:1; Described ultrasonic time is 1-3 hour.
In the preparation method of palladium/nitrogen-doped graphene of the present invention, in the 7th step, the consumption of hydrazine hydrate is 5-10 times of palladium nitrate quality; The described reaction time is 2-4 hour, and reaction temperature is 20 DEG C-30 DEG C.
The present invention compared with prior art, its advantage is: the melamine-graphite oxide mixed system that can be obtained covalent bonding in (1) preparation process by nucleophilic substitution, for preparing high nitrogen, Uniform Doped graphene composite material provide basis; (2), in preparation process, adopt gentle method of reducing by Pd nano particle in-situ deposition on nitrogen-doped graphene surface, do not need HTHP, simply controlled, repeatability better; (3) nitrogen-doped graphene is adopted to be that palladium/nitrogen-doped graphene composite electrocatalyst prepared by carrier has excellent chemical property as direct methanol/aminic acid fuel battery anode material, the forward peak current density of its catalysis Oxidation of Formic Acid is in acid condition 1690mA/mg, the forward peak current density 1425mA/mg of catalysis methanol oxidation under alkali condition, simultaneously anti-poisoning capability strong, have extended cycle life, be expected to be applied in energy storage field.
Accompanying drawing explanation
Fig. 1 is preparation method's schematic diagram of palladium of the present invention/nitrogen-doped graphene combination electrode catalyst.
Fig. 2 is the transmission electron microscope (a is low multiple, and b is high multiple) of palladium/nitrogen-doped graphene prepared by example 3 of the present invention, field emission scanning electron microscope and mapping picture.
Fig. 3 is that to formic acid, (Fig. 3 a) and the cyclic voltammogram of methyl alcohol (Fig. 3 b) catalytic oxidation respectively for palladium/nitrogen-doped graphene combination electrode catalyst prepared by example 3 of the present invention, palladium/graphene catalyst, palladium/carbon nano-tube catalyst, palladium/activated-carbon catalyst.
Embodiment
Principle of the present invention:
Graphite oxide (GO) surface is containing the abundant oxygen-containing functional group such as hydroxyl, carboxyl, epoxy radicals, and the reactivity of its epoxy group is the highest, and ring-opening reaction (S easily occurs
n2 attacks).Containing a pair lone pair electrons in organic nitrogen source melamine molecule (melamine), electronics can be provided for the nucleophilic substitution of epoxy radicals, form the melamine-GO blend of covalent bonding.Afterwards when heat treatment temperature arrives 550 DEG C, melamine molecule can form the g-C of thin layer at graphite oxide in situ Polymerization
3n
4nanometer layer, and then raise heat treatment temperature, g-C
3n
4nanometer layer resolves into some nitrogenous Small molecular sheet (C
2n
2 +, C
3n
2 +, C
3n
3 +deng) penetrate in Graphene lattice, the final Graphene (N-doped graphene) forming N doping.Finally, Pd nano particle is reduced by the graphenic surface of softening method at N doping, forms Pd-N-doped graphene composite catalyst.
As Fig. 1, palladium of the present invention/nitrogen-doped graphene combination electrode catalyst is prepared by following steps:
The first step, by graphite oxide ultrasonic disperse 1-3 hour in water;
Second step, adds melamine and add hot reflux 2-4 hour at 60-100 DEG C in the system of the first step;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, in 400-600 DEG C of heat treatment 1-2 hour, then raised temperature is to 700-900 DEG C of heat treatment 1-2 hour, the Graphene of obtained N doping;
5th step, is placed in ethylene glycol solution ultrasonic disperse 1-3 hour by the product obtained in the 4th step;
6th step, adds palladium nitrate solution and mix and blend 20-60 minute in the system of the 5th step;
7th step, adds hydrazine hydrate solution and at room temperature stirring reaction 2-4 hour in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
Embodiment 1:
The first step: 200mg graphite oxide is carried out ultrasonic disperse 2 hours in 50mL deionized water, obtains graphene oxide solution;
Second step, adds 200mg melamine in the system of the first step, and at 80 DEG C, add hot reflux 2 hours, stirs and is down to room temperature;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, 500 DEG C of heat treatment 1 hour, then raised temperature to 700 DEG C heat treatment 2 hours, the Graphene of obtained N doping;
5th step, is placed in 80mL ethylene glycol solution ultrasonic disperse 2 hours by the nitrogen-doped graphene 10mg obtained in the 4th step, obtains the dispersion soln of nitrogen-doped graphene;
6th step, adds the palladium nitrate solution of the 0.73mol/L of 0.025mL and mix and blend 20 minutes in the system of the 5th step;
7th step, adds the hydrazine hydrate solution of 50% of 0.425mL and at room temperature stirring reaction 4 hours in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
Embodiment 2:
The first step: 100mg graphite oxide is carried out ultrasonic disperse 2 hours in 100mL deionized water, obtains graphene oxide solution;
Second step, adds 300mg melamine in the system of the first step, and at 80 DEG C, add hot reflux 2 hours, stirs and is down to room temperature;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, 700 DEG C of heat treatment 4 hours, the Graphene of obtained N doping;
5th step, is placed in 50mL ethylene glycol solution ultrasonic disperse 2 hours by the nitrogen-doped graphene 10mg obtained in the 4th step, obtains the dispersion soln of nitrogen-doped graphene;
6th step, adds the palladium nitrate solution of the 0.73mol/L of 0.012mL and mix and blend 20 minutes in the system of the 5th step;
7th step, adds the hydrazine hydrate solution of 50% of 0.2mL and at room temperature stirring reaction 2 hours in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
Embodiment 3:
The first step: 200mg graphite oxide is carried out ultrasonic disperse 2 hours in 100mL deionized water, obtains graphene oxide solution;
Second step, adds 400mg melamine in the system of the first step, and at 80 DEG C, add hot reflux 2 hours, stirs and is down to room temperature;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, 550 DEG C of heat treatment 2 hours, then raised temperature to 800 DEG C heat treatment 2 hours, the Graphene of obtained N doping;
5th step, is placed in 100mL ethylene glycol solution ultrasonic disperse 2 hours by the nitrogen-doped graphene 10mg obtained in the 4th step, obtains the dispersion soln of nitrogen-doped graphene;
6th step, adds the palladium nitrate solution of the 0.73mol/L of 0.025mL and mix and blend 20 minutes in the system of the 5th step;
7th step, adds the hydrazine hydrate solution of 50% of 0.425mL and at room temperature stirring reaction 2 hours in the system of the 6th step;
8th step, the system centrifugation of the 7th step is gone out solid product, spend deionized water, palladium/nitrogen-doped graphene combination electrode catalyst is obtained after drying, its projection Electronic Speculum and field emission scanning electron microscope are as shown in Figure 2, Pd nano particle domain size distribution is narrower, and about 4nm, Pd, C, N element are uniformly distributed in catalyst surface.The palladium of preparation/nitrogen-doped graphene compound is made electrode and carries out electrochemical property test, result is as shown in Fig. 3 and table 1 (palladium/nitrogen-doped graphene combination electrode catalyst compares from the electrochemically active specific surface area of different palladium-based catalyst and the peak current value of catalysis formic acid and Methanol Decomposition), with palladium/common nitrogen-doped graphene catalyst, palladium/graphene catalyst, palladium/carbon nano-tube catalyst, palladium/activated-carbon catalyst is compared, palladium/nitrogen-doped graphene composite catalyst not only has very high electro catalytic activity (forward peak current density 1690mA/mg) to Oxidation of Formic Acid in acid condition, and to methanol oxidation, also there is higher electro catalytic activity (forward peak current density 1425mA/mg) in the basic conditions.
Embodiment 4:
The first step: 200mg graphite oxide is carried out ultrasonic disperse 2 hours in 200mL deionized water, obtains graphene oxide solution;
Second step, adds 800mg melamine in the system of the first step, and at 80 DEG C, add hot reflux 2 hours, stirs and is down to room temperature;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, 600 DEG C of heat treatment 1 hour, then raised temperature to 800 DEG C heat treatment 3 hours, the Graphene of obtained N doping;
5th step, is placed in 100mL ethylene glycol solution ultrasonic disperse 2 hours by the nitrogen-doped graphene 10mg obtained in the 4th step, obtains the dispersion soln of nitrogen-doped graphene;
6th step, adds the palladium nitrate solution of the 0.73mol/L of 0.025mL and mix and blend 20 minutes in the system of the 5th step;
7th step, adds the hydrazine hydrate solution of 50% of 0.425mL and at room temperature stirring reaction 2 hours in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
Contrast embodiment:
The first step: 200mg graphite oxide is carried out ultrasonic disperse 2 hours in 200mL deionized water, obtains graphene oxide solution;
Second step, adds 400mg melamine in the system of the first step, and at 80 DEG C, add hot reflux 2 hours, stirs and is down to room temperature;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, 800 DEG C of heat treatment 4 hours, the Graphene of obtained common N doping;
5th step, is placed in 100mL ethylene glycol solution ultrasonic disperse 2 hours by the Graphene 10mg of the common N doping obtained in the 4th step, obtains the dispersion soln of nitrogen-doped graphene;
6th step, adds the palladium nitrate solution of the 0.73mol/L of 0.025mL and mix and blend 20 minutes in the system of the 5th step;
7th step, adds the hydrazine hydrate solution of 50% of 0.425mL and at room temperature stirring reaction 2 hours in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/common nitrogen-doped graphene combination electrode catalyst after drying.Carrier is changed to Graphene, carbon nano-tube, active carbon, repeats step 5 to step 8, prepare palladium/graphene catalyst, palladium/carbon nano-tube catalyst, palladium/activated-carbon catalyst.
Table 1
Claims (9)
1. palladium/nitrogen-doped graphene combination electrode catalyst, it is characterized in that, described catalyst is prepared by following steps:
The first step, obtains graphite oxide dispersion by graphite oxide ultrasonic disperse in water;
Second step, in the system of the first step, add melamine and at 60-100 DEG C heating reflux reaction;
3rd step, by the reaction system freeze drying of second step;
4th step, by the powder that obtains after the 3rd step freeze drying in a nitrogen atmosphere, heat treatment 1-2 hour at 500-600 DEG C, then raised temperature is to heat treatment 1-2 hour at 700-900 DEG C, the Graphene of obtained N doping;
5th step, is placed in ethylene glycol solution ultrasonic disperse by the Graphene of the N doping obtained in the 4th step;
6th step, adds palladium nitrate solution and ultrasonicly to mix in the system of the 5th step;
7th step, adds hydrazine hydrate solution and stirring reaction in the system of the 6th step;
8th step, goes out solid product by the system centrifugation of the 7th step, spends deionized water, obtains palladium/nitrogen-doped graphene combination electrode catalyst after drying.
2. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, is characterized in that, in the first step, described graphite oxide adopts Hummer legal system standby, the ultrasonic disperse time is 1-3 hour, and temperature is 20-40 DEG C, and the concentration of described graphite oxide dispersion is 1-4g/L.
3. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, it is characterized in that, in second step, described melamine and the mass ratio of graphite oxide are 1:2-4:1, and heating return time is 1-2 hour.
4. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, it is characterized in that, in the 3rd step, cryodesiccated temperature is-40 DEG C ~-50 DEG C.
5. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, it is characterized in that, in the 4th step, at 500-600 DEG C, heat treated heating rate is 2.3 DEG C/min, and at 700-800 DEG C, heat treated heating rate is 5 DEG C/min.
6. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, it is characterized in that, in the 5th step, the Graphene of N doping and the mass ratio of ethylene glycol are 1:10-1:30, and described ultrasonic time is 1-3 hour.
7. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, it is characterized in that, in the 6th step, the mass ratio of described Metal Palladium and nitrogen-doped graphene compound is 1:49-1:1; Described ultrasonic time is 1-3 hour.
8. palladium/nitrogen-doped graphene combination electrode catalyst as claimed in claim 1, is characterized in that, in the 7th step, the consumption of hydrazine hydrate is 5-10 times of palladium nitrate quality; The described reaction time is 2-4 hour, and reaction temperature is 20 DEG C-30 DEG C.
9. the preparation method of the palladium/nitrogen-doped graphene combination electrode catalyst as described in as arbitrary in claim 1-8.
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