CN104923204B - A kind of preparation method and applications of graphene coated catalyst with metal nanoparticles - Google Patents
A kind of preparation method and applications of graphene coated catalyst with metal nanoparticles Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of sited catalyst on graphene coated load iron, the CNT of nitrogen, the raw materials used wide material sources of this method, carbon source, nitrogen source material are with low cost, sample high income, advantageously reduce the production cost of fuel cell, Fe, N content in catalyst is made controllable, while keeping larger specific surface area, overcomes the problem of conventional metal nanoparticle is easily reunited.Preparation method includes：(1) Fe, N are supported in carbon nano tube surface and are obtained Fe N CNT；(2) composite of the hydro-thermal method synthesis in Fe N CNT surface coated graphite alkene presomas；(3) Fe N CNT@GN are made in the calcining of composite；Material made from the inventive method is compared with conventional fuel cell negative electrode Pt/C catalyst, and cost is low, and catalytic activity is of a relatively high, and stability is good, and methanol tolerance is strong, there is good commercial application prospect.
Description
Technical field
The invention belongs to energy and material and electrochemical technology field, it is related to a kind of anti-applied to fuel battery negative pole hydrogen reduction
Answer the preparation method of elctro-catalyst, and in particular to the metal nanoparticle supported on the carbon nanotubes to a kind of graphene coated is urged
The preparation method of agent.
Background technology
The problems such as fossil resource exhaustion is with environmental degradation constantly aggravates, and cleaning, the exploitation of regenerative resource turn into complete
The ball focus of attention.Low-temperature fuel cell is the electrochemical reaction appts that the chemical energy of fuel is converted into electric energy, structure letter
The features such as list, theoretical energy density height, environmental protection, be the focus that recent domestic scholars study.But current low temperature
Commercializing fuel cells still face certain challenge, and one of them is that cathodic oxygen reduction (ORR) process kineticses process is slower.
At present, pallium-on-carbon and platinum alloy catalyst are that performance is best, most popular fuel cell oxygen reduction catalyst, but Pt bases electricity
Poor catalyst stability, price are high, limit the large-scale commercial of fuel cell, thus exploitation has higher catalytic activity
Had important practical significance and application value with stability, catalyst corrosion-resistant, with low cost.
Metal-nitrogen-carbon material is considered as the base metal ORR elctro-catalysts for most having application prospect at present, but at present
Still suffer from some problems：Irrational mix or easily reunion make metal-nitrogen-carbonizable substance disperse uneven, limit to have and urge
Change the load capacity of active metal-nitrogen-carbon material, reduce the overall nitrogen density of material, reduce rate of metal (general to only have
2-5%)；Degree of graphitization is low, poorly conductive；Less specific surface area, makes ORR mass-transfer efficiencies low；It is more importantly common
Metal-nitrogen-carbon material active sites in electrolyte solution are easily corroded, so as to reduce catalytic activity and the life-span of catalyst.
Bao.et.al seminars (Angew.Chem.Int.Ed.2015,54,1-6) are made using method " from top to bottom "
Co2+,Ni+Solution and tetrasodium ethylenediamine tetraacetate solution (EDTA4+) fully occur complex reaction generation CoNi EDTA, Zhi Hougao
Warm solution forms graphene coated Co, Ni material.The material catalytic hydrogen evolution reactivity is higher, can mutually be equal to Pt/C catalyst
It is beautiful, it was demonstrated that graphene coated structures of metal nanoparticles has excellent corrosion resistance and catalytic performance.However, the preparation method
Poor repeatability, metal nanoparticle is easily reunited, poor to ORR catalytic performances.Therefore, preparation method of the present invention from material, pattern
Further improvement has been done in terms of feature, active bit architecture.Use for reference above-mentioned graphene coated and improve the think of that material antiseptic loses ability
Road, the present invention is the coated graphite alkene on load iron, the CNT of nitrogen, is prepared for a kind of degree of graphitization height, conductive
Property good, stability good catalyst high to ORR catalytic activity.
The content of the invention
In view of the shortcomings of the prior art, the present invention has using the CNT of functionalization large specific surface area, structure
The stable property for being difficult to reunite, Fe, N element are loaded using " one kettle way " on the carbon nanotubes, regulate and control the content of Fe, N presoma
To control Fe, N to form rational active bit architecture；Combined afterwards using hydro-thermal method synthesizing graphite alkene presoma with CNT
Composite, the adjusting hydrothermal time, optimal screening went out to ORR performances to control the growth conditions of active sites and the thickness of graphene
Composite catalyst.
Concrete scheme preparation process is as follows：
1) carbon carrier, molysite and nitrogen source is taken to be scattered in the mixed solution of water and ethanol；The nitrogen source is dicyandiamide, trimerization
Any of cyanamide, ammoniacal liquor；The one kind of the molysite in iron chloride, ferrous sulfate, ferric ammonium sulfate；
2) step (1) resulting solution is stirred into 1-3h under the conditions of 25-50 DEG C；
3) by a certain amount of disodium EDTA (EDTA2+) and methanol add in mixed solution obtained by step (2), and
The hydro-thermal reaction 3-24h at 120-180 DEG C；
4) mixed solution obtained by step (3) is washed with water to neutrality, filters, and the drying >=5h at 50-100 DEG C obtains Fe-
N-CNT@EDTA composites；
5) in an inert atmosphere, temperature programming is to 500-900 DEG C, and constant temperature processing 1-5h makes for composite obtained by step (4)
Obtain Fe-N-CNT@GN materials；
Carbon carrier is described in above-mentioned steps (1)：CNT, carbon black (Vulcan-72), graphite oxide and graphene
Class；The concentration of carbon carrier, molysite and nitrogen source in mixed solution is respectively：Carbon carrier concentration is 3.33-16.67g L-1、
0.003-0.006mol L-1With 0.013-0.039mol L-1, the ratio of water and ethanol：1:1-3:1.
The amount of disodium EDTA is the amount of 2 times of molysite in above-mentioned steps (3), and the concentration of methanol is 5.2-
8.2mol L-1；
In above-mentioned steps (4), the drying process is oven drying, dry stirring, freeze-drying or true in air atmosphere
Sky is dried；
In above-mentioned steps (5), the inert gas is nitrogen, argon gas, and the inert gas flow velocity is 10-40mL min-1；
The heating rate of described program temperature-rise period is 1-10 DEG C of min-1。
The graphene coated Fe-N-CNT@GN catalyst can be used as Proton Exchange Membrane Fuel Cells, alkali anion and hand over
Change the negative electrode ORR elctro-catalysts of membrane cell, metal-air battery etc..
Compared with prior art, the preparation method of Fe-N-CNT@GN catalyst of the present invention has advantages below：
1) the Fe-N-CNT@GN catalyst prepared using the method for the invention, in preparation process by adjust carbon carrier,
Ingredient proportion, species between nitrogen source and molysite can Effective Regulation material surface Fe, N content and surface nature；
2) the Fe-N-CNT@GN catalyst prepared using the method for the invention, the functionalized carbon used in preparation process is received
Mitron has large specific surface area, good electric conductivity and Stability Analysis of Structures are difficult to reunite, the property more than adsorption activity position, and this has
Beneficial to the formation of ORR active sites；
3) the Fe-N-CNT@GN catalyst prepared using the method for the invention, is prepared using " one kettle way " in carbon nanometer
Fe, N are supported on pipe.Operating method is easy and effective, and ORR activity is added while CNT itself advantageous property is kept
Position；
4) the Fe-N-CNT@GN catalyst prepared using the method for the invention, the graphene forerunner that preparation process is used
Body can not only be used for carbon source, but also as nitrogen source, adds the electric conductivity of coated graphite alkene, is conducive to ORR processes；
5) the Fe-N-CNT@GN catalyst prepared using the method for the invention, reagent toxicity needed for preparation process is small, peace
Loopful is protected, low raw-material cost, and preparation technology is simple, is conducive to large-scale production；
6) the Fe-N-CNT@GN catalyst prepared using the method for the invention is high to ORR electro catalytic activity, stably
The good, methanol tolerance of property is good.
Brief description of the drawings
Fig. 1 a are the TEM photos that sample is made according to embodiment 6.
Fig. 1 b are the TEM photos that sample is made according to embodiment 10.
Fig. 2 is the XRD spectra that sample is made according to embodiment 6 and example 10.
Fig. 3 is the sample prepared according to embodiment 1-4 in O2The 0.1mol L of saturation-1Circulation in KOH electrolyte
Volt-ampere (CV) curve, sweeps speed：10mV s-1, rotating speed：1600rpm, room temperature.
Fig. 4 is the sample prepared according to embodiment 3 and embodiment 5-7 in O2The 0.1mol L of saturation-1KOH electrolyte
In cyclic voltammetric (CV) curve, sweep speed：10mV s-1, rotating speed：1600rpm, room temperature.
Fig. 5 is the sample prepared according to example 6 and example 8,9 in O2The 0.1mol L of saturation-1In KOH electrolyte
Cyclic voltammetric (CV) curve, sweeps speed：10mV s-1, rotating speed：1600rpm, room temperature.
Fig. 6 is the sample prepared according to embodiment 6 and embodiment 10 in O2The 0.1mol L-1KOH electrolyte of saturation
In cyclic voltammetric (CV) curve, sweep speed：10mV s-1, rotating speed：1600rpm, room temperature.
Fig. 7 is the sample prepared according to embodiment 10 and comparative example 1-3 in O2The 0.1mol L of saturation-1KOH is electrolysed
Cyclic voltammetric (CV) curve in liquid, sweeps speed：10mV s-1, rotating speed：1600rpm, room temperature.
Fig. 8 is the sample and commercialization 20wt.%Pt/C prepared according to embodiment 10 in O2The 0.1mol L of saturation- 1Chronoa mperometric plot (I-t figures) in KOH electrolyte, voltage：0.4V (vs.Ag/AgCl), testing time：2400s, room temperature.
Fig. 9 is commercialization 20wt.%Pt/C in N2The 0.1mol L of saturation-1KOH electrolyte, O2The 0.1mol L of saturation- 1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1(CV) curve in KOH electrolyte, sweeps speed：10mV s-1,
Room temperature.
Figure 10 is the sample for preparing of embodiment 10 in N2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
0.1mol L-1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1(CV) curve in KOH electrolyte, sweeps speed：
10mV s-1, room temperature.
Embodiment
The present invention is explained in detail with reference to instantiation, but the present invention is not limited only to these specific implementations
Example.
Embodiment 1：Fe8%-N0.5-CNT-E2-24-600(Fe8%The mass content for referring to Fe in material is 8%, N0.5Refer to nitrogen source
The quality of melamine is 0.5 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite,
24 refer to the hydro-thermal reaction time for 24h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.0500g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N0.5-CNT@EDTA-24；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N0.5- CNT@GN-24-600 materials.
Embodiment 2：Fe8%-N1-CNT-E2-24-600(Fe8%The mass content for referring to Fe in material is 8%, N1Refer to nitrogen source three
The quality of poly cyanamid is 1 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite, and 24 refer to
The hydro-thermal reaction time is 24h, and 600 refer to calcining heat for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1000g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1-CNT@EDTA-24；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1- CNT@GN-24-600 materials.
Embodiment 3：Fe8%-N1.25-CNT-E2-24-600(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer to nitrogen
The quality of source melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is the 2 of molysite
Times, 24 refer to hydro-thermal time response for 24h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.25-CNT@EDTA-24；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1.25- CNT@GN-24-600 materials.
Embodiment 4：Fe8%-N1.5-CNT-E2-24-600(Fe8%The mass content for referring to Fe in material is 8%, N1.5Refer to nitrogen source
The quality of melamine is 1.5 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite,
24 refer to the hydro-thermal reaction time for 24h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1500g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.5-CNT@EDTA-24；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1.5- CNT@GN-24-600 materials.
Embodiment 5：Fe8%-N1.25-CNT-E2-3-600(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer to nitrogen source
The quality of melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite,
3 refer to the hydro-thermal reaction time for 3h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 3h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.25-CNT@EDTA-3；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1.25- CNT@GN-3-600 materials.
Embodiment 6：Fe8%-N1.25-CNT-E2-6-600(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer to nitrogen source
The quality of melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite,
6 refer to hydro-thermal time response for 6h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.25-CNT@EDTA-6；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1.25- CNT@GN-6-600 materials.
Embodiment 7：Fe8%-N1.25-CNT-E2-10-600(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer to nitrogen
The quality of source melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is the 2 of molysite
Times, 10 refer to hydro-thermal time response for 10h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 10h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.25-CNT@EDTA-10；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe8%-N1.25- CNT@GN-10-600 materials.
Embodiment 8：Fe5%-N1.25-CNT-E2-6-600(Fe5%The mass content for referring to Fe in material is 5%, N1.25Refer to nitrogen source
The quality of melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is 2 times of molysite,
6 refer to hydro-thermal time response for 6h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0241g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe5%-N1.25-CNT@EDTA-6；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe5%-N1.25- CNT@GN-6-600 materials.
Embodiment 9：Fe10%-N1.25-CNT-E2-6-600(Fe10%The mass content for referring to Fe in material is 10%, N1.25Refer to
The quality of nitrogen source melamine is 1.25 times of carboxylic carbon nano-tube, E2It is molysite to refer to the quality of disodium EDTA
2 times, 6 refer to hydro-thermal time response for 6h, and 600 refer to calcining heats for 600 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0483g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe10%-N1.25-CNT@EDTA-6；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 600 DEG C, and it is constant at such a temperature
3h is reacted, natural cooling obtains Fe10%-N1.25- CNT@GN-6-600 materials.
Embodiment 10：Fe8%-N1.25-CNT-E2-6-900(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer to nitrogen
The quality of source melamine is 1.25 times of carboxylic carbon nano-tube, E2The quality for referring to disodium EDTA is the 2 of molysite
Times, 6 refer to hydro-thermal time response for 6h, and 900 refer to calcining heats for 900 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes it be uniformly dispersed, and then in 50 DEG C of magnetic agitation 2h, then takes 0.0772g ethylenediamine tetraacetics
Acetic acid disodium salt adds above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h with 10mL methanol, washing, filtering, vacuum 80
DEG C it is dried to obtain composite Fe8%-N1.25-CNT@EDTA-6；
By above-mentioned material in N2With 3 DEG C of min under atmosphere-1Rate program be warming up to 900 DEG C, and it is constant at such a temperature
1h is reacted, natural cooling obtains Fe8%-N1.25- CNT@GN-6-900 materials.
Comparative example 1：Fe8%-CNT-6-900(Fe8%The mass content for referring to Fe in material is 8%, and 6 refer to the hydro-thermal time for 6h,
900 refer to calcining heat for 900 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride to add the mixed solution to 30mL water and ethanol, surpass
Sound 30min makes its dispersed, then in 50 DEG C of magnetic agitation 2h, then takes 10mL methanol to add above-mentioned mixed solution and 150
After DEG C hydro-thermal reaction 6h, washing, filtering, 80 DEG C of dryings of vacuum, afterwards in N2With 3 DEG C of min under atmosphere-1Rate program liter
Temperature to 900 DEG C, and it is constant react 1h at such a temperature, natural cooling obtains supporting the carbon material of iron.
Comparative example 2：N1.25-CNT-6-900(N1.25The quality for referring to nitrogen source melamine is the 1.25 of carboxylic carbon nano-tube
Times, 6 refer to the hydro-thermal time for 6h, and 900 refer to calcining heats for 900 DEG C)
0.1000g carboxylic carbon nano-tubes, 0.1250g melamines is taken to add the mixed solution to 30mL water and ethanol,
Ultrasonic 30min makes its dispersed, then in 50 DEG C of magnetic agitation 2h, then take 10mL methanol add above-mentioned mixed solution and
After 150 DEG C of hydro-thermal reaction 6h, washing, filtering, 80 DEG C of dryings of vacuum, afterwards in N2With 3 DEG C of min under atmosphere-1Rate program
Be warming up to 900 DEG C, and it is constant react 1h at such a temperature, natural cooling obtains supporting the carbon material of nitrogen.
Comparative example 3：Fe8%-N1.25-CNT-6-900(Fe8%The mass content for referring to Fe in material is 8%, N1.25Refer in raw material
The quality of melamine is 1.25 times of carboxylic carbon nano-tube, and 6 refer to the hydro-thermal time for 6h, and 900 refer to calcining heats for 900 DEG C)
Take 0.1000g carboxylic carbon nano-tubes, 0.0386g iron chloride and 0.1250g melamines add to 30mL water and
The mixed solution of ethanol, ultrasonic 30min makes its dispersed, then 50 DEG C of magnetic agitation 2h, then takes the addition of 10mL methanol above-mentioned
Mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtering, 80 DEG C of dryings of vacuum, afterwards in N2With 3 DEG C under atmosphere
min-1Rate program be warming up to 900 DEG C, and it is constant react 1h at such a temperature, natural cooling obtains supporting the carbon materials of iron, nitrogen
Material.
Fig. 1 (a) is the TEM photos that the sample of example 6 is 20nm in scale；(b) it is the sample of example 10 and is 20nm in scale
TEM photos.Black particle is metal nanoparticle in Fig. 1 (a), and particle diameter is about in 5nm or so, while also can be seen that carbon nanometer
Pipe is covered by graphene by graphene coated and load nano-particle on the carbon nanotubes.
Fig. 2 is the XRD spectra of the sample prepared according to embodiment 6 and example 10.As shown in Figure 2, in calcining heat
When being 600 DEG C, material degree of graphitization is higher, illustrates outer layer formation graphene-structured, and this is consistent with electromicroscopic photograph reflection,
43.431 ° there is Fe3, there is Fe respectively in 42.879 °, 54.398 °, 78.592 ° in the peak of N (111) crystal face3C(211)、Fe3C
(230)、Fe3C (133) peak；And when calcining heat is 900 DEG C, degree of graphitization is high, and Fe3C almost disappearance, this can
ORR processes can be conducive to.
Fig. 3 is embodiment 1-4 samples in O2The 0.1mol L of saturation-1Cyclic voltammetry curve in KOH electrolyte.By Fig. 3
It can be seen that, each embodiment ORR take-off potentials are almost identical, fed intake mass ratio 1 with CNT and melamine:0.5 is changed to 1:
1.5, ORR limiting current density first increases and then decreases, are 1 in rate of charge:Limiting current density and half wave potential highest when 1.25.
Fig. 4 is embodiment 3 and embodiment 5-7 samples in O2The 0.1mol L of saturation-1Cyclic voltammetric in KOH electrolyte is bent
Line.From fig. 4, it can be seen that with the increase of hydro-thermal time, ORR take-off potential first increases and then decreases, from ORR take-off potentials and half-wave electricity
Position aspect is analyzed, and is the optimal hydro-thermal time during 6h, and its corresponding limiting current density is also higher, therefore it is presumed that during hydro-thermal
Between influence Fe and EDTA2+The complexing degree of solution, so as to influence ORR mass transfer dynamicses.
Fig. 5 is embodiment 6 and the sample of embodiment 8,9 in O2The 0.1mol L of saturation-1Cyclic voltammetric in KOH electrolyte is bent
Line.As seen from Figure 5, when CNT and the melamine mass ratio that feeds intake are 1:When 1.25, with the increase of Fe contents, ORR startings
Current potential and limiting current density first increases and then decreases, when Fe contents are 8%, most just, carrying current is close for ORR starting hydrogen reduction current potential
Degree is maximum.
Fig. 6 is embodiment 6 and the sample of embodiment 10 in O2The 0.1mol L of saturation-1Cyclic voltammetric in KOH electrolyte is bent
Line.As seen from Figure 6, by precursor material Fe8%-N1.25-CNT-E2When -6 calcining heat is increased to 900 DEG C, limiting current density
Increase, from XRD data, Fe is reduced in high-temperature calcination3C generation, this may be favourable to ORR processes.
Fig. 7 is embodiment 10 and comparative example 1-3 samples in O2The 0.1mol L of saturation-1Cyclic voltammetric in KOH electrolyte
Curve.In order to analyze Fe, N, EDTA influence, the catalyst without Fe, N, EDTA is prepared respectively and is contrasted, as a result such as Fig. 7
It is shown.As seen from the figure, the ORR take-off potentials and limiting current density of graphene coated metal nano particle material increase, can
Know that material prepared by the present invention is conducive to ORR activity raisings.
Fig. 8 is the sample of embodiment 10 and commercialization 20wt.%Pt/C in O2The 0.1mol L of saturation-1In KOH electrolyte
I-t schemes.As seen from Figure 8, ORR run 2400s when, graphene coated Fe-N-CNT@GN catalyst current attenuations to 95%,
Pt/C current attenuations are to 83%, and graphene coated Fe-N-CNT@GN catalyst stabilities are better than commercialization Pt/C.
Fig. 9, Figure 10 are respectively commercialization 20wt.%Pt/C and the sample of embodiment 10 in N2The 0.1mol L of saturation-1KOH electricity
Solve liquid, O2The 0.1mol L of saturation-1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1Circulated in KOH electrolyte
Volt-ampere curve.As seen from Figure 9, Pt/C is containing 3mol L-1CH3In OH KOH electrolyte, can catalysis methanol oxidation (- 0.3V is extremely
0.3V), methanol tolerance is very poor.And the embodiment 10 (Figure 10) in the condition electrolyte without obvious oxidation current, show that this is urged
Change the methanol tolerance better performances of material.
Claims (5)
1. a kind of preparation method of graphene coated catalyst with metal nanoparticles, it is characterised in that step is as follows：
1) carbon carrier, molysite and nitrogen source is taken to be scattered in the mixed solution of water and ethanol；Wherein carbon carrier concentration is 3.33-
16.67g·L-1, the concentration of molysite is 0.003-0.006molL-1, the concentration of nitrogen source is 0.013-0.039molL-1, water
With the volume ratio 1 of ethanol:1-3:1；The carbon carrier is CNT, carbon black, graphite oxide and graphite alkenes；The nitrogen source is
One kind in dicyandiamide, melamine, ammoniacal liquor；The one kind of the molysite in iron chloride, ferrous sulfate, ferric ammonium sulfate；
2) by step 1) gained mixed solution 1-3h is stirred under the conditions of 25-50 DEG C；
3) disodium EDTA and methanol are added into step 2) in gained mixed solution, hydro-thermal is anti-at 120-180 DEG C
Answer 3-24h；The quality of disodium EDTA is the quality of 2 times of molysite, and the concentration of methanol is 5.2-8.2molL-1；
4) by step 3) obtained by mixed solution be washed to neutrality, filter, the drying >=5h at 50-100 DEG C obtains Fe-N-
CNT@EDTA composites；
5) by step 4) gained Fe-N-CNT@EDTA composites in an inert atmosphere, in 500-900 DEG C of high-temperature process 1-5h,
Fe-N-CNT@GN materials, as graphene coated catalyst with metal nanoparticles is made.
2. preparation method according to claim 1, it is characterised in that described inert gas is nitrogen, argon gas, described lazy
Property gas flow rate be 10-40mLmin-1。
3. preparation method according to claim 1 or 2, it is characterised in that the drying process is baking oven in air atmosphere
Dry, stirring is dried, is freeze-dried or is dried in vacuo.
4. the application for the graphene coated catalyst with metal nanoparticles that the preparation method described in claim 1 or 2 is obtained, it is special
Levy and be, the graphene coated catalyst with metal nanoparticles is used as Proton Exchange Membrane Fuel Cells, alkali anion and exchanged
The negative electrode ORR elctro-catalysts of membrane cell or metal-air battery.
5. the application for the graphene coated catalyst with metal nanoparticles that the preparation method described in claim 3 is obtained, its feature
It is, the graphene coated catalyst with metal nanoparticles is used as Proton Exchange Membrane Fuel Cells, alkaline anion-exchange membrane
The negative electrode ORR elctro-catalysts of fuel cell or metal-air battery.
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