CN104923204A - Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst - Google Patents
Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method for a graphene-coated iron-loaded and nitrogen-loaded active site catalyst on a carbon nano tube (CNT); sources of raw materials used for the method are extensive; carbon source and nitrogen source materials are low in cost; the sample yield is high; the production cost of a fuel cell is helped to be reduced; the content of Fe and N in the prepared catalyst is controllable, and meanwhile, bigger specific surface area is kept so as to overcome the problem that metal nanometer particles are easy to aggregate in the past. The preparation method comprises the following steps: (1) supporting Fe and N to the surface of the carbon nano tube to obtain Fe-N-CNT; (2) synthetizing a composite material, formed by coating the surface of the Fe-N-CNT with graphene precursors, by a hydrothermal method; (3) calcining the composite material to obtain Fe-N-CNT&GN. Compared with a traditional fuel cell cathode Pt/C catalyst, the catalyst prepared by the method disclosed by the invention is low in cost, relatively higher in catalytic activity, high in stability, high in methanol tolerance, and has a good commercial application prospect.
Description
Technical field
The invention belongs to energy and material and technical field of electrochemistry, relate to a kind of preparation method being applied to fuel battery negative pole oxygen reduction reaction eelctro-catalyst, be specifically related to the preparation method that a kind of graphene coated supports catalyst with metal nanoparticles on the carbon nanotubes.
Background technology
The problems such as fossil resource exhaustion and environment deterioration are constantly aggravated, and exploitation that are clean, regenerative resource become global concern focus.Low-temperature fuel cell is the electrochemical reaction appts chemical energy of fuel being converted into electric energy, and structure is simple, and the features such as theoretical energy density is high, environmental protection are the focuses that recent domestic scholars study.But low-temperature fuel cell commercialization at present still faces certain challenge, one of them is that cathodic oxygen reduction (ORR) process kinetics process is slower.At present, carbon carries platinum and platinum alloy catalyst is best, the most popular fuel cell oxygen reduction catalyst of performance, but Pt base eelctro-catalyst poor stability, price are high, limit the large-scale commercial of fuel cell, thus exploitation has higher catalytic activity and stability, catalyst corrosion-resistant, with low cost have important practical significance and using value.
Metal-nitrogen-material with carbon element is considered to the base metal ORR eelctro-catalyst having application prospect at present most, but still there are some problems at present: irrational mix or easily reunion make metal-nitrogen-carbonizable substance dispersion uneven, limit the load capacity with catalytically-active metals-nitrogen-material with carbon element, decrease the overall nitrogen density of material, reduce using rate of metal (generally only having 2-5%); Degree of graphitization is low, poorly conductive; Less specific area, makes ORR mass-transfer efficiency low; The more important thing is that common metal-nitrogen-material with carbon element active sites in electrolyte solution is easily corroded, thus reduce catalytic activity and the life-span of catalyst.
Bao.et.al seminar (Angew.Chem.Int.Ed.2015,54,1 – 6) adopts the method for " from top to bottom " to make Co
2+, Ni
+solution and tetrasodium ethylenediamine tetraacetate solution (EDTA
4+) fully there is complex reaction generation CoNiEDTA, high temperature pyrolysis forms the material of graphene coated Co, Ni afterwards.This material catalyzes evolving hydrogen reaction activity is higher, can compare favourably with Pt/C catalyst, proves that graphene coated structures of metal nanoparticles has excellent corrosion resistance and catalytic performance.But this preparation method's poor repeatability, metal nanoparticle is easily reunited, poor to ORR catalytic performance.Therefore, the present invention has done further improvement from the aspect such as preparation method, shape characteristic, active sites structure of material.Use for reference the thinking that above-mentioned graphene coated improves material antiseptic erosion ability, the present invention is coated graphite alkene on the CNT of load iron, nitrogen element, has prepared a kind of degree of graphitization high, good conductivity, high to ORR catalytic activity, the catalyst of good stability.
Summary of the invention
For the deficiencies in the prior art, the character of not easily reuniting compared with bigger serface, Stability Analysis of Structures that the present invention utilizes the CNT of functionalization to have, adopt " one kettle way " load Fe, N element on the carbon nanotubes, the content of regulation and control Fe, N presoma forms rational active sites structure with control Fe, N; Adopt the composite that water heat transfer Graphene presoma is combined with CNT afterwards, the adjusting hydrothermal time, optimal screening went out the composite catalyst to ORR performance with the thickness of the growth conditions and Graphene that control active sites.
Concrete scheme preparation process is as follows:
1) getting carbon carrier, source of iron and nitrogenous source is scattered in the mixed solution of water and ethanol; Described nitrogenous source is any one in dicyandiamide, melamine, ammoniacal liquor; Described molysite is selected from the one in iron chloride, ferrous sulfate, ferric ammonium sulfate;
2) step (1) gained solution is stirred 1-3h under 25-50 DEG C of condition;
3) by a certain amount of disodium EDTA (EDTA
2+) and methyl alcohol add in step (2) gained mixed solution, and at 120-180 DEG C hydro-thermal reaction 3-24h;
4) step (3) gained mixed solution is washed with water to neutrality, and filter, drying >=5h at 50-100 DEG C, obtains Fe-N-CNTEDTA composite;
5) step (4) gained composite in an inert atmosphere, and temperature programming is to 500-900 DEG C, and constant temperature process 1-5h, obtains Fe-N-CNTGN material;
Described in above-mentioned steps (1), carbon carrier is: CNT, carbon black (Vulcan-72), graphite oxide and Graphene class; Carbon carrier, source of iron and the nitrogenous source concentration 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.
In above-mentioned steps (3), the amount of disodium EDTA is the amount of 2 times of molysite, and the concentration of methyl alcohol is 5.2-8.2mol L
-1;
In above-mentioned steps (4), described dry run is oven drying in air atmosphere, stirs drying, freeze drying or vacuum drying;
In above-mentioned steps (5), described inert gas is nitrogen, argon gas, and described inert gas flow velocity is 10-40mLmin
-1; The heating rate of described Temperature Programmed Processes is 1-10 DEG C of min
-1.
Described graphene coated Fe-N-CNTGN catalyst can be used as the negative electrode ORR eelctro-catalyst of Proton Exchange Membrane Fuel Cells, alkaline anion-exchange membrane fuel cell, metal-air battery etc.
Compared with prior art, the preparation method of Fe-N-CNTGN catalyst of the present invention has the following advantages:
1) adopt the Fe-N-CNTGN catalyst prepared of the method for the invention, in preparation process by adjustment carbon carrier, ingredient proportion between nitrogenous source and source of iron, kind can the Fe of Effective Regulation material surface, N content and surface nature;
2) the Fe-N-CNTGN catalyst adopting the method for the invention to prepare, preparation process functionalized carbon nano-tube used has not easily reunites compared with bigger serface, good electric conductivity and Stability Analysis of Structures, the character that adsorption activity position is many, this is conducive to the formation of ORR active sites;
3) the Fe-N-CNTGN catalyst adopting the method for the invention to prepare, preparation adopts " one kettle way " to support Fe, N on the carbon nanotubes.Method of operating is simply effective, while maintenance CNT self advantageous property, add ORR active sites;
4) the Fe-N-CNTGN catalyst adopting the method for the invention to prepare, the Graphene presoma that preparation process uses both can be used as carbon source, can be used as nitrogenous source again, added the electric conductivity of coated graphite alkene, be conducive to ORR process;
5) the Fe-N-CNTGN catalyst adopting the method for the invention to prepare, needed for preparation process, reagent toxicity is little, safety and environmental protection, low raw-material cost, and preparation technology is simple, is conducive to large-scale production;
6) the Fe-N-CNTGN catalyst prepared of the method for the invention is adopted, high to the electro catalytic activity of ORR, good stability, methanol tolerance are good.
Accompanying drawing explanation
Fig. 1 a is the TEM photo obtaining sample according to embodiment 6.
Fig. 1 b is the TEM photo obtaining sample according to embodiment 10.
Fig. 2 is the XRD spectra obtaining sample according to embodiment 6 and example 10.
Fig. 3 is that the sample for preparing according to embodiment 1-4 is at O
2saturated 0.1mol L
-1cyclic voltammetric (CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, rotating speed: 1600rpm, room temperature.
Fig. 4 is that the sample for preparing according to embodiment 3 and embodiment 5-7 is at O
2saturated 0.1mol L
-1cyclic voltammetric (CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, rotating speed: 1600rpm, room temperature.
Fig. 5 is that the sample for preparing according to example 6 and example 8,9 is at O
2saturated 0.1mol L
-1cyclic voltammetric (CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, rotating speed: 1600rpm, room temperature.
Fig. 6 is that the sample for preparing according to embodiment 6 and embodiment 10 is at O
2cyclic voltammetric (CV) curve in saturated 0.1mol L-1KOH electrolyte, sweeps speed: 10mV s
-1, rotating speed: 1600rpm, room temperature.
Fig. 7 is that the sample for preparing according to embodiment 10 and comparative example 1-3 is at O
2saturated 0.1mol L
-1cyclic voltammetric (CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, rotating speed: 1600rpm, room temperature.
Fig. 8 is that the sample and commercialization 20wt.%Pt/C that prepare according to embodiment 10 are at O
2saturated 0.1mol L
-1chronoa mperometric plot (I-t figure) in KOH electrolyte, voltage: 0.4V (vs.Ag/AgCl), testing time: 2400s, room temperature.
Fig. 9 is that commercialization 20wt.%Pt/C is at N
2saturated 0.1mol L
-1kOH electrolyte, O
2saturated 0.1mol L
-1kOH electrolyte, O
2saturated 3mol L
-1cH
3oH+0.1mol L
-1(CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, room temperature.
Figure 10 is that the sample for preparing of embodiment 10 is at N
2saturated 0.1mol L
-1kOH electrolyte, O
2saturated 0.1mol L
-1kOH electrolyte, O
2saturated 3mol L
-1cH
3oH+0.1mol L
-1(CV) curve in KOH electrolyte, sweeps speed: 10mV s
-1, room temperature.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is explained in detail, but the present invention is not limited only to these specific embodiments.
Embodiment 1:Fe
8%-N
0.5-CNT-E
2-24-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
0.5the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 0.5 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 24 refer to that the hydro-thermal reaction time is 24h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.0500g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
0.5-CNTEDTA-24;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
0.5-CNTGN-24-600 material.
Embodiment 2:Fe
8%-N
1-CNT-E
2-24-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 24 refer to that the hydro-thermal reaction time is 24h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1000g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1-CNTEDTA-24;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1-CNTGN-24-600 material.
Embodiment 3:Fe
8%-N
1.25-CNT-E
2-24-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 24 refer to that hydro-thermal time response is 24h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.25-CNTEDTA-24;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1.25-CNTGN-24-600 material.
Embodiment 4:Fe
8%-N
1.5-CNT-E
2-24-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.5the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.5 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 24 refer to that the hydro-thermal reaction time is 24h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1500g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 24h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.5-CNTEDTA-24;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1.5-CNTGN-24-600 material.
Embodiment 5:Fe
8%-N
1.25-CNT-E
2-3-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 3 refer to that the hydro-thermal reaction time is 3h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 3h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.25-CNTEDTA-3;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1.25-CNTGN-3-600 material.
Embodiment 6:Fe
8%-N
1.25-CNT-E
2-6-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 6 refer to that hydro-thermal time response is 6h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.25-CNTEDTA-6;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1.25-CNTGN-6-600 material.
Embodiment 7:Fe
8%-N
1.25-CNT-E
2-10-600 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 10 refer to that hydro-thermal time response is 10h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 10h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.25-CNTEDTA-10;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
8%-N
1.25-CNTGN-10-600 material.
Embodiment 8:Fe
5%-N
1.25-CNT-E
2-6-600 (Fe
5%in finger material, the mass content of Fe is 5%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 6 refer to that hydro-thermal time response is 6h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0241g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
5%-N
1.25-CNTEDTA-6;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
5%-N
1.25-CNTGN-6-600 material.
Embodiment 9:Fe
10%-N
1.25-CNT-E
2-6-600 (Fe
10%in finger material, the mass content of Fe is 10%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 6 refer to that hydro-thermal time response is 6h, and 600 refer to that calcining heat is 600 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0483g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
10%-N
1.25-CNTEDTA-6;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 600 DEG C, and constantly react 3h at such a temperature, naturally cool, obtain Fe
10%-N
1.25-CNTGN-6-600 material.
Embodiment 10:Fe
8%-N
1.25-CNT-E
2-6-900 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25the quality of finger nitrogenous source melamine is carboxylic carbon nano-tube 1.25 times, E
2refer to that the quality of disodium EDTA is 2 times of molysite, 6 refer to that hydro-thermal time response is 6h, and 900 refer to that calcining heat is 900 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it be uniformly dispersed, then at 50 DEG C of magnetic agitation 2h, get 0.0772g disodium EDTA and 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings obtain composite Fe
8%-N
1.25-CNTEDTA-6;
By above-mentioned material at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 900 DEG C, and constantly react 1h at such a temperature, naturally cool, obtain Fe
8%-N
1.25-CNTGN-6-900 material.
Comparative example 1:Fe
8%-CNT-6-900 (Fe
8%in finger material, the mass content of Fe was 8%, 6 finger hydro-thermal times is 6h, and 900 refer to that calcining heats are 900 DEG C)
Get 0.1000g carboxylic carbon nano-tube, mixed solution that 0.0386g iron chloride is added to 30mL water and ethanol, ultrasonic 30min makes it dispersed, then at 50 DEG C of magnetic agitation 2h, get 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings, afterwards at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 900 DEG C, and constantly react 1h at such a temperature, naturally cool, obtain the material with carbon element supporting iron.
Comparative example 2:N
1.25-CNT-6-900 (N
1.25refer to that the quality of nitrogenous source melamine is 1.25 times of carboxylic carbon nano-tube, 6 refer to that the hydro-thermal time is 6h, and 900 refer to that calcining heat is 900 DEG C)
Get 0.1000g carboxylic carbon nano-tube, mixed solution that 0.1250g melamine is added to 30mL water and ethanol, ultrasonic 30min makes it dispersed, then at 50 DEG C of magnetic agitation 2h, get 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings, afterwards at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 900 DEG C, and constantly react 1h at such a temperature, naturally cool, obtain the material with carbon element supporting nitrogen.
Comparative example 3:Fe
8%-N
1.25-CNT-6-900 (Fe
8%in finger material, the mass content of Fe is 8%, N
1.25refer to that the quality of melamine in raw material is 1.25 times of carboxylic carbon nano-tube, 6 refer to that the hydro-thermal time is 6h, and 900 refer to that calcining heat is 900 DEG C)
Get the mixed solution that 0.1000g carboxylic carbon nano-tube, 0.0386g iron chloride and 0.1250g melamine are added to 30mL water and ethanol, ultrasonic 30min makes it dispersed, then 50 DEG C of magnetic agitation 2h, get 10mL methyl alcohol again and add above-mentioned mixed solution and after 150 DEG C of hydro-thermal reaction 6h, washing, filtration, vacuum 80 DEG C of dryings, afterwards at N
2with 3 DEG C of min under atmosphere
-1rate program be warming up to 900 DEG C, and constantly react 1h at such a temperature, naturally cool, obtain the material with carbon element supporting iron, nitrogen.
Fig. 1 (a) for example 6 sample be the TEM photo of 20nm at scale; B () is for example 10 sample and be the TEM photo of 20nm at scale.Black particle is metal nanoparticle in Fig. 1 (a), particle diameter greatly about about 5nm, also can see simultaneously CNT by graphene coated and load nano particle be on the carbon nanotubes covered by Graphene.
Fig. 2 is the XRD spectra of the sample prepared according to embodiment 6 and example 10.As shown in Figure 2, when calcining heat is 600 DEG C, material degree of graphitization is higher, and outer formation graphene-structured is described, it is consistent that this and electromicroscopic photograph reflect, occurs Fe at 43.431 °
3, there is Fe respectively at 42.879 °, 54.398 °, 78.592 ° in the peak of N (111) crystal face
3c (211), Fe
3c (230), Fe
3the peak of C (133); And when calcining heat is 900 DEG C, degree of graphitization is high, and Fe
3the almost disappearance of C, this may be conducive to ORR process.
Fig. 3 is that embodiment 1-4 sample is at O
2saturated 0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.As seen from Figure 3, each embodiment ORR take-off potential is almost identical, is changed to 1:1.5, ORR limiting current density first increases and then decreases with CNT and the melamine mass ratio 1:0.5 that feeds intake, when rate of charge is 1:1.25 limiting current density and half wave potential the highest.
Fig. 4 is that embodiment 3 and embodiment 5-7 sample are at O
2saturated 0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.As seen from Figure 4, along with the increase of hydro-thermal time, ORR take-off potential first increases and then decreases, analyze from ORR take-off potential and half wave potential aspect, be the best hydro-thermal time during 6h, and its corresponding limiting current density is also higher, therefore we infer hydro-thermal time effects Fe and EDTA
2+the complexing degree of solution, thus affect the mass transfer dynamics of ORR.
Fig. 5 is that embodiment 6 and embodiment 8,9 sample are at O
2saturated 0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.As seen from Figure 5, when CNT and melamine feed intake mass ratio be 1:1.25 time, with the increase of Fe content, ORR take-off potential and limiting current density first increases and then decreases, when Fe content is 8%, the most just, limiting current density is maximum for the initial hydrogen reduction current potential of ORR.
Fig. 6 is that embodiment 6 and embodiment 10 sample are at O
2saturated 0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.As seen from Figure 6, by precursor material Fe
8%-N
1.25-CNT-E
2when the calcining heat of-6 is elevated to 900 DEG C, limiting current density increases, and from XRD data, reduces Fe in high-temperature calcination
3the generation of C, this may be favourable to ORR process.
Fig. 7 is that embodiment 10 and comparative example 1-3 sample are at O
2saturated 0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.In order to analyze the impact of Fe, N, EDTA, prepare respectively and do not contrast containing the catalyst of Fe, N, EDTA, result as shown in Figure 7.As seen from the figure, the ORR take-off potential of graphene coated metal nano particle material and limiting current density all increase, and material prepared by known the present invention is conducive to ORR activity and improves.
Fig. 8 is that embodiment 10 sample and commercialization 20wt.%Pt/C are at O
2saturated 0.1mol L
-1i-t figure in KOH electrolyte.As seen from Figure 8, when ORR runs 2400s, the current attenuation to 95% of graphene coated Fe-N-CNTGN catalyst, Pt/C current attenuation to 83%, graphene coated Fe-N-CNTGN catalyst stability is better than commercialization Pt/C.
Fig. 9, Figure 10 are respectively commercialization 20wt.%Pt/C and embodiment 10 sample at N
2saturated 0.1molL
-1kOH electrolyte, O
2saturated 0.1mol L
-1kOH electrolyte, O
2saturated 3mol L
-1cH
3oH+0.1mol L
-1cyclic voltammetry curve in KOH electrolyte.As seen from Figure 9, Pt/C is containing 3molL
-1cH
3in the KOH electrolyte of OH, can be oxidized (-0.3V is to 0.3V) by catalysis methanol, methanol tolerance is very poor.And this embodiment 10 (Figure 10) at this condition electrolyte without obvious oxidation current, show the methanol tolerance better performances of this catalysis material.
Claims (5)
1. a preparation method for graphene coated catalyst with metal nanoparticles, is characterized in that, step is as follows:
1) getting carbon carrier, source of iron and nitrogenous source is scattered in the mixed solution of water and ethanol; Wherein carbon carrier concentration is 3.33-16.67g L
-1, the concentration of source of iron is 0.003-0.006mol L
-1, the concentration of nitrogenous source is 0.013-0.039molL
-1, the volume ratio 1:1-3:1 of water and ethanol; Described carbon carrier is CNT, carbon black, graphite oxide and Graphene class; Described nitrogenous source is the one in dicyandiamide, melamine, ammoniacal liquor; Described molysite is selected from the one in iron chloride, ferrous sulfate, ferric ammonium sulfate;
2) by step 1) gained mixed solution stirs 1-3h under 25-50 DEG C of condition;
3) disodium EDTA and methyl alcohol are added step 2) in gained mixed solution, hydro-thermal reaction 3-24h at 120-180 DEG C; The quality of disodium EDTA is the quality of 2 times of molysite, and the concentration of methyl alcohol is 5.2-8.2mol L
-1;
4) by step 3) mixed solution of gained is washed to neutrality, and filter, drying >=5h at 50-100 DEG C, obtains Fe-N-CNTEDTA composite;
5) by step 4) gained Fe-N-CNTEDTA composite in an inert atmosphere, at 500-900 DEG C of high-temperature process 1-5h, obtained Fe-N-CNTGN material, is graphene coated catalyst with metal nanoparticles.
2. preparation method according to claim 1, is characterized in that, described inert gas is nitrogen, argon gas, and described inert gas flow velocity is 10-40mL min
-1.
3. preparation method according to claim 1 and 2, is characterized in that, described dry run is oven drying in air atmosphere, stirs drying, freeze drying or vacuum drying.
4. the application of the graphene coated catalyst with metal nanoparticles that the preparation method described in claim 1 or 2 obtains, it is characterized in that, described graphene coated catalyst with metal nanoparticles is used as the negative electrode ORR eelctro-catalyst of Proton Exchange Membrane Fuel Cells, alkaline anion-exchange membrane fuel cell or metal-air battery.
5. the application of graphene coated catalyst with metal nanoparticles that obtains of preparation method according to claim 3, it is characterized in that, described graphene coated catalyst with metal nanoparticles is used as the negative electrode ORR eelctro-catalyst of Proton Exchange Membrane Fuel Cells, alkaline anion-exchange membrane fuel cell or metal-air battery.
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