CN103962139B - The preparation method and application of the base metal eelctro-catalyst that a kind of Graphene supports - Google Patents
The preparation method and application of the base metal eelctro-catalyst that a kind of Graphene supports Download PDFInfo
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Abstract
The preparation method and application of the base metal eelctro-catalyst that a kind of Graphene supports, concretely comprise the following steps: in a heated condition, containing n-donor ligand and slaine are mixed to form coordination compound, by cooling, the coordination compound formed is deposited in graphene oxide carrier, add reducing agent redox graphene, scrubbed, dry, heat treatment and pickling and obtain the base metal eelctro-catalyst that Graphene supports.Prepared by the present invention particles supported that base metal eelctro-catalyst is 2 200nm or be coated on the graphene oxide being reduced.In the basic conditions, the base metal eelctro-catalyst that prepared by present invention take-off potential relatively 20wt% commodity platinum/carbon eelctro-catalyst in oxygen reduction reaction has shuffled the ability of 35mV, durability and anti methanol toxication also superior to 20wt% commodity platinum/carbon eelctro-catalyst.Loaded base metal eelctro-catalyst prepared by the present invention can be applicable to Proton Exchange Membrane Fuel Cells.
Description
Technical field
The invention belongs to Electro Catalysts for PEMFC field, be specifically related to a kind of Graphene
The preparation method and application of the base metal eelctro-catalyst supported.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) eelctro-catalyst based on noble metal platinum and alloy thereof,
But due to platinum expensive, scarcity of resources, poor durability, easily the shortcoming such as poisoned, seriously hinder
The commercialization process of fuel cell.One possible solution the non-noble gold being to research and develop alternative platinum
Belong to eelctro-catalyst, reduce fuel cell cost.
Chinese patent (CN102324531A) reports a kind of carbon and carries CoN fuel-cell catalyst
Preparation method and applications, under inert atmosphere protection, high-temperature heat treatment Co salt, nitrogen compound and carbon
The mixture of material is prepared for carbon-supported CoN eelctro-catalyst, and it has certain oxygen in alkaline environment
Reducing activity.Chinese patent (CN101859906A) reports with cobalt source, nitrogen source (tripolycyanamide
Or hexamethylenetetramine), white carbon black be the cheap eelctro-catalyst of Material synthesis, it is in sour environment
There is certain oxygen reduction activity.Chinese patent (CN102626649A) reports nitrogen containing monomer
Introducing layered inorganic compound, nitrogen containing monomer is polymerized at interlayer, pyrolysis is formed has graphite-like structure
N doping base metal eelctro-catalyst, this eelctro-catalyst has good oxygen reduction catalytic activity with stable
Property.P.Zelenay etc. are with nitrogen source (polyaniline), transition metal source (ferrum and cobalt) and carbon source (Ketjen
Black EC-300J) it is Material synthesis PANI-FeCo-C series eelctro-catalyst, in acid system
Show excellent Activity and stabill (G.Wu, K.L.More, C.M.Johnston, P.Zelenay,
Science, 2011,332,443-447).J.P.Dodelet etc. utilize cyanamide, FeSO4·7H2O and Black
Pearls2000 be Material synthesis carbon carry Fe/N/C base metal eelctro-catalyst, this catalyst through ball milling,
Under acid system, certain oxygen reduction activity (J.Tian, L.Birry, F. is had after pickling and heat treatment
Jaouen, J.P.Dodelet, Electrochim.Acta2011,56,3,276 3285).J.J.Zhang etc.
It is prepared for carbon with the mixture of nitride (TPTZ), Fe salt and material with carbon element and carries Fe TPTZ/C
Eelctro-catalyst, this catalyst shows certain oxygen reduction activity (L.C.Wang, L. after high-temperature process
Zhang, J.J.Zhang, Electrochim.Acta2011,13,447 449).United States Patent (USP) (US
2011/0281204A1) report a series of carbon and carry PANI(polyaniline)-Fe-C eelctro-catalyst,
There is under acid system certain oxygen reduction activity.
Said method is all only with a kind of containing n-donor ligand, and the particle diameter of prepared eelctro-catalyst is big, property
Bigger gap can be had compared with platinum-based electrocatalyst.Therefore, it is high that research and development have oxygen reduction activity, resistance to
For a long time property is good and the base metal eelctro-catalyst of the feature such as anti-poisoning is still section's knowledge urgently to be resolved hurrily
Topic.
Graphene has high specific surface area, good electric conductivity, high mechanical properties and hardness and excellent
Good chemical stability, can serve as the carrier of base metal eelctro-catalyst.
The present invention provides a kind of new preparation method, with Graphene as carrier, use two kinds or two kinds with
Upper containing n-donor ligand (such as: Phen and tripolycyanamide), uses two kinds of slaines (such as iron salt and cobalt salt),
It is prepared for the base metal eelctro-catalyst of Novel series.This preparation method successfully by N doping in being gone back
In former graphene oxide, be effectively improved nitrogen content, and supported ferrum, cobalt/cobalt oxide nanometer
The size of granule is less, and density is high, is uniformly dispersed.In the basic conditions, prepared base metal
The oxygen reduction activity of eelctro-catalyst is close with 20wt% business platinum/carbon eelctro-catalyst, good endurance, anti-first
Alcoholism, and there is the hydrogen reduction process of nearly four electron transfers, can be applicable to fuel cell.
Summary of the invention
It is an object of the invention to provide the preparation method of the base metal eelctro-catalyst that a kind of Graphene supports
And application, the method abundant raw material source, simple to operate, it is easy to controlling, preparation cost is low, gained
The oxygen reduction activity of base metal eelctro-catalyst is high, and good endurance has the features such as anti methanol toxication.
The invention provides the preparation method of the base metal eelctro-catalyst that a kind of Graphene supports, adding
Under heat condition, two or more containing n-donor ligand is mixed with two or more slaine
Form coordination compound, by cooling, the coordination compound formed is deposited in graphene oxide carrier, add
Reducing agent redox graphene, scrubbed, dry, heat treatment and pickling obtain what Graphene supported
Base metal eelctro-catalyst；
Concretely comprise the following steps:
By containing n-donor ligand and dissolving metal salts in the water of 50 ~ 100 ° of C, return stirring 0.5 ~ 24h；Will
Graphene oxide is ultrasonic disperse in water, preheats 0.5 ~ 24h, obtain graphene oxide under 50 ~ 100 ° of C
Aqueous solution, mixes graphene oxide water solution with above-mentioned solution, and return stirring 0.5 ~ 24h is cooled to
Room temperature；Add reducing agent solid or its aqueous solution, react 0.5 ~ 24h；Sucking filtration, drying；?
Roasting 0.5 ~ 5h in carrier gas under 400 ~ 1200 ° of C, is cooled to room temperature；Add 5 ~ 5000mL acid
Aqueous solution, after the 0.5 ~ 24h that refluxes in the water-bath of 50 ~ 100 ° of C, sucking filtration, it is washed to neutrality, dries
Dry.
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described nitrogenous
Part includes in 4,4 '-bipyridyl, 2,2 '-bipyridyl, Phen, pyridine diamidogen or tripolycyanamide
Two or more mixture；Containing n-donor ligand with the mass percent of graphene oxide is
1:100~1:1。
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described metal
Salt include the chloride of Fe, Co, Cr, Cu, Ni, Mn, Zn, Mg, acetylacetone,2,4-pentanedione based compound,
Nitrate, acetate, carbonate, phosphate, sulfate, two or more in oxalates
Mixture, described slaine carrying capacity on graphite is dilute is 0.1-50%.
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described oxidation
The concentration of graphene aqueous solution is 0.1 ~ 100mg/mL.
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described reduction
Agent solid or its aqueous solution include formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, boron
Hydrogenated amines, methanol, ethanol, polyhydric alcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, Fructus Vitis viniferae
The mixing of one or two or more kinds in sugar, sucrose, ascorbic acid and their derivant and the like
Thing；In whole system, the ultimate density of reducing agent is 0.5 ~ 1000mmol/L.
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described carrier gas
Including the mixed gas of one or two or more kinds in helium, neon, argon, nitrogen, ammonia.
The preparation method of the base metal eelctro-catalyst that the Graphene that the present invention provides supports, described acidity
Aqueous solution include boric acid, sulphuric acid, benzenesulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, wolframic acid,
One or more mixture in Fluohydric acid., phosphotungstic acid, nitric acid, perchloric acid；Acid water-soluble
The concentration of liquid is 0.1 ~ 10mol/L.
Present invention also offers the base metal electro-catalysis that Graphene prepared by a kind of described method supports
Agent, this catalyst is the particles supported of 2-200nm or is coated on the graphene oxide being reduced.
The base metal eelctro-catalyst that the Graphene that the present invention provides supports is applied to pem fuel
Battery.
Compared with the base metal eelctro-catalyst that the material with carbon element of existing report supports, the present invention has following
Advantage:
A) use two or more containing n-donor ligand as nitrogen source, thus improve base metal electro-catalysis
The oxygen reduction activity of agent.
B) utilize Graphene as carrier, improve oxygen reduction activity, increase the stability of eelctro-catalyst.
C) reaction condition is gentle, it is to avoid under high temperature, high pressure, Ostwald ripening phenomenon and recrystallization are existing
As, obtain that density is high, be uniformly dispersed, nano-particle that size is less.
D) this base metal eelctro-catalyst can be used for Proton Exchange Membrane Fuel Cells.In the basic conditions
In oxygen reduction reaction, the take-off potential (0.153V) of base metal eelctro-catalyst is higher than 40ugPtcm-2
The take-off potential (0.148V) of 20wt% business platinum/carbon eelctro-catalyst；Its half wave potential and 20
ugPtcm-2The half wave potential of business platinum/carbon eelctro-catalyst only negative move 30mV, with 40 μ gPtcm-2's
20wt% business platinum/carbon eelctro-catalyst is only negative moves 45mV.And the electronics of this base metal eelctro-catalyst
Mean transferred number is 3.6, close to 4, shows that oxygen reduction reaction mainly generates H by four electronic processes2O,
Only have a small amount of by-product H2O2Generate.Through the cyclic voltammetry scan of 1500 circles, at electrode potential
For 0V(vs.Hg/HgO) time, the electric current density of this base metal eelctro-catalyst reduced by only 13.6%,
20wt% business platinum/carbon eelctro-catalyst then decreases 42.9%, and the durability of this eelctro-catalyst is described
Preferably.Found by methanol oxidation experiment, this base metal eelctro-catalyst oxygen in methanol solution
Reducing activity is not changed in, and business platinum/carbon eelctro-catalyst then changes significantly, and base metal is described
Eelctro-catalyst has preferable anti methanol toxication ability.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) picture that the embodiment of the present invention 1 prepares product；
Fig. 2 is X-ray diffraction (XRD) spectrogram that the embodiment of the present invention 1 prepares product；
Fig. 3 is the x-ray photoelectron power spectrum (XPS) that the embodiment of the present invention 1 prepares product；
Fig. 4 is the x-ray photoelectron power spectrum (XPS-Co2p) that the embodiment of the present invention 1 prepares product；
Fig. 5 is the x-ray photoelectron power spectrum (XPS-Fe2p) that the embodiment of the present invention 1 prepares product；
Fig. 6 is the x-ray photoelectron power spectrum (XPS-N1s) that the embodiment of the present invention 1 prepares product；
Fig. 7 is the base metal eelctro-catalyst that the embodiment of the present invention 1 uses that different containing n-donor ligand prepares
Polarization curves of oxygen reduction；
Fig. 8 is that the embodiment of the present invention 1 prepares product cyclic voltammetry curve under nitrogen and oxygen atmosphere；
Fig. 9 is that the embodiment of the present invention 1 prepares product hydrogen reduction polarization in oxygen, under different rotating speeds
Curve；
Figure 10 is 20wt% commodity platinum/carbon electricity that the embodiment of the present invention 1 prepares product and different Pt carrying capacity
Catalyst (5,10,15,20 and 40 μ gPtcm-2) in 0.1M KOH electrolyte, 1600rpm turns
Polarization curves of oxygen reduction under Su；
Figure 11 is that the embodiment of the present invention 1 prepares product and 20wt% commodity platinum/carbon eelctro-catalyst 1500
During the cyclic voltammetry scan of circle, 0V(vs.Hg/HgO) under the change of corresponding electric current density,
Lifetime testing conditions: under 25 ° of C in the KOH aqueous solution of the 0.1M that oxygen is saturated, at-0.8-0.2V
(vs.Hg/HgO) electric potential scanning test is carried out under voltage, every 200,400,600,1000,1500
Circle measures the polarization curves of oxygen reduction of catalyst；
Figure 12 is that 20wt% commodity platinum/carbon eelctro-catalyst is in 0.1M potassium hydroxide and 0.1M hydroxide
Polarization curves of oxygen reduction in potassium+0.5M methanol system；
Figure 13 is that the embodiment of the present invention 1 prepares product at 0.1M potassium hydroxide and 0.1M potassium hydroxide
Test comparison figure in+0.5M methanol system；
Figure 14 is that the embodiment of the present invention 2 prepares product oxygen under 450 ° of C and 900 ° of C sintering temperatures
Reduction polarization curve.
Detailed description of the invention
The present invention will be further described by the following examples, but the most therefore limit this
Bright.
Embodiment 1:
The tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100mL deionized water,
Heating in the water-bath of 80 ° of C is until dissolving, by the CoCl of 31mg2·H2The FeCl of O and 66mg3
It is dissolved in respectively in 10mL deionized water, preheats in the water-bath of 80 ° of C after mixing, by above-mentioned two
Plant the solution mixing after preheating, return stirring 30min in the water-bath of 80 DEG C.Weighing quality is 200
The graphene oxide of mg is ultrasonic 40min in the deionized water of 100mL, after being uniformly dispersed, is placed in
The water-bath of 80 ° of C preheats, is then added in above-mentioned reaction solution, cold after return stirring 30min
But to room temperature.Weigh the NaBH of 400mg4It is dissolved in 50mL deionized water, drops to reactant
In system, react 30min, sucking filtration, be vacuum dried at 65 DEG C.Under argon gas atmosphere is protected, program
It is warming up to 800 ° of C, after stablizing heat treatment 2h, naturally cools to room temperature.Again through 0.5M H2SO4Solution
It is washed to neutrality, sucking filtration after stirring 30min under the water-bath of 80 ° of C, is vacuum dried at 65 DEG C,
Finally give black precipitate pulverulent solids.
As Fig. 1, TEM transmission electron microscope results shows that the pattern of the product of embodiment 1 gained is nanometer
Grain supports or is coated on the graphene oxide being reduced, and the particle diameter of granule is 2-200nm.
Product such as Fig. 2, XRD diffraction maximum display embodiment 1 gained is mixture, mainly by ferrum and
The oxide composition of cobalt, the most a small amount of ferrum simple substance, may contain ferrum and the nitride of cobalt.
Such as Fig. 3, XPS analysis determines, the product of embodiment 1 gained mainly by C, N, O, Fe and
Co forms.
Such as Fig. 4, XPS analysis determines, in the product of embodiment 1 gained, Fe is+2 and+trivalent mixed
Close valence state.
Such as Fig. 5, XPS analysis determines, in the product of embodiment 1 gained, Co is+2 and+trivalent mixed
Close valence state.
Such as Fig. 6, XPS analysis determines, has N: the pyrrole of three kinds of forms in the product of embodiment 1 gained
Pyridine type, pyrroles's type and quaternary.
Such as Fig. 7, polarization curves of oxygen reduction shows in the product of embodiment 1 gained double containing n-donor ligands and singly contains
The oxygen reduction activity contrast of nitrogen ligand, uses the activity of the base metal eelctro-catalyst of double containing n-donor ligand to want
It is better than using the base metal eelctro-catalyst of single containing n-donor ligand.
Such as Fig. 8, cyclic voltammetry curve shows that the product of embodiment 1 gained has significantly under oxygen atmosphere
Hydrogen reduction peak.
Such as Fig. 9, polarization curves of oxygen reduction shows what the product of embodiment 1 gained obtained under different rotating speeds
Polarization curve is different, and electric current density increases with the raising of rotating speed.According to Koutecky Levich equation,
Obtaining n value is 3.6, close to 4, it was demonstrated that this hydrogen reduction process is mainly raw by 4 electron transfers
Cheng Shui, and 2 a small amount of electron transfers generation by-product hydrogen peroxide.
Hydrogen reduction such as Figure 10, the product of embodiment 1 gained and business 20wt% platinum/carbon eelctro-catalyst
Polarization curve, the take-off potential (0.153V) of the product of embodiment 1 gained is higher than 40 μ gPtcm-2's
The take-off potential (0.148V) of business platinum/carbon eelctro-catalyst；Its half wave potential and 20 μ gPtcm-2Business
The half wave potential of industry platinum/carbon eelctro-catalyst is only negative moves 30mV, with 40 μ gPtcm-2Platinum/carbon eelctro-catalyst
Half wave potential compare and negative move 45mV, the product of illustrated example 1 gained oxygen in alkaline system is also
Former activity is the most close with the oxygen reduction activity of business platinum/carbon eelctro-catalyst.
Such as Figure 11, life test demonstrates the durability of the product of embodiment 1 gained than 20wt% commodity
The good endurance of platinum/carbon eelctro-catalyst.
If Figure 12,20wt% business platinum/carbon eelctro-catalyst is at 0.1M potassium hydroxide+0.5M methanol solution
In have significantly decay, the anti methanol toxication ability of business platinum/carbon eelctro-catalyst is described.
Such as Figure 13, the product of embodiment 1 gained in the case of with or without methanol without significant difference, explanation
This product has anti methanol toxication ability.
Embodiment 2
Different heat treatment temperature: the tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100
In mL deionized water, heating in the water-bath of 80 DEG C is until dissolving, by the CoCl of 31mg2·H2O
FeCl with 66mg3It is dissolved in respectively in 10mL deionized water, enters in the water-bath of 80 ° of C after mixing
Row preheating, solution mixing, return stirring 30min in the water-bath of 80 DEG C after above two is preheated.
Weigh graphene oxide ultrasonic 40min in the deionized water of 100mL that quality is 200mg, point
After dissipating uniformly, it is placed in the water-bath of 80 ° of C and preheats, be then added in above-mentioned reaction solution, backflow
It is cooled to room temperature after stirring 30min.Weigh the NaBH of 400mg4It is dissolved in 50mL deionized water,
Drop in reaction system, react 30min, sucking filtration, be vacuum dried at 65 DEG C.In argon gas atmosphere
Under protection, temperature programming to 450 ° C or 900 ° of C, naturally cool to room temperature after stablizing heat treatment 2h.
Again through 0.5M H2SO4Solution is washed to neutrality after stirred in water bath 30min of 80 ° of C, sucking filtration,
It is vacuum dried under 65 ° of C, finally gives black precipitate pulverulent solids.
Such as Figure 14, in embodiment 2, under 450 ° of C or 900 ° of C, the hydrogen reduction polarization of the product of gained is bent
Line, shows that the oxygen reduction activity of the product of embodiment 2 gained is had an impact by different sintering temperature.
Embodiment 3
Three kinds of containing n-donor ligands: by the Phen of 35mg, the tripolycyanamide of 22mg and 27mg4,4 '-
Bipyridyl is placed in 100mL deionized water and heats in the water-bath of 80 DEG C until dissolving, by 31mg
CoCl2·H2The FeCl of O and 66mg3It is dissolved in respectively in 10mL deionized water, at 80 ° of C after mixing
Water-bath in preheat, by above-mentioned two preheating after solution mixing, return stirring in the water-bath of 80 ° of C
30min.Weigh graphene oxide that quality is 200mg in the deionized water of 100mL ultrasonic 40
Min, after being uniformly dispersed, is placed in the water-bath of 80 DEG C and preheats, be then added to above-mentioned reaction solution
In, it is cooled to room temperature after return stirring 30min.Weigh the NaBH of 400mg4It is dissolved in 50mL to go
In ionized water, drop in reaction system, react 30min, sucking filtration, be vacuum dried at 65 DEG C.
Under argon gas atmosphere is protected, temperature programming to 800 ° C, naturally cool to room temperature after stablizing heat treatment 2h.
Again through 0.5M H2SO4Solution is washed to neutrality after stirring 30min under the water-bath of 80 ° of C, sucking filtration,
It is vacuum dried under 65 ° of C, finally gives black precipitate pulverulent solids.
The pattern of embodiment 3 products therefrom is similar to embodiment 1 products therefrom with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Embodiment 4
Use two kinds of transition metal salts of Fe, Ni: by the trimerization of the Phen of 105mg Yu 66mg
Cyanamide is placed in 100mL deionized water and heats in the water-bath of 80 ° of C until dissolving, by 97mg's
NiCl2H2The FeCl of O and 66mg3It is dissolved in respectively in 10mL deionized water, at 80 ° of C after mixing
Water-bath in preheat, by above-mentioned two preheating after solution mixing, return stirring in the water-bath of 80 ° of C
30min.Weigh graphene oxide that quality is 200mg in the deionized water of 100mL ultrasonic 40
Min, after being uniformly dispersed, is placed in the water-bath of 80 DEG C and preheats, be then added to above-mentioned reaction solution
In, it is cooled to room temperature after return stirring 30min.Weigh the NaBH of 400mg4It is dissolved in 50mL to go
In ionized water, drop in reaction system, react 30min, sucking filtration, be vacuum dried at 65 DEG C.
Under argon gas atmosphere is protected, temperature programming to 800 ° C, naturally cool to room temperature after stablizing heat treatment 2h.
Again through 0.5M H2SO4Solution is washed to neutrality after stirring 30min under the water-bath of 80 ° of C, sucking filtration,
It is vacuum dried under 65 ° of C, finally gives black precipitate pulverulent solids.
The pattern of embodiment 4 products therefrom is similar to the product of embodiment 1 gained with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Embodiment 5
The tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100mL deionized water,
Heating in the water-bath of 80 ° of C is until dissolving, by the CoCl of 31mg2·H2The FeCl of O and 66mg3
It is dissolved in respectively in 10mL deionized water, preheats in the water-bath of 80 ° of C after mixing, by above-mentioned two
Plant the solution mixing after preheating, return stirring 24h in the water-bath of 80 ° of C.Weighing quality is 200mg
Graphene oxide ultrasonic 40min in the deionized water of 100mL, after being uniformly dispersed, be placed in 80 ° of C
Water-bath in preheat, be then added in above-mentioned reaction solution, after return stirring 24h, be cooled to room
Temperature.Weigh the NaBH of 400mg4It is dissolved in 50mL deionized water, drops in reaction system,
Reaction 24h, sucking filtration, it is vacuum dried at 65 DEG C.Under argon gas atmosphere is protected, temperature programming is extremely
800 ° of C, naturally cool to room temperature after stablizing heat treatment 2h.Again through 0.5M H2SO4Solution is at 80 ° of C
Water-bath under stir and be washed to neutrality after 24h, sucking filtration, be vacuum dried at 65 DEG C, finally give
Black precipitate pulverulent solids.
The pattern of embodiment 5 products therefrom is similar to the product of embodiment 1 gained with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Embodiment 6
The tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100mL deionized water,
Heating in the water-bath of 80 DEG C is until dissolving, by the CoCl of 31mg2·H2The FeCl of O and 66mg3
It is dissolved in respectively in 10mL deionized water, preheats in the water-bath of 80 ° of C after mixing, by above-mentioned two
Plant the solution mixing after preheating, return stirring 12h in the water-bath of 80 ° of C.Weighing quality is 200mg
Graphene oxide ultrasonic 40min in the deionized water of 100mL, after being uniformly dispersed, be placed in 80 ° of C
Water-bath in preheat, be then added in above-mentioned reaction solution, after return stirring 12h, be cooled to room
Temperature.Weigh the NaBH of 400mg4It is dissolved in 50mL deionized water, drops in reaction system,
Reaction 12h, sucking filtration, it is vacuum dried at 65 DEG C.Under argon gas atmosphere is protected, temperature programming is extremely
800 ° of C, naturally cool to room temperature after stablizing heat treatment 2h.Again through 0.5M H2SO4Solution is at 80 ° of C
Water-bath under stir and be washed to neutrality after 12h, sucking filtration, be vacuum dried at 65 DEG C, finally give
Black precipitate pulverulent solids.
The pattern of embodiment 6 products therefrom is similar to the product of embodiment 1 gained with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Embodiment 7
The tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100mL deionized water,
Heating in the water-bath of 80 ° of C is until dissolving, by the CoCl of 31mg2·H2The FeCl of O and 66mg3
It is dissolved in respectively in 10mL deionized water, preheats in the water-bath of 80 ° of C after mixing, by above-mentioned two
Plant the solution mixing after preheating, return stirring 30min in the water-bath of 80 DEG C.Weighing quality is 171
The graphene oxide of mg is ultrasonic 40min in the deionized water of 100mL, after being uniformly dispersed, is placed in
The water-bath of 80 ° of C preheats, is then added in above-mentioned reaction solution, cold after return stirring 30min
But to room temperature.Weigh the NaBH of 400mg4It is dissolved in 50mL deionized water, drops to reactant
In system, react 30min, sucking filtration, be vacuum dried at 65 DEG C.Under argon gas atmosphere is protected, program
It is warming up to 800 DEG C, after stablizing heat treatment 2h, naturally cools to room temperature.Again through 0.5M H2SO4Solution
It is washed to neutrality, sucking filtration after stirring 30min under the water-bath of 80 ° of C, is vacuum dried at 65 DEG C,
Finally give black precipitate pulverulent solids.
The pattern of embodiment 7 products therefrom is similar to the product of embodiment 1 gained with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Embodiment 8
The tripolycyanamide of the Phen of 105mg Yu 66mg is placed in 100mL deionized water,
Heating in the water-bath of 80 DEG C is until dissolving, by the CoCl of 31mg2·H2The FeCl of O and 66mg3
It is dissolved in respectively in 10mL deionized water, preheats in the water-bath of 80 ° of C after mixing, by above-mentioned two
Plant the solution mixing after preheating, return stirring 30min in the water-bath of 80 ° of C.Weighing quality is 17100
The graphene oxide of mg is ultrasonic 40min in the deionized water of 100mL, after being uniformly dispersed, is placed in
The water-bath of 80 DEG C preheats, is then added in above-mentioned reaction solution, cold after return stirring 30min
But to room temperature.Weigh the KBH of 400mg4It is dissolved in 50mL deionized water, drops to reaction system
In, react 30min, sucking filtration, be vacuum dried under 65 ° of C.Under nitrogen atmosphere is protected, program liter
Temperature, to 800 ° of C, naturally cools to room temperature after stablizing heat treatment 2h.Again through 0.5M HCl solution 80
It is washed to neutrality, sucking filtration after stirring 30min under the water-bath of ° C, is vacuum dried under 65 ° of C, finally
Obtain black precipitate pulverulent solids.
The pattern of embodiment 8 products therefrom is similar to the product of embodiment 1 gained with size, less than 200
The subsphaeroidal particles supported of nm or be coated on the graphene oxide being reduced, does not has agglomeration.
Claims (7)
1. the preparation method of the base metal eelctro-catalyst that a Graphene supports, it is characterised in that: will
Containing n-donor ligand and dissolving metal salts in the water of 50～100 DEG C, return stirring 0.5～24h；Stone will be aoxidized
Ink alkene ultrasonic disperse in water, preheats 0.5～24h, obtains graphene oxide water solution at 50～100 DEG C,
Graphene oxide water solution is mixed with above-mentioned solution, return stirring 0.5～24h, be cooled to room temperature；Add
Enter reducing agent solid or its aqueous solution, react 0.5～24h；Sucking filtration, drying；At 400～1200 DEG C
Carrier gas in roasting 0.5～5h, be cooled to room temperature；Add 5～5000mL acidic aqueous solutions,
In the water-bath of 50～100 DEG C after backflow 0.5～24h, sucking filtration, it is washed to neutrality, dries；
Described containing n-donor ligand include 4,4 '-bipyridyl, 2,2 '-bipyridyl, Phen, pyridine diamidogen or
Two or more mixture in tripolycyanamide；Containing n-donor ligand and the quality hundred of graphene oxide
Proportion by subtraction is 1:100～1:1；
Described slaine includes the chloride of Fe, Co, Cr, Cu, Ni, Mn, Zn, Mg, acetyl
Acetonyl compound, nitrate, acetate, carbonate, phosphate, sulfate, in oxalates
Two or more mixture, described slaine carrying capacity on graphite is dilute is 0.1-50%.
2. the preparation method of the base metal eelctro-catalyst supported according to Graphene described in claim 1,
It is characterized in that: the concentration of described graphene oxide water solution is 0.1～100mg/mL.
3. the preparation method of the base metal eelctro-catalyst supported according to Graphene described in claim 1,
It is characterized in that: described reducing agent includes formaldehyde, formic acid, lithium borohydride, sodium borohydride, hydroboration
Potassium, hydroboration amine, methanol, ethanol, polyhydric alcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid,
The mixture of one or two or more kinds in glucose, sucrose, ascorbic acid and their derivant；
In whole system, the ultimate density of reducing agent is 0.5～1000mmol/L.
4. the preparation method of the base metal eelctro-catalyst supported according to Graphene described in claim 1,
It is characterized in that: described carrier gas includes the one in helium, neon, argon, nitrogen, ammonia or two
Plant above mixed gas.
5. the preparation method of the base metal eelctro-catalyst supported according to Graphene described in claim 1,
It is characterized in that: described acidic aqueous solution include boric acid, sulphuric acid, benzenesulfonic acid, hydrochloric acid, hydrobromic acid,
In hydroiodic acid, phosphoric acid, wolframic acid, Fluohydric acid., phosphotungstic acid, nitric acid, perchloric acid one or both with
On mixture；The concentration of acidic aqueous solution is 0.1～10mol/L.
6. the base metal eelctro-catalyst that the Graphene that prepared by method described in claim 1 supports,
It is characterized in that: this catalyst is the particles supported of 2-200nm or is coated on the graphite oxide being reduced
On alkene.
7. the base metal eelctro-catalyst that Graphene described in a claim 6 supports is applied to proton and hands over
Change membrane cell.
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| CN104353480B (en) * | 2014-09-26 | 2017-01-11 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN104399462B (en) * | 2014-10-11 | 2016-08-24 | 南京大学 | A kind of copper-graphite nano-complex and its preparation method and application |
| CN104261401A (en) * | 2014-10-14 | 2015-01-07 | 钱景 | Preparation method of graphene |
| CN105633358B (en) * | 2014-11-28 | 2018-11-27 | 中国科学院大连化学物理研究所 | A kind of FeP/ graphene composite material and preparation method thereof |
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| CN106450355A (en) * | 2016-11-01 | 2017-02-22 | 首都师范大学 | Oxygen reduction catalyst and preparation method thereof |
| CN106944057A (en) * | 2017-03-31 | 2017-07-14 | 深圳市国创新能源研究院 | A kind of preparation method of monoatomic metal carbon composite catalytic agent for electrocatalytic reaction |
| CN107910565B (en) * | 2017-10-26 | 2020-11-13 | 青岛大学 | Preparation method of monatomic cobalt/graphene proton exchange membrane fuel cell catalyst |
| CN109755442B (en) * | 2019-02-28 | 2020-08-25 | 大连理工大学 | Preparation method of network-like carbon-supported iron-based compound material and application of network-like carbon-supported iron-based compound material in lithium-sulfur battery |
| CN112886028B (en) * | 2019-11-29 | 2022-03-08 | 中国科学院大连化学物理研究所 | Self-supporting porous air electrode material and preparation and application thereof |
| CN112652780B (en) * | 2020-12-15 | 2022-11-11 | 河南师范大学 | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN114335574A (en) * | 2021-12-10 | 2022-04-12 | 先进能源产业研究院(广州)有限公司 | Non-noble metal catalyst for fuel cell and preparation method thereof |
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