CN103413951A - Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof - Google Patents
Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and a preparation method thereof. According to the technical scheme, the preparation method comprises the following steps: uniformly stirring graphene oxide, ethanediol and N-methylpyrrolidone in a mass ratio of (30 to 60): (1100 to 2800): (500 to 1600), and performing an ultrasonic dispersion treatment, so as to obtain a uniformly-dispersed suspension liquid; adding a metal salt solution and an H2PtCl6.6H2O solution in the uniformly-dispersed suspension liquid, uniformly stirring, and performing an ultrasonic dispersion treatment, so as to obtain a precursor; heating the precursor to 90-180 DEG C in an oil bath in a stirring condition, insulating heat, and performing condensation reflux for 1 to 5 hours, so as to obtain a black turbid liquid; performing vacuum suction filtration on the black turbid liquid, sequentially washing by acetone, distilled water and absolute ethyl alcohol, and performing vacuum drying at a room temperature to obtain the nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst. The preparation method disclosed by the invention is simple in process and low in energy consumption; the prepared nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst is high in catalytic activity, good in stability, uniform in the dispersion of nanometre particles, and controllable in the particle size of the nanometre particles.
Description
Technical field
The invention belongs to the fuel-cell catalyst technical field, be specifically related to a kind of nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst and preparation method thereof.
Background technology
Along with the exhaustion day by day of the energy, energy problem has become the hot issue of the world today.Fuel cell, as a kind of novel power generation device that is different from traditional energy-storage battery, has become an important channel that solves energy problem.The methyl alcohol of take is simple in structure as the direct methanol fuel cell of fuel not only has, low to be polluted, working temperature is low and the energy conversion efficiency advantages of higher, and because the methyl alcohol energy density is high, chemism is high, low price, source enrich, be easy to carry and store, suitable to especially compact power and electric motor car power supply, thereby have broad application prospects.
Take Pt as the anode catalyst of representative has very high catalytic activity to methyl alcohol, is one of most popular catalyst of direct methanol fuel cell.Yet the active sites that the intermediate product of the similar CO of methanol oxidation very easily occupies the Pt surface makes Pt poisoning, and precious metals pt is expensive, resource-constrained.Therefore, activity and the utilance of raising Pt catalyst are the keys of direct methanol fuel cell sustainable development.At present, anti-CO poisoning capability catalyst preferably is the alloy of Pt, and as PtRu, PtCo, PtNi and PtSn etc., the type catalyst has obtained research and development more widely.
As everyone knows, catalyst carrier has determined that size, pattern and the particle diameter of Pt and Pt alloy nano particle distribute, thereby performance and the utilance of catalyst had a great impact.Good catalyst carrier must have the character such as high-specific surface area, high conductivity, strong affinity, strong resistance to acids and bases, be beneficial to the dispersion of Pt and Pt alloy nano particle, reduce the impedance of electrode, electronics in the accelerating oxidation reduction process shifts, effective fixedly Pt and Pt alloy nano particle, and maintain catalyst stablizing in running environment.Carbon black, carbon fiber and carbon nano-tube etc. are current most popular catalyst carrier materials, have obtained research widely and application.
Recently, the research of Graphene has caused the great interest of people.Graphene is the cancellated individual layer nanometer sheet of a kind of bi-dimensional cellular by the monolayer carbon atomic building, have that conductivity is high, specific area is large and good chemical stability, at electrochemical energy storage and conversion field, having good application prospect, is the novel electro-catalyst carrier material of a class.Simultaneously, introduce foreign atom in the Graphene lattice, as contain B, contain N functional group, can regulate and control chemistry and the electronic structure of Graphene, obtained studying more widely and reporting thereby further improve its performance, particularly nitrogen-doped graphene.At present, take nitrogen-doped graphene as Pt and the Pt alloy catalyst of carrier be mainly to synthesize (Zhang L S, Liang X Q etc., Physical Chemistry Chemical Physics, 2010,12,12055-12059 by multistep reaction; Xiong B, Zhou Y K etc., Carbon, 2013,52,181-192), the graphene oxide of namely first take is raw material, prepares under certain conditions nitrogen-doped graphene, then on nitrogen-doped graphene supporting Pt or Pt alloy nano particle.Not only technical process is more complicated for the major defect of multistep processes, production cost is higher, and subsequent treatment has a certain impact to the character of nitrogen-doped graphene.
Summary of the invention
The present invention is intended to overcome the prior art defect, and purpose provides a kind of technique simply and the preparation method of the nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst that energy consumption is low; The catalytic activity of the kind nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst prepared by the method is high, good stability, nano particle is uniformly dispersed and particle diameter is controlled.
For achieving the above object, the technical solution used in the present invention is: in nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst, Pt base bianry alloy or Pt base ternary alloy are 5 ~ 30wt%, nitrogen-doped graphene is 70 ~ 95 wt%, and the particle diameter of Pt base bianry alloy or Pt base ternary alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 10wt%.
Described Pt base bianry alloy is a kind of in PtRu, PtCo, PtNi and PtFe; In bianry alloy: in Pt and Ru, Co, Ni and Fe, the ratio of the amount of substance of arbitrary element is 1 ︰ 3 ~ 3 ︰ 1.
Described Pt base ternary alloy is a kind of in PtRuCo, PtRuNi and PtRuFe; In ternary alloy three-partalloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and in Pt and Co, Ni, Fe, the ratio of the amount of substance of arbitrary element is 1 ︰ 3 ~ 3 ︰ 1.
The preparation method of described nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 60 ︰ 1100 ~ 2800 ︰ 500 ~ 1600.
(2) in described Monodispersed suspension, add metal salt solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: metal salt solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 30 ︰ 95 ~ 70; The concentration of graphene oxide solution is 2 ~ 10g/L; Metal salt solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 180 ℃, and insulation and condensing reflux 1 ~ 5 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst.
Described metal salt solution is RuCl
33H
2O solution, CoCl
26H
2O solution, NiCl
26H
2O solution, FeCl
36H
2O solution, RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution, RuCl
33H
2O solution and NiCl
26H
2The mixed liquor of O solution, RuCl
33H
2O solution and FeCl
36H
2A kind of in the mixed solution of O solution.
Owing to adopting technique scheme, the present invention compared with prior art has following outstanding feature:
(1) to adopt 1-METHYLPYRROLIDONE be that nitrogenous source carries out the nitrogen doping to Graphene in the present invention, and nitrogen content was regulated by addition, reaction temperature and the reaction time of controlling 1-METHYLPYRROLIDONE.Nitrogen-doped graphene is as carrier, and catalyst obviously improves the electro catalytic activity of methyl alcohol.
(2) the present invention adopts a step liquid phase reduction to prepare nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst.Compared with prior art, do not need first synthetic nitrogen doped graphene, do not need very high synthesis temperature yet; But the load of the doping of the nitrogen of Graphene and Pt base alloy nano particle is carried out simultaneously, reaction temperature is 90 ~ 180 ℃, the reaction time is 1 ~ 5 h, therefore technique is simple and energy consumption is low; Employing oil bath heating, keep in heating process stirring, and reactant is heated evenly; Adopt condensing reflux, can effectively maintain the stable of reaction system component; In catalyst, total metal content is controlled in 5 ~ 30wt% scope, and the utilance of noble metal is high.
(3) the nitrogen-doped graphene supporting Pt base alloy nano catalyst for preparing of the present invention, pass through transmission electron microscope observing: Pt base alloy nano particle high degree of dispersion is on the nitrogen-doped graphene surface, its particle size range is 0.5 ~ 4.5 nm, average grain diameter is 1.8 ~ 3.7 nm, and the XRD material phase analysis has (111), (200), (220), (311) face diffraction maximum of very strong Graphene (002) face diffraction maximum and Pt base alloy.Wherein the nitrogen-doped graphene specific area is large, good conductivity, and Pt base alloy nano particle decentralization is high, is uniformly dispersed, thereby can effectively improves the utilance of noble metal.
The present invention adopts three-electrode system to test its Electrocatalytic Oxidation of Methanol performance, the Nation solution of catalyst, 5wt% and absolute ethyl alcohol are mixed under ul-trasonic irradiation, this uniform slurry is coated on glass-carbon electrode, under 60 ℃, dries, as measuring work electrode.Measuring is carbon-point to electrode, and reference electrode is Ag/AgCl electrode (3.5 M KCl), and electrolyte is 1 M CH
3OH+0.5 M H
2SO
4.By cyclic voltammetry, estimate Pt base alloy nano eelctro-catalyst prepared by this embodiment electro catalytic activity to methanol oxidation, sweep speed is 10 ~ 200 mV/s, the peak current density of methanol electro-oxidizing is 45.3 ~ 817.3 A/g, the ratio of the peak current density that forward and reverse scanning is corresponding is 0.82 ~ 4.64, shows the very high electro catalytic activity to methanol oxidation and anti-CO poisoning capability.With chronoamperometry, estimate the stability of Pt base alloy nano eelctro-catalyst prepared by this embodiment, initial potential is 0.6 V, through 2000 s, the methanol oxidation current density of catalyst is 5 ~ 128.5 A/g, the current density conservation rate is 3.5 % ~ 53.5 %, therefore prepared nitrogen-doped graphene support type Pt base binary (PtRu, PtCo, PtNi, PtFe) and ternary (PtRuCo, PtRuNi, PtRuFe) the alloy nano eelctro-catalyst of the present invention has excellent stability to methanol electro-oxidizing.
Therefore, the present invention has the simple and low characteristics of energy consumption of technique, and prepared nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst catalytic activity is high, good stability, nano particle is uniformly dispersed and particle diameter is controlled.
The accompanying drawing explanation
Fig. 1 is the TEM figure of a kind of nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst of preparing of the present invention;
Fig. 2 is the particle diameter distribution histogram of the described eelctro-catalyst of Fig. 1;
Fig. 3 is the XRD figure of the described eelctro-catalyst of Fig. 1;
Fig. 4 is the anodic oxidation of methanol cyclic voltammetry curve of the described eelctro-catalyst of Fig. 1 under different scanning speed;
Fig. 5 is the electric current-time graph of the described eelctro-catalyst of Fig. 1.
Embodiment
The following examples have been described preparation process, sign and the performance test results of catalyst provided by the present invention, but catalyst provided by the invention is not restricted to following embodiment.
A kind of nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst and preparation method thereof.PtRu in described nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtRu alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 4 ~ 10 wt%.
In described PtRu alloy: Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Ru element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Ru alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10g/L; RuCl
33H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst.
A kind of nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst and preparation method thereof.PtRu in described nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst is 5 ~ 20wt%, and nitrogen-doped graphene is 80 ~ 95wt%, and the particle diameter of PtRu alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtRu alloy: Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Ru element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Ru alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10g/L; RuCl
33H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst.
A kind of nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst and preparation method thereof.PtCo in described nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtCo alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the nitrogen doping is 4 ~ 10 wt%.
In described PtCo alloy: Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Co element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Co alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that the pure ︰ ︰ 1-METHYLPYRROLIDONE of graphite olefinic oxide ︰ second two is 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add CoCl
26H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: CoCl
26H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10g/L; , CoCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst.
A kind of nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst and preparation method thereof.PtCo in described nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtCo alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtCo alloy: Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Co element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Co alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add CoCl
26H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: CoCl
26H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10g/L; CoCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Co alloy nano eelctro-catalyst.
Embodiment 5
A kind of nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst and preparation method thereof.PtNi in described nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 4 ~ 10 wt%.
In described PtNi alloy: Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Ni element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Ni alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add NiCl
26H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: NiCl
26H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10g/L; , NiCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst.
Embodiment 6
A kind of nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst and preparation method thereof.PtNi in described nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the content of nitrogen is 1 ~ 6 wt%.
In described PtNi alloy: Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Ni element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Ni alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add NiCl
26H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: NiCl
26H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10 g/L; NiCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Ni alloy nano eelctro-catalyst.
Embodiment 7
A kind of nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst and preparation method thereof.PtFe in described nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 4 ~ 10 wt%.
In described PtNi alloy: Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Fe element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Fe alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add FeCl
36H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: FeCl
36H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10g/L; , FeCl
36H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst.
Embodiment 8
A kind of nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst and preparation method thereof.PtFe in described nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtNi alloy: Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Fe element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment Fe alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add FeCl
36H
2O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: FeCl
36H
2O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10g/L; FeCl
36H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt Fe alloy nano eelctro-catalyst.
Embodiment 9
A kind of nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst and preparation method thereof.PtRuCo in described nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtRuCo alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 4 ~ 10 wt%.
In described PtRuCo alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Co element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuCo alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10 g/L; RuCl
33H
2O solution, CoCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst.
A kind of nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst and preparation method thereof.PtRuCo in described nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtRuCo alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtRuCo alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Co element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuCo alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein, RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10g/L; RuCl
33H
2O solution, CoCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuCo alloy nano eelctro-catalyst.
Embodiment 11
A kind of nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst and preparation method thereof.PtRuNi in described nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtRuNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 4 ~ 10 wt%.
In described PtRuNi alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Ni element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuNi alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and NiCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O solution and NiCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10g/L; RuCl
33H
2O solution, NiCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst.
Embodiment 12
A kind of nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst and preparation method thereof.PtRuNi in described nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtRuNi alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtRuNi alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Ni element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuNi alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and NiCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein, RuCl
33H
2O solution and NiCl
26H
2The mixed solution of O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10 g/L; RuCl
33H
2O solution, NiCl
26H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma oil bath under stirring condition step (2) obtained is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst.
Embodiment 13
A kind of nitrogen-doped graphene supporting Pt RuFe alloy nano eelctro-catalyst and preparation method thereof.PtRuNi in described nitrogen-doped graphene supporting Pt RuFe alloy nano eelctro-catalyst is 15 ~ 30 wt%, and nitrogen-doped graphene is 70 ~ 85 wt%, and the particle diameter of PtRuFe alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is for being 4 ~ 10 wt%.
In described PtRuFe alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru; Pt is 1 ︰ 3 ~ 1 ︰ 1 with the ratio of the amount of substance of Fe element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuFe alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 45 ︰ 1100 ~ 2000 ︰ 1000 ~ 1600.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and FeCl
36H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O solution and FeCl
36H
2The mixed solution of O solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 15 ~ 30 ︰ 70 ~ 85; The concentration of graphene oxide solution is 2 ~ 10 g/L; RuCl
33H
2O solution, FeCl
36H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 150 ℃, and insulation and condensing reflux 1 ~ 3 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuFe alloy nano eelctro-catalyst.
Embodiment 14
A kind of nitrogen-doped graphene supporting Pt RuFe alloy nano eelctro-catalyst and preparation method thereof.PtRuFe in described nitrogen-doped graphene supporting Pt RuFe alloy nano eelctro-catalyst is 5 ~ 20 wt%, and nitrogen-doped graphene is 80 ~ 95 wt%, and the particle diameter of PtRuFe alloy is 0.5 ~ 4.5 nm.
In described nitrogen-doped graphene, the doping of nitrogen is 1 ~ 6 wt%.
In described PtRuFe alloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru; Pt is 1 ︰ 1 ~ 3 ︰ 1 with the ratio of the amount of substance of Fe element.
The preparation method of the described nitrogen-doped graphene supporting Pt of the present embodiment RuFe alloy nano eelctro-catalyst is:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension.
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 45 ~ 60 ︰ 1800 ~ 2800 ︰ 500 ~ 1200.
(2) in described Monodispersed suspension, add RuCl
33H
2O solution and FeCl
36H
2The mixed solution of O solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma.Wherein: RuCl
33H
2O and FeCl
36H
2The mixed solution of O and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 20 ︰ 80 ~ 95; The concentration of graphene oxide solution is 2 ~ 10 g/L; RuCl
33H
2O solution, FeCl
36H
2O solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L.
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 120 ~ 180 ℃, and insulation and condensing reflux 2 ~ 5 h, obtain black suspension.
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt RuNi alloy nano eelctro-catalyst.
This embodiment compared with prior art has following outstanding feature:
(1) this embodiment employing 1-METHYLPYRROLIDONE is that nitrogenous source carries out the nitrogen doping to Graphene, and nitrogen content was regulated by addition, reaction temperature and the reaction time of controlling 1-METHYLPYRROLIDONE.Nitrogen-doped graphene is as carrier, and catalyst obviously improves the electro catalytic activity of methyl alcohol.
(2) this embodiment adopts a step liquid phase reduction to prepare nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst.Compared with prior art, do not need first synthetic nitrogen doped graphene, do not need very high synthesis temperature yet; But the load of the doping of the nitrogen of Graphene and Pt base alloy nano particle is carried out simultaneously, reaction temperature is 90 ~ 180 ℃, the reaction time is 1 ~ 5 h, therefore technique is simple and energy consumption is low; Employing oil bath heating, keep in heating process stirring, and reactant is heated evenly; Adopt condensing reflux, can effectively maintain the stable of reaction system component; In catalyst, total metal content is controlled in 5 ~ 30wt% scope, and the utilance of noble metal is high.
Nitrogen-doped graphene supporting Pt base alloy nano catalyst prepared by this embodiment, pass through transmission electron microscope observing: Pt base alloy nano particle high degree of dispersion is on the nitrogen-doped graphene surface, its particle size range is 0.5 ~ 4.5 nm, average grain diameter is 1.8 ~ 3.7 nm, and the XRD material phase analysis has (111), (200), (220), (311) face diffraction maximum of very strong Graphene (002) face diffraction maximum and Pt base alloy.Fig. 1 ~ Fig. 3 is TEM figure, particle diameter distribution histogram and the XRD figure about the prepared a kind of nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst of embodiment 1, and as can be seen from Figure 1: PtRu nano particle high degree of dispersion is on the nitrogen-doped graphene surface; As can be seen from Figure 2: particle size range is 0.5 ~ 4.5 nm, and average grain diameter is 2.3 nm; As can be seen from Figure 3: the XRD material phase analysis has (111), (200), (220), (311) face diffraction maximum of very strong Graphene (002) face diffraction maximum and PtRu alloy.
This embodiment adopts three-electrode system to test its Electrocatalytic Oxidation of Methanol performance, the Nation solution of catalyst, 5wt% and absolute ethyl alcohol are mixed under ul-trasonic irradiation, this uniform slurry is coated on glass-carbon electrode, under 60 ℃, dries, as measuring work electrode.Measuring is carbon-point to electrode, and reference electrode is Ag/AgCl electrode (3.5 M KCl), and electrolyte is 1 M CH
3OH+0.5 M H
2SO
4.By cyclic voltammetry, estimate Pt base alloy nano eelctro-catalyst prepared by this embodiment electro catalytic activity to methanol oxidation, sweep speed is 10 ~ 200 mV/s, the peak current density of methanol electro-oxidizing is 45.3 ~ 817.3 A/g, the ratio of the peak current density that forward and reverse scanning is corresponding is 0.82 ~ 4.64, shows the very high electro catalytic activity to methanol oxidation and anti-CO poisoning capability.With chronoamperometry, estimate the stability of Pt base alloy nano eelctro-catalyst prepared by this embodiment, initial potential is 0.6 V, through 2000 s, the methanol oxidation current density of catalyst is 5 ~ 128.5 A/g, the current density conservation rate is 3.5 % ~ 53.5 %, therefore prepared nitrogen-doped graphene support type Pt base binary (PtRu, PtCo, PtNi, PtFe) and ternary (PtRuCo, PtRuNi, PtRuFe) the alloy nano eelctro-catalyst of this embodiment has excellent stability to methanol electro-oxidizing.
Fig. 4 and Fig. 5 are about prepared anodic oxidation of methanol cyclic voltammetry curve and the electric current-time graph of a kind of nitrogen-doped graphene supporting Pt Ru alloy nano eelctro-catalyst under different scanning speed of embodiment 1; As can be seen from Figure 4: the peak current density of methanol electro-oxidizing is 405.3 ~ 717.3 A/g
PtRu, the ratio of the peak current density that forward and reverse scanning is corresponding is 1.12 ~ 1.64, shows the very high electro catalytic activity to methanol oxidation and anti-CO poisoning capability; As can be seen from Figure 5: use the stability of chronoamperometry evaluate catalysts as shown in Figure 5, initial potential is 0.6 V, and through 2000 s, the methanol oxidation current density of catalyst is 58.5 A/g
PtRu, the current density conservation rate is 13.5 %, shows that catalyst has good stability.
Therefore, this embodiment has the simple and low characteristics of energy consumption of technique, and prepared nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst catalytic activity is high, good stability, nano particle is uniformly dispersed and particle diameter is controlled.
Claims (6)
1. nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst, it is characterized in that in described eelctro-catalyst that Pt base bianry alloy or Pt base ternary alloy are 5 ~ 30wt%, nitrogen-doped graphene is 70 ~ 95wt%, and the particle diameter of Pt base bianry alloy or Pt base ternary alloy is 0.5 ~ 4.5 nm.
2. nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst as described in claim 1, the doping that it is characterized in that nitrogen in described nitrogen-doped graphene is 1 ~ 10wt%.
3. nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst as described in claim 1, is characterized in that described Pt base bianry alloy is a kind of in PtRu, PtCo, PtNi and PtFe; In bianry alloy: in Pt and Ru, Co, Ni and Fe, the ratio of the amount of substance of arbitrary element is 1 ︰ 3 ~ 3 ︰ 1.
4. nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst as described in claim 1, is characterized in that described Pt base ternary alloy is a kind of in PtRuCo, PtRuNi and PtRuFe; In ternary alloy three-partalloy: Pt is 1 ︰ 1 with the ratio of the amount of substance of Ru, and in Pt and Co, Ni, Fe, the ratio of the amount of substance of arbitrary element is 1 ︰ 3 ~ 3 ︰ 1.
5. the preparation method of nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst as claimed in claim 1, is characterized in that its preparation method comprises the steps:
(1) graphene oxide solution, ethylene glycol and 1-METHYLPYRROLIDONE are stirred, ultrasonic dispersion treatment 1 ~ 3h, obtain Monodispersed suspension;
Wherein the mass ratio of graphene oxide, ethylene glycol and 1-METHYLPYRROLIDONE is that graphite olefinic oxide ︰ second two pure ︰ 1-METHYLPYRROLIDONEs are 30 ~ 60 ︰ 1100 ~ 2800 ︰ 500 ~ 1600;
(2) in described Monodispersed suspension, add metal salt solution and H
2PtCl
66H
2O solution, stir, and ultrasonic dispersion treatment 1 ~ 3h, obtain presoma; Wherein: metal salt solution and H
2PtCl
66H
2Metallic element Zhi in O solution is with the mass ratio of ︰ graphene oxide is 5 ~ 30 ︰ 95 ~ 70; The concentration of graphene oxide solution is 2 ~ 10g/L; Metal salt solution and H
2PtCl
66H
2The concentration of O solution is 5 ~ 20 g/L;
(3) the presoma (2) step obtained oil bath under stirring condition is heated to 90 ~ 180 ℃, and insulation and condensing reflux 1 ~ 5 h, obtain black suspension;
(4) black suspension step obtained in is (3) carried out vacuum filtration, uses successively acetone, distilled water and absolute ethanol washing, and then vacuumize 24 h at ambient temperature, obtain nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst.
6. the preparation method of the nitrogen-doped graphene supporting Pt base alloy nano eelctro-catalyst described in a claim 4, is characterized in that described metal salt solution is RuCl
33H
2O solution, CoCl
26H
2O solution, NiCl
26H
2O solution, FeCl
36H
2O
Solution, RuCl
33H
2O solution and CoCl
26H
2The mixed solution of O solution, RuCl
33H
2O solution and NiCl
26H
2The mixed liquor of O solution, RuCl
33H
2O solution and FeCl
36H
2A kind of in the mixed solution of O solution.
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