CN103816894B - Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof - Google Patents
Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.Its technical scheme is: by graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O be 70 ~ 90: 15 ~ 65: 5 ~ 40 raw material stir, add urea or boric acid wherein, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma; Ground by presoma, by the precursor powder solid phase reaction 5 ~ 120min under inert gas shielding and 400 ~ 1000 DEG C of conditions obtained after grinding, cooling, obtains black solid powder; Black solid powder is ground, washing, dry, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst; Wherein, PtRu alloy is 10 ~ 30wt%, and doping type Graphene is 70 ~ 90wt%.The present invention has the advantages that technique is simple and energy consumption is low, and prepared product catalytic activity is high, all even size tunable of good stability, nanoparticle dispersion.
Description
Technical field
The invention belongs to fuel cell catalyst technical field.Be specifically related to a kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.
Background technology
DMFC has that structure is simple, cold-starting speed is fast, fuel is cheap and easy to get, cleanliness without any pollution, specific energy are high and energy conversion efficiency high; be expected to the main flow power supply becoming future portable electronic product and electric automobile, aircraft etc., and the energy crisis can alleviated because the fossil energy such as coal, oil day by day exhausted causes and because of problems such as the environmental pollutions that uses fossil energy to bring.
Pt is known, use more widely catalyst active better to methanol electro-oxidizing-catalyzing.But, be that catalyst also exists high cost and opposing CO similar intermediate product and poisons the problems such as ability is poor with metal platinum.Research finds, Ru atom can adsorb the oxygenate of some similar OH-in methanol oxidation process, and these oxygenates can react by similar intermediate product with the CO being adsorbed on Pt atomic surface, thus alleviate the poisoning of Pt catalyst.Therefore, adopt PtRu alloy as anode catalysts for direct methanol fuel cell, effectively can improve activity and the utilization rate of precious metals pt catalyst.
In order to improve the utilization rate of noble metal catalyst further, reduce the cost of DMFC, adopt the material load Pt nano particles such as carbon black, Carbon fibe, CNT, Graphene, the size of Pt nano particle, pattern and domain size distribution can be adjusted, improve the performance of catalyst.Wherein, Graphene has the features such as electric conductivity is high, specific area is large, chemical stability is good, is a kind of novel, efficient catalyst carrier material., Graphene is adulterated meanwhile, as introduced the foreign atoms such as B, N in lattice, electronics and the band structure of Graphene can be regulated and controled, and improve its physics, chemical property further.At present, Pt and the Pt alloy catalyst being carrier with doping type Graphene is mainly by multistep reaction synthesis (ZhangLS, LiangXQ etc., PhysicalChemistryChemicalPhysics, 2010,12,12055-12059; XiongB, ZhouYK etc., Carbon, 2013,52,181-192), namely first adulterate to Graphene, then at doping type graphenic surface supporting Pt or Pt alloy nano particle, this preparation method's technical process is more complicated, the production cycle is longer, production cost is higher and be unfavorable for a large amount of production.
Summary of the invention
The object of the invention is to overcome prior art defect, the preparation method of the doping type graphene-supported PtRu alloy nano eelctro-catalyst that a kind of technique is simple and energy consumption is low is provided; The catalytic activity of the doping type prepared by the method graphene-supported PtRu alloy nano eelctro-catalyst is high, all even size tunable of good stability, nanoparticle dispersion.
To achieve these goals, the technical solution used in the present invention is: in described eelctro-catalyst: PtRu alloy is 10 ~ 30wt%, and doping type Graphene is 70 ~ 90wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm.
Doped chemical in described doping type Graphene is the one in N and B; The doping of N or B is 1 ~ 10wt% of doping type Graphene.
In described PtRu alloy, the ratio of the amount of substance of Pt and Ru is 1: (0.5 ~ 2).
The preparation method of described doping type graphene-supported PtRu alloy nano eelctro-catalyst, its concrete steps are:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 70 ~ 90: 15 ~ 65: 5 ~ 40; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L.
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma.
Wherein, alloy is the one in urea and boric acid, and the mass ratio of alloy and graphene oxide is (1 ~ 3) ︰ 1.
(3) presoma that step (2) obtains is ground, obtain precursor powder.
(4) precursor powder step (3) obtained is solid phase reaction 5 ~ 120min under inert gas shielding and 400 ~ 1000 DEG C of conditions, then cools, obtains black solid powder.
Wherein, inert gas is the one in nitrogen and argon gas.
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
Owing to adopting technique scheme, the present invention compared with prior art has following outstanding feature:
(1) the present invention adopts urea to be nitrogenous source to Graphene to carry out N doping or adopt boric acid to be that boron doping is carried out to Graphene in boron source, and the content of nitrogen or boron regulates by controlling the addition of urea or boric acid, reaction temperature and reaction time; Alloy is directly dissolved in graphene oxide solution, and alloy fully contacts with graphene oxide, can realize the doping of Graphene quickly and efficiently; Doping type Graphene is as carrier, and PtRu alloy nano particle is uniformly dispersed, and the electro catalytic activity of catalyst to methyl alcohol significantly improves.
(2) the present invention adopts a step solid phase reduction legal system for doping type graphene-supported PtRu alloy nano eelctro-catalyst, compared with prior art, does not need first synthesizing doped type Graphene, does not also need the reaction time grown very much; But the load of the doping of Graphene and PtRu alloy nano particle is carried out simultaneously, reaction temperature is 400 ~ 1000 DEG C, and the reaction time is 5 ~ 120min, therefore technique is simple, and energy consumption is low; Adopt inert gas shielding, effectively can prevent the oxidation of Graphene and noble metal; Adopt the method that high temperature burns till and cools fast, can by controlling size and the domain size distribution of firing temperature and temperature retention time control PtRu alloy particle; In catalyst, noble metal total content is controlled within the scope of 10 ~ 30wt%, and the utilization rate of noble metal is high.
Doping type prepared by the present invention graphene-supported PtRu alloy nano eelctro-catalyst, by transmission electron microscope observing: PtRu alloy nano particle is highly dispersed at doping type graphenic surface, its particle size range is (111), (200), (220) face diffraction maximum that 0.5 ~ 9.5nm, XRD material phase analysis has very strong Graphene (002) face diffraction maximum and PRu alloy.Wherein doping type Graphene specific area is large, and PtRu alloy nano particle decentralization is high, thus effectively can improve the utilization rate 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, dries at 60 DEG C, as measuring working electrode.Measuring is carbon-point to electrode, and reference electrode is Ag/AgCl electrode (3.5MKCl), and electrolyte is 1MCH
3oH+0.5MH
2sO
4.PtRu alloy nano eelctro-catalyst prepared by the present invention is evaluated to the electro catalytic activity of methanol oxidation by cyclic voltammetry, sweep speed is 10mV/s, the peak current density of methanol electro-oxidizing is 15.3 ~ 257.3A/g, the ratio of the peak current density that forward and reverse scanning is corresponding is 1.32 ~ 3.51, shows the very high electro catalytic activity to methanol oxidation and CO tolerance catalysts ability.The stability of doping type graphene-supported PtRu alloy nano eelctro-catalyst prepared by the present invention is evaluated with chronoamperometry, initial potential is 0.6V, through 500s, the methanol oxidation current density of catalyst is 5 ~ 108.5A/g, current density conservation rate is 8.9 ~ 43.1%, has excellent stability to methanol electro-oxidizing.
Therefore, the present invention has the advantages that technique is simple and energy consumption is low, and prepared doping type graphene-supported PtRu alloy nano eelctro-catalyst catalytic activity is high, all even size tunable of good stability, nanoparticle dispersion.
Accompanying drawing explanation
Fig. 1 is the TEM figure of a kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst prepared by the present invention;
The domain size distribution histogram that Fig. 2 is eelctro-catalyst described in Fig. 1;
The XRD that Fig. 3 is eelctro-catalyst described in Fig. 1 schemes;
Fig. 4 is the anodic oxidation of methanol cyclic voltammetry curve figure of eelctro-catalyst described in Fig. 1 under 10mV/s sweep speed;
The current versus time curve figure that Fig. 5 is eelctro-catalyst described in Fig. 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, preparation process of the present invention, sign and the performance test results are further described, but catalyst provided by the invention is not restricted to following case study on implementation.
embodiment 1
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.In described eelctro-catalyst: PtRu alloy is 25 ~ 30wt%, doping type Graphene is 70 ~ 75wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm.
Doped chemical in described doping type Graphene is N; The doping of N is 7 ~ 10wt% of doping type Graphene.
In described PtRu alloy, the ratio of the amount of substance of Pt and Ru is 1: (1.6 ~ 2).
The preparation method of described doping type graphene-supported PtRu alloy nano eelctro-catalyst, its concrete steps are:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 70 ~ 75: 50 ~ 65: 30 ~ 40; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L.
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma.
Wherein, alloy is urea, and the mass ratio of urea and graphene oxide is (2.5 ~ 3) ︰ 1.
(3) presoma that step (2) obtains is ground, obtain precursor powder.
(4) precursor powder step (3) obtained is solid phase reaction 90 ~ 120min under inert gas shielding and 700 ~ 1000 DEG C of conditions, then cools, obtains black solid powder.
Wherein, inert gas is nitrogen.
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
embodiment 2
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.In described eelctro-catalyst: PtRu alloy is 20 ~ 25wt%, doping type Graphene is 75 ~ 80wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm.
Doped chemical in described doping type Graphene is N; The doping of N is 5 ~ 8wt% of doping type Graphene.
In described PtRu alloy, the ratio of the amount of substance of Pt and Ru is 1: (1.2 ~ 1.6).
The preparation method of described doping type graphene-supported PtRu alloy nano eelctro-catalyst, its concrete steps are:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 75 ~ 80: 40 ~ 55: 20 ~ 30; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L.
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma.
Wherein, alloy is urea, and the mass ratio of urea and graphene oxide is (2 ~ 2.5) ︰ 1.
(3) presoma that step (2) obtains is ground, obtain precursor powder.
(4) precursor powder step (3) obtained is solid phase reaction 60 ~ 90min under inert gas shielding and 600 ~ 900 DEG C of conditions, then cools, obtains black solid powder.
Wherein, inert gas is argon gas.
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
embodiment 3
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.In described eelctro-catalyst: PtRu alloy is 15 ~ 20wt%, doping type Graphene is 80 ~ 85wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm.
Doped chemical in described doping type Graphene is N; The doping of N is 3 ~ 6wt% of doping type Graphene.
In described PtRu alloy, the ratio of the amount of substance of Pt and Ru is 1: (0.8 ~ 1.2).
The preparation method of described doping type graphene-supported PtRu alloy nano eelctro-catalyst, its concrete steps are:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 80 ~ 85: 30 ~ 45: 10 ~ 20; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L.
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma.
Wherein, alloy is urea, and the mass ratio of urea and graphene oxide is (1.5 ~ 2) ︰ 1.
(3) presoma that step (2) obtains is ground, obtain precursor powder.
(4) precursor powder step (3) obtained is solid phase reaction 30 ~ 60min under inert gas shielding and 500 ~ 800 DEG C of conditions, then cools, obtains black solid powder.
Wherein, inert gas is nitrogen.
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
embodiment 4
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.In described eelctro-catalyst: PtRu alloy is 10 ~ 15wt%, doping type Graphene is 85 ~ 90wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm.
Doped chemical in described doping type Graphene is N; The doping of N is 1 ~ 4wt% of doping type Graphene.
In described PtRu alloy, the ratio of the amount of substance of Pt and Ru is 1: (0.5 ~ 0.8).
The preparation method of described doping type graphene-supported PtRu alloy nano eelctro-catalyst, its concrete steps are:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 85 ~ 90: 15 ~ 35: 5 ~ 15; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L.
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma.
Wherein, alloy is urea, and the mass ratio of urea and graphene oxide is (1 ~ 1.5) ︰ 1.
(3) presoma that step (2) obtains is ground, obtain precursor powder.
(4) precursor powder step (3) obtained is solid phase reaction 5 ~ 30min under inert gas shielding and 400 ~ 700 DEG C of conditions, then cools, obtains black solid powder.
Wherein, inert gas is argon gas.
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
embodiment 5
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.Except following technical parameter, all the other are with embodiment 1:
Doped chemical in described doping type Graphene is B; Described alloy is boric acid; Described inert gas is argon gas.
embodiment 6
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.Except following technical parameter, all the other are with embodiment 2:
Doped chemical in described doping type Graphene is B; Described alloy is boric acid; Described inert gas is nitrogen.
embodiment 7
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.Except following technical parameter, all the other are with embodiment 3:
Doped chemical in described doping type Graphene is B; Described alloy is boric acid; Described inert gas is argon gas.
embodiment 8
A kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof.Except following technical parameter, all the other are with embodiment 4:
Doped chemical in described doping type Graphene is B; Described alloy is boric acid; Described inert gas is nitrogen.
This detailed description of the invention compared with prior art has following outstanding feature:
(1) this detailed description of the invention adopts urea to be nitrogenous source to Graphene to carry out N doping or adopt boric acid to be that boron doping is carried out to Graphene in boron source, and the content of nitrogen or boron regulates by controlling the addition of urea or boric acid, reaction temperature and reaction time; Alloy is directly dissolved in graphene oxide solution, and alloy fully contacts with graphene oxide, can realize the doping of Graphene quickly and efficiently; Doping type Graphene is as carrier, and PtRu alloy nano particle is uniformly dispersed, and the electro catalytic activity of catalyst to methyl alcohol significantly improves.
(2) this detailed description of the invention adopts a step solid phase reduction legal system for doping type graphene-supported PtRu alloy nano eelctro-catalyst, compared with prior art, does not need first synthesizing doped type Graphene, does not also need the reaction time grown very much; But the load of the doping of Graphene and PtRu alloy nano particle is carried out simultaneously, reaction temperature is 400 ~ 1000 DEG C, and the reaction time is 5 ~ 120min, therefore technique is simple, and energy consumption is low; Adopt inert gas shielding, effectively can prevent the oxidation of Graphene and noble metal; Adopt the method that high temperature burns till and cools fast, can by controlling size and the domain size distribution of firing temperature and temperature retention time control PtRu alloy particle; In catalyst, noble metal total content is controlled within the scope of 10 ~ 30wt%, and the utilization rate of noble metal is high.
Doping type graphene-supported PtRu alloy nano eelctro-catalyst prepared by this detailed description of the invention, PtRu alloy nano particle is highly dispersed at doping type graphenic surface, and its particle size range is 0.5 ~ 9.5nm, has the face diffraction maximum of very strong Graphene and PRu alloy.Wherein doping type Graphene specific area is large, and PtRu alloy nano particle decentralization is high, thus effectively can improve the utilization rate of noble metal.As shown in Figure of description: Fig. 1 ~ Fig. 3 is a kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst TEM figure, domain size distribution histogram and the XRD figure that prepare about embodiment 1; As can be seen from Figure 1, PtRu alloy nano particle is highly dispersed at doping type graphenic surface; As can be seen from Figure 2, its particle size range is 0.5 ~ 9.5nm; As can be seen from Figure 3, XRD material phase analysis has (111), (200), (220) face diffraction maximum of very strong Graphene (002) face diffraction maximum and PtRu alloy.
This detailed description of the 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, dries at 60 DEG C, as measuring working electrode.Measuring is carbon-point to electrode, and reference electrode is Ag/AgCl electrode (3.5MKCl), and electrolyte is 1MCH
3oH+0.5MH
2sO
4.PtRu alloy nano eelctro-catalyst prepared by this detailed description of the invention is evaluated to the electro catalytic activity of methanol oxidation by cyclic voltammetry, sweep speed is 10mV/s, the peak current density of methanol electro-oxidizing is 15.3 ~ 257.3A/g, the ratio of the peak current density that forward and reverse scanning is corresponding is 1.32 ~ 3.51, shows the very high electro catalytic activity to methanol oxidation and CO tolerance catalysts ability.The stability of doping type graphene-supported PtRu alloy nano eelctro-catalyst prepared by this detailed description of the invention is evaluated with chronoamperometry, initial potential is 0.6V, through 500s, the methanol oxidation current density of catalyst is 5 ~ 108.5A/g, current density conservation rate is 8.9 ~ 43.1%, therefore the doping type graphene-supported PtRu alloy nano eelctro-catalyst prepared by this detailed description of the invention has excellent stability to methanol electro-oxidizing.Fig. 4 ~ Fig. 5 is the anodic oxidation of methanol cyclic voltammetry curve of a kind of doping type graphene-supported PtRu alloy nano eelctro-catalyst under 10mV/s sweep speed and current versus time curve prepared about embodiment 1, as can be seen from Figure 4, the peak current density of methanol electro-oxidizing is 229.2A/g, the ratio of the peak current density that forward and reverse scanning is corresponding is 2.13, shows the very high electro catalytic activity to methanol oxidation and CO tolerance catalysts ability; As can be seen from Figure 5, through 500s, the methanol oxidation current density of catalyst is 95.3A/g, and current density conservation rate is 33.7%, shows that catalyst has good stability.
Therefore, this detailed description of the invention has the advantages that technique is simple and energy consumption is low, and prepared doping type graphene-supported PtRu alloy nano eelctro-catalyst catalytic activity is high, all even size tunable of good stability, nanoparticle dispersion.
Claims (3)
1. a doping type graphene-supported PtRu alloy nano eelctro-catalyst, is characterized in that in described eelctro-catalyst: PtRu alloy is 10 ~ 30wt%, and doping type Graphene is 70 ~ 90wt%; The particle diameter of PtRu alloy is 0.5 ~ 9.5nm;
The step of the preparation method of described eelctro-catalyst is:
(1) by graphene oxide solution, H
2ptCl
66H
2o solution and RuCl
33H
2o solution stirs, and obtains Monodispersed suspension;
Wherein, graphene oxide: H
2ptCl
66H
2o: RuCl
33H
2the mass ratio of O is 70 ~ 90: 15 ~ 65: 5 ~ 40; The concentration of graphene oxide solution is 2 ~ 10g/L, H
2ptCl
66H
2the concentration of O solution is 5 ~ 20g/L, RuCl
33H
2the concentration of O solution is 5 ~ 20g/L;
(2) add alloy in the Monodispersed suspension obtained to step (1), after stirring and dissolving, freeze-day with constant temperature under stirring and 20 ~ 60 DEG C of conditions, obtains presoma;
Wherein, alloy is the one in urea and boric acid, and the mass ratio of alloy and graphene oxide is (1 ~ 3) ︰ 1;
(3) presoma that step (2) obtains is ground, obtain precursor powder;
(4) precursor powder step (3) obtained is solid phase reaction 5 ~ 120min under inert gas shielding and 400 ~ 1000 DEG C of conditions, then cools, obtains black solid powder;
Wherein, inert gas is the one in nitrogen and argon gas;
(5) the black solid powder that step (4) obtains is ground, use distilled water and absolute ethanol washing successively, then at 10 ~ 80 DEG C of freeze-day with constant temperature, obtained doping type graphene-supported PtRu alloy nano eelctro-catalyst.
2. as described in claim 1 doping type graphene-supported PtRu alloy nano eelctro-catalyst, the doped chemical that it is characterized in that in described doping type Graphene is the one in N and B; The doping of N or B is 1 ~ 10wt% of doping type Graphene.
3. doping type graphene-supported PtRu alloy nano eelctro-catalyst as described in claim 1, is characterized in that the ratio of the amount of substance of Pt and Ru in described PtRu alloy is 1: (0.5 ~ 2).
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| US9847534B2 (en) * | 2012-04-26 | 2017-12-19 | Indian Institute Of Technology Madras | Metal-alloy graphene nanocomposites and methods for their preparation and use |
| CN105435780A (en) * | 2015-12-29 | 2016-03-30 | 南京大学（苏州）高新技术研究院 | Nano platinum-ruthenium alloy supporting nitrogen-doped graphene catalyst |
| CN107732260A (en) * | 2017-09-26 | 2018-02-23 | 天津工业大学 | A kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure |
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| CN109482214A (en) * | 2018-10-23 | 2019-03-19 | 深圳市本征方程石墨烯技术股份有限公司 | The catalyst and preparation method of a kind of graphene-supported ruthenium metal and application |
| CN109596686B (en) * | 2018-12-06 | 2020-08-04 | 山西大学 | Electrochemical sensor for simultaneously detecting guanine and adenine and preparation method thereof |
| CN114512687B (en) * | 2020-10-23 | 2023-11-28 | 中国石油化工股份有限公司 | Carbon-supported noble metal nano catalyst and preparation method and application thereof |
| CN114497583B (en) * | 2022-01-12 | 2024-05-07 | 青岛创启新能催化科技有限公司 | Preparation method of PtRu/CN catalyst for fuel cell |
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| CN101740786A (en) * | 2009-12-14 | 2010-06-16 | 浙江大学 | PtRu/graphene nano electro-catalyst and preparation method thereof |
| WO2012088678A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt-ru nano-alloy/graphene catalyst, preparation method and use thereof |
| KR20120121716A (en) * | 2011-04-27 | 2012-11-06 | 한국지질자원연구원 | Pt/GR nanocomposites and method for producing thesame |
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| CN103413951A (en) * | 2013-08-28 | 2013-11-27 | 武汉科技大学 | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof |
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| CN101740786A (en) * | 2009-12-14 | 2010-06-16 | 浙江大学 | PtRu/graphene nano electro-catalyst and preparation method thereof |
| WO2012088678A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt-ru nano-alloy/graphene catalyst, preparation method and use thereof |
| KR20120121716A (en) * | 2011-04-27 | 2012-11-06 | 한국지질자원연구원 | Pt/GR nanocomposites and method for producing thesame |
| KR20130001876A (en) * | 2011-06-28 | 2013-01-07 | (주) 디에이치홀딩스 | Method for manufacturing catalyst for fuel cell |
| CN103212408A (en) * | 2013-02-28 | 2013-07-24 | 北京化工大学常州先进材料研究院 | Preparation method of high-CO-toxicity-resistant Pt-M/graphene catalyst |
| CN103332687A (en) * | 2013-07-11 | 2013-10-02 | 黑龙江大学 | Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source |
| CN103413951A (en) * | 2013-08-28 | 2013-11-27 | 武汉科技大学 | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof |
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