CN103894187B - The preparation method of fuel cell Pt/Graphene catalyst - Google Patents
The preparation method of fuel cell Pt/Graphene catalyst Download PDFInfo
- Publication number
- CN103894187B CN103894187B CN201410105211.1A CN201410105211A CN103894187B CN 103894187 B CN103894187 B CN 103894187B CN 201410105211 A CN201410105211 A CN 201410105211A CN 103894187 B CN103894187 B CN 103894187B
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- graphite oxide
- catalyst
- fuel cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 64
- 239000010439 graphite Substances 0.000 claims abstract description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- -1 platinum ion Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method of fuel cell Pt/Graphene catalyst, its method is as follows: (1) adopts the Hummers method improved to prepare graphite oxide; (2) graphite oxide grind into powder, calcines in Muffle furnace, obtains expansion graphite oxide; (3) microwave assistant glycol method is adopted to prepare the catalyst of graphene-supported platinum.The present invention adopts the graphite oxide of expansion as the presoma of reaction to prepare Pt/Graphene catalyst, and do not add dispersion aids in course of reaction, its advantage makes the reduction of the Graphene of product more thorough, and avoid the catalytic activity that remaining dispersion aids affects catalyst, thus make the hydrogen reduction performance of product better.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, this catalyst application is in fuel cell.
Background technology
Current commercial fuel cell cathod catalyst is the catalyst of platinum C catalyst and activated carbon supported platinum, and platinum is expensive and the corrosion resistance of active carbon is not very well, is the major reason that fuel cell does not have the marketization at present.Under these conditions, scientific researcher is studied it, is devoted to the catalyst working out low cost, reduces the cost of fuel cell, thus makes fuel cell can realize the target of industrialization early.
Catalytic activity is high, good stability, corrosion resistant catalyst are that fuel battery cathod catalyst realizes business-like key point.In loaded catalyst, carrier serves crucial effect, a lot of document reports this point, and research is expanded to various catalyst carrier, wherein mainly contain: carbon black (acetylene black, VulcanXC-72 active carbon and BleakPearl2000 etc.), CNT, Graphene.Studies have found that, Graphene as carrier than other two kinds of carriers stability in the electrolytic solution and catalytic activity all better.And since A.Geim and the K.Novoselov professor of Univ Manchester UK in 2004 finds Graphene, the research boom of Graphene is always surging.Graphene (Graphene) is a kind of by SP
2the monolayer species of two-dimentional crystalline flake graphite after peeling off of hydbridized carbon atoms form, heat endurance is better than other forms of carbon.Theoretical surface is long-pending is about 2600m
2/ g, this two-dimensional catalysts carrier making Graphene become desirable.And due to graphene-structured be plane hexagonal lattice, can be regarded as the graphitic molecules that one deck is stripped, each carbon atom is sp
2hydridization, and contribute the electronics on residue p track to form large π key, pi-electron can move freely, and makes it have unique electric conductivity, and in addition, adopt natural flake graphite as original raw material, cost is lower, and has remarkable corrosion resistance.These excellent character make it can be used as the foundation of the theoretical research of fuel battery cathod catalyst carrier.
Summary of the invention
The object of this invention is to provide a kind of preparation method of fuel cell Pt/Graphene catalyst, the graphite oxide expanded is adopted to prepare Pt/Graphene catalyst as the presoma of reaction, and do not add dispersion aids in course of reaction, its advantage makes the reduction of the Graphene of product more thorough, and avoid the catalytic activity that remaining dispersion aids affects catalyst, thus make the hydrogen reduction performance of product better.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of fuel cell Pt/Graphene catalyst, adopt the graphite oxide of expansion, the ethylene glycol solution of chloroplatinic acid as the presoma of reaction, microwave certain hour can prepare the catalyst (Pt/Graphene) of graphene-supported platinum, and its concrete steps are as follows:
(1) preparation of graphite oxide
250ml there-necked flask is placed in ice-water bath, 80 ~ 120ml concentrated sulfuric acid is poured in there-necked flask, and add crystalline flake graphite (Graphite) and 0.5 ~ 1.5 gram of sodium nitrate of 1 ~ 3 gram, start mechanical agitation.In 1 ~ 4 hour, slowly add the potassium permanganate powder of 10 ~ 15 grams, stir 2 ~ 10 hours in ice bath, this is chilling process; Then be placed in oil bath, timing is started when temperature rises to 35 ~ 40 DEG C, heated at constant temperature is after 5 ~ 20 hours at this temperature, slowly add the deionized water of 80 ~ 160ml in mixed solution, when temperature rises to 85 DEG C ~ 95 DEG C, continue heating after 15 ~ 30 minutes, there-necked flask is taken out from oil bath pan, be cooled to room temperature, add the hydrogenperoxide steam generator of 10 ~ 30ml, solution becomes glassy yellow from brown, then washs to solution in neutral successively by hydrochloric acid and deionized water, vacuum drying.
In this step, the mass concentration of described hydrogenperoxide steam generator is 30%.
In this step, the volumetric concentration of described hydrochloric acid is 10%.
(2) preparation of expansion graphite oxide (ThermalExpandedGraphiteOxide, TGO)
By the graphite oxide grind into powder that step (1) is prepared, calcine 30 ~ 50 seconds at 800 ~ 1000 DEG C in Muffle furnace, make its rapid expanding, obtain expansion graphite oxide.
(3) preparation of graphene-supported platinum catalyst
Microwave assistant glycol method is adopted to prepare the catalyst of graphene-supported platinum, its preparation method is as follows: take 3 ~ 6mg expansion graphite oxide and be placed in beaker, add the ethylene glycol of 30 ~ 60ml and account for the deionized water of total solvent volume 0 ~ 50%, stir and ultrasonic 20 ~ 40 minutes, the chloroplatinic acid ethylene glycol solution that 0.1 ~ 0.3ml concentration is 0.0386mol/L is added in ultrasonic procedure, adjust ph 7 ~ 9 after stirring, continue stirring and within 10 ~ 20 minutes, to be placed in microwave reactor microwave 1 ~ 3 minute, room temperature is cooled to after reaction terminates, filter, washing, dry, obtaining platinum content is that the Pt/Graphene sample of 20wt.% is for subsequent use.
In this step, the mass ratio of described expansion graphite oxide and ethylene glycol is preferably 1: 5.
In this step, the described microwave time is preferably 50s-(suspending 30s)-60s-(suspending 40s)-60s
In this step, described pH value is preferably 7.
In this step, the volume that the addition of described deionized water accounts for total solvent is preferably 30%.
The present invention uses the method for microwave radiation technology ethylene glycol to prepare the catalyst of graphene-supported platinum, the Pt/Graphene catalyst oxygen reduction performance prepared when adding 30% deionized water, under the microwave time is 50s-(suspending 30s)-60s-(suspending 40s)-60s condition is best, and half wave potential is 0.65V.
Compared with prior art, the present invention does not only use the material such as surfactant, dispersion aids, and reaction raw materials adopts the graphite oxide after expanding to be presoma instead of directly adopts graphite oxide to be presoma.Advantage mainly contains two aspects: one be expand after graphite oxide comparatively fluffy, specific area is large.After expanding, it still having the existence of oxygen-containing functional group, is pt
4+absorption provide binding site, issue raw reduction reaction in the radiation of microwave.Due to its large surface area, platinum particles can be evenly distributed on carrier thus improve the catalytic activity of nano particle.Two is in preparation process, add isopropyl alcohol unlike traditional preparation method, the dispersion aids such as polyvinylpyrrolidone, but the ethylene glycol solution directly adopting water content 30% is reducing agent, make that the material of preparation does not have other impurity, comparatively " totally ", and the addition of graphite oxide after expanding during reaction is 1: 5 (unit mg) with the ratio of the amount of ethylene glycol, so both reduce the viscosity of solvent, make again solvents a large amount of in ultrasonic procedure can insert the interlayer of graphite oxide simultaneously, it is made to peel off better, metal can well be dispersed on carrier, uniform load.Pt/Graphene catalyst oxygen reduction performance prepared in the present invention is good, and stability is high, can be durable for a long time.
Accompanying drawing explanation
Fig. 1 is experiment flow figure;
The linear scan curve map of the material of Fig. 2 prepared by embodiment 1;
The linear scan curve map of the material of Fig. 3 prepared by embodiment 2;
The linear scan curve map of the material of Fig. 4 prepared by embodiment 3;
Fig. 5 is that standard P DF (card number is 23-0298) the card XRD of platinum schemes;
Fig. 6 is the XRD figure of crystalline flake graphite (a), graphite oxide (b), expansion graphite oxide (c), Pt/Graphene catalyst (d);
Fig. 7 is the transmission electron microscope picture of Pt/Graphene catalyst in embodiment 4;
Fig. 8 is the grain size distribution of Pt/Graphene catalyst in embodiment 4;
Fig. 9 is the cyclic voltammogram of Pt/Graphene catalyst (a) and commercial catalysts (b) in embodiment 4;
Figure 10 is the linear scan figure of Pt/Graphene catalyst (a) and commercial catalysts (b) in embodiment 4;
Figure 11 is the time current curve map of 4Pt/Graphene catalyst (a) and commercial catalysts (b) in embodiment.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
As shown in Figure 1, the present embodiment prepares Pt/Graphene catalyst in accordance with the following steps:
(1) preparation of graphite oxide
Since Brodie prepared in 1855 the history that graphite oxide (GraphiteOxide, GO) had for 105 more than ten years so far, period has worked out the multiple method preparing graphite oxide.Preparation method main at present has three kinds, that is: Brodie method, Staudenmaier method and Hummers method.Wherein Hummers method preparation process ageing relatively better and also safer in preparation process, be one the most frequently used at present.The present invention, on the basis of original Hummers, makes improvements, and adopts the flow process of low temperature intercalation, middle temperature deep oxidation, high temperature exhaustive oxidation to prepare graphite oxide.As shown in Figure 1, concrete steps are as follows:
250ml there-necked flask is placed in ice-water bath, the 100ml concentrated sulfuric acid is poured in there-necked flask, and add crystalline flake graphite (Graphite) and 1 gram of sodium nitrate of 2 grams, start mechanical agitation.In 3 hours, slowly add the potassium permanganate powder of 15 grams, stir 6 hours in ice bath, this is chilling process; Then be placed in oil bath, timing is started when temperature rises to 35 DEG C, middle temperature heating is after 16 hours, after slowly adding the deionized water (needing to install condensing unit) of 160ml, at 90 DEG C, heat 15 minutes, there-necked flask is taken out from oil bath pan, to be cooled to room temperature time, add the hydrogenperoxide steam generator of the mass fraction 30% of 12ml, solution becomes glassy yellow from brown, then with 2L volume fraction be 10% hydrochloric acid and deionized water wash to solution in neutral successively, vacuum drying.
This step adopts the Hummers method improved to prepare graphite oxide, and this method raw material crystalline flake graphite cost used is lower, and course of reaction safety, easily controls, and the graphite oxide degree of oxidation that the graphite oxide prepared is prepared compared to additive method is better.
(2) preparation of expansion graphite oxide (ThermalExpandedGraphiteOxide, TGO)
By the graphite oxide grind into powder prepared, calcine 30 seconds at 800 ~ 1000 DEG C in Muffle furnace, rapid expanding, obtains expansion graphite oxide.
(3) preparation of graphene-supported platinum catalyst
In order to contrast the impact of microwave time on catalyst performance, change the performance of microwave time study catalyst in the present embodiment.Operating procedure is as follows:
Microwave assistant glycol method is adopted to prepare the catalyst that platinum mass fraction is the graphene-supported platinum of 20%.Preparation method: the expansion graphite oxide taking 5mg is placed in beaker, add the ethylene glycol of 50ml and a certain amount of deionized water, stir and ultrasonic 30 minutes, the chloroplatinic acid ethylene glycol solution that 0.16ml concentration is 0.0386mol/L is added in ultrasonic procedure, stir one hour, stir 10 minutes again with after the NaOH ethylene glycol solution adjust ph of 0.5mol/L, be placed in microwave reactor microwave, microwave set of time is as shown in following table 1-1.Be cooled to room temperature after reaction terminates, with filtering with microporous membrane, cleaning solution is absolute ethyl alcohol, after washing three times, is put in 45 DEG C of vacuum drying chambers and dries, obtain Pt/Graphene sample for subsequent use.
Different microwave set of time catalog data during table 1-1 Kaolinite Preparation of Catalyst
| Catalyst is numbered | Microwave time/s |
| a | 2 ~ 5 [50s-(10s)] cycle |
| b | 30s-(40s)-60s-(50s)-60s |
| c | 50s-(30s)-60s-(40s)-60s |
| d | 60s-(30s)-60s-(40s)-60s |
Embodiment 2:
In experimentation, find that adding a small amount of water can make the hydrogen reduction performance of catalyst change to some extent, is provided with four group reactions to explore the impact of content on catalyst performance of water for this reason.Under the condition of optimum microwave time, the capacity adding water is respectively 0%, 10%, 30%, 50% of total solvent volume (cumulative volume of deionized water and ethylene glycol) to explore the impact of solvent on catalyst performance.
Embodiment 3:
Adopt the optimum solvent ratio explored in the best microwave time and embodiment 2 obtained in embodiment 1 to explore the impact of pH value on catalyst performance.Explore the impact of catalyst when pH=4, pH=7, pH=8, pH=9 respectively.
Embodiment 4:
Adopt the optimum preparating condition of above-mentioned exploration to prepare Pt/Graphene catalyst (a), and the performance of itself and commercial catalysts (b) is compared.
The means such as prepared sample x-ray diffractometer, Fourier infrared spectrograph, transmission electron microscope, electrochemical property test (comprising cyclic voltammetry curve test, the test of linear scan curve, the test of stable state chrono-amperometric) are characterized.
Fig. 2 is the linear scan curve map of material prepared in embodiment 1, when from figure, we can find out that the microwave time is 50s-(30s)-60s-(40s)-60s, the half wave potential of catalyst is 0.52V, maximum in this four class mean, reason may be that catalyst particle size size is less under this microwave condition, distribution uniform, more electro catalytic activity site can be provided, oxygen is made more easily to be diffused into electrochemical reaction surface, reduce the impedance that activation polarization causes, show more excellent electro-chemical activity.This microwave time is all used to explore in research below.
The different catalyst oxygen reduction performance data list prepared by the microwave time of table 1-2
| Catalyst is numbered | Microwave time/s | Half wave potential/V |
| a | 2 ~ 5 [50s-(10s)] circulates | 0.45 |
| b | 30s-(40s)-60s-(50s)-60s | 0.48 |
| c | 50s-(30s)-60s-(40s)-60s | 0.52 |
| d | 60s-(30s)-60s-(40s)-60s | 0.46 |
Fig. 3 is the linear scan curve map of material prepared in embodiment 2, as can be seen from the figure add volume fraction be 30% water as solvent time, the hydrogen reduction better performances of material, half wave potential is 0.65V, compared to other several groups experiments, the half wave potential of this reaction is maximum.Reason may have two aspects: one is the amount of solvent is increased and dilutes the viscosity of ethylene glycol to a certain extent adding of water, the graphite oxide after expanding is made to be more prone to be stripped out during ultrasonic disperse, thus platinum ion can be dispersed on carrier with teaching, and then be reduced.Two is owing to adding certain water in ethylene glycol solvent, the boiling point of ethylene glycol is changed slightly, and under the above-mentioned microwave time, ethylene glycol not easily seethes with excitement vaporization.It is better that the reduction of ethylene glycol plays, and platinum ion is well reduced, and down studies based on this.
Fig. 4 is the linear scan curve map of material prepared in embodiment 3, and when pH value is 7, half wave potential is maximum, is 0.65V.This may be that the amount of solvent added due to the presoma (expansion graphite oxide) relative to reaction is very large, the graphite oxide after expansion can be made to spread out in a solvent, without the need to regulating solution acid alkalinity, peracid or excessively alkali make the existence form of effects of ion change on the contrary, are unfavorable for that it disperses.
Fig. 5 is crystalline flake graphite (a), graphite oxide (b), expansion graphite oxide (c), Pt/Graphene (d), platinum standard P DF card XRD scheme.Natural flake graphite is that 26.17 ° of places have a significantly strong diffraction maximum at 2 θ angles, this peak is the characteristic diffraction peak of graphite crystal f (002), peak shape is narrow and sharp-pointed, show that the degree of crystallinity of graphite raw material used is better, the space arrangement of crystalline flake graphite crystallite lamella is very regular, the X-ray diffractogram of contrast crystalline flake graphite, the diffraction maximum in graphite f (002) face disappears, be the diffraction maximum that 11.46 ° of places have a peak shape wider at 2 θ angles after sample drying after crystalline flake graphite is oxidized, this peak is the diffraction maximum of graphite oxide f (001), the reason that this peak occurs is that graphite is after oxidation, the a large amount of oxygen-containing functional group of atomic structure of carbon Intercalation reaction, lattice layer spacing is caused to increase, form compound between graphite layers, and the graphite oxide that expands is 25.20 ° of places at 2 θ angles a characteristic peak, this peak intensity dies down and peak shape is wider, the known stacked direction degree of order is very poor, consult pertinent literature, this peak may be the characteristic peak of Graphene, detect through FTIR spectrum and know that this material still exists remaining hydrogen, oxygen atom, graphite oxide is not fully reduced to Graphene, this material is the middle transition product of graphite oxide and Graphene strictly speaking, fluffy therefore be referred to as expansion graphite oxide because of it.
As can be seen from Figure 6 the appearance of the characteristic peak of Graphene is had and the f (111) of face-centered cubic platinum, f (200), f (220), peak corresponding to f (311) and the diffraction maximum one_to_one corresponding of standard platinum, in known experiment, platinum particles has been loaded on Graphene, has prepared the catalyst of graphene-supported platinum.From Fig. 6, we can see that f (111) peak, face is the strongest, close with the peak corresponding to f (200).It is better that all the other two peaks disperse.
Fig. 7, Fig. 8 is respectively the grain size distribution of the platinum of institute's load on the transmission electron microscope picture of Pt/Graphene catalyst in embodiment 4 and Pt/Graphene catalyst, from figure, we can find out that nano platinum particle is dispersed on Graphene, are about 4.1nm by the particle size calculating nano particle.
Fig. 9, Figure 10 and Figure 11 are respectively the cyclic voltammetry curve figure of Pt/Graphene catalyst, linear scan curve map, time current curve map.The preparation method of sample is as follows: by the catalyst of 2 ~ 8mg, be dispersed in the middle of the deionized water of 2 ~ 10ml and the mixed solution of absolute ethyl alcohol (1: 1), after ultrasonic 10 minutes, pipetting 8 μ L with pipettor drips on polished glass-carbon electrode, treat its natural air drying in atmosphere, then dry with 8 μ L0.05wt.%Nafion ethanolic solution coated electrode surfaces.In the present invention, cyclic voltammetry curve test condition is: the H of the 0.5M that nitrogen is saturated
2sO
4electrolyte, sweeps speed for 50mVs
-1; The test condition of rotating disk electrode (r.d.e) (rotatingdiskelectrode, RDE) linear scan is: the H of the 0.5mol/L that oxygen is saturated
2sO
4electrolyte, rotating speed is 1600rpm, and sweep speed is 0.001V/S.In electro-chemical test herein, reference electrode is saturated calomel electrode (saturatedcalomelelectrode, SCE), is platinum electrode to electrode.Stable state chronoa mperometric plot (i.e. time current curve) is at the H of the saturated 0.5mol/L of oxygen
2sO
4in electrolyte, polarization potential is test under the condition of 0.5V ~ 0.7V.Comprehensive analysis, we can know the Pt/graphene catalyst (from controlling catalyst) prepared by the present embodiment, and the electrochemical active surface of this catalyst (average grain diameter is 4.1nm) is 571cm
2mg
-1, specific mass mark is the electrochemical active surface 803cm of the platinum C catalyst of 20%
2mg
-1little, and half-wave is 0.65V in the linear scan curve of prepared catalyst, only 0.01V less of the half wave potential (0.66V) of commercial catalysts, show to be more or less the same from the electron transfer number of controlling catalyst in hydrogen reduction process and commercial catalysts, in oxygen reduction reaction the effect that rises almost identical.With regard to electrochemical stability, laboratory prepared catalyst catalytic activity is good, and stability is high, compares commercial catalysts more durable.
Claims (6)
1. the preparation method of fuel cell Pt/Graphene catalyst, is characterized in that described method step is as follows:
(1) preparation of graphite oxide
250ml there-necked flask is placed in ice-water bath, 80 ~ 120ml concentrated sulfuric acid is poured in there-necked flask, and adds crystalline flake graphite and 0.5 ~ 1.5 gram of sodium nitrate of 1 ~ 3 gram, start mechanical agitation, in 1 ~ 4 hour, slowly add the potassium permanganate powder of 10 ~ 15 grams, stir 2 ~ 10 hours in ice bath; Then be placed in oil bath, when temperature rises to 35 ~ 40 DEG C, start timing, heated at constant temperature is after 5 ~ 20 hours at this temperature, slowly adds the deionized water of 80 ~ 160ml in mixed solution, when temperature rises to 85 ~ 95 DEG C, continue heating after 15 ~ 30 minutes, there-necked flask is taken out from oil bath pan, is cooled to room temperature, add the hydrogenperoxide steam generator of 10 ~ 30ml, solution becomes glassy yellow from brown, then washs to solution in neutral successively by hydrochloric acid and deionized water, vacuum drying;
(2) preparation of expansion graphite oxide
By the graphite oxide grind into powder that step (1) is prepared, calcine at 800 ~ 1000 DEG C in Muffle furnace, obtain expansion graphite oxide;
(3) preparation of graphene-supported platinum catalyst
Take 3 ~ 6mg expansion graphite oxide and be placed in beaker, add the ethylene glycol of 30 ~ 60ml and account for the deionized water of total solvent volume 30-50%, stir and ultrasonic 20 ~ 40 minutes, the chloroplatinic acid ethylene glycol solution that 0.1 ~ 0.3ml concentration is 0.0386mol/L is added in ultrasonic procedure, adjust ph 7 ~ 9 after stirring, continue stirring and within 10 ~ 20 minutes, to be placed in microwave reactor microwave 1 ~ 3 minute, room temperature is cooled to after reaction terminates, filter, wash, dry, obtain the Pt/Graphene sample that platinum content is 20wt.%.
2. the preparation method of fuel cell Pt/Graphene catalyst according to claim 1, it is characterized in that in described step (1), the mass concentration of hydrogenperoxide steam generator is 30%.
3. the preparation method of fuel cell Pt/Graphene catalyst according to claim 1, it is characterized in that in described step (1), the volumetric concentration of hydrochloric acid is 10%.
4. the preparation method of fuel cell Pt/Graphene catalyst according to claim 1, is characterized in that in described step (3), and the microwave time is that microwave 50s-suspends 30s-microwave 60s-and suspends 40s-microwave 60s.
5. the preparation method of fuel cell Pt/Graphene catalyst according to claim 1, is characterized in that, in described step (3), pH value is 7.
6. the preparation method of fuel cell Pt/Graphene catalyst according to claim 1, is characterized in that, in described step (3), the addition of deionized water accounts for 30% of total solvent volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410105211.1A CN103894187B (en) | 2014-03-20 | 2014-03-20 | The preparation method of fuel cell Pt/Graphene catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410105211.1A CN103894187B (en) | 2014-03-20 | 2014-03-20 | The preparation method of fuel cell Pt/Graphene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103894187A CN103894187A (en) | 2014-07-02 |
| CN103894187B true CN103894187B (en) | 2016-01-20 |
Family
ID=50985943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410105211.1A Expired - Fee Related CN103894187B (en) | 2014-03-20 | 2014-03-20 | The preparation method of fuel cell Pt/Graphene catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103894187B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879859A (en) * | 2014-10-10 | 2016-08-24 | 南京大学 | Method for preparing oxidized graphene-supported spherical dendritic platinum nano composite |
| CN106159282A (en) * | 2015-03-30 | 2016-11-23 | 宜兴市四通家电配件有限公司 | Membrane electrode of fuel batter with proton exchange film eelctro-catalyst and preparation method thereof |
| CN105013483B (en) * | 2015-07-08 | 2016-06-08 | 青岛大学 | Platinum palladium platinum/manganese dioxide/Graphene stratiform structure catalyst and preparation method |
| CN105817240A (en) * | 2016-04-15 | 2016-08-03 | 华中科技大学 | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst |
| CN108878902B (en) * | 2018-07-06 | 2020-11-06 | 中国科学院大连化学物理研究所 | Preparation and application of double-effect oxygen electrode catalyst with iridium black as carrier |
| CN110197908A (en) * | 2019-03-27 | 2019-09-03 | 内蒙古科技大学 | The method for preparing anode catalyst of different carbon carriers |
| CN110252290A (en) * | 2019-06-18 | 2019-09-20 | 苏州朗泰新能源科技有限公司 | High dispersive Pt/C catalyst and the preparation method and application thereof |
| CN113659160B (en) * | 2021-08-17 | 2023-08-29 | 中汽创智科技有限公司 | Preparation method of mesoporous carbon loaded nano platinum catalyst |
| CN114639504A (en) * | 2022-05-18 | 2022-06-17 | 广州优刻谷科技有限公司 | Graphene-silver composite RFID tag and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
| CN103007958A (en) * | 2012-11-23 | 2013-04-03 | 浙江工业大学 | Expanded graphite supported platinum-cobalt catalyst and application thereof |
| CN103456969A (en) * | 2013-09-06 | 2013-12-18 | 哈尔滨工业大学 | Preparation method of Pt-Co/C-single-layer graphene for fuel cell |
-
2014
- 2014-03-20 CN CN201410105211.1A patent/CN103894187B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
| CN103007958A (en) * | 2012-11-23 | 2013-04-03 | 浙江工业大学 | Expanded graphite supported platinum-cobalt catalyst and application thereof |
| CN103456969A (en) * | 2013-09-06 | 2013-12-18 | 哈尔滨工业大学 | Preparation method of Pt-Co/C-single-layer graphene for fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| 氧化石墨及石墨烯材料的制备;雷芸等;《非金属矿》;20110131;第34卷(第1期);第4页1.4节 * |
| 铂/石墨烯复合材料的合成及性能表征;陈宽等;《功能材料》;20120630;第43卷(第12期);第1594页第1节第2段、第2节至第1595页第3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103894187A (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103894187B (en) | The preparation method of fuel cell Pt/Graphene catalyst | |
| CN105460921B (en) | A kind of selenizing molybdenum nanometer sheet/graphene nano belt composite and preparation method thereof | |
| CN105529472B (en) | Flake porous two-dimentional carbon material of a kind of Co-N codope and preparation method thereof | |
| Yuan et al. | Nitrogen-doped carbon sheets derived from chitin as non-metal bifunctional electrocatalysts for oxygen reduction and evolution | |
| CN106807416A (en) | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof | |
| CN106000439B (en) | A kind of sulphur, the preparation of nitrogen co-doped three-dimensional grapheme/manganese sulfide composite material and its electro-catalysis applied to oxygen restore | |
| CN107256972A (en) | A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth | |
| CN106467299A (en) | A kind of graphene-based multi-stage porous electric capacity charcoal and preparation method thereof and capacitor | |
| CN104475172A (en) | Preparation method and application of three-dimensional porous heteroatom-doped graphene | |
| CN112499613A (en) | Preparation method of nitrogen and phosphorus doped porous carbon for wide pH range oxygen reduction electrocatalysis | |
| Long et al. | Effect of pyrolysis conditions on nitrogen-doped ordered mesoporous carbon electrocatalysts | |
| CN104882295B (en) | The preparation method of carbonization absorbent cotton/graphene composite material | |
| CN102921444B (en) | A kind of method preparing P25/ nitrogen-doped graphene composite | |
| CN111992228A (en) | Molybdenum disulfide and carbon nanotube composite material catalyst, and preparation and application thereof | |
| CN109449006A (en) | A kind of preparation process of phosphorus nitrogen-doped graphene porous carbon composite | |
| Razmjooei et al. | Superior pore network retention of carbon derived from naturally dried ginkgo leaves and its enhanced oxygen reduction performance | |
| CN106492843A (en) | A kind of ultra-dispersed MoS2The preparation method of/rGO nano hybridization water electrolysis hydrogen production catalyst | |
| CN111282588A (en) | Catalyst for hydrogen evolution by electrolyzing water and preparation method and application thereof | |
| CN104645989A (en) | Heteroatom-doping porous carbon material and preparation method thereof | |
| CN109482214A (en) | The catalyst and preparation method of a kind of graphene-supported ruthenium metal and application | |
| Jiang et al. | Fungi-derived, functionalized, and wettability-improved porous carbon materials: an excellent electrocatalyst toward VO2+/VO2+ redox reaction for vanadium redox flow battery | |
| CN103831103A (en) | Graphene aerogel catalyst and preparation method thereof | |
| Wang et al. | Self‑nitrogen-doped carbon materials derived from microalgae by lipid extraction pretreatment: Highly efficient catalyst for the oxygen reduction reaction | |
| Xu et al. | Efficient utilization of crude bio-oil: the synthesis of nitrogen-doped hierarchically porous carbon as electrocatalysts for the oxygen reduction reaction | |
| CN108565469B (en) | Cobalt-nitrogen doped carbon composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |