CN107565141A - The carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm - Google Patents
The carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm Download PDFInfo
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Abstract
The invention provides a kind of carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm.The present invention has synthesized the WMC of different pore size by improved sol-gel technique, as carrier, polyol process technology is helped to be prepared for the PtRu catalyst of serial WMC load using pulse microwave, and physical and chemical performance to catalyst and electrocatalysis characteristic have carried out system testing and analysis.The present invention have studied influence of the pore size of carrier to PtRu electro-catalysis methanol oxidative activities by studying the PtRu catalyst using the WMCs of three kinds of different pore sizes as carrier.Research is found：1) when using identical pattern, the high-area carbon that specific surface area is larger but aperture is different, prepared catalyst Pt Ru particles are essentially identical；2) size of carrier aperture has conclusive influence to PtRu catalytic activity.
Description
Technical field
The present invention relates to a kind of carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm, belong to catalyst technical field.
Background technology
DMFC (DMFC) directly supplies source by fuel of methanol aqueous solution, has battery structure letter
Singly, the advantages that energy density is high, has successfully shown and may be used as portable power source and household electrical appliance micro battery.But DMFC body
Still there is a big difference for product, weight, the system integration and the requirement of practical application.This is largely determined by DMFC application foundation and new skill
Art novel aspects can not meet the needs of practical application, many matter of science and technologys be present, as methanol oxidation kinetics process compared with
Slowly, electrode catalyst is easily poisoned by CO class species, the infiltration of methanol from anode to negative electrode etc..In recent years, critical material (electro-catalysis
Agent and dielectric film) and key technology (electrode prepare and membrane electrode package technique) develop into solve the above problems provide it is good
Good opportunity.The polynary elctro-catalyst of carbon-carried Pt-based, such as PtRu/C, PtIr/C, PtRuIr/C, PtRhPd/C improve low-temp methanol
The dynamic process of oxidation, and inhibit catalyst poisoning.Wherein PtRu is still the practical activity of generally acknowledged DMFC and stability
Best anode electrocatalyst.But to improve DMFC activity and stability, PtRu carrying capacity is high.To improve noble metal utilisation,
Reduce its usage amount, generally use supported PtRu elctro-catalyst.
Currently used high-area carbon is the Vulcan XC-72 activated carbons of Cabot companies of U.S. production.But its specific surface area
Low (~250m2/ g), essentially from the hole that the secondary stacking of outer surface and nanocarbon particle is formed, this can be by Vulcan XC-
The N of 72 activated carbons2Adsorption-desorption experimental result and transmission electron microscope picture (Fig. 1) can be seen that.
Further, since Vulcan XC-72 activated carbons are spherical (Fig. 1 illustrations), and are short of surface chemistry functional group, no
Active component positioning of anchor or curable grip can be effectively provided, then active component such as Pt particles are easily shifted, reunited, and cause catalyst particles
Grain length is big, inactivation, stability decline.In addition, electrochemical reaction needs ion conductor to realize charge balance, and ion is in~1nm
In micropore in transport number ratio in body phase electrolyte small several orders of magnitude.This means the micropore that material can transmit leads to
Road, wherein electrochemical reaction can not but carry out.Therefore electro-catalysis system needs to minimize micropore specific area, and by constructing
Mesopore and macropore, which maximize, can utilize specific surface area.Especially in PEMFC electrodes, proton conductor is Nafion resins, and its is micro-
Newborn cluster diameter is about 4nm, requires higher to the architectural characteristic in the hole of electro-catalysis system.Therefore the exploitation of new high-area carbon enjoys
Concern, high-specific surface area, high conductivity, suitable pore structure and hole pattern and appropriate surfaces chemistry are especially constructed from minute yardstick
Novel porous Carbon Materials turn into one of focus and emphasis of current electrocatalysis material and PEMFC area researches.
In recent years, mesoporous carbon material in catalysis material due to the mass transfer ability more excellent compared with micropore carbon material, leading
Domain attracts wide attention.These mesoporous carbon materials show superiority in ultracapacitor, electro-catalyst carrier etc.
Energy.Compared to traditional Vulcan XC-72 activated carbons, the excellent structural characteristic of mesoporous carbon material is allowed to be expected to extensive in PEMFC fields
Using.The micro-scaled structures of mesoporous carbon material directly affect the aperture that charcoal carries the chemical property, wherein Carbon Materials of elctro-catalyst
Size plays conclusive effect in the transmitting procedure of reactant, product and electrolyte, and reactant is equal to reaction
Probe, different reactant (fuel or oxidant) are different to the susceptibility in aperture.In addition, pore size is straight with BET surface area
Connect correlation, it is impossible to which as a result increase aperture simply but reduces BET surface area, this can cause active component to be disperseed to promote mass transfer
Degree declines.It is therefore desirable to construct the high-area carbon that pattern is identical but aperture is different, to explore the suitable charcoal of suitable methanol electro-oxidizing
Aperture.
In the mesoporous carbon material developed in the recent period, the poroid mesoporous carbon of worm (Wormhole like mesoporous
Carbon, WMC) there is unique tridimensional network, specific surface area is high and pore capacities are high, be widely used in battery electrode,
In Water warfare, gas separation.After high temperature carbonization, WMC good conductivity, stability is high, thus is suitable for as fuel electricity
Electro-catalyst carrier in pond.Catalyst HF is especially introduced in TEOS sol-gel process by improved technology in Wu etc.,
And by change its dosage can gradual change the regulation and control for realizing aperture, its application obtains more concerns.Song etc. reports different holes
Influence of the Pt particles that footpath WMC is supported to hydrogen electroxidation, it is found that aperture has to the utilization rate and catalytic activity of Pt in catalyst
Conclusive influence,.When WMC apertures are more than 2 times of Pt particle diameters, Pt electrochemical area and utilization rate substantially increase,
Correspondingly its electrocatalysis characteristic significantly improves, but when WMC apertures are less than Pt particle diameters, due to the Pt particles in WMC ducts without
Method utilizes, and Pt electrochemical area and utilization rate substantially reduce.Methanol is liquid, and its molecular diameter is much larger than hydrogen, Er Qiejia
Gas is produced in alcohol oxidizing process, is gas-liquid mixture, therefore influence of the aperture of carrier to mass transport process and chemical property
Can be more directly and more obvious than its influence to hydrogen electroxidation.
The content of the invention
It is an object of the invention to provide a kind of carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm.
A kind of carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm, made using the electro-catalyst carrier WMC of different pore size
For PtRu carrier, wherein, Pt carrying capacity is 20.0wt.%, Pt:Ru=1:1 (atomic ratio).
Ru carrying capacity is 10.0wt.%.
Polyalcohol technology is helped to prepare supported PtRu catalyst using pulse microwave,
The electro-catalyst carrier preparation method of the different pore size is as follows：
A) according to predetermined formulation, sucrose：PH=2.0 sulfuric acid solution：TEOS=2.00g：3.0mL：4.0mL, by sucrose
Mixed with sulfuric acid solution, then add TEOS and stir to mixture into transparent and homogeneous liquid；
B) then, the 4wt.%HF solution of scheduled volume is added immediately as catalyst, is positioned over 40 after quickly stirring evenly immediately
DEG C constant temperature oven reacts 48 hours, and then constant temperature 6 hours at 100 DEG C and 160 DEG C respectively；
C) obtained sample is carbonized 3 hours for 900 DEG C in a nitrogen atmosphere, and then washes away silicon mould with 40wt.% HF
Plate, obtain the poroid Carbon Materials of worm (wormholelikemesoporous carbon, WMC)；
D) according to HF/TEOS rate of charge, it is respectively by HF/TEOS molar feed ratios：0th, 1/30 or 1/7 counter sample
It is respectively designated as WMC-F0, WMC-F30 and WMC-F7.
The present invention have studied the aperture of carrier by studying the PtRu catalyst using the WMCs of three kinds of different pore sizes as carrier
Influence of the size to PtRu electro-catalysis methanol oxidative activities.
Research is found：
1) when using identical pattern, the high-area carbon that specific surface area is larger but aperture is different, prepared catalyst Pt Ru
Particle is essentially identical；
2) size of carrier aperture has conclusive influence to PtRu catalytic activity.When high-area carbon bore dia is more than Pt
During 2 times of diameter of grain, Pt electrochemical area and utilization rate substantially increase, and correspondingly, the performance of its electro-catalysis methanol oxidation is notable
Improve, to be slightly above currently used commercialization XC-72R activated carbon supported for the methanol electro-oxidizing performance of its PtRu catalyst loaded
PtRu catalyst performance；Urged when high-area carbon bore dia is less than Pt particle diameters, or between 1 times of catalyst particle size with 2 times
When between agent particle diameter due in hole metallic particles can not utilize, Pt electrochemical area and utilization rate substantially reduce, accordingly
Electro catalytic activity also reduces.
Brief description of the drawings
Fig. 1 is Vulcan XC-72 activated carbons N2Adsorption isotherm and transmission electron microscope picture.
Fig. 2 is that pulse microwave helps polyalcohol technology to prepare PtRu/WMC catalyst preparation process schematic diagrames.
Nitrogen adsorption-desorption curve (A) of the poroid mesoporous carbon of Fig. 3 different pore size worms
Pore-size distribution (B) corresponding to nitrogen adsorption-desorption curve of the poroid mesoporous carbon of Fig. 4 different pore size worms
The XRD picture of the PtRu catalyst of the WMCs loads of Fig. 5 different pore sizes, 10 ° of min of sweep speed-1(A)
Fig. 6 is the material phase analysis step footpath scanning at Fig. 5 and its corresponding Pt (220) peak, 1 ° of min of sweep speed-1(B)
Fig. 7 is the SEM-EDS figures of PtRu@WMC-F7 catalyst
Fig. 8 is PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst in 0.5molL-1H2SO4The aqueous solution
In CV curves, 25 DEG C, sweep speed 20mVs-1
Fig. 9 be PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst at 25 DEG C in 0.5molL- 1H2SO4+1.0mol·L-1CH3Cyclic voltammetry curve in OH solution, sweep speed：50mV s-1
The chemical property that Figure 10 is catalyst Pt Ru@WMC-F7 and PtRu@XC-72C compares, and (A) is in 0.5molL- 1H2SO4CV curves in solution, sweep speed：20mVs-1, 25 DEG C
The chemical property that Figure 11 is catalyst Pt Ru@WMC-F7 and PtRu@XC-72C compares, and (B) is in 0.5molL- 1H2SO4+1.0mol·L-1CH3CV curves in OH solution, sweep speed：50mVs-1, 25 DEG C
Figure 12 is PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst 0.5mol L at 30 DEG C- 1H2SO4+1.0mol L-1CH3Cyclic voltammetry curve in OH, sweep speed：50mV s-1
Figure 13 is PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst 0.5mol L at 60 DEG C- 1H2SO4+1.0mol L-1CH3Cyclic voltammetry curve in OH, sweep speed：50mV s-1
Figure 14 is PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst in 0.5mol L-1H2SO4+
1.0mol L-1CH3Cyclic voltammetry curve in OH (A) solution, sweep speed 50mVs-1
Figure 15 is PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst in 0.5mol L-1H2SO4+
1.0mol L-1C2H5Cyclic voltammetry curve in OH (B) solution, sweep speed 50mVs-1
Figure 16 and PtRu@WMC-F0, PtRu@WMC-F30 and PtRu@WMC-F7 catalyst are in 0.5mol L-1H2SO4+
1.0mol L-1(CH3)2Cyclic voltammetry curve in CHOH (C) solution, sweep speed 50mVs-1
PtRu@WMC-F0, the electrochemistry of PtRu@WMC-F30 and PtRu@WMC-F7 catalyst are lived in Figure 17 different electrolytes
Property compares
Figure 18 is CH3OH alkanol molecule models.
Figure 19 is C2H5OH alkanol molecule models.
Figure 20 is CH3CHOHCH3Alkanol molecule model.
Embodiment：
First, the preparation of electro-catalyst carrier (WMC)
Using carriers of the WMC of different pore size as PtRu, influence of the research different carriers aperture to catalyst activity.Tool
Preparation is as follows：According to predetermined formulation (sucrose：PH=2.0 sulfuric acid solution：TEOS=2.00g：3.0mL：4.0mL),
Sucrose and sulfuric acid solution are mixed, TEOS is then added and stirs to mixture into transparent and homogeneous liquid.Then, add immediately predetermined
The 4wt.%HF solution (table 3-1) of amount is used as catalyst, is positioned over 40 DEG C of constant temperature ovens after quickly stirring evenly immediately and reacts 48 hours,
And then constant temperature 6 hours at 100 DEG C and 160 DEG C respectively.By obtained sample in a nitrogen atmosphere 900 DEG C carbonize 3 hours, tightly
Then wash away silicon template with 40wt.% HF, obtain the poroid Carbon Materials of worm (wormholelikemesoporous carbon,
WMC).According to HF/TEOS rate of charge, it is respectively by HF/TEOS molar feed ratios：0th, 1/30,1/7 counter sample is ordered respectively
Entitled WMC-F0, WMC-F30 and WMC-F7.
Table 3-1 different pore sizes WMC prepares the dosage for using HF
2nd, the preparation of catalyst (PtRu/WMC)
Using the WMC of different pore size as carrier, polyalcohol (second two is helped using pulse microwave (10S is opened, 10S is closed, and is repeated 5 times)
Alcohol) technology prepares supported PtRu catalyst, wherein, Pt carrying capacity is 20.0wt.%, and Ru carrying capacity is 10.0wt.%, is about
Pt:Ru=1:1 (atomic ratio).Preparation process schematic diagram is shown in Fig. 2.
In addition, enter for the ease of comparing WMC with commercial vectors XC-72R activated carbons (Cabot Corp.) general at present
Row compares, and same method is additionally used in experiment and is prepared for PtRu catalyst using XC-72R activated carbons as carrier, is labeled as
PtRu@XC-72C。
The present invention has synthesized the WMC of different pore size by improved sol-gel technique, micro- using pulse as carrier
Ripple helps polyol process technology to be prepared for the PtRu catalyst that serial WMC is loaded, and the physical and chemical performance to catalyst and electro-catalysis
Performance has carried out system testing and analysis.
It is further to analyze WMCs apertures to catalyst material transmittability and then to the influence of its electrocatalysis characteristic, if
Following two groups of experiments are counted：1) at different temperatures (30 DEG C and 60 DEG C), catalyst sample is in 0.5molL-1H2SO4+
1.0mol·L-1CH3Cyclic voltammetric polarization curve in OH solution；2) (25 DEG C) at identical temperature, catalyst is to different size of
Reaction molecular probe (CH3OH、C2H5OH and (CH3)2CHOH electrooxidation activity), test respectively in 0.5molL-1H2SO4+
1.0mol·L-1CH3OH、0.5mol·L-1H2SO4+1.0mol·L-1C2H5OH and 0.5molL-1H2SO4+1.0mol·L-1
(CH3)2Carried out in the CHOH aqueous solution.
PtRu@WMC-F0, tri- kinds of PtRu@WMC-F30 and PtRu@WMC-F7 are urged when Figure 12,13 give 30 DEG C and 60 DEG C
The cyclic voltammetry curve of the methanol electro-oxidizing of agent.Can intuitively it be observed from figure, with the rise of temperature, methanol oxidation
Activity increase.Specifically (it is shown in Table 3-3), the peak current (Ip) that methanol aoxidizes on PtRu@WMC-F7 is by 44.0mA cm-2(30
DEG C) increase to 170.2mA cm-2(60 DEG C), activity add 3.9 times, and PtRu@WMC-F0 and PtRu@WMC-F30 catalyst,
Corresponding Ip is respectively by 19.7mA cm-2(30℃)、34.9mA cm-2(30 DEG C) increase to 56.0mA cm-2(60 DEG C), activity is
Add 2.8 times.Clearly for it is rear both, the increased amplitude of activity is less than PtRu@WMC-F7.Illustrate for PtRu@WMC-F0
With PtRu@WMC-F30 catalyst, (temperature rise increase activity), also other factors in addition to temperature factor influences its performance
Inhibit active influence of the temperature to activity.Compare the situation of three, it can be deduced that, mainly due to PtRu@WMC-F0 and PtRu@
Two kinds of carriers WMC-F0, WMC-F30 aperture are small used by WMC-F30, cause reactant can not reach partially catalyzed activity
Position, catalytic activity reduce.
The methanol oxidation peak peak current density of different pore size WMCs supporting Pt Ru catalyst under table 3-3 different temperatures
*r：Same catalyst, the peak current ratio at peak current and 30 DEG C at 60 DEG C
, to catalyst material transmittability and then to the influence of its electrocatalysis characteristic, enter for further relatively WMCs apertures
Go group experiment 2), test PtRu@WMC-F0 under the same conditions, PtRu@WMC-F30 and PtRu@WMC-F7 exist respectively
0.5mol L-1H2SO4+1.0mol L-1CH3OH、0.5mol L-1H2SO4+1.0mol L-1C2H5OH and 0.5mol L-1H2SO4+
1.0mol L-1(CH3)2Cyclic voltammetry curve in the CHOH aqueous solution, as a result as shown in Figure 14,15,16.Obviously, PtRu@WMC-
F7 is respectively provided with highest electro catalytic activity to methanol, ethanol and isopropanol oxidation.Aperture pair is summed up to make a concrete analysis of and being beneficial to
The influence of catalyst chemical property, the oxidation peak current density of each alcohols in different catalysts and its mutual comparison are closed
System is summarized in table 3-4.Herein, it is specified that ratio of profit increase r1And r2, refer to formula (3-2) and (3-3)：
r1=
[Ip(PtRu@WMC-F7)-Ip(PtRu@WMC-F30)]/Ip(PtRu@WMC-F30)] * 100% (3-2)
r2=[Ip(PtRu@WMC-F7)-Ip(PtRu@WMC-F0)]/Ip(PtRu@WMC-F0)] * 100% (3-3)
Wherein IpFor the peak current density of oxidation of alcohols, r1It is relative for PtRu@WMC-F7
PtRu@WMC-F30 are to the ratio of profit increase of the oxidation activity of each alcohols, r2It is the relative PtRu@WMC-F0 of PtRu@WMC-F7
To the ratio of profit increase of the oxidation activity of each alcohols.
As can be seen from the table, the WMC-F30 that relative aperture is 4.4nm is the PtRu catalyst of carrier, aperture 8.5nm
WMC-F7 by carrier PtRu catalyst to the ratio of profit increase r for the oxidation of three kinds of alkanol molecules studied1Relatively, about
70% or so, influenceed by molecular polarity and molecular dimension small.But the WMC-F0 that relative aperture is 3.0nm is that the PtRu of carrier is urged
Agent aperture is by PtRu catalyst that 8.5nm WMC-F7 is carrier to the ratio of profit increase for the oxidation of three kinds of alkanol molecules studied
R2 is different significantly different with alkanol molecule, and PtRu@WMC-F7 are to PtRu@WMC-F30 methanol, ethanol and isopropanol electricity oxygen
Change peak current density ratio of profit increase r2Respectively 85%, 326% and 557%.This obvious difference can be observed intuitively by Figure 17,
This is mainly by caused by carrier mass transfer effect.Reaction molecular probe size is bigger and polarity is smaller, and transmission course of material is got over
It is difficult.(being shown in Table 3-5) is understood according to first-principles calculations, the molecular dimension size order of methanol, ethanol and isopropanol is
CH3OH<C2H5OH<(CH3)2CHOH, and the size order of molecular polarity is CH3OH>C2H5OH>(CH3)2CHOH, therefore, pass through
Compare and show that the order from the easier to the more advanced of mass transfer is：CH3OH>C2H5OH>(CH3)2CHOH.Understand molecular dimension it is larger and
During the less Isopropanol electrooxidation of polarity, two kinds of catalyst carrier WMC-F7 and WMC-F0 due to aperture is different and caused mass transfer
Difference on effect will become more apparent.
PtRu@WMC-F0, the electrochemistry of PtRu@WMC-F30 and PtRu@WMC-F7 catalyst in table 3-4 different electrolytes
Activity
The molecular dimension of table 3-5 first-principles calculations methanol, ethanol and isopropanol
The present invention have studied the aperture of carrier by studying the PtRu catalyst using the WMCs of three kinds of different pore sizes as carrier
Influence of the size to PtRu electro-catalysis methanol oxidative activities.Research is found：1) using identical pattern, specific surface area it is larger but
During the different high-area carbon in aperture, prepared catalyst Pt Ru particles are essentially identical；2) size of carrier aperture is catalyzed to PtRu
Activity has conclusive influence.
Claims (4)
- A kind of 1. carrier loaded PtRu catalyst of the poroid mesoporous carbon of worm, using the electro-catalyst carrier WMC conducts of different pore size PtRu carrier, wherein, Pt carrying capacity is 20.0wt.%, Pt:Ru=1:1 (atomic ratio).
- 2. catalyst according to claim 1, it is characterised in that：Ru carrying capacity is 10.0wt.%.
- 3. catalyst according to claim 1, it is characterised in that：Polyalcohol technology is helped to prepare support type using pulse microwave PtRu catalyst.
- 4. according to the catalyst described in claim 1,2 or 3, it is characterised in that the electro-catalyst carrier system of the different pore size Preparation Method is as follows：A) according to predetermined formulation, sucrose：PH=2.0 sulfuric acid solution：TEOS=2.00g：3.0mL：4.0mL, by sucrose and sulphur Acid solution mixes, and then adds TEOS and stirs to mixture into transparent and homogeneous liquid；B) then, the 4wt.%HF solution of scheduled volume is added immediately as catalyst, is positioned over 40 DEG C of perseverances after quickly stirring evenly immediately Warm baking oven reacts 48 hours, and then constant temperature 6 hours at 100 DEG C and 160 DEG C respectively；C) obtained sample is carbonized 3 hours for 900 DEG C in a nitrogen atmosphere, and then washes away silicon template with 40wt.% HF, obtain To the poroid Carbon Materials of worm (wormholelikemesoporous carbon, WMC)；D) according to HF/TEOS rate of charge, it is respectively by HF/TEOS molar feed ratios：0th, 1/30 or 1/7 counter sample difference It is named as WMC-F0, WMC-F30 and WMC-F7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020064852A (en) * | 2018-10-17 | 2020-04-23 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst for electrochemical device, electrode catalyst layer for electrochemical device, membrane/electrode assembly for electrochemical device, electrochemical device, manufacturing method of electrode catalyst for electrochemical device, and manufacturing method of membrane/electrode assembly for electrochemical device |
| WO2022085693A1 (en) * | 2020-10-19 | 2022-04-28 | 日鉄ケミカル＆マテリアル株式会社 | Carbon material for polymer electrolyte fuel cell catalyst carriers, catalyst layer for polymer electrolyte fuel cells, and fuel cell |
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| US20060166811A1 (en) * | 2004-12-30 | 2006-07-27 | Industrial Technology Research Institute | Hollow mesoporous carbon electrode-catalyst for direct methanol fuel cell and preparation thereof |
| CN103508436A (en) * | 2013-07-25 | 2014-01-15 | 隋吴彬 | Cane sugar / biological template method for preparing three-dimensional ordered porous charcoal material |
| CN104209122A (en) * | 2014-08-14 | 2014-12-17 | 中国科学院长春应用化学研究所 | PtRu/C catalyst and its preparation method |
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| US20060166811A1 (en) * | 2004-12-30 | 2006-07-27 | Industrial Technology Research Institute | Hollow mesoporous carbon electrode-catalyst for direct methanol fuel cell and preparation thereof |
| CN103508436A (en) * | 2013-07-25 | 2014-01-15 | 隋吴彬 | Cane sugar / biological template method for preparing three-dimensional ordered porous charcoal material |
| CN104209122A (en) * | 2014-08-14 | 2014-12-17 | 中国科学院长春应用化学研究所 | PtRu/C catalyst and its preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020064852A (en) * | 2018-10-17 | 2020-04-23 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst for electrochemical device, electrode catalyst layer for electrochemical device, membrane/electrode assembly for electrochemical device, electrochemical device, manufacturing method of electrode catalyst for electrochemical device, and manufacturing method of membrane/electrode assembly for electrochemical device |
| WO2022085693A1 (en) * | 2020-10-19 | 2022-04-28 | 日鉄ケミカル＆マテリアル株式会社 | Carbon material for polymer electrolyte fuel cell catalyst carriers, catalyst layer for polymer electrolyte fuel cells, and fuel cell |
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