CN104485464B - Based on the preparation method that Prussian blue fuel cell Pt is catalyst based - Google Patents
Based on the preparation method that Prussian blue fuel cell Pt is catalyst based Download PDFInfo
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- CN104485464B CN104485464B CN201410765013.8A CN201410765013A CN104485464B CN 104485464 B CN104485464 B CN 104485464B CN 201410765013 A CN201410765013 A CN 201410765013A CN 104485464 B CN104485464 B CN 104485464B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- 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
A kind of catalyst based and preparation method thereof based on Prussian blue fuel cell high stability, high activity Pt, relate to a kind of fuel cell Pt catalyst based and preparation method thereof.In order to solve stability and the activity problems of fuel battery cathod catalyst, described catalyst is the composite catalyst of Pt, Prussian blue and carrier composition, wherein: Pt and Prussian blue mass ratio are 1～20: 1, Pt is 2.5～60: 100 with the mass ratio of composite catalyst total amount.Pt based composite catalyst in the present invention is compared with business-like Pt/C, and stability and activity all have bigger lifting, and the Prussian blue cooperation mechanism of Pt-simultaneously proposing to be correlated with, to explain stability and the lifting of activity, still belongs to the first time.
Description
Technical field
The present invention relates to a kind of fuel cell Pt catalyst based and preparation method thereof, be specifically related to a kind of catalyst based and preparation method thereof based on Prussian blue fuel cell high stability, high activity Pt.
Background technology
Fuel cell have energy density transformation efficiency high, high, low operating temperature, pollution-free, can the advantage such as rapid starting/stopping; thus be considered as the effective energy reforming unit that can effectively contain ecological deterioration, solution energy crisis, it is subject to the extensive attention of national governments, scientific research institution.But, owing to using the noble metals such as Pt, fuel cell high cost, wherein Pt catalyst accounts for more than the 40% of totle drilling cost, seriously hinders the commercialization process of fuel cell.Therefore improve the activity of fuel-cell catalyst and service life is the essential condition of commercializing fuel cells.
Current fuel-cell catalyst subject matter concentrate on activity can not practical requirement, Simultaneous Stabilization is relatively poor.The electro catalytic activity electric current that catalyst activity deficiency is embodied in unit Pt mass is less.Need to use substantial amounts of Pt catalyst for reaching suitable output, cause the rising of cost, be unfavorable for commercialized development.Wherein fuel battery negative pole embodies and becomes apparent from, and main cause is anode reaction (as the oxidation of hydrogen reacts) good reversibility of fuel cell, and its reaction rate opposing cathode is higher, and therefore, comparatively speaking, the demand of cathod catalyst is bigger.The unit mass activity improving cathod catalyst is one of most important target in catalyst research process.Additionally, the less stable of current catalyst, cause corresponding fuel cell articles performance degradation quickly, it is necessary to frequently change.By narration above, fuel cell is relatively costly, upgrades demand frequently and causes the spending that consumer is difficult to bear fuel cell aspect, thus limiting its commercialization process.In sum, the activity of fuel-cell catalyst and stability problem are the two big major issues restricting its commercialization process.
Summary of the invention
In order to solve activity and the stability problem of fuel battery cathod catalyst, the invention provides a kind of catalyst based and preparation method thereof based on Prussian blue fuel cell high stability, high activity Pt.Pt in the present invention is catalyst based and compared with business-like Pt/C, stability and activity all have bigger lifting, and the Prussian blue cooperation mechanism of Pt-simultaneously proposing to be correlated with, to explain stability and active lifting, still belongs to the first time.
It is an object of the invention to be achieved through the following technical solutions:
A kind of catalyst based based on Prussian blue fuel cell high stability, high activity Pt, general structure is as shown in Figure 1.This catalyst is the composite catalyst of platinum (Pt), Prussian blue (Prussianblue, PB) and carrier composition, and wherein: the mass ratio of Pt and PB is 1～20: 1, the mass ratio of Pt and composite catalyst total amount is 2.5～60: 100.
In the present invention, described carrier can be conventional fuel-cell catalyst carbon carrier, such as VulcanXC-72, VulcanXC-72R, BP2000, Ketjen black, CNT and carbon fiber etc.；Can also be some oxide carrier, such as CeO2、TiO2、IrO2、In2O3、SnO2Or tin indium oxide etc.；Can also is that some carbide, such as WC, C3N4Or B4C etc..
In the present invention, described Prussian blue for crystal with non-crystal mixture, wherein: described Prussian blue crystal is the nano-particle of uniform particle sizes, particle size distribution 2-5nm；The described Prussian blue noncrystal film like for amorphous state.
The preparation process of above-mentioned catalyst is as in figure 2 it is shown, specifically comprise the following steps that
One, preparation Pt nano-particle colloid: Pt presoma is dissolved in 100～500mL water, adds a certain amount of stabilizer so that the mole ratio of Pt presoma and stabilizer is 1: 1～20.Stirring 20～40min, adds strong reductant NaBH4, controls Pt presoma and NaBH4Mol ratio be 1: 5～15, under room temperature continue stirring 2～10h, Pt presoma is reduced completely, Pt nano-particle colloid can be obtained.
In this step, described Pt presoma includes the one in chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, potassium chloroplatinate.
In this step, described stabilizer includes the one in diallyl dimethyl ammoniumchloride, sodium citrate, polyacrylic acid, polyvinylpyrrolidone etc..
Two, Prussian blue colloid is prepared: preparing two kinds of solution containing the potassium ferrocyanide that mol ratio is 3: 4 and ferric chloride, concentration is 0.01mmolL-1～0.1molL-1.Adding a certain amount of hydrogen peroxide in liquor ferri trichloridi, hydrogen peroxide (mass fraction is 30%) and liquor ferri trichloridi volume ratio are 0.5～10: 100, be rapidly added potassium ferrocyanide solution, ultrasonic 2～4h, obtain PB colloid after 5～30s.
Three, above two colloid solution is mixed 24～48h and obtain Pt-PB composite colloidal solution, be then added thereto to the carrier of corresponding proportion, fully ultrasonic 2～10h, stirs 24～48h.For making Pt-PB composite colloid granule deposit to carrier surface, need to adding precipitant, precipitant concentration is 0.1molL-1～1molL-1.Continuing stirring 24～48h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.
In this step, described precipitant includes strong acid (such as nitric acid etc.), highly basic (such as NaOH etc.) or strong electrolyte (such as KNO3Deng) one.
Present invention have the advantage that
1, the Prussian blue structure of special construction is synthesized first.This is Prussian blue by crystal with noncrystal collectively constitute.State chat as follows: according to Fig. 3, this is Prussian blue is macroscopically the structure of film like, it does not have significantly crystal structure exists.Choose electronogram accordingly and also demonstrate that this point (Fig. 4).The multiple amplifying Electronic Speculum is observed, as it is shown in figure 5, there is the crystal grain with fixing character striped inside amorphous film, as arrow indicates.In X-ray diffraction (Fig. 6) spectrogram, relatively sharp-pointed peak also demonstrate that the existence of PB crystal, illustrates that the particle diameter of these crystal grains is smaller simultaneously.
2, first by Pt and the Prussian blue compound that carries out to build catalyst, electro catalytic activity and stability for fuel battery negative pole reaction are studied.Composite catalyst has a characteristic that the particle diameter of Pt nano-particle is about 2.3nm, and is uniformly distributed, as shown in Figure 7；Owing in catalyst, Fe derives from Prussian blue, therefore the distribution situation that the distribution situation reaction of Fe is Prussian blue can be passed through, as shown in Figure 8, in a certain region of composite catalyst, the distribution of Fe is uniform, illustrates that Prussian blue is uniformly be attached to carrier surface；The position relationship of Pt nano-particle, PB and carrier is that PB uniformly spreads over carrier surface, and Pt load is on PB surface, as shown in Figure 1.
3, the catalyst system that the present invention proposes can promote the carrying out of oxygen electrocatalytic reduction.As shown in figs. 9-11, catalyst for Pt and PB mass ratio 4: 1, the catalysis activity of its Cathodic oxygen reduction is much better than commercial Pt/C catalyst, and the yields of hydrogen peroxide being embodied in reduction process is relatively low (Fig. 9), and plays spike potential and half wave potential higher (Figure 10).Another feature is that of this catalyst, along with the reduction of reaction potential, compared with commercial Pt/C, the catalysis activity of this composite catalyst promotes amplitude increasing (Figure 10 and table 1), 0.85V place, and this catalyst activity is 1.67 times of commercial Pt/C, and 0.7V place, this multiple increases to 3.4.The composite catalyst oxygen reduction activity of other ratios is also better than commercial Pt/C catalyst (Figure 11).
The catalyst of a certain ratio and commercial Pt/C catalyst activity data in the present invention under table 1 different potentials
4, the present invention proposes the synergism mechanism of Pt and PB as shown in Figure 1: first Dissociative reaction occurs oxygen on Prussian blue surface, and the oxygen-containing Particle diffusion of intermediate state produced subsequently is reduced further to Pt nano grain surface.So, same reaction (hydrogen reduction) is considered to separate and carries out two active sites, drastically increases electro catalytic activity.
5, the special construction of the composite catalyst of the present invention determines that the special construction on Pt meeting loaded body surface is Prussian blue fixing, makes Pt nano-particle be difficult to occur to dissolve migrate, thus increasing the stability of catalyst.
Accompanying drawing explanation
Fig. 1 is composite catalyst structure schematic diagram and the cooperation mechanism schematic diagram to oxygen reduction reaction thereof；
Fig. 2 is composite catalyst preparation flow schematic diagram；
Fig. 3 is the electromicroscopic photograph that the special construction related in the present invention is Prussian blue；
Fig. 4 is the electronogram that the special construction related in the present invention is Prussian blue；
Fig. 5 is the high power electromicroscopic photograph that the special construction related in the present invention is Prussian blue；
Fig. 6 is the X-ray diffractogram that the special construction related in the present invention is Prussian blue；
Fig. 7 is the composite catalyst electromicroscopic photograph that Pt and PB mass ratio is 4: 1 related in the present invention；
Fig. 8 is the composite catalyst Elemental redistribution that Pt and PB mass ratio is 4: 1 related in the present invention；
Fig. 9 is that in the present invention, Pt and PB mass ratio is the catalyst of 4: 1 and commercial Pt/C catalyst yields of hydrogen peroxide contrast；
Figure 10 be in the present invention Pt and PB mass ratio be 4: 1 catalyst and commercial Pt/C catalyst catalysis activity that cathodic oxygen reduction react contrast；
Figure 11 be in the present invention Pt and PB mass ratio be 2: 1,4: 1,8: 1 catalyst and commercial Pt/C catalyst catalysis activity that cathodic oxygen reduction react contrast；
Figure 12 is the electromicroscopic photograph of the Pt nano-particle colloid of embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme is further described; but it is not limited thereto; every technical solution of the present invention modified or equivalent replaces, without deviating 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:
Take 2.8mL platinum acid chloride solution (Pt content: 3.8mgPtmL-1) be dissolved in 100mL water, add 150 μ L diallyl dimethyl ammoniumchloride as stabilizer, stir 30min.Add strong reductant NaBH4Solution (20mgNaBH4It is dissolved in 10mL water), continue stirring 2h under room temperature, Pt presoma is reduced completely, Pt nano-particle colloid can be obtained.
This Pt nano-particle size uniformity, particle size distribution is about 2.3nm, such as Figure 12 institute not.
Embodiment 2:
Take 4.6mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 3.4mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in embodiment 1 with PB colloid mixing 24h, is added thereto to 35mgVulcanXC-72R, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 2: 1, and the total mass ratio of Pt and composite catalyst is 20: 100.Chemical property is as shown in figure 11.
Embodiment 3:
Take 2.3mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in embodiment 1 with PB colloid mixing 24h, is added thereto to 37.5mgVulcanXC-72R, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 4: 1, and the total mass ratio of Pt and composite catalyst is 20: 100.
As seen in figures 3-6, with elements distribution feature as Figure 7-8, chemical property feature is as shown in figs. 9-10 for its pattern of composite catalyst for PB gel characteristics.
Embodiment 4:
Take 1.15mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 0.85mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in example 1 with PB colloid mixing 24h, is added thereto to 38.75mgVulcanXC-72R, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 8: 1, and the total mass ratio of Pt and composite catalyst is 20: 100.Chemical property is as shown in figure 11.
Embodiment 5:
Take 2.3mL liquor ferri trichloridi (1.25mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (1.25mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in embodiment 1 with PB colloid mixing 24h, is added thereto to 39.4mg CNT, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 16: 1, and the total mass ratio of Pt and composite catalyst is 20: 100.
Embodiment 6:
Take 2.3mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in embodiment 1 with PB colloid mixing 24h, is added thereto to 187.5mgVulcanXC-72R, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 4: 1, and the total mass ratio of Pt and composite catalyst is 5: 100.
Embodiment 7:
Take 2.3mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in embodiment 1 with PB colloid mixing 24h, is added thereto to 87.5mgVulcanXC-72R, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 4: 1, and the total mass ratio of Pt and composite catalyst is 10: 100.
Embodiment 8:
Take 2.3mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in example 1 with PB colloid mixing 24h, is added thereto to 12.5mg CNT, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 4: 1, and the total mass ratio of Pt and composite catalyst is 40: 100.
Embodiment 9:
Take 2.3mL liquor ferri trichloridi (5mmolL-1) add the dilution of 100mL water.It is added thereto to 1.5mLH2O2(30wt%) ultrasonic 20s afterwards, adds 1.7mL potassium ferrocyanide solution (5mmolL immediately-1), ultrasonic 2h, obtain PB colloid.Preparation process shown in Fig. 2, obtains Pt-PB composite colloidal solution by Pt colloid solution in example 1 with PB colloid mixing 24h, is added thereto to 37.5mg CNT, abundant ultrasonic 2h, stirs 24h.For making Pt-PB composite colloid granule deposit to carrier surface, KNO need to be added3, precipitant concentration is 0.5molL-1.Continuing stirring 24h makes Pt-PB composite colloid granule deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.In this composite catalyst, the mass ratio of Pt and PB is 4: 1, and the total mass ratio of Pt and composite catalyst is 20: 100.
Claims (4)
1. based on the preparation method that Prussian blue fuel cell Pt is catalyst based, described catalyst is the composite catalyst of Pt, Prussian blue and carrier composition, wherein: the mass ratio that Pt and Prussian blue mass ratio are 1 ~ 20:1, Pt and composite catalyst total amount is 2.5 ~ 60:100
It is characterized in that described method specifically comprises the following steps that
One, preparation Pt nano-particle colloid: Pt presoma is dissolved in 100 ~ 500mL water, adds a certain amount of stabilizer so that the mole of Pt presoma and stabilizer ratio for 1:1 ~ 20, stirs 20 ~ 40min, adds strong reductant NaBH4, control Pt presoma and NaBH4Mol ratio be 1:5 ~ 15, under room temperature continue stirring 2 ~ 10h, Pt presoma is reduced completely, Pt nano-particle colloid can be obtained；
Two, Prussian blue colloid is prepared: preparing two kinds of solution containing the potassium ferrocyanide that mol ratio is 3:4 and ferric chloride, concentration is 0.01mmolL-1~0.1molL-1, in liquor ferri trichloridi, adding a certain amount of hydrogen peroxide, hydrogen peroxide and liquor ferri trichloridi volume ratio are 0.5 ~ 10:100, be rapidly added potassium ferrocyanide solution, ultrasonic 2 ~ 4h, obtain Prussian blue colloid after 5 ~ 30s；
Three, above two colloid solution is mixed 24 ~ 48h and obtain the Prussian blue composite colloidal solution of Pt-, be then added thereto to the carrier of corresponding proportion, fully ultrasonic 2 ~ 10h, stir 24 ~ 48h, add precipitant, precipitant concentration is 0.1molL-1~1molL-1, continue stirring 24 ~ 48h and make the Prussian blue composite colloid granule of Pt-deposit to carrier surface, by catalyst sucking filtration or centrifugal, washing and drying, can obtain based on Prussian blue Pt based composite catalyst.
2. the preparation method catalyst based based on Prussian blue fuel cell Pt according to claim 1, it is characterised in that described Pt presoma is the one in chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, potassium chloroplatinate.
3. the preparation method catalyst based based on Prussian blue fuel cell Pt according to claim 1, it is characterised in that described stabilizer is the one in diallyl dimethyl ammoniumchloride, sodium citrate, polyacrylic acid, polyvinylpyrrolidone.
4. the preparation method catalyst based based on Prussian blue fuel cell Pt according to claim 1, it is characterised in that described precipitant is the one of strong acid, highly basic, strong electrolyte.
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| CN108598506B (en) * | 2016-07-29 | 2020-07-21 | 杭州富阳伟文环保科技有限公司 | Application of composite nano material |
| CN107464936A (en) * | 2017-06-13 | 2017-12-12 | 北京大学深圳研究生院 | A kind of catalyst of air electrode of zinc-air cell and its preparation method and application |
| CN107342418B (en) * | 2017-06-21 | 2019-07-16 | 浙江大学 | A kind of ferrocyanogen positive electrode and its preparation method and application |
| CN108461765B (en) * | 2018-05-29 | 2021-04-16 | 武汉大学 | N-Fe/FeC3Air cathode electro-catalytic material of @ AC microbial fuel cell and preparation method thereof |
| CN110729495B (en) * | 2019-11-08 | 2020-11-17 | 广东伟的新材料股份有限公司 | CNSs-Ni@Pt/PM-g-C3N4Electrocatalyst and method of making |
| CN111632624B (en) * | 2020-06-22 | 2022-10-28 | 陕西科技大学 | Anode catalyst for water electrolysis and preparation method thereof |
| CN111715248B (en) * | 2020-06-22 | 2022-11-01 | 陕西科技大学 | Cathode catalyst for hollow nano electrolyzed water and preparation method thereof |
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| EP2535971A1 (en) * | 2010-02-10 | 2012-12-19 | Showa Denko K.K. | Method of producing fuel cell electrode catalyst, method of producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses of same |
| CN103506161A (en) * | 2013-09-22 | 2014-01-15 | 青岛大学 | Graphene composite, application of graphene composite to catalytic methanol oxidation, chemically modified electrode and preparation method of graphene composite |
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| EP2535971A1 (en) * | 2010-02-10 | 2012-12-19 | Showa Denko K.K. | Method of producing fuel cell electrode catalyst, method of producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses of same |
| CN103506161A (en) * | 2013-09-22 | 2014-01-15 | 青岛大学 | Graphene composite, application of graphene composite to catalytic methanol oxidation, chemically modified electrode and preparation method of graphene composite |
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