CN103825034A - Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof - Google Patents

Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof Download PDF

Info

Publication number
CN103825034A
CN103825034A CN201410056151.9A CN201410056151A CN103825034A CN 103825034 A CN103825034 A CN 103825034A CN 201410056151 A CN201410056151 A CN 201410056151A CN 103825034 A CN103825034 A CN 103825034A
Authority
CN
China
Prior art keywords
mwcnt
palladium
tin
ethanol
catalyst
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.)
Pending
Application number
CN201410056151.9A
Other languages
Chinese (zh)
Inventor
易清风
楚浩
阳铮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan University of Science and Technology
Original Assignee
Hunan University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hunan University of Science and Technology filed Critical Hunan University of Science and Technology
Priority to CN201410056151.9A priority Critical patent/CN103825034A/en
Publication of CN103825034A publication Critical patent/CN103825034A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
    • 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 metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and a preparation method thereof, a glycol and water mixed solution is used as a reaction solvent, palladium chloride, tin chloride and nickel chloride are reduced under the action of reducing agent NaBH4, obtained metal palladium, tin and nickel are deposited on multi walled carbon nanotubes (MWCNT) to obtain ternary PdSnNi / MWCNT nano metal catalyst particles loaded on the MWCNT. The PdSnNi / MWCNT nano metal catalyst has a strong electrocatalytic activity for ethanol oxidation in a sodium hydroxide solution, the content of palladium in the catalyst is decreased, and the catalyst is simple in preparing process, and has the widespread application in ethanol fuel cells.

Description

A kind of palladium-tin-nickel ternary metal nanometer electrical catalyst, preparation method and application for fuel cell oxidation of ethanol reaction
Technical field
The invention belongs to fuel cell technology and new energy materials technical field, be specifically related to a kind of many walls and carry nano tube supported palladium-tin-nickel ternary metal nanometer electrical catalyst particle, preparation method and application.
Background technology
Fuel cell is a kind ofly will to be present in chemical energy in fuel and oxidant and to be converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy, it is one of direction of giving priority to of new energy field, there is the advantages such as efficient, clean and low noise, be subject to national governments and scientist's great attention.Directly liquid alcohol fuel cell (DAFC) is except utilizing methyl alcohol to do fuel, the alcohol that also can utilize ethanol etc. to regenerate is fuel, and fuel cell take ethanol as fuel also has the advantages such as theoretical specific energy is high, environmental pollution is little, fuel source is abundant, thereby cause the great interest of people.Ethanol electro-oxidation is the anode reaction of DAFC, and has lower equilibrium potential (E o).Preparation has the electrode material of high degree of electrical catalytic activity DAFC is studied and had great importance to oxidation of ethanol.But in practical operation, owing to existing electrode material to reasons such as the activity of alcohol oxidation are limited, cause the actual take-off potential of oxidation of ethanol will be higher than E o.Because there is the C-C key of more difficult fracture in ethanol, so ethanol complete oxidation is CO 2more difficult.
At present, the electrode material that oxidation of ethanol is had to a greater activity is mainly platinum and palladium.With regard to DAFC, platinum is considered to the comparatively suitable anode material of alcohol oxidation, but in alcohol oxidizing process, platinum can produce " certainly suppressing " phenomenon and make its active decline rapidly, and this is because ethanol is finally oxidized to CO on Pt class catalyst 2experience multistep reaction process, have multiple possible reaction intermediates, and wherein have the CO that the generation of Pt surface is poisoned strongly to effect, so ethanol is difficult to complete oxidation.
Palladium does not have electroactive in acid solution to oxidation of ethanol, but in alkaline environment, its oxidation is had to strong electrochemical catalysis activity.These palladium catalysts comprise nanoporous Pd/Ti, Pd/C, Pd/ MWCNT, Pd nano wire etc.Oxidation of ethanol is shown to high catalytic activity with the synthetic Pd-Au of chemical reduction method and Pd-Sn bimetallic electrode material; Adopt the Pd-Ni bimetal nano electrode of electrodeposition process or chemical preparation, in alkaline solution, to alcohol, oxidation also shows high electroactive; In addition, also have Pd-Pb/C, PdBi/C, Pt-Pd/Ru, Pd-Ag/C containing bimetallic or many metal electrics catalyst of palladium ]etc..
In sum, palladium is that a kind of cost compared with platinum is low and ethanol is had to a metal of excellent electro catalytic activity.Will further improve the electro catalytic activity of palladium to oxidation of ethanol, by palladium nanometer, and add the transition metal that other cost is lower, make that its electro catalytic activity improves more, cost official adds decline, be the important content of Direct Ethanol Fuel Cell research, exploitation.It is reaction dissolvent that the present invention utilizes the mixed solution of ethylene glycol and water, under existing, reducing agent Metal Palladium, tin are deposited on together with nickel on multi-walled carbon nano-tubes (MWCNT), form the ternary PdSnNi/MWCNT metallic catalyst particle of MWCNT load, this catalyst granules not only greatly reduces the consumption of Metal Palladium, and they increase significantly with respect to pure Technique of Nano Pd (Pd/MWCNT), PdSn/MWCNT and PdNi/MWCNT particle for the electro catalytic activity of oxidation of ethanol reaction.
Summary of the invention
The object of this invention is to provide a kind of carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst for fuel cell oxidation of ethanol reaction, its take-off potential to oxidation of ethanol reaction declines (negative moving), oxidation of ethanol kinetic current density is significantly increased, and in this ternary metal nanometer electrical catalyst, the consumption of Metal Palladium also declines.
The object of the invention is also to provide a kind of preparation method of the carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst for fuel cell oxidation of ethanol reaction.
For achieving the above object, embodiment of the present invention are: a kind of carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst for fuel cell oxidation of ethanol reaction, to utilize the mixed solution of ethylene glycol and water as reaction dissolvent, under reducing agent exists, Metal Palladium, tin are deposited on to multi-walled carbon nano-tubes (MWCNT) together with nickel upper, form the ternary PdSnNi/MWCNT metallic catalyst particle of MWCNT load.
A preparation method for the carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst reacting for fuel cell oxidation of ethanol, concrete steps are as follows:
(1) multi-walled carbon nano-tubes (MWCNT) is mixed with the concentrated sulfuric acid, red fuming nitric acid (RFNA), by mixture stirring and refluxing reaction at 60 ℃, centrifugal, with pure water washing, to neutral, vacuumize at 60 ℃, obtains the MWCNT after acidifying.
(2) in weight portion, by 8.9 parts of PdCl 2, 0～2.8 part of SnCl 22H 2o and 0～3.0 part of NiCl 26H 2o is dissolved in the mixed solution of ethylene glycol and water (3 ﹕ 1), fully stirs, and dissolves completely, adds 30 parts of MWCNT after acidifying, and ultrasonic 30min, obtains black mixture.
(3) by mass/volume ratio, NaBH 4/ ethylene glycol=0.5/12, by NaBH 4be dissolved in ethylene glycol, this solution is dropwise joined in above-mentioned black mixture, fully stirring reaction 4h.Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains the metal nano catalyst of MWCNT load.
The application of carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst of described fuel cell oxidation of ethanol reaction, concrete grammar is: the metal nano catalyst of described MWCNT load is mixed with absolute ethyl alcohol, add again Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode.
It is reaction dissolvent that the present invention adopts the mixture of ethylene glycol and water, under MWCNT exists, palladium salt, pink salt and nickel salt is reduced simultaneously, obtains three Metal Palladium-tin-nickel nanocatalyst particle of MWCNT load.The catalyst of this three metals not only consumption of palladium reduces, and it obviously increases the electro catalytic activity of oxidation of ethanol.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammetry curve of the prepared carbon multi-wall nano tube loaded palladium nanocatalyst Pd/MWCNT of embodiment 1 to oxidation of ethanol.
Fig. 2 is the cyclic voltammetry curve of the prepared carbon multi-wall nano tube loaded palladium-sijna rice catalyst P dSn/MWCNT of embodiment 1 to oxidation of ethanol.
Fig. 3 is the cyclic voltammetry curve of the prepared carbon multi-wall nano tube loaded palladium-nickel nanometer catalyst PdNi/MWCNT of embodiment 1 to oxidation of ethanol.
Fig. 4 is the cyclic voltammetry curve of the prepared carbon multi-wall nano tube loaded palladium-tin-nickel nanocatalyst PdSnNi/MWCNT of embodiment 1 to oxidation of ethanol.
Embodiment 1:
First, 2g multi-walled carbon nano-tubes (MWCNT) is mixed with the 90 mL concentrated sulfuric acids, 30 mL red fuming nitric acid (RFNA)s, by mixture stirring and refluxing reaction 4h at 60 ℃.Afterwards, centrifugal, with pure water washing, to neutral, vacuumize 12h at 60 ℃, obtains the MWCNT after acidifying.Then, by 8.9 mg PdCl 2be dissolved in the mixed solution of 12mL ethylene glycol and 4mL water, fully stir, treat to dissolve completely, add 30mg acidifying MWCNT, ultrasonic 30min, obtains black mixture.In addition, by 0.5g NaBH 4be dissolved in 12mL ethylene glycol, under agitation, this solution dropwise joined in above-mentioned black mixture, fully stirring reaction 4h.Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains the Metal Palladium nanocatalyst Pd/MWCNT of MWCNT load.Subsequently, the Metal Palladium nanocatalyst Pd/MWCNT 5mg of this MWCNT load is mixed with 0.95mL absolute ethyl alcohol, add again 50uL Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode at 1 mol L -1in NaOH solution, measure its electro catalytic activity to oxidation of ethanol.1 mol L -1in NaOH solution, concentration of alcohol is 0.5 mol L -1, sweep speed 50 mV s -1, corresponding cyclic voltammetry curve is shown in Fig. 1.Oxidation of ethanol take-off potential is-0.64 V, and when forward scan, the current density at ethanol anodic oxidation peak is 52.4 mA cm -2.
Embodiment 2:
First, 2g multi-walled carbon nano-tubes (MWCNT) is mixed with the 90 mL concentrated sulfuric acids, 30 mL red fuming nitric acid (RFNA)s, by mixture stirring and refluxing reaction 4h at 60 ℃.Afterwards, centrifugal, with pure water washing, to neutral, vacuumize 12h at 60 ℃, obtains the MWCNT after acidifying.Then, by 8.9 mg PdCl 2with 2.8 mg SnCl 22H 2o is dissolved in the mixed solution of 12mL ethylene glycol and 4mL water, fully stirs, and treats to dissolve completely, adds 30mg acidifying MWCNT, and ultrasonic 30min, obtains black mixture.In addition, by 0.5g NaBH 4be dissolved in 12mL ethylene glycol, under agitation, this solution dropwise joined in above-mentioned black mixture, fully stirring reaction 4h.Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains Metal Palladium-sijna rice catalyst P dSn/MWCNT of MWCNT load.Subsequently, Metal Palladium-sijna rice catalyst P dSn/MWCNT 5mg of this MWCNT load is mixed with 0.95mL absolute ethyl alcohol, add again 50uL Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode at 1 mol L -1in NaOH solution, measure its electro catalytic activity to oxidation of ethanol.1 mol L -1in NaOH solution, concentration of alcohol is 0.5 mol L -1, sweep speed 50 mV s -1, corresponding cyclic voltammetry curve is shown in Fig. 2.Oxidation of ethanol take-off potential is 0.64 V, and when forward scan, the current density at ethanol anodic oxidation peak is 76.7 mA cm -2.
Embodiment 3:
First, 2g multi-walled carbon nano-tubes (MWCNT) is mixed with the 90 mL concentrated sulfuric acids, 30 mL red fuming nitric acid (RFNA)s, by mixture stirring and refluxing reaction 4h at 60 ℃.Afterwards, centrifugal, with pure water washing, to neutral, vacuumize 12h at 60 ℃, obtains the MWCNT after acidifying.Then, by 8.9 mg PdCl 2with 3.0 mg NiCl 26H 2o is dissolved in the mixed solution of 12mL ethylene glycol and 4mL water, fully stirs, and treats to dissolve completely, adds 30mg acidifying MWCNT, and ultrasonic 30min, obtains black mixture.In addition, by 0.5g NaBH 4be dissolved in 12mL ethylene glycol, under agitation, this solution dropwise joined in above-mentioned black mixture, fully stirring reaction 4h.Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains Metal Palladium-nickel nanometer catalyst PdNi/MWCNT of MWCNT load.Subsequently, Metal Palladium-nickel nanometer catalyst PdNi/MWCNT 5mg of this MWCNT load is mixed with 0.95mL absolute ethyl alcohol, add again 50uL Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode at 1 mol L -1in NaOH solution, measure its electro catalytic activity to oxidation of ethanol.1 mol L -1in NaOH solution, concentration of alcohol is 0.5 mol L -1, sweep speed 50 mV s -1, corresponding cyclic voltammetry curve is shown in Fig. 3.Oxidation of ethanol take-off potential is 0.64 V, and when forward scan, the current density at ethanol anodic oxidation peak is 63.3 mA cm -2.
Embodiment 4:
First, 2g multi-walled carbon nano-tubes (MWCNT) is mixed with the 90 mL concentrated sulfuric acids, 30 mL red fuming nitric acid (RFNA)s, by mixture stirring and refluxing reaction 4h at 60 ℃.Afterwards, centrifugal, with pure water washing, to neutral, vacuumize 12h at 60 ℃, obtains the MWCNT after acidifying.Then, by 8.9 mg PdCl 2, 1.4 mg SnCl 22H 2o and 1.5 mg NiCl 26H 2o is dissolved in the mixed solution of 12mL ethylene glycol and 4mL water, fully stirs, and treats to dissolve completely, adds 30mg acidifying MWCNT, and ultrasonic 30min, obtains black mixture.In addition, by 0.5g NaBH 4be dissolved in 12mL ethylene glycol, under agitation, this solution dropwise joined in above-mentioned black mixture, fully stirring reaction 4h.Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains Metal Palladium-tin-nickel nanocatalyst PdSnNi/MWCNT of MWCNT load.Subsequently, Metal Palladium-tin-nickel nanocatalyst PdSnNi/MWCNT 5mg of this MWCNT load is mixed with 0.95mL absolute ethyl alcohol, add again 50uL Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode at 1 mol L -1in NaOH solution, measure its electro catalytic activity to oxidation of ethanol.1 mol L -1in NaOH solution, concentration of alcohol is 0.5 mol L -1, sweep speed 50 mV s -1, corresponding cyclic voltammetry curve is shown in Fig. 4.Oxidation of ethanol take-off potential is 0.65 V, and when forward scan, the current density at ethanol anodic oxidation peak is 83.8 mA cm -2.

Claims (3)

1. the carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst for fuel cell oxidation of ethanol reaction, to utilize the mixed solution of ethylene glycol and water as reaction dissolvent, under reducing agent exists, Metal Palladium, tin are deposited on to multi-walled carbon nano-tubes (MWCNT) together with nickel upper, form the ternary PdSnNi/MWCNT metallic catalyst particle of MWCNT load.
2. a preparation method for the carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst reacting for fuel cell oxidation of ethanol, is characterized in that, concrete steps are as follows:
(1) multi-walled carbon nano-tubes (MWCNT) is mixed with the concentrated sulfuric acid, red fuming nitric acid (RFNA), by mixture stirring and refluxing reaction at 60 ℃, centrifugal, with pure water washing, to neutral, vacuumize at 60 ℃, obtains the MWCNT after acidifying;
(2) in weight portion, by 8.9 parts of PdCl 2, 0～2.8 part of SnCl 22H 2o and 0～3.0 part of NiCl 26H 2o is dissolved in the mixed solution of ethylene glycol and water (3 ﹕ 1), fully stirs, and dissolves completely, adds 30 parts of MWCNT after acidifying, and ultrasonic 30min, obtains black mixture;
(3) by mass/volume ratio, NaBH 4/ ethylene glycol=0.5/12, by NaBH 4be dissolved in ethylene glycol, this solution is dropwise joined in above-mentioned black mixture, fully stirring reaction 4h;
Question response is complete, suction filtration, and with ultra-pure water washing, to neutral, vacuumize 10h at 40 ℃, obtains the metal nano catalyst of MWCNT load.
3. the application of carbon multi-wall nano tube loaded palladium-tin-nickel ternary metal nanometer electrical catalyst of fuel cell oxidation of ethanol reaction claimed in claim 1, concrete grammar is: the metal nano catalyst of described MWCNT load is mixed with absolute ethyl alcohol, add again Nafion(mass percent 5%) solution, then will after ultrasonic mixture 40min, form pastel, finally this pastel is dripped in glass-carbon electrode surface, dry after as work electrode.
CN201410056151.9A 2014-02-19 2014-02-19 Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof Pending CN103825034A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410056151.9A CN103825034A (en) 2014-02-19 2014-02-19 Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410056151.9A CN103825034A (en) 2014-02-19 2014-02-19 Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN103825034A true CN103825034A (en) 2014-05-28

Family

ID=50759976

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410056151.9A Pending CN103825034A (en) 2014-02-19 2014-02-19 Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN103825034A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104037440A (en) * 2014-05-30 2014-09-10 湖南科技大学 Membrane-free direct alcohol fuel cell in acid solution and preparation method thereof
CN105810923A (en) * 2014-12-31 2016-07-27 中国科学院宁波材料技术与工程研究所 Preparation method of ultra-small particle size tin and tin-based alloy nano-particle and application thereof
CN106910906A (en) * 2017-02-28 2017-06-30 上海电力学院 A kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application
CN107460463A (en) * 2017-06-23 2017-12-12 安庆师范大学 A kind of method that electricity displacement prepares Pd Co Ni alloy films in ionic liquid
CN108448126A (en) * 2018-02-09 2018-08-24 中南大学 A kind of PtAuTi nanowire catalytics material and preparation method thereof and application as fuel-cell catalyst
CN113745552A (en) * 2021-08-17 2021-12-03 西安交通大学 Carbon-supported palladium tin tantalum nitride nano electro-catalyst for direct ethanol and methanol fuel cell and preparation method thereof
CN113839056A (en) * 2021-08-28 2021-12-24 西安交通大学 Carbon-supported palladium niobium nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102166523A (en) * 2011-01-20 2011-08-31 北京化工大学 Preparation method of nickel nanoparticles-loaded multi-wall carbon nanotube catalytic agent
KR20120021385A (en) * 2010-07-29 2012-03-09 한국과학기술원 Method for one-pot synthesizing of catalyst for fuel cell having nano structure shape
US20120077031A1 (en) * 2009-12-22 2012-03-29 Korea Kumho Petrochemical Co., Ltd. Catalyst composition for the synthesis of thin multi-walled carbon nanotube
CN102916209A (en) * 2012-11-02 2013-02-06 湖南科技大学 Maskless direct alcohol fuel cell and preparation method thereof
CN103050715A (en) * 2013-01-14 2013-04-17 太原理工大学 Palladium-copper-tin ternary alloy nano-catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120077031A1 (en) * 2009-12-22 2012-03-29 Korea Kumho Petrochemical Co., Ltd. Catalyst composition for the synthesis of thin multi-walled carbon nanotube
KR20120021385A (en) * 2010-07-29 2012-03-09 한국과학기술원 Method for one-pot synthesizing of catalyst for fuel cell having nano structure shape
CN102166523A (en) * 2011-01-20 2011-08-31 北京化工大学 Preparation method of nickel nanoparticles-loaded multi-wall carbon nanotube catalytic agent
CN102916209A (en) * 2012-11-02 2013-02-06 湖南科技大学 Maskless direct alcohol fuel cell and preparation method thereof
CN103050715A (en) * 2013-01-14 2013-04-17 太原理工大学 Palladium-copper-tin ternary alloy nano-catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙丽枝: ""钯基纳米催化剂的制备及其对C2-C4醇氧化的电催化活性"", 《中国学位论文全文数据库》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104037440A (en) * 2014-05-30 2014-09-10 湖南科技大学 Membrane-free direct alcohol fuel cell in acid solution and preparation method thereof
CN105810923A (en) * 2014-12-31 2016-07-27 中国科学院宁波材料技术与工程研究所 Preparation method of ultra-small particle size tin and tin-based alloy nano-particle and application thereof
CN106910906A (en) * 2017-02-28 2017-06-30 上海电力学院 A kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application
CN107460463A (en) * 2017-06-23 2017-12-12 安庆师范大学 A kind of method that electricity displacement prepares Pd Co Ni alloy films in ionic liquid
CN108448126A (en) * 2018-02-09 2018-08-24 中南大学 A kind of PtAuTi nanowire catalytics material and preparation method thereof and application as fuel-cell catalyst
CN108448126B (en) * 2018-02-09 2020-09-04 中南大学 PtAuTi nanowire catalytic material, preparation method thereof and application of PtAuTi nanowire catalytic material as fuel cell catalyst
CN113745552A (en) * 2021-08-17 2021-12-03 西安交通大学 Carbon-supported palladium tin tantalum nitride nano electro-catalyst for direct ethanol and methanol fuel cell and preparation method thereof
CN113745552B (en) * 2021-08-17 2024-04-09 西安交通大学 Carbon-supported palladium-tin tantalum nitride nano electrocatalyst for direct ethanol and methanol fuel cells and preparation method thereof
CN113839056A (en) * 2021-08-28 2021-12-24 西安交通大学 Carbon-supported palladium niobium nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof
CN113839056B (en) * 2021-08-28 2024-04-09 西安交通大学 Carbon-supported palladium niobium nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof

Similar Documents

Publication Publication Date Title
CN103825034A (en) Palladium-tin-nickel ternary metallic nano electrocatalyst for fuel cell ethanol oxidation reaction and preparation method and application thereof
CN103545536B (en) A kind of carbon fiber loaded metallic catalyst and its preparation method and application
CN102723504B (en) Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method
CN102489314B (en) Graphene-loaded double-metal nano particles for methanol and ethanol fuel cells, and preparation method for graphene-loaded double-metal nano particles
CN103752328B (en) A kind of preparation method of the hollow core-shell catalyst for fuel cell
CN110038634A (en) A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction
CN105334251B (en) The Fe-Ni double-metal hydroxides of class tremelliform analyse oxygen electrode and its preparation method and application
CN102166523B (en) Preparation method of nickel nanoparticles-loaded multi-wall carbon nanotube catalytic agent
CN102024955B (en) Three-dimensional mesh nano porous palladium-ruthenium electrode material for fuel cell and preparation method thereof
Liu et al. Manganese dioxide coated graphene nanoribbons supported palladium nanoparticles as an efficient catalyst for ethanol electrooxidation in alkaline media
CN105858815A (en) Preparation method for NiCo2S4@NiCo2O4 nanoneedle composite catalytic electrode with core-shell structure
CN102380400B (en) Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof
CN103227336A (en) Band-shaped carbon-carrier metal catalyst, preparation method and application thereof
CN104538642A (en) Sulfur-doped carbon nanotube Pt-loaded catalyst for direct methanol fuel cell and preparation method of catalyst
CN102266770A (en) Preparation method of platinum/graphene nanometer electro-catalyst used for proton exchange membrane fuel cell
CN107486233A (en) A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst
CN109935840A (en) A kind of preparation method of fuel cell Pt base catalyst
CN106207205A (en) A kind of fuel cell PtPd eelctro-catalyst and preparation method thereof
CN101694880A (en) Electrode catalyst of fuel cell
CN107138172A (en) A kind of preparation method of electrode catalytic materialses and its application in glucose fuel cell
CN108746659B (en) Flower-shaped AgPd nano alloy and preparation and use methods thereof
Hosseini et al. MnNi2O4-MWCNTs as a nano-electrocatalyst for methanol oxidation reaction
CN105845952A (en) Preparation method for positive electrode catalyst of fuel cell
CN103381365A (en) Catalyst for preparing liquid fuel through carbon dioxide electrochemical reduction and preparation method thereof
CN101185900A (en) Method for preparing direct alcohols fuel cell anode catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140528