CN106299391B - A kind of palladium-cuprous oxide mesh nano catalysis material and its preparation and application - Google Patents

A kind of palladium-cuprous oxide mesh nano catalysis material and its preparation and application Download PDF

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CN106299391B
CN106299391B CN201610651332.5A CN201610651332A CN106299391B CN 106299391 B CN106299391 B CN 106299391B CN 201610651332 A CN201610651332 A CN 201610651332A CN 106299391 B CN106299391 B CN 106299391B
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palladium
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phytate
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cuprous
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CN106299391A (en
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杨海峰
吉媛媛
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Shanghai Normal University
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • 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
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 present invention relates to a kind of palladium-cuprous oxide mesh nano catalysis material and its preparations and application; the nano catalytic material is made up of following steps: (1) taking pre-assigned phytate solution; deionized water is added and is heated with stirring to boiling; it is charged with copper salt solution and lye again; heating stirring reaction; phytate is added again to get the cupric oxide nano-rod suspension protected to phytate；(2) the cupric oxide nano-rod suspension for taking step (1), is diluted with water, and sequentially adds tetrachloro-palladium acid salting liquid and ascorbic acid solution, and agitating and heating is centrifuged, and washing obtains palladium/cuprous nano catalysis material.Compared with prior art, nano catalytic material of the invention has higher catalytic activity, anti-poisoning ability and stability, and preparation method is environmentally protective etc..

Description

A kind of palladium-cuprous oxide mesh nano catalysis material and its preparation and application
Technical field
The present invention relates to nano catalytic material fields, more particularly, to a kind of palladium-cuprous oxide mesh nano catalysis material And its it prepares and applies.
Background technique
Compared to conventional fossil fuel, direct alcohol fuel cell has remarkable advantage, for example, high-energy density, low operation Temperature, environmentally protective, easily stored and transport etc..Direct alcohol fuel cell is in traffic transport industry and portable equipment field There is quite extensive practical application.Catalyst is the core component in fuel cell reaction, develops the pass of fuel cell Key concentrates on novel in design and superior anode catalysis material and optimum synthesis technique.Platinum based catalyst is current fuel cell The most effective catalyst in field, but since its higher cost and reserves are limited so that the business application of platinum in a fuel cell by Limit.The carbon intermediate product such as carbon monoxide can be generated in catalytic process simultaneously, it can occupy platinum surface-active site, make platinum by an oxygen Change carbon to poison and reduce catalytic activity.Therefore study it is a kind of low cost, the new catalyst of high electrochemical activity it is extremely important.
Another the efficient catalyst of precious metal palladium as industrial catalyst, has a wide range of applications.Due to palladium and platinum For same major element, electronics difference is only 0.77%, and palladium relative price is cheap, the catalysis with higher especially in alkaline medium Activity, and have stronger anti-poisoning ability.Therefore palladium has extensive prospect in direct alcohol fuel cell.Further Catalytic performance and the utilization rate for improving palladium-based catalyst are most important for the development of fuel cell.A large amount of work is right This problem is studied, and specific strategy has: (1) introduce other metals formed bimetallic or three metal alloy catalysts with Improve the utilization rate of palladium, such as PdCu, PdNi, Au@AgPd, PdPtRu etc.；(2) it mixes metal oxide or utilizes carbonaceous material (such as carbon black, graphene, carbon nanotube, carbon cloth etc.) is as load to improve palladium-based catalyst anti-poisoning ability and stabilization Performance.Studies have shown that the oxygen-containing group on some transition metal oxides, which can effectively aoxidize removing, is adsorbed on platinum or palladium table The carbon intermediate product such as carbon monoxide on the active site of face.
Secondly studies have shown that the pattern of nanoparticle also has important influence to catalytic performance, for example, cube, it is rodlike, Octahedron, nano-core-shell structure etc., these patterns present superior performance.And it is some in the recent period three-dimensional mostly empty, reticular structure at For the direction that new pattern controls, since these structures can provide more surface areas, a large amount of catalytic site of exposure is conducive to Electrocatalytic reaction process.
But the simple scheme by introducing other adminiclies or formation unique morphology all cannot significantly improve palladium base The performance of catalyst.
It is that still there is an urgent need to find the performance (catalysis for further increasing palladium-based catalyst in the problems of the field Activity, anti-poisoning ability, stability) and utilization rate scheme, it is superior that final design goes out a performance, has in a fuel cell The catalyst of broad application prospect.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of highly active catalytic first The preparation method of the palladium cuprous nano meshed anode material of alcohol.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of palladium-cuprous oxide mesh nano catalysis material, the nano catalytic material is by the Cu that individually disperses2O/Pd Nanoparticle is accumulated, microcosmic lower in reticular structure.
Preferably, the Cu2O/Pd nano-particles size is 5-15nm.
Palladium-cuprous oxide mesh nano catalysis material preparation method, comprising the following steps:
(1) it takes pre-assigned phytate solution, deionized water is added and is heated with stirring to boiling, then to be charged with mantoquita molten Phytate is added again to get the cupric oxide nano-rod suspension protected to phytate in liquid and lye, heating stirring reaction；
(2) the cupric oxide nano-rod suspension for taking step (1), is diluted with water, sequentially add tetrachloro-palladium acid salting liquid and Ascorbic acid solution, agitating and heating are centrifuged, and washing obtains palladium/cuprous nano catalysis material.
Preferably, step (1) and the additive amount of each raw material in step (2) meet: phytate, mantoquita, alkali, tetrachloro-palladium acid salt Molar ratio with ascorbic acid is 0.06:(8-12): (320-480): (0.3-0.4): (1.8-2.5).
It is furthermore preferred that the phytate is sodium phytate, mantoquita is copper chloride, and tetrachloro-palladium acid salt is sodium tetrachloropallate.It plants Hydrochlorate, mantoquita and tetrachloro-palladium acid salt may be other solubility salts.
Preferably, the molar ratio for the phytate being added twice in step (1) is 1:1-2.
Preferably, the concentration of pre-assigned phytate solution is 0.5-1mM, and the concentration of copper salt solution is 5-10mM, lye Concentration be 1-2M, the concentration of tetrachloro-palladium acid salt is 10-20mM, and the concentration of ascorbic acid solution is 0.1-0.2M.
Preferably, the temperature that heating stirring is reacted in step (1) is 90-100 DEG C, time 20-60min；
The temperature of agitating and heating is 70-100 DEG C in step (2).
Palladium-cuprous oxide mesh nano catalysis material is for constructing the electrode material with highly active catalytic methanol.
Preferably, the electrode material is made up of following steps:
(a) palladium-cuprous oxide mesh nano catalysis material is taken, the suspension of concentration 0.1-0.2mg/mL is made into；
(b) glass-carbon electrode for taking polishing to clean up, the suspension into its surface drop Tu step (a), naturally dry, i.e., Obtain the electrode material with highly active catalytic methanol.
Compared with prior art, the invention has the following advantages that
(1) catalysis material prepared by the present invention is in Nanostructure Network, which has hole abundant and heterogeneous interface, Be conducive to the transmitting, diffusion and improvement catalytic performance of reactant and product.And palladium and cuprous oxide in synthetic material Between strong electron interaction can occur to modify the electronic structure of palladium, improve the catalytic activity of palladium.Due to oxidation The oxygen-containing group of cuprous Adsorption on Surface can effectively aoxidize the carbon monoxide etc. for removing and being adsorbed on palladium active site surface Carbon intermediate product, the catalyst have better anti-poisoning ability and stability relative to commercial catalyst.
(2) present invention uses two environmentally protective, easy to operate one-step hydrothermals, is protected using the sodium phytate of first step synthesis Cupric oxide nano-rod, be successfully prepared for cuprous oxide modification palladium Nanostructure Network, the structure is by smaller nanometer kind Sub (about 10nm) composition.
Detailed description of the invention
Fig. 1 is palladium of the invention-cuprous oxide mesh nano catalysis material reaction mechanism figure；
Fig. 2 is transmission electron microscope shape appearance figure, wherein (A) is the transmission electron microscope pattern of cupric oxide nano-rod Figure, (B) are palladium/cuprous nano net transmission electron microscope shape appearance figure；
Fig. 3 is the palladium cuprous nano net (Cu of the high degree of dispersion obtained for 80 DEG C2O/Pd Networks), quotient With palladium black (Pd black), commercial palladium carbon (Pd/C) modified glassy carbon electrode 0.5M potassium hydroxide and 1.0M methanol solution circulation Voltammogram, sweeping speed is 50mV/s.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the palladium cuprous nano meshed anode material of highly active catalytic methanol, comprising the following steps:
(1) 300 μ L sodium phytate solutions (1mM) are added in 10mL deionized water to be sufficiently stirred and are heated to boiling, by 10mM's Copper chloride solution is added in phytic acid sodium water solution, keeps 90-100 DEG C of temperature, and 2M sodium hydroxide solution is added, is stirred continuously, It reacts 30 minutes, the sodium phytate with last time equivalent is added again, the cupric oxide nano-rod of sodium phytate protection is made, 10000 Be centrifuged 10min under~20000rpm revolving speed, be settled to 1mL, obtain cupric oxide nano-rod suspension (in this step, sodium phytate, chlorine Change copper, the molar ratio of alkali is 0.03:5:200)；
(2) it takes the cupric oxide nano-rod suspension of 15 μ L steps (1) to be scattered in 10mL deionized water, be stirred continuously and add The temperature of heat to 70-100 DEG C is added tetrachloro-palladium acid sodium solution, 200 μ L of 0.1mol/L ascorbic acid is then added dropwise, keeps 70- 100 DEG C, stirring 2h waits for reacting completely, and palladium cuprous nano net is made.Initial before this pale brown of the color of reaction process solution Color slowly becomes brownish black.Product obtained is cooled down at room temperature, 10min is centrifuged under 10000~20000rpm revolving speed, washes It washs 3~5 times, is scattered in spare in 1mL deionized water.
(3) in the glassy carbon electrode surface (diameter 3mm) polished and cleaned up, the palladium cuprous oxide of drop coating step (2) is received Rice net suspension (10 μ L) obtains the netted catalysis material of palladium cuprous nano of highly active catalytic methanol after natural drying Electrode material.
Fig. 1 shows the preparating mechanism figures of palladium cuprous nano Web materials.Sodium phytate IP6It indicates, sodium hydroxide is used NaOH expression, sodium tetrachloropallate Na2PdCl4It indicates, ascorbic acid is indicated with Ascorbic acid, and reduction reaction is used Reduction is indicated.
In Fig. 2, A figure indicates the transmission electron microscope image for the cupric oxide nano-rod that the first step obtains, cupric oxide nano The club shaped structure of rule is presented in particle, is uniformly dispersed, the length of single cupric oxide nano-rod about 10~20nm, width is about 5nm. B figure indicates the transmission electron microscope image of the palladium cuprous nano Web materials of second step synthesis, which presents netted Pattern is composed of the nanoparticle accumulation of individual relative distribution, and single nano-particles size is about 10nm or so, is had Good dispersibility.
Fig. 3 shows to test the electro-catalysis that different modifying electrode aoxidizes methanol under alkaline condition by cyclic voltammetry Performance.The experiment using CHI 660D type electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) by being carried out, using tradition Three-electrode system, wherein modified electrode is as working electrode, and platinum electrode is used as to electrode, and silver/silver chloride electrode is used as ginseng Compare electrode.It may be concluded that palladium cuprous nano Web materials (Cu from figure2O/Pd Networks) modified electrode The mass activity highest of catalysis methanol electrochemical oxidation reactions is commercial palladium black (Pd black), palladium carbon (Pd/C) modification respectively 3.03,2.73 times of electrode.This is the result shows that prepared palladium cuprous nano Web materials are a kind of the straight of function admirable Connect methanol fuel cell anode catalyzer.
The experimental results showed that synthesized catalysis material have for electrochemical oxidation of the methanol in alkaline environment it is excellent Catalytic performance.
Embodiment 2
A kind of preparation method using palladium-cuprous oxide mesh nano catalysis material modification electrode material, including it is following Step:
(1) sodium phytate solution of pre-assigned 0.5mM is taken, deionized water is added and is heated with stirring to boiling, holding temperature is 90 DEG C, then it is charged with the copper chloride solution of 5mM and the NaOH solution of 1M, it is stirred to react 60min, sodium phytate is added again, The cupric oxide nano-rod suspension of sodium phytate protection is obtained, it is 1:2 that the ratio between amount of sodium phytate is added twice.
(2) the cupric oxide nano-rod suspension for taking step (1) is diluted with water and is heated with stirring to 100 DEG C, sequentially adds The tetrachloro-palladium acid sodium solution of 20mM and the ascorbic acid solution of 0.2M can be prepared by palladium/cuprous nano particle, centrifuge washing Afterwards, it is dispersed in water palladium/cuprous nano suspension of obtained concentration 0.2mg/mL；Each raw material in step (1) and step (2) Additive amount meet: phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid molar ratio be 0.06:8:320:0.4:1.8.
(3) glass-carbon electrode for taking polishing to clean up, palladium/cuprous nano into its surface drop Tu step (2) are outstanding Supernatant liquid, at 20-25 DEG C naturally dry to get to highly active catalytic methanol electrode material.
Embodiment 3
A kind of preparation method using palladium-cuprous oxide mesh nano catalysis material modification electrode material, including it is following Step:
(1) sodium phytate solution of pre-assigned 0.8mM is taken, deionized water is added and is heated with stirring to boiling, holding temperature is 95 DEG C, then it is charged with the copper chloride solution of 8mM and the NaOH solution of 1.6M, it is stirred to react 20min, phytic acid is added again Sodium is 1:1.5 to get the ratio between amount of sodium phytate to the cupric oxide nano-rod suspension of sodium phytate protection, is added twice.
(2) the cupric oxide nano-rod suspension for taking step (1) is diluted with water and is heated with stirring to 90 DEG C, sequentially adds The tetrachloro-palladium acid sodium solution of 15mM and the ascorbic acid solution of 0.15M, can be prepared by palladium/cuprous nano particle, and centrifugation is washed After washing, it is dispersed in water palladium/cuprous nano suspension of obtained concentration 0.1mg/mL；Step (1) and step (2) Zhong Geyuan The additive amount of material meets: phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid molar ratio be 0.06:12:480:0.3: 2.5。
(3) glass-carbon electrode for taking polishing to clean up, palladium/cuprous nano into its surface drop Tu step (2) are outstanding Supernatant liquid, at 20-25 DEG C naturally dry to get to highly active catalytic methanol electrode material.
Embodiment 4
A kind of preparation method using palladium-cuprous oxide mesh nano catalysis material modification electrode material, including it is following Step:
(1) sodium phytate solution of pre-assigned 1mM is taken, deionized water is added and is heated with stirring to boiling, keeping temperature is 100 DEG C, then it is charged with the copper chloride solution of 10mM and the NaOH solution of 2M, it is stirred to react 30min, sodium phytate is added again, i.e., The cupric oxide nano-rod suspension of sodium phytate protection is obtained, it is 1:1 that the ratio between amount of sodium phytate is added twice.
(2) the cupric oxide nano-rod suspension for taking step (1) is diluted with water and is heated with stirring to 70 DEG C, sequentially adds The tetrachloro-palladium acid sodium solution of 10mM and the ascorbic acid solution of 0.1M can be prepared by palladium/cuprous nano particle, centrifuge washing Afterwards, it is dispersed in water palladium/cuprous nano suspension of obtained concentration 0.15mg/mL；Step (1) and step (2) Zhong Geyuan The additive amount of material meets: phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid molar ratio be 0.06:10:400:0.35: 2.2。
(3) glass-carbon electrode for taking polishing to clean up, palladium/cuprous nano into its surface drop Tu step (2) are outstanding Supernatant liquid, at 20-25 DEG C naturally dry to get to highly active catalytic methanol electrode material.
Embodiment 5
A kind of preparation method using palladium-cuprous oxide mesh nano catalysis material modification electrode material, including it is following Step:
(1) sodium phytate solution of pre-assigned 1mM is taken, deionized water is added and is heated with stirring to boiling, keeping temperature is 93 DEG C, then it is charged with the copper chloride solution of 7mM and the NaOH solution of 1.4M, it is stirred to react 30min, sodium phytate is added again, The cupric oxide nano-rod suspension of sodium phytate protection is obtained, it is 1:1.8 that the ratio between amount of sodium phytate is added twice.
(2) the cupric oxide nano-rod suspension for taking step (1) is diluted with water and is heated with stirring to 90 DEG C, sequentially adds The tetrachloro-palladium acid sodium solution of 12mM and the ascorbic acid solution of 0.18M, can be prepared by palladium/cuprous nano particle, and centrifugation is washed After washing, it is dispersed in water palladium/cuprous nano suspension of obtained concentration 0.12mg/mL；It is each in step (1) and step (2) The additive amount of raw material meets: phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid molar ratio be 0.06:9:360: 0.34:2.
(3) glass-carbon electrode for taking polishing to clean up, palladium/cuprous nano into its surface drop Tu step (2) are outstanding Supernatant liquid, at 20-25 DEG C naturally dry to get to highly active catalytic methanol electrode material.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention Within protection scope.

Claims (2)

1. a kind of palladium-cuprous oxide mesh nano catalysis material preparation method, which is characterized in that nano catalytic material is by independent The Cu of dispersion2O/Pd nanoparticle is accumulated, it is microcosmic it is lower be in reticular structure, preparation method the following steps are included:
(1) take pre-assigned phytate solution, deionized water be added and is heated with stirring to boiling, then be charged with copper salt solution with Phytate is added again to get the cupric oxide nano-rod suspension protected to phytate in lye, heating stirring reaction；
(2) the cupric oxide nano-rod suspension for taking step (1), is diluted with water, and sequentially adds tetrachloro-palladium acid salting liquid and anti-bad Hematic acid solution, agitating and heating are centrifuged, and washing obtains palladium/cuprous nano catalysis material；
The additive amount of each raw material meets in step (1) and step (2): phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid Molar ratio be 0.06:(8-12): (320-480): (0.3-0.4): (1.8-2.5)；
The phytate is sodium phytate, and mantoquita is copper chloride, and lye is NaOH solution, and tetrachloro-palladium acid salt is sodium tetrachloropallate；
The molar ratio for the phytate being added twice in step (1) is 1:1-2；
The concentration of pre-assigned phytate solution is 0.5-1 mM, and the concentration of copper salt solution is 5-10 mM, and the concentration of lye is 1- 2 M, the concentration of tetrachloro-palladium acid salt are 10-20 mM, and the concentration of ascorbic acid solution is 0.1-0.2M；
The temperature that heating stirring is reacted in step (1) is 90-100 DEG C, and the time is 20-60 min；
The temperature of agitating and heating is 70-100 DEG C in step (2).
2. a kind of palladium according to claim 1-cuprous oxide mesh nano catalysis material preparation method, feature exist In the Cu2O/Pd nano-particles size is 5-15 nm.
CN201610651332.5A 2016-08-10 2016-08-10 A kind of palladium-cuprous oxide mesh nano catalysis material and its preparation and application Expired - Fee Related CN106299391B (en)

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CN108321205B (en) * 2018-01-22 2019-12-03 江苏大学 Based on gold-nano cuprous oxide wire reticular structure phasmon FET and preparation method
CN110241438A (en) * 2018-03-08 2019-09-17 天津大学 Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof
CN112023937B (en) * 2019-11-26 2022-10-21 天津大学 Nano copper oxide coated palladium nanowire heterogeneous catalyst, preparation method thereof and application thereof in methanol electrocatalytic oxidation
CN111841568B (en) * 2020-07-02 2022-02-01 广州大学 Preparation and application of cuprous oxide loaded Pd composite photocatalytic material for photocatalytic reduction of carbon dioxide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734614A (en) * 2009-12-22 2010-06-16 上海大学 Method for manufacturing metal oxide nano-wire/noble metal nanocrystalline composite material
CN103977814A (en) * 2014-05-14 2014-08-13 中国科学技术大学 Size-controllable palladium-cuprous oxide nano catalyst as well as preparation method and catalysis application of catalyst
CN104289725A (en) * 2014-09-15 2015-01-21 中国科学院深圳先进技术研究院 Pd-based composite nano particle and preparation method thereof
US9005816B2 (en) * 2013-03-06 2015-04-14 Uchicago Argonne, Llc Coating of porous carbon for use in lithium air batteries

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734614A (en) * 2009-12-22 2010-06-16 上海大学 Method for manufacturing metal oxide nano-wire/noble metal nanocrystalline composite material
US9005816B2 (en) * 2013-03-06 2015-04-14 Uchicago Argonne, Llc Coating of porous carbon for use in lithium air batteries
CN103977814A (en) * 2014-05-14 2014-08-13 中国科学技术大学 Size-controllable palladium-cuprous oxide nano catalyst as well as preparation method and catalysis application of catalyst
CN104289725A (en) * 2014-09-15 2015-01-21 中国科学院深圳先进技术研究院 Pd-based composite nano particle and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Cu2O/Pd 网状结构制备及其对甲醇高电催化活性及其高抗毒化性能;吉媛媛等;《中国化学会第30届学术年会摘要集-第三十分会：化学电源》;20160701;第1页第1段

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