CN106299391A - A kind of palladium Red copper oxide mesh nano catalysis material and preparation thereof and application - Google Patents
A kind of palladium Red copper oxide mesh nano catalysis material and preparation thereof and application Download PDFInfo
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- CN106299391A CN106299391A CN201610651332.5A CN201610651332A CN106299391A CN 106299391 A CN106299391 A CN 106299391A CN 201610651332 A CN201610651332 A CN 201610651332A CN 106299391 A CN106299391 A CN 106299391A
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- 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
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- 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]
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a kind of palladium Red copper oxide mesh nano catalysis material and preparation thereof and application; described nano catalytic material is made by following steps: (1) takes pre-assigned phytate solution; add deionized water and be heated with stirring to boiling; it is charged with copper salt solution and alkali liquor again; heated and stirred is reacted; again add phytate, i.e. obtain the cupric oxide nano-rod suspension of phytate protection；(2) take the cupric oxide nano-rod suspension of step (1), dilute, sequentially add tetrachloro-palladium acid saline solution and ascorbic acid solution, agitating heating, be centrifuged, washing, i.e. prepare palladium/cuprous nano catalysis material.Compared with prior art, the nano catalytic material of the present invention has higher catalysis activity, anti-poisoning ability and stability, preparation method environmental protection etc..
Description
Technical field
The present invention relates to nano catalytic material field, especially relate to a kind of palladium-Red copper oxide mesh nano catalysis material
And prepare and application.
Background technology
Comparing conventional fossil fuel, direct alcohol fuel cell has remarkable advantage, such as, high-energy-density, low operation
Temperature, environmental protection, it is easy to store and transport etc..Direct alcohol fuel cell is in traffic transport industry and portable equipment field
There is actual application.Catalyst is the core component in fuel cell reaction, the pass of development 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 maximally effective catalyst in field, but owing to it is relatively costly and reserves are limited so that platinum business application in a fuel cell is subject to
Limit.Can produce the carbon intermediate products such as carbon monoxide in catalytic process, it can occupy platinum surface activity site, makes platinum by an oxygen simultaneously
Change carbon to poison and reduce catalysis activity.Therefore study a kind of low cost, high electrochemical activity new catalyst extremely important.
Precious metal palladium, as another efficient catalyst of 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, especially has higher catalysis in alkaline medium
Activity, and have stronger anti-poisoning ability.Therefore palladium has prospect widely in direct alcohol fuel cell.Further
The catalytic performance and the utilization rate that improve palladium-based catalyst are most important for the development of fuel cell.Substantial amounts of work is the most right
This problem is studied, and concrete strategy has: (1) introduce other metals formed bimetallic or three metal alloy catalyst with
Improve the utilization rate of palladium, such as PdCu, PdNi, Au@AgPd, PdPtRu etc.；(2) mix metal-oxide or utilize carbonaceous material
(such as carbon black, Graphene, CNT, carbon cloth etc.) is as loading to improve palladium-based catalyst anti-poisoning ability and stablizing
Performance.Research shows, the oxy radical on some transition metal oxides can aoxidize removing absorption effectively at platinum or palladium table
The carbon intermediate products such as the carbon monoxide on the avtive spot of face.
Secondly research shows, the pattern of nanoparticle also has an important impact to catalytic performance, such as cube, bar-shaped,
Octahedron, nano-core-shell structure etc., these patterns present superior performance.And how empty some three-dimensionals are in the recent period, network structure becomes
For the direction of new morphology control, owing to these structures are provided that more surface area, expose substantial amounts of catalytic site, be conducive to
Electrocatalytic reaction process.
But simple all can not significantly improve palladio by the scheme introducing other adminiclies or formation unique morphology
The performance of catalyst.
It is still in the urgent need to finding the performance (catalysis improving palladium-based catalyst further in the problem existing for this field
Activity, anti-poisoning ability, stability) and the scheme of utilization rate, final design goes out a superior performance, has in a fuel cell
It is widely applied the catalyst of prospect.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of highly active catalytic first is provided
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-Red copper oxide mesh nano catalysis material, described nano catalytic material is by independent scattered Cu2O/Pd
Nanoparticle is piled up and is formed, in network structure under its microcosmic.
Preferably, described Cu2O/Pd nano-particles size is 5-15nm.
The preparation method of palladium-Red copper oxide mesh nano catalysis material, comprises the following steps:
(1) take pre-assigned phytate solution, add deionized water and be heated with stirring to boiling, then it is molten to be charged with mantoquita
Liquid and alkali liquor, heated and stirred is reacted, is again added phytate, i.e. obtains the cupric oxide nano-rod suspension of phytate protection；
(2) take the cupric oxide nano-rod suspension of step (1), dilute, sequentially add tetrachloro-palladium acid saline solution and
Ascorbic acid solution, agitating heating, centrifugal, washing, i.e. prepare palladium/cuprous nano catalysis material.
Preferably, step (1) meets with the addition of each raw material in step (2): phytate, mantoquita, alkali, tetrachloro-palladium acid salt
It is 0.06:(8-12 with the mol ratio of ascorbic acid): (320-480): (0.3-0.4): (1.8-2.5).
It is furthermore preferred that described phytate is sodium phytate, mantoquita is copper chloride, and tetrachloro-palladium acid salt is tetrachloro-palladium acid sodium.Plant
Hydrochlorate, mantoquita and tetrachloro-palladium acid salt can also be other solubility salts.
Preferably, in step (1), the mol ratio of the phytate of twice addition 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, alkali liquor
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, in step (1), the temperature of heated and stirred reaction is 90-100 DEG C, and the time is 20-60min；
In step (2), the temperature of agitating heating is 70-100 DEG C.
Palladium-Red copper oxide mesh nano catalysis material is for constructing the electrode material with highly active catalytic methanol.
Preferably, described electrode material is made by following steps:
A () takes palladium-Red copper oxide mesh nano catalysis material, be made into the suspension of concentration 0.1-0.2mg/mL；
B () takes the glass-carbon electrode that polishing cleans up, drip the suspension in step (a) toward its surface, naturally dry, i.e.
Obtain the electrode material with highly active catalytic methanol.
Compared with prior art, the invention have the advantages that
(1) catalysis material prepared by the present invention is Nanostructure Network, and this structure has abundant hole and heterogeneous interface,
Be conducive to reactant and the transmission of product, spread and improve catalytic performance.And the palladium in synthetic material and Red copper oxide
Between strong electron interaction can occur thus modify the electronic structure of palladium, improve the catalysis activity of palladium.Due to oxidation
The oxy radical of cuprous Adsorption on Surface can aoxidize the carbon monoxide etc. removing absorption on palladium avtive spot surface effectively
Carbon intermediate product, this catalyst has more preferable anti-poisoning ability and stability relative to commercial catalyst.
(2) present invention uses environmental protection, two one-step hydrothermals simple to operate, utilizes the sodium phytate protection that the first step synthesizes
Cupric oxide nano-rod, be successfully prepared for Red copper oxide modify palladium Nanostructure Network, this structure is by less nanometer kind
Son (about 10nm) composition.
Accompanying drawing explanation
Fig. 1 is the reaction mechanism figure of the palladium-Red copper oxide mesh nano catalysis material of the present invention；
Fig. 2 is transmission electron microscope shape appearance figure, and wherein, (A) is the transmission electron microscope pattern of cupric oxide nano-rod
Figure, (B) is the transmission electron microscope shape appearance figure of palladium/cuprous nano net；
Fig. 3 is the palladium cuprous nano net (Cu of the high degree of dispersion obtained as a example by 80 DEG C2O/Pd Networks), business
With palladium black (Pd black), commercial palladium carbon (Pd/C) modified glassy carbon electrode in 0.5M potassium hydroxide and the circulation of 1.0M methanol solution
Voltammogram, sweeps speed for 50mV/s.
Detailed description of the invention
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, comprises the following steps:
(1) will 300 μ L sodium phytate solution (1mM) addition 10mL deionized waters be sufficiently stirred for being heated to boiling, by 10mM's
Copper chloride solution adds in sodium phytate aqueous solution, keeps the temperature of 90-100 DEG C, adds 2M sodium hydroxide solution, is stirred continuously,
React 30 minutes, again add and the sodium phytate of equivalent last time, prepare the cupric oxide nano-rod of sodium phytate protection, 10000
～centrifugal 10min under 20000rpm rotating speed, be settled to 1mL, obtain cupric oxide nano-rod suspension (in this step, sodium phytate, chlorine
Change copper, the mol ratio of alkali is 0.03:5:200)；
(2) the cupric oxide nano-rod suspension taking 15 μ L step (1) is scattered in 10mL deionized water, is stirred continuously and adds
The temperature of heat to 70-100 DEG C, adds tetrachloro-palladium acid sodium solution, subsequently dropping 0.1mol/L ascorbic acid 200 μ L, keeps 70-
100 DEG C, stirring 2h treats to react completely, prepares palladium cuprous nano net.The most initial pale brown of the color of course of reaction solution
Color slowly becomes brownish black.At room temperature being cooled down by prepared product, under 10000～20000rpm rotating speeds, centrifugal 10min, washes
Wash 3～5 times, be scattered in 1mL deionized water standby.
(3) in the glassy carbon electrode surface (diameter 3mm) polished and clean up, the palladium Red copper oxide of drop coating step (2) is received
Rice net suspension (10 μ L), i.e. obtains the netted catalysis material of palladium cuprous nano of highly active catalytic methanol after naturally drying
Electrode material.
Fig. 1 represents the preparating mechanism figure of palladium cuprous nano Web materials.Sodium phytate IP6Representing, sodium hydroxide is used
NaOH represents, tetrachloro-palladium acid sodium Na2PdCl4Representing, ascorbic acid Ascorbic acid represents, reduction reaction is used
Reduction represents.
In Fig. 2, the transmission electron microscope image of the cupric oxide nano-rod that the A figure expression first step obtains, cupric oxide nano
Particle presents the club shaped structure of rule, is uniformly dispersed, and the length of single cupric oxide nano-rod about 10～20nm, width is about 5nm.
B figure represents the transmission electron microscope image of the palladium cuprous nano Web materials of second step synthesis, and this material presents netted
Pattern, is piled up by the nanoparticle of single relative distribution and combines, and single nano-particles size is about about 10nm, has
Good dispersibility.
Fig. 3 shows to test, by cyclic voltammetry, the electro-catalysis that methanol is aoxidized by different modifying electrode in the basic conditions
Performance.This experiment, by utilizing CHI 660D type electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) to carry out, uses tradition
Three-electrode system, wherein modified electrode is as working electrode, and platinum electrode is 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 of catalysis methanol electrochemical oxidation reactions is the highest, is commercial palladium black (Pd black), palladium carbon (Pd/C) modification respectively
The 3.03 of electrode, 2.73 times.This result shows that prepared palladium cuprous nano Web materials is the straight of a kind of function admirable
Connect methanol fuel cell anode catalyzer.
Test result indicate that synthesized catalysis material has excellence for methanol electrochemical oxidation in alkaline environment
Catalytic performance.
Embodiment 2
The preparation method of a kind of electrode material using palladium-Red copper oxide mesh nano catalysis material to modify, including following
Step:
(1) taking the sodium phytate solution of pre-assigned 0.5mM, add deionized water and be 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, stirring reaction 60min, again add sodium phytate,
I.e. obtaining the cupric oxide nano-rod suspension of sodium phytate protection, the ratio of the amount that twice adds sodium phytate is 1:2.
(2) taking the cupric oxide nano-rod suspension of step (1), dilute is also 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
After, it is dispersed in water the palladium/cuprous nano suspension of prepared concentration 0.2mg/mL；Step (1) and each raw material in step (2)
Addition meet: the mol ratio of phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid is 0.06:8:320:0.4:1.8.
(3) take the glass-carbon electrode that polishing cleans up, drip the palladium/cuprous nano in step (2) toward its surface and hang
Supernatant liquid, dries at 20-25 DEG C naturally, i.e. obtains the electrode material with highly active catalytic methanol.
Embodiment 3
The preparation method of a kind of electrode material using palladium-Red copper oxide mesh nano catalysis material to modify, including following
Step:
(1) taking the sodium phytate solution of pre-assigned 0.8mM, add deionized water and be 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, stirring reaction 20min, again add phytic acid
Sodium, i.e. obtains the cupric oxide nano-rod suspension of sodium phytate protection, and the ratio of the amount that twice adds sodium phytate is 1:1.5.
(2) taking the cupric oxide nano-rod suspension of step (1), dilute is also 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, is centrifuged and washes
After washing, it is dispersed in water the palladium/cuprous nano suspension of prepared concentration 0.1mg/mL；Step (1) and step (2) Zhong Geyuan
The addition of material meets: the mol ratio of phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid is 0.06:12:480:0.3:
2.5。
(3) take the glass-carbon electrode that polishing cleans up, drip the palladium/cuprous nano in step (2) toward its surface and hang
Supernatant liquid, dries at 20-25 DEG C naturally, i.e. obtains the electrode material with highly active catalytic methanol.
Embodiment 4
The preparation method of a kind of electrode material using palladium-Red copper oxide mesh nano catalysis material to modify, including following
Step:
(1) taking the sodium phytate solution of pre-assigned 1mM, add deionized water and be 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, and stirring reaction 30min, again add sodium phytate, i.e.
Obtaining the cupric oxide nano-rod suspension of sodium phytate protection, the ratio of the amount that twice adds sodium phytate is 1:1.
(2) taking the cupric oxide nano-rod suspension of step (1), dilute is also 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
After, it is dispersed in water the palladium/cuprous nano suspension of prepared concentration 0.15mg/mL；Step (1) and step (2) Zhong Geyuan
The addition of material meets: the mol ratio of phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid is 0.06:10:400:0.35:
2.2。
(3) take the glass-carbon electrode that polishing cleans up, drip the palladium/cuprous nano in step (2) toward its surface and hang
Supernatant liquid, dries at 20-25 DEG C naturally, i.e. obtains the electrode material with highly active catalytic methanol.
Embodiment 5
The preparation method of a kind of electrode material using palladium-Red copper oxide mesh nano catalysis material to modify, including following
Step:
(1) taking the sodium phytate solution of pre-assigned 1mM, add deionized water and be 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, and stirring reaction 30min, again add sodium phytate,
I.e. obtaining the cupric oxide nano-rod suspension of sodium phytate protection, the ratio of the amount that twice adds sodium phytate is 1:1.8.
(2) taking the cupric oxide nano-rod suspension of step (1), dilute is also 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, is centrifuged and washes
After washing, it is dispersed in water the palladium/cuprous nano suspension of prepared concentration 0.12mg/mL；Step (1) is each with step (2)
The addition of raw material meets: the mol ratio of phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid is 0.06:9:360:
0.34:2.
(3) take the glass-carbon electrode that polishing cleans up, drip the palladium/cuprous nano in step (2) toward its surface and hang
Supernatant liquid, dries at 20-25 DEG C naturally, i.e. obtains the electrode material with highly active catalytic methanol.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention.
These embodiments obviously easily can be made various amendment by person skilled in the art, and described herein typically
Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel should be the present invention's according to the announcement of the present invention, the improvement made without departing from scope and amendment
Within protection domain.
Claims (10)
1. palladium-Red copper oxide mesh nano catalysis material, it is characterised in that described nano catalytic material is by individually disperseing
Cu2O/Pd nanoparticle is piled up and is formed, in network structure under its microcosmic.
A kind of palladium-Red copper oxide mesh nano catalysis material the most according to claim 1, it is characterised in that described
Cu2O/Pd nano-particles size is 5-15nm.
3. the preparation method of palladium-Red copper oxide mesh nano catalysis material as claimed in claim 1 or 2, it is characterised in that bag
Include following steps:
(1) take pre-assigned phytate solution, add deionized water be heated with stirring to boiling, then be charged with copper salt solution and
Alkali liquor, heated and stirred is reacted, is again added phytate, i.e. obtains the cupric oxide nano-rod suspension of phytate protection；
(2) take the cupric oxide nano-rod suspension of step (1), dilute, sequentially add tetrachloro-palladium acid saline solution and anti-bad
Hematic acid solution, agitating heating, centrifugal, washing, i.e. prepare palladium/cuprous nano catalysis material.
The preparation method of a kind of palladium the most according to claim 3-Red copper oxide mesh nano catalysis material, its feature exists
In, step (1) meets with the addition of each raw material in step (2): phytate, mantoquita, alkali, tetrachloro-palladium acid salt and ascorbic acid
Mol ratio is 0.06:(8-12): (320-480): (0.3-0.4): (1.8-2.5).
The preparation method of a kind of palladium the most according to claim 4-Red copper oxide mesh nano catalysis material, its feature exists
In, described phytate is sodium phytate, and mantoquita is copper chloride, and alkali liquor is NaOH solution, and tetrachloro-palladium acid salt is tetrachloro-palladium acid sodium.
The preparation method of a kind of palladium the most according to claim 3-Red copper oxide mesh nano catalysis material, its feature exists
In, in step (1), the mol ratio of the phytate of twice addition is 1:1-2.
The preparation method of a kind of palladium the most according to claim 3-Red copper oxide mesh nano catalysis material, its feature exists
In, the concentration of pre-assigned phytate solution is 0.5-1mM, and the concentration of copper salt solution is 5-10mM, and the concentration of alkali liquor is 1-2M,
The concentration of tetrachloro-palladium acid salt is 10-20mM, and the concentration of ascorbic acid solution is 0.1-0.2M.
The preparation method of a kind of palladium the most according to claim 3-Red copper oxide mesh nano catalysis material, its feature exists
In, in step (1), the temperature of heated and stirred reaction is 90-100 DEG C, and the time is 20-60min；
In step (2), the temperature of agitating heating is 70-100 DEG C.
9. palladium-Red copper oxide mesh nano catalysis material as claimed in claim 1 or 2 is used for constructing and has highly active catalytic first
The electrode material of alcohol.
The application of palladium the most according to claim 9-Red copper oxide mesh nano catalysis material, it is characterised in that described
Electrode material is made by following steps:
A () takes palladium-Red copper oxide mesh nano catalysis material, be made into the suspension of concentration 0.1-0.2mg/mL；
B () takes the glass-carbon electrode that polishing cleans up, drip the suspension in step (a) toward its surface, naturally dry, i.e. obtain
There is the electrode material of highly active catalytic methanol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321205A (en) * | 2018-01-22 | 2018-07-24 | 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 |
| CN111841568A (en) * | 2020-07-02 | 2020-10-30 | 广州大学 | Preparation and application of cuprous oxide loaded Pd composite photocatalytic material for photocatalytic reduction of carbon dioxide |
| CN112023937A (en) * | 2019-11-26 | 2020-12-04 | 天津大学 | Nano copper oxide coated palladium nanowire heterogeneous catalyst, preparation method thereof and application thereof in methanol electrocatalytic oxidation |
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| CN108321205A (en) * | 2018-01-22 | 2018-07-24 | 江苏大学 | Based on gold-nano cuprous oxide wire reticular structure phasmon FET and preparation method |
| 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 |
| CN112023937A (en) * | 2019-11-26 | 2020-12-04 | 天津大学 | Nano copper oxide coated palladium nanowire heterogeneous catalyst, preparation method thereof and application thereof in methanol electrocatalytic oxidation |
| 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 |
| CN111841568A (en) * | 2020-07-02 | 2020-10-30 | 广州大学 | Preparation and application of cuprous oxide loaded Pd composite photocatalytic material for photocatalytic reduction of carbon dioxide |
| 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 |
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