CN110241438A - Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof - Google Patents
Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof Download PDFInfo
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- CN110241438A CN110241438A CN201810191589.6A CN201810191589A CN110241438A CN 110241438 A CN110241438 A CN 110241438A CN 201810191589 A CN201810191589 A CN 201810191589A CN 110241438 A CN110241438 A CN 110241438A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
Abstract
The present invention discloses foam copper and supports palladium-copper alloy nanocages catalyst and preparation method thereof; under complexing agent protection; potassium chloropalladite solution is added in copper nanocube mixed solution; displacement generates Pd-Cu alloy nano cage; Nafion solution is added in Pd-Cu alloy nano cage again; mixing fullys shake, is uniformly brushed in foam copper substrate.Compared with the existing technology, palladium-copper alloy nanocages of the present invention are evenly distributed on foam copper, and catalyst is made to have more excellent catalytic activity, and catalyst of the invention is conducive to cost control and efficiency guarantee in large-scale production.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more particularly more particularly to a kind of foam copper
(CF) palladium-copper alloy nanocages (Pd-Cu) catalyst and preparation method thereof is supported.
Background technique
80% energy needed for mankind's activity is all from the burning of fossil fuel (natural gas, coal, petroleum etc.), such as electricity
Power, communications and transportation, manufacturing industry etc. generate about 1,000,000,000 carbon dioxide every year.Studies have shown that from the industrial revolution in 1750 to now
Atmospheric carbon dioxide levels are increased present 400ppm, the increase pair of gas concentration lwevel by past 280ppm
Terrestrial climate, ocean pH value etc. bring the damaging influence that can not be reversed.As in the past 100 years, Global Temperature increases 0.6 DEG C,
Mid-21st Century is expected, Global Temperature will increase 1.5-4.5 DEG C.The good news is carbon dioxide can be from combustion of fossil fuel
The captured at jobsite such as power generation, industrial premises waste gas stream, the natural gas well, and carbon dioxide capture and Plugging Technology Applied and cost have in recent years
Very big breakthrough.Carbon dioxide itself is also the carbon source for producing petroleum substance, if by carbon dioxide conversion at can be stored
Renewable energy, to reduce the discharge of carbon dioxide, this imagination will be extremely urgent, especially in existing carbon dioxide in an atmosphere
In the case where surging.Since carbon dioxide is one of the carbon compound of thermodynamicaHy most stable, it is translated into other carbon
Compound needs high energy reducing agent or external energy source.In recent years, electro-catalysis restored carbon dioxide because it is efficient, simple
Mode and receive significant attention and study.Having elctro-catalyst of the report display based on Nanoalloy structure can be in low overpotential
Lower realization carbon dioxide reduction.Well-known, ideal elctro-catalyst needs to meet under lower overpotential, with higher electric current effect
Rate generates single product.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide foam coppers to support palladium-copper alloy nanocages catalyst
And preparation method thereof.
Technical purpose of the invention is achieved by following technical proposals:
Foam copper supports palladium-copper alloy nanocages catalyst, and there is foam copper (CF) to support palladium-copper alloy nanocages (Pd-
Cu) structure, the Pd-Cu alloy nano cage based on hollow structure are carried in the foam copper substrate of porous structure.
Moreover, the particle size of the Pd-Cu alloy nano cage is 3-20 nanometers, preferably 8-12nm；And palladium in alloy
Content accounts for 10% of alloy gross mass or more, preferably 20-60%.
When being prepared, carry out as steps described below:
Step 1, potassium chloropalladite aqueous solution is added in the water phase of evenly dispersed copper nanocube, is protected in complexing agent
Displacement reaction is carried out under shield, to generate Pd-Cu alloy nano cage；
In step 1, the following method of copper nanocube is prepared: will stir 15 minutes through 80 DEG C of vigorous magnetics
Copper source and TOPO afterwards is dissolved in the oleyl amine of three-neck flask.Acquired solution is heated rapidly to 200-220 DEG C, and warm herein
Be back to few 1 hour under degree, 20-25 degrees Celsius of cooled to room temperature to get copper nanocube, copper source is copper nitrate, nitre
Sour cuprous, copper bromide or cuprous bromide.
In step 1, potassium chloropalladite, copper nanocube, complexing agent mass ratio be (0.5-3.5): (3-5):
(50-60), preferably (1-3): (3-4): (50-55), i.e. potassium chloropalladite dosage are 0.5-3.5 mass parts, copper nanometer is vertical
Cube dosage is 3-5 mass parts, amount of complex is 50-60 mass parts.
In step 1, complexing agent is citric acid, water-soluble citrate, ammonium hydroxide, (weight average molecular weight is 30000-to PVP
Or EDTA 55000).
In step 1, copper nanocube is added in water phase, oil bath stirring per minute 100-200 at 80-90 DEG C
Turn, add complexing agent, be diluted to 50-100mL with ultrapure water, 20-30min will be preheated, potassium chloropalladite aqueous solution passes through
Ejection of syringe pump keeps solution cooling into being put it into 0-4 DEG C of cold water immediately after reaction vessel, sodium chloride is added thereto until
Saturation, later with 5000-10000rpm be centrifuged 10-20min, then with ultrapure water clean and with same revolving speed centrifugation three times, i.e.,
Pd-Cu alloy nano cage can be obtained.
Step 2, Pd-Cu alloy nano cage prepared by step 1 is dispersed in Nafion aqueous solution, then uniformly brushed
Onto foam copper substrate, drying and moulding.
In step 2,20-are dried in 30-40 DEG C of vacuum ovens for 24 hours.
In step 2, foam copper of the foam copper between -120 mesh of 50 mesh.
In step 2, before brushing, foam copper is pre-processed, in 10-20% aqueous acetic acid of mass percent
10-20s are impregnated, it is dry in vacuum drying oven after deionized water cleaning is net.
In step 2, Nafion aqueous solution is the 10%Nafion solution of deionized water, mass percent 10-20%
(commercially available) is with isometric than uniformly mixed solution.
In step 2, the mass ratio of Pd-Cu alloy nano cage and Nafion aqueous solution is (1-1.5): (4-6), preferably
(1-1.2): (4-5).
Compared with the existing technology, palladium-copper alloy nanocages of the present invention are evenly distributed on foam copper, have catalyst more excellent
Different catalytic activity is conducive to cost control and efficiency guarantee in large-scale production, compared to monometallic Nanometer Copper and Technique of Nano Pd
Catalyst, the adsorption capacity that foam copper supports palladium-copper alloy nanocages catalyst is stronger, increases electrochemical surface area, can provide
More catalytic activity points, improve selectivity of product and efficiency.
Specific embodiment
It elaborates With reference to embodiment to the present invention.
Catalyst of the invention is that foam copper supports palladium-copper alloy nanocages catalyst, and the preparation method of catalyst includes
S1: palladium-copper alloy nanocages preparation step；S2: foam copper supports palladium-copper alloy step.However, those skilled in the art can manage
Solution, preparation method of the invention is not intended to be limited to above-mentioned 2 steps, other than above-mentioned 2 step, can also include for example after
Pre-treatment step, cleaning step and drying steps for stating etc..Hereinafter, successively being said to above-mentioned operation S1~S2 and other process
It is bright.
S1: palladium-copper alloy nanocages preparation step
By after 80 DEG C of vigorous magnetics stir 15 minutes copper source and TOPO be dissolved in three-neck flask oleyl amine in, by gained
Solution is heated rapidly to 210 DEG C, and flows back 1 hour at this temperature, and cooled to room temperature obtains copper nanocube, tool
Body bibliography: Zhao Xueyu, the controlledly synthesis of noble metal composite nanostructure and its property research [D] Chinese science technology are big
It learns, 2015.Complexing agent protection under, by preheat 20min after certain mass ratio potassium chloropalladite solution by syringe pump with
0.25mL/min flow velocity injects in copper nanocube mixed solution, and displacement generates Pd-Cu alloy nano cage；Copper nanocube
Mixed solution is the Cu nanocube of certain mass ratio and the ultrapure water diluent of complexing agent.The mixing temperature condition is 90
DEG C oil bath stirring；The displacement reaction process are as follows: the round-bottomed flask after potassium chloropalladite solution is added is immediately placed in cold water, to
After solution is cooling, sodium chloride is added until saturation, centrifugation.Then again with ultrapure washing and with same revolving speed centrifugation three times.Sample
It is dispersed in ultrapure water；
S2: foam copper supports palladium-copper alloy nanocages step
Nafion solution is added in Pd-Cu alloy nano cage, mixing fullys shake, is uniformly brushed to after foam copper substrate
It is dried for 24 hours in 35 DEG C of vacuum ovens.10s need to be impregnated in 20% dilute acetic acid solution before use, removes the oxidation on the surface CF
Layer and dirt；It is cleaned up using deionized water and is dried in vacuum drying oven afterwards.decagram Commissioning foam copper, uniformly divides in Copper substrate
Cloth the novel and multifunctional material of a large amount of connections or non-intercommunicating pore hole, apply in electrode material, catalyst, Heat Conduction Material, noise reduction
And shielding material, filtering material and Fluid pressure padded coaming, it is purchased from Kunshan Long Shengbao Electron Material Co., Ltd；Chlorine Asia palladium acid
Potassium, alias: tetrachloro-palladium potassium chlorate, molecular formula: K2PdCl4；Molecular weight: 326.427；105 DEG C of fusing point (dec.) (lit.)；Density
2.67g/mL at 25℃(lit.)；0-6 DEG C of condition of storage, it is purchased from upper object Science and Technology Ltd., Haikang nangzan；Nafion solution
It is perfluorosulfonic acid type polymer solution, forms membrane electrode, coating and carrier of the Nafion solution as catalyst, due to catalyst
Catalytic Layer it is very thin, reduce the transport resistance of substance and the resistance of electrode, substantially increase the utilization rate of Pt, by membrane electrode
It carries platinum amount and falls below 0.4mg/cm2, Nafion solution forms polymeric membrane after air-drying, and has selective penetrated property, while inhaling
Water can allow hydrogen ion to pass through without allowing methanol to pass through later；Since glass-carbon electrode is easy to be destroyed, Nafion solution is used
Protection can be played the role of to electrode by forming polymeric membrane, be purchased from Jiangsu Huayuan H-Power Technology Development Co., Ltd；TOPO is
Three n-octyl phosphorous oxides, organic solvent, extractant, boiling point: 210-215 degree, fusing point 48-50 degree lead to moral biology purchased from Tianjin
Science and Technology Ltd..
Embodiment 1
By taking palladium accounts for the 10% of Pd-Cu alloy nano cage gross mass as an example.
6mmol CuBr and 50mmolTOPO are dissolved in 20mL oleyl amine, divided at 80 DEG C with 10000rpm magnetic agitation 15
Clock.Acquired solution is heated rapidly to 210 DEG C, and is flowed back 1 hour at this temperature, it is vertical that cooled to room temperature obtains copper nanometer
Cube.The copper nanocube of 3.50mg is added in 250mL round-bottomed flask, oil bath is stirred at 90 DEG C.Add 50mg PVP
(M.W.=55,000), 50mL is diluted to ultrapure water.20min will be preheated, 2.5 μm of ol concentration are that 0.5mM potassium chloropalladite is molten
Liquid keeps solution cold into being put it into 4 DEG C of cold water immediately after round-bottomed flask by syringe pump with the speed injection of 0.25mL/min
But, sodium chloride is added thereto until saturation, is centrifuged 10min later with 10000rpm.Again with ultrapure water clean and equally to turn
Speed centrifugation three times.Pd-Cu alloy nano cage is dispersed in ultrapure water.Deionized water and 10% is added in Pd-Cu alloy nano cage
Mixing fullys shake with the mixed liquor of 1:1 ratio in Nafion, is dried in vacuo after being uniformly brushed to the copper-based bottom of 60 mesh of foam at 35 DEG C
It is dried for 24 hours in case.10s need to be impregnated in 20% dilute acetic acid solution before use, removes the oxide layer and dirt on the surface CF；After make
It is cleaned up with deionized water and dry in vacuum drying oven.
decagram Commissioning
Embodiment 2
By taking palladium accounts for the 30% of Pd-Cu alloy nano cage gross mass as an example.
3mmol CuBr and 25mmolTOPO are dissolved in 10mL oleyl amine, divided at 80 DEG C with 10000rpm magnetic agitation 15
Clock.Acquired solution is heated rapidly to 210 DEG C, and is flowed back 1 hour at this temperature, it is vertical that cooled to room temperature obtains copper nanometer
Cube.The copper nanocube of 3.50mg is added in 250mL round-bottomed flask, oil bath is stirred at 90 DEG C.Add 50mg PVP
(M.W.=55,000), is diluted to 50mL with ultrapure water.20min will be preheated, 7.5 μm of ol concentration are that 0.5mM potassium chloropalladite is molten
Liquid keeps solution cold into being put it into 4 DEG C of cold water immediately after round-bottomed flask by syringe pump with the speed injection of 0.25mL/min
But, sodium chloride is added thereto until saturation, is centrifuged 10min later with 10000rpm.Again with ultrapure water clean and equally to turn
Speed centrifugation three times.Pd-Cu alloy nano cage is dispersed in ultrapure water.Deionized water and 10% is added in Pd-Cu alloy nano cage
Mixing fullys shake with the mixed liquor of 1:1 ratio in Nafion, does after being uniformly brushed to the foam copper substrate of 90 mesh in 35 DEG C of vacuum
It is dried for 24 hours in dry case.10s need to be impregnated in 20% dilute acetic acid solution before use, removes the oxide layer and dirt on the surface CF；Afterwards
It is cleaned up using deionized water and dry in vacuum drying oven.
Embodiment 3
By taking palladium accounts for the 60% of Pd-Cu alloy nano cage gross mass as an example.
3mmol CuBr and 25mmolTOPO are dissolved in 10mL oleyl amine, divided at 80 DEG C with 10000rpm magnetic agitation 15
Clock.Acquired solution is heated rapidly to 210 DEG C, and is flowed back 1 hour at this temperature, it is vertical that cooled to room temperature obtains copper nanometer
Cube.The copper nanocube of 3.50mg is added in 250mL round-bottomed flask, oil bath is stirred at 90 DEG C.Add 50mg PVP
(M.W.=55,000), is diluted to 50mL with ultrapure water.20min will be preheated, 10.0 μm of ol concentration are that 0.5mM potassium chloropalladite is molten
Liquid keeps solution cold into being put it into 4 DEG C of cold water immediately after round-bottomed flask by syringe pump with the speed injection of 0.25mL/min
But, sodium chloride is added thereto until saturation, is centrifuged 10min later with 10000rpm.Again with ultrapure water clean and equally to turn
Speed centrifugation three times.Pd-Cu alloy nano cage is dispersed in ultrapure water.Deionized water and 10% is added in Pd-Cu alloy nano cage
Mixing fullys shake with the mixed liquor of 1:1 ratio in Nafion, does after being uniformly brushed to the foam copper substrate of 120 mesh in 35 DEG C of vacuum
It is dried for 24 hours in dry case.10s need to be impregnated in 20% dilute acetic acid solution before use, removes the oxide layer and dirt on the surface CF；Afterwards
It is cleaned up using deionized water and dry in vacuum drying oven.
Process according to the invention parameter is adjusted the preparation that catalyst can be achieved, and shows basic with embodiment
Consistent performance.Illustrative description has been done to the present invention above, it should explanation, in the feelings for not departing from core of the invention
Under condition, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work
Each fall within protection scope of the present invention.
Claims (10)
1. foam copper supports palladium-copper alloy nanocages catalyst, which is characterized in that have foam copper to support palladium-copper alloy nanocages
Structure, the Pd-Cu alloy nano cage based on hollow structure are carried in the foam copper substrate of porous structure, the Pd-Cu alloy
The particle size of nanocages is 3-20 nanometers, and the content of palladium accounts for 10% of alloy gross mass or more in alloy.
2. foam copper according to claim 1 supports palladium-copper alloy nanocages catalyst, which is characterized in that the Pd-Cu
The particle size of alloy nano cage is 8-12 nanometers, and the content of palladium accounts for 20-the 60% of alloy gross mass in alloy.
3. the preparation method that foam copper supports palladium-copper alloy nanocages catalyst, which is characterized in that carry out as steps described below:
Step 1, potassium chloropalladite aqueous solution is added in the water phase of evenly dispersed copper nanocube, under complexing agent protection
Carry out displacement reaction, to generate Pd-Cu alloy nano cage, potassium chloropalladite, copper nanocube, complexing agent mass ratio be
(0.5-3.5): (3-5): (50-60)；
Step 2, Pd-Cu alloy nano cage prepared by step 1 is dispersed in Nafion aqueous solution, then is uniformly brushed to bubble
On the copper-based bottom of foam, drying and moulding；The mass ratio of Pd-Cu alloy nano cage and Nafion aqueous solution is (1-1.5): (4-
6)。
4. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 1, the following method of copper nanocube is prepared: by the copper source after 80 DEG C of vigorous magnetics stir 15 minutes
It is dissolved in the oleyl amine of three-neck flask with TOPO.Acquired solution is heated rapidly to 200-220 DEG C, and is flowed back at this temperature
At least 1 hour, 20-25 degrees Celsius of cooled to room temperature to get copper nanocube, copper source is copper nitrate, cuprous nitrate,
Copper bromide or cuprous bromide.
5. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 1, potassium chloropalladite, copper nanocube, complexing agent mass ratio be (1-3): (3-4): (50-55).
6. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 1, complexing agent be citric acid, water-soluble citrate, ammonium hydroxide, PVP (weight average molecular weight is 30000-55000) or
Person EDTA.
7. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 1, copper nanocube is added in water phase, 100-200 turns per minute of oil bath stirring, adds at 80-90 DEG C
Complexing agent is diluted to 50-100mL with ultrapure water, will preheat 20-30min, potassium chloropalladite aqueous solution passes through ejection of syringe pump
Being put it into 0-4 DEG C of cold water immediately after into reaction vessel keeps solution cooling, and sodium chloride is added thereto until being saturated, later
10-20min are centrifuged with 5000-10000rpm, then is cleaned with ultrapure water and is centrifuged three times with same revolving speed, Pd- can be obtained
Cu alloy nano cage.
8. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 2, the mass ratio of Pd-Cu alloy nano cage and Nafion aqueous solution is (1-1.2): (4-5).
9. the preparation method that foam copper according to claim 3 supports palladium-copper alloy nanocages catalyst, which is characterized in that
In step 2, foam copper of the foam copper between -120 mesh of 50 mesh；Before brushing, foam copper is pre-processed, quality percentage
10-20s are impregnated in 10-20% aqueous acetic acid of number, it is dry in vacuum drying oven after deionized water cleaning is net；Nafion is water-soluble
Liquid is the 10%Nafion solution of deionized water, mass percent 10-20% with isometric solution than being uniformly mixed.
10. foam copper according to claim 3 supports the preparation method of palladium-copper alloy nanocages catalyst, feature exists
In in step 2, dry 20-for 24 hours in 30-40 DEG C of vacuum ovens.
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690977A (en) * | 2009-09-14 | 2010-04-07 | 西安交通大学 | Preparation method of hollow noble metal nanoparticles |
| CN101808634A (en) * | 2006-06-13 | 2010-08-18 | 利兰·斯坦福青年大学托管委员会 | The epoxide inhibitors of cysteine proteinase |
| CN102179248A (en) * | 2011-03-22 | 2011-09-14 | 上海师范大学 | Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| CN102989450A (en) * | 2012-12-03 | 2013-03-27 | 中国科学院大连化学物理研究所 | Preparation method, structural feature and application of carrying type nanometer electrocatalyst |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN103208616A (en) * | 2013-03-05 | 2013-07-17 | 浙江大学 | Method for water-soluble template synthesis of one-dimensional hollow nano spindle structure with functional layer coated with foam metal |
| CN104308172A (en) * | 2014-08-11 | 2015-01-28 | 常州大学 | Method for preparing hollow cubic micro-nano metal |
| CN104624186A (en) * | 2015-02-05 | 2015-05-20 | 俞杏英 | Dendritic platinum-palladium alloy nanometer catalyst as well as preparation method and application thereof |
| CN105396600A (en) * | 2015-11-10 | 2016-03-16 | 中国科学院福建物质结构研究所 | Pd5.12Cu dendritic nanocrystalline catalyst as well as preparation and application thereof |
| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN105597780A (en) * | 2015-12-29 | 2016-05-25 | 中国科学院福建物质结构研究所 | Self-assembled Pd-Cu bimetal dendritic nanocrystal catalyst as well as preparation and application thereof |
| CN106299390A (en) * | 2015-06-24 | 2017-01-04 | 中国科学院金属研究所 | Nano-particle is embedded in nano composite material and the preparation method of CNT tube wall |
| CN106299391A (en) * | 2016-08-10 | 2017-01-04 | 上海师范大学 | A kind of palladium Red copper oxide mesh nano catalysis material and preparation thereof and application |
| CN106784295A (en) * | 2016-11-18 | 2017-05-31 | 南京航空航天大学 | A kind of multi-pore channel IPMC electro-active materials based on foam metal and preparation method thereof |
| CN106910907A (en) * | 2017-04-14 | 2017-06-30 | 中国科学院深圳先进技术研究院 | A kind of catalyst with core-casing structure, Preparation Method And The Use |
| CN106914238A (en) * | 2017-03-27 | 2017-07-04 | 中国科学技术大学 | A kind of palladium-silver double metallic composite material and preparation method thereof |
| CN107037027A (en) * | 2016-11-16 | 2017-08-11 | 贵州师范学院 | A kind of wide area surface strengthens the preparation method of Raman scattering substrate |
| CN107482234A (en) * | 2017-08-25 | 2017-12-15 | 河南师范大学 | A kind of preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope |
| CN108933265A (en) * | 2018-09-18 | 2018-12-04 | 深圳先进技术研究院 | A kind of alloy nano cage catalyst and its preparation method and application |
-
2018
- 2018-03-08 CN CN201810191589.6A patent/CN110241438A/en active Pending
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808634A (en) * | 2006-06-13 | 2010-08-18 | 利兰·斯坦福青年大学托管委员会 | The epoxide inhibitors of cysteine proteinase |
| CN101690977A (en) * | 2009-09-14 | 2010-04-07 | 西安交通大学 | Preparation method of hollow noble metal nanoparticles |
| CN102179248A (en) * | 2011-03-22 | 2011-09-14 | 上海师范大学 | Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| CN102989450A (en) * | 2012-12-03 | 2013-03-27 | 中国科学院大连化学物理研究所 | Preparation method, structural feature and application of carrying type nanometer electrocatalyst |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN103208616A (en) * | 2013-03-05 | 2013-07-17 | 浙江大学 | Method for water-soluble template synthesis of one-dimensional hollow nano spindle structure with functional layer coated with foam metal |
| CN104308172A (en) * | 2014-08-11 | 2015-01-28 | 常州大学 | Method for preparing hollow cubic micro-nano metal |
| CN104624186A (en) * | 2015-02-05 | 2015-05-20 | 俞杏英 | Dendritic platinum-palladium alloy nanometer catalyst as well as preparation method and application thereof |
| CN106299390A (en) * | 2015-06-24 | 2017-01-04 | 中国科学院金属研究所 | Nano-particle is embedded in nano composite material and the preparation method of CNT tube wall |
| CN105396600A (en) * | 2015-11-10 | 2016-03-16 | 中国科学院福建物质结构研究所 | Pd5.12Cu dendritic nanocrystalline catalyst as well as preparation and application thereof |
| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN105597780A (en) * | 2015-12-29 | 2016-05-25 | 中国科学院福建物质结构研究所 | Self-assembled Pd-Cu bimetal dendritic nanocrystal catalyst as well as preparation and application thereof |
| CN106299391A (en) * | 2016-08-10 | 2017-01-04 | 上海师范大学 | A kind of palladium Red copper oxide mesh nano catalysis material and preparation thereof and application |
| CN107037027A (en) * | 2016-11-16 | 2017-08-11 | 贵州师范学院 | A kind of wide area surface strengthens the preparation method of Raman scattering substrate |
| CN106784295A (en) * | 2016-11-18 | 2017-05-31 | 南京航空航天大学 | A kind of multi-pore channel IPMC electro-active materials based on foam metal and preparation method thereof |
| CN106914238A (en) * | 2017-03-27 | 2017-07-04 | 中国科学技术大学 | A kind of palladium-silver double metallic composite material and preparation method thereof |
| CN106910907A (en) * | 2017-04-14 | 2017-06-30 | 中国科学院深圳先进技术研究院 | A kind of catalyst with core-casing structure, Preparation Method And The Use |
| CN107482234A (en) * | 2017-08-25 | 2017-12-15 | 河南师范大学 | A kind of preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope |
| CN108933265A (en) * | 2018-09-18 | 2018-12-04 | 深圳先进技术研究院 | A kind of alloy nano cage catalyst and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| ZHANG, NAN 等: ""A novel adsorbent TEMPO-mediated oxidized cellulose nanofibrils modified with PEI: Preparation, characterization, and application for Cu(II) removal"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 王录才 等: "《泡沫金属制备、性能及应用》", 31 October 2012, 国防工业出版社 * |
| 赵雪宇: ""贵金属复合纳米结构的可控合成及其性质研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169809A (en) * | 2020-11-03 | 2021-01-05 | 西安工程大学 | Preparation method of flexible nano Pd/CuO particle @ foam Cu catalyst |
| CN112169809B (en) * | 2020-11-03 | 2024-01-19 | 深圳万知达科技有限公司 | Preparation method of flexible nano Pd/CuO particle@foam Cu catalyst |
| CN112974826A (en) * | 2021-02-10 | 2021-06-18 | 中国科学技术大学 | Palladium-cadmium intermetallic compound/alloy catalyst material and synthesis method and application thereof |
| CN113059178A (en) * | 2021-03-16 | 2021-07-02 | 中国石油大学(北京) | Hollow alloy nano-particles and preparation method and application thereof |
| CN113463114A (en) * | 2021-06-30 | 2021-10-01 | 河南师范大学 | Nano-alloy cubic hollow shell structure CO2Preparation method of electro-reduction catalyst |
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