CN102389794B - Method for preparing Pd catalyst with three-dimensional nano meshy structure by reduction of nitrile rubber precursor - Google Patents
Method for preparing Pd catalyst with three-dimensional nano meshy structure by reduction of nitrile rubber precursor Download PDFInfo
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- CN102389794B CN102389794B CN2011103065926A CN201110306592A CN102389794B CN 102389794 B CN102389794 B CN 102389794B CN 2011103065926 A CN2011103065926 A CN 2011103065926A CN 201110306592 A CN201110306592 A CN 201110306592A CN 102389794 B CN102389794 B CN 102389794B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000009467 reduction Effects 0.000 title claims abstract description 27
- 229920000459 Nitrile rubber Polymers 0.000 title abstract 5
- 239000002243 precursor Substances 0.000 title abstract 2
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 235000019253 formic acid Nutrition 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 132
- 239000003292 glue Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 14
- 241000370738 Chlorion Species 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 44
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a Pd catalyst with three-dimensional nano meshy structure by reduction of a nitrile rubber precursor, which comprises: mixing K3Co(CN)6 and K2PdC14 by ultrasonic according to a molar ratio of 1:2 in a temperature range of 0 to 100 DEG C, standing and obtaining nitrile rubber A, adding reducer in the same amount or an excessive amount into the nitrile rubber A, standing for 0.1 to 24 hours, reacting nitrile rubber with the reducer, obtaining a component B after reducing the Pd metal , washing the component B, and drying the component B to obtain a palladium catalyst. The catalyst prepared by the method has a three-dimensional meshy structure, has high homogeneity and dispensability, and has high electric catalytic activity and stability for formic acid oxidization. The preparation method disclosed by the invention is simple and economic and is suitable for industrial large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of direct methanoic acid fuel cell catalyst, particularly relate to a kind of method of utilizing the reduction of cyanogen glue presoma to prepare the palladium catalyst (Pd-NNWs) with tridimensional nano net structure, this catalyst has excellent catalytic performance and stability to the electrochemical oxidation of formic acid.
Background technology
The energy is of close concern to each other with human survival and development; along with the fossil energies such as coal, oil, natural gas are day by day exhausted; the mankind are faced with energy crisis, use fossil energy also to cause serious environmental pollution, so the development and utilization of green energy resource is the inevitable choice that realizes energy sustainable development.Fuel cell becomes following best " clean energy resource " owing to have the advantages such as energy conversion efficiency height, environmental pollution are little.
At present, efficient, the convenient favor that is subject to people of fuel cell, it is that the chemical energy that will be present in the fuel is converted into the green energy resource device that electric energy is exported, and also has the advantages such as construction period weak point, easy care and low cost.Yet, also having a segment distance from the fuel cell commercialization at present, the catalytic efficiency that its anode and cathode is lower and fancy price are one of bottlenecks that suppresses its development.Therefore, improve the active and stable of catalyst, reduce the carrying capacity of noble metal, the manufacturing cost that effectively reduces battery is the key problem in technology of fuel cell.
Many studies show that, the precious metal material of nanoscale has outstanding catalytic property, electrical property, magnetic property and optical property.In recent years, for the preparation method of non-loading type metal nanoparticle widely research is arranged, because the shape of these metal nanoparticles is determining their character and range of application, such as catalysis, photoelectricity, sensor and fuel cell etc.
With platinum catalyst Comparatively speaking, palladium catalyst has higher electro catalytic activity for the oxidation of formic acid, and huge application potential is arranged in direct methanoic acid fuel cell.It is active that Pd metal pair formic acid has unique catalytic oxidation.But the average grain diameter of the Pd catalyst particle that conventional liquid-phase reduction method makes is larger, and the Pd metallic catalyst is very unstable, and easy oxidized inactivation therefore in the urgent need to the Pd catalyst of preparation small particle diameter, high stability, improves the utilization rate of Pd catalyst.Therefore, exploring the method can be used for preparation of industrialization high-performance Pd catalyst is one and makes problems of concern.
Summary of the invention
The purpose of this invention is to provide that a kind of anode palladium catalyst with direct methanoic acid fuel cell of tridimensional nano net structure---the preparation method of Pd-NNWs catalyst, prepared catalyst has very high catalytic activity and stability to Oxidation of Formic Acid.
The technical scheme of finishing the foregoing invention task is:
A kind of method of utilizing the reduction of cyanogen glue presoma to prepare the Pd catalyst (Pd-NNWs) with tridimensional nano net structure is characterized in that: in 0 ℃ of-100 ℃ of scope, with K
3Co (CN)
6And K
2PdCl
4To leave standstill preparation cyanogen glue A after the ultrasonic mixing of mol ratio 1:2; In cyanogen glue A, add equivalent or excessive reducing agent, left standstill 0.1-24 hour, make the reaction of cyanogen glue A and reducing agent, get B component after the metal Pd reduction; The Pd-NNWs catalyst is washed, is drying to obtain to B component.
Described cyanogen glue A is a kind of inorganic polymer hydrogel with tridimensional network.In the process of reduction gel, Pd is reduced along gel networks, obtains loose porous tridimensional nano net structure Pd particle agglomeration.
Compare the liquid-phase system that presoma is shla molecule or ion, the inventive method uses cyanogen glue as presoma, prepare the palladium catalyst of tridimensional nano net structure along cyanogen glue skeleton reducing metal Pd, it possesses higher stability and to the electro catalytic activity of formic acid.
More particularly, the method for utilizing the reduction of cyanogen glue presoma to prepare the Pd catalyst with tridimensional nano net structure of the present invention may further comprise the steps:
1) synthetic cyanogen glue presoma: in 0 ℃ of-100 ℃ of scope, with K
3Co (CN)
6And K
2PdCl
4To leave standstill after the ultrasonic mixing of mol ratio 1:2, prepare cyanogen glue A;
2) cyanogen glue skeleton reduction: add equivalent or excessive reducing agent in cyanogen glue A, left standstill 0.1-24 hour, make the reaction of cyanogen glue and reducing agent, reducing agent gets B component with the reduction of the metal Pd in the cyanogen glue skeleton;
3) post processing: B component is used HClO successively
4And pure water washing, and with the liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion, under vacuum or inert gas atmosphere, be drying to obtain subsequently the Pd-NNWs catalyst.
Described cyanogen glue presoma is to pass through K
3Co (CN)
6And K
2PdCl
4Make to leave standstill after the ultrasonic mixing of mol ratio 1:2.
Described reducing agent is NaBH
4, inferior sodium phosphate, formic acid or formaldehyde etc.
Described inert gas atmosphere is Ar or N
2Deng.
The invention has the advantages that:
The inventive method makes Pd catalyst as presoma through in-situ reducing by cyanogen glue, has special tridimensional nano net structure from the Pd catalyst of gel reducing process preparation, the result shows that the Pd catalyst of the tridimensional nano net structure for preparing has good homogeneity and decentralization, and it shows very excellent electro catalytic activity and stability to Oxidation of Formic Acid.And preparation method of the present invention is simple, and economy is fit to industrial mass production.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1: the SEM photo of Pd-NNWs catalyst.
Fig. 2: the TEM photo of Pd-NNWs catalyst.
Fig. 3: (a) commercialization Pd black and (b) the prepared Pd-NNWs catalyst of cyanogen glue method of reducing at the HClO of 1.0 M
4Cyclic voltammetry curve among+1.0 M HCOOH.Sweep speed: 50 mV/s, temperature: 30 ℃.
The specific embodiment
Embodiment one
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment two
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (NaH
2PO
2), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment three
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (HCOOH), leave standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment four
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (HCHO), leave standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment five
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.1 mol/L K
2PdCl
4Solution and 1.0 ml, 0.1 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment six
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.2 mol/L K
2PdCl
4Solution and 1.0 ml, 0.2 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment seven
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.5 mol/L K
2PdCl
4Solution and 1.0 ml, 0.5 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment eight
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) under 0 ℃ of condition, slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment nine
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) under 35 ℃ of conditions, slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Embodiment ten
Utilize cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, may further comprise the steps:
1) pipettes 2.0 ml, 0.05 mol/L K
2PdCl
4Solution and 1.0 ml, 0.05 mol/L K
3Co (CN)
6Solution, half an hour, left standstill in ultrasonic mixing, obtains cyanogen glue presoma.
2) under 45 ℃ of conditions, slowly add excessive reductant solution (NaBH
4), left standstill 24 hours, make cyanogen glue presoma and reducing agent complete reaction.
3) through HClO
4And after the washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.Namely get Pd-NNWs after placing the vacuum desiccator drying.
Fig. 1 is the SEM figure of Pd-NNWs catalyst, can find out obviously that from figure the Pd catalyst of preparing with cyanogen glue reducing process has a kind of special tridimensional network, and no longer be that form with single particle exists, this network structure is owing to reducing agent forms along cyanogen glue skeleton reducing metal Pd.
Fig. 2 is the TEM figure of Pd-NNWs catalyst, and TEM figure shows that the Pd-NNWs by the preparation of cyanogen glue reducing process has good homogeneity and decentralization.
Fig. 3 be (a) commodity Pd black and (b) cyanogen glue reducing process gained Pd-NNWs catalyst at the HClO of 1.0 M
4Cyclic voltammetry curve comparison diagram among+1.0 M HCOOH.As seen from the figure, the oxidation peak current of formic acid on the Pd-NNWs catalyst be apparently higher than the black catalyst of commercial Pd, shows that reducing prepared Pd-NNWs by cyanogen glue has higher electro catalytic activity to formic acid.
Claims (3)
1. one kind is utilized cyanogen glue presoma reduction preparation to have the method for the Pd catalyst of tridimensional nano net structure, it is characterized in that: in 0 ℃ of-100 ℃ of scope, with K
3Co (CN)
6And K
2PdCl
4To leave standstill after the ultrasonic mixing of mol ratio 1:2, prepare cyanogen glue A; In cyanogen glue A, add equivalent or excessive reducing agent, left standstill 0.1-24 hour, make the reaction of cyanogen glue and reducing agent, get B component after the metal Pd reduction; Described Pd catalyst with tridimensional nano net structure is washed, is drying to obtain to B component.
2. the method for utilizing the reduction preparation of cyanogen glue presoma to have the Pd catalyst of tridimensional nano net structure according to claim 1 is characterized in that described method may further comprise the steps:
1) synthetic cyanogen glue presoma: in 0 ℃ of-100 ℃ of scope, with K
3Co (CN)
6And K
2PdCl
4To leave standstill after the ultrasonic mixing of mol ratio 1:2, prepare cyanogen glue A;
2) cyanogen glue skeleton reduction: add equivalent or excessive reducing agent in cyanogen glue A, left standstill 0.1-24 hour, make the reaction of cyanogen glue and reducing agent, reducing agent gets B component with the reduction of the metal Pd in the cyanogen glue skeleton;
3) post processing: B component is used HClO successively
4And pure water washing, and with the liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion, under vacuum or inert gas atmosphere, be drying to obtain subsequently the Pd catalyst with tridimensional nano net structure.
3. the method for utilizing the reduction of cyanogen glue presoma to prepare the Pd catalyst with tridimensional nano net structure according to claim 1 and 2 is characterized in that described reducing agent is NaBH
4, inferior sodium phosphate, formic acid or formaldehyde.
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| CN103290246B (en) * | 2013-05-27 | 2015-06-24 | 南京师范大学 | Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode |
| CN104174867A (en) * | 2014-08-15 | 2014-12-03 | 南京师范大学 | Preparation method of tin-cobalt-nickel ternary alloy anode material adopting micro-nano hierarchical structure for lithium ion battery |
| CN107086314B (en) * | 2017-06-09 | 2019-07-09 | 南京师范大学 | A kind of preparation method of the porous noble metal base nano-catalyst of two dimension |
| CN107308940B (en) * | 2017-07-25 | 2020-05-29 | 陕西师范大学 | Preparation method of ultrathin porous Co nanosheet |
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| CN109647460B (en) * | 2019-01-30 | 2021-06-22 | 浙江师范大学 | Method for preparing NiCoP @ NiCoPOx oxygen evolution catalyst with porous three-dimensional core-shell structure by one-step reduction method |
| CN113714507B (en) * | 2021-08-02 | 2024-03-05 | 南京师范大学 | Cyano-modified three-dimensional palladium-copper nano coral and preparation method and application thereof |
| CN114426257B (en) * | 2021-11-15 | 2023-03-21 | 南京师范大学 | Three-dimensional porous PdH 0.649 Preparation method and application of nano coral |
| CN114204043A (en) * | 2021-12-10 | 2022-03-18 | 先进能源产业研究院(广州)有限公司 | Alkaline system hydrazine hydrate fuel cell cathode material and preparation method thereof |
| CN114335574A (en) * | 2021-12-10 | 2022-04-12 | 先进能源产业研究院(广州)有限公司 | Non-noble metal catalyst for fuel cell and preparation method thereof |
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| Title |
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| Electro-catalytic performance of PdCo bimetallic hollow nano-spheres for the oxidation of formic acid;Yawen Tang et al.;《J Solid State Electrochem》;20100324;第14卷;2077-2082 * |
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