CN107447209A - A kind of method for preparing Pd Co P composite membranes using chemical plating displacement - Google Patents
A kind of method for preparing Pd Co P composite membranes using chemical plating displacement Download PDFInfo
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- CN107447209A CN107447209A CN201710487486.XA CN201710487486A CN107447209A CN 107447209 A CN107447209 A CN 107447209A CN 201710487486 A CN201710487486 A CN 201710487486A CN 107447209 A CN107447209 A CN 107447209A
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- chemical plating
- displacement
- liquid
- plating
- composite membranes
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- 238000007747 plating Methods 0.000 title claims abstract description 25
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims abstract description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 229910001096 P alloy Inorganic materials 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
- 238000007772 electroless plating Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- XVBDCEZPZVUCJD-UHFFFAOYSA-N [Cl+].CCCC[N+]=1C=CN(C)C=1 Chemical compound [Cl+].CCCC[N+]=1C=CN(C)C=1 XVBDCEZPZVUCJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- GCFSKCZBSOKYLJ-UHFFFAOYSA-N [Na].O[PH2]=O Chemical compound [Na].O[PH2]=O GCFSKCZBSOKYLJ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- ADDFGXAESAZSBJ-UHFFFAOYSA-N CC=1NC=CN1.[Cl] Chemical compound CC=1NC=CN1.[Cl] ADDFGXAESAZSBJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000006184 cosolvent Substances 0.000 abstract 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LZIYMYUNSGZACR-UHFFFAOYSA-N N-(dimethylcarbamoyl)-2-hydroxyacetamide Chemical compound CN(C(NC(CO)=O)=O)C LZIYMYUNSGZACR-UHFFFAOYSA-N 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium hypophosphites Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/33—
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
A kind of method for preparing Pd Co P composite membranes using chemical plating displacement of the present invention, comprises the following steps：First with the methylimidazole chlorine (BMIMCl) of 1 butyl 3, liquid containing cobalt ions [BMIM] CoCl3And sodium hypophosphite NaH2PO2As chemical plating raw material, a small amount of DMH keeps certain temperature and mixing speed, chemical plating is carried out on graphite cake, gained chemistry plating piece is put into Ch containing palladium ionic liquids as cosolvent2PdCl4Displacement liquid in, under stirring action and certain temperature, immersion obtain Pd Co P composite membranes, the 3D network architectures are presented in composite membrane obtained by this method, with higher electro catalytic activity and durability, and process conditions require low, are a kind of more promising film catalyst preparation technologies.
Description
Technical field
The present invention relates to a kind of method that Pd-Co-P composite membranes are prepared using chemical plating-displacement, belong to catalyst preparation skill
Art field.
Background technology
It is widely studied at present that active component or chief active group are mainly used as using Pt with the fuel-cell catalyst of application
The catalyst divided.But Pt is expensive, anti-poisoning capability is poor, and the fast development and popularization to fuel cell are provided with obstacle.
Therefore, new no-Pt catalyst is explored and develops to be of great significance the commercialization process tool for promoting fuel cell.Pd
It is the preferable selection for substituting Pt, Pd is preferable in catalytic process moderate resistance poisoning capability, and price is only Pt half, in fuel cell
Field has a good application prospect.How further to improve Pd catalytic performance is the key that Pd can replace Pt catalyst.People
Generally use other metals are introduced into pure Pd or nonmetallic method is modified to it.The focus studied at present adds your non-gold
Category element is Co, Ni etc., at room temperature with double Pd-Co alloy catalysts its oxygen reduction catalytic activities under the same conditions with polycrystalline
Pt is sufficiently close to, and the ability poisoned with preferable methanol tolerance.Some nonmetallic doping can also promote Pd catalytic
Energy.Addition such as P can improve electro catalytic activity and stability of the Pd catalyst to Oxidation of Formic Acid.By these elements compoundings add
Into Pd, it is expected to obtain more preferable catalytic performance.But it is difficult due to preparing, it is more than ternary or ternary compound on being carried out in Pd
The report of film is also seldom.
The present invention is prepared for Pd-Co-P composite membranes, obtained composite membrane in ionic liquid using chemical plating-displacement method
With very high mechanical strength, electric conductivity and good catalytic activity, and process is simple and environmentally-friendly, is a kind of more promising
Polynary Pd group compound films preparation method.
The content of the invention
Based on problem present in background technology, the invention provides Pd-Co-P composite membranes are prepared in a kind of ionic liquid
Method.The purpose of this method is formed in realizing the addition base metal Co and nonmetallic P into Pd by chemical plating-displacement method
Pd-Co-P composite membranes with good catalytic and use value, while provide a kind of technique simple production method.
A kind of method that Pd-Co-P composite membranes are prepared using chemical plating-displacement proposed by the present invention, in electroless plating tank,
Add ionic liquid 1-butyl-3-methyl imidazolium chlorine (BMIMCl), liquid containing cobalt ions [BMIM] CoCl3, sodium hypophosphite
NaH2PO2And DMH (DMH) is used as chemical plating fluid, the scattered stirring of ultrasonic wave, chemical plating is carried out on graphite cake, is obtained
Co-P alloy plating pieces；Choline Chloride and urea (mol ratio 1 are added in reaction vessel is replaced:2) anhydrous low melting point mixing is molten
Agent, Ch containing palladium ionic liquids2PdCl4As displacement liquid, Co-P alloy plating pieces are put into displacement liquid and soak a period of time, be made
Pd-Co-P composite membranes.
Preferably, component composition of the Co-P chemical plating fluids based on mass volume ratio：Liquid containing cobalt ions [BMIM] CoCl3For
6~30g/L, sodium hypophosphite NaH2PO2It is 0~5g/L for 1.5-6g/L, DMH (DMH).Chemical plating fluid temperature is 70-
100 DEG C, mixing speed is 200-400 rpms, electroless plating time 20-40 minutes.
Preferably, Ch containing palladium ionic liquids in displacement liquid2PdCl4For 3~8g/L, alloy plating piece soaks 3- in displacement liquid
8h, temperature are kept for 80~100 DEG C, and mixing speed is controlled in 150rm.
A kind of method that Pd-Co-P composite membranes are prepared using chemical plating-displacement, it is comprised the following steps that：
Step 1, using pretreated graphite cake as depositing base, take a certain amount of ionic liquid 1- butyl -3- methyl
Imidazoles chlorine (BMIMCl) is put into coating bath, and a certain amount of liquid containing cobalt ions [BMIM] is then separately added into ionic liquid
CoCl3, sodium hypophosphite NaH2PO2And a small amount of DMH (DMH), the scattered stirring of ultrasonic wave, changed on graphite cake
Learn plating；Take out plating piece and use ethanol and deionized water rinsing successively, dry up, produce Co-P alloy layers.
Specific reaction equation is as follows：
3H2PO2 –=H2PO3 -+2P↓+H2O+2OH-
H2PO2 -+H2O=H2PO3 -+H2↑
CoCl3 -+H2PO2 -+H2O=Co ↓+H2PO3 -+2HCl+Cl-
Step 2, in inert-gas environment, take a certain amount of, take a certain amount of Choline Chloride and urea (mol ratio 1:2) nothing
Water low melting point mixed solvent is put into displacement reaction vessel, is then separately added into low melting point in the mixed solvent containing palladium ionic liquids
Ch2PdCl4, the alloy plating piece that step 1 obtains is put into displacement liquid and soaked, Pd-Co-P composite membranes are made by replacing to react.
The chemical reaction that replacement process occurs is as follows：
[PdCl4]-2+Co→Pd+CoCl3 -
The lower metallic cobalt displacement Pd using on matrix belongs to kinetics and controlled for diffusion in ionic liquid, so instead
Answer temperature critically important, temperature is too low, is unfavorable for reaction and carries out, too high, then considers energy consumption, selecting 80~100 DEG C is advisable.
It is characteristic of the invention that：
(1) present invention is effectively adjusted Pd-Co-P composite membrane geometry, electronics and surface texture, is in due to Co, P addition
The existing 3D network architectures, make it have higher electro catalytic activity and durability.
(2) present invention process is simple, and raw material is easy to get, and it is easy to prepare, and cheap, energy consumption is smaller.
Brief description of the drawings
Fig. 1 is the compound membrane preparation device figures of Pd-Co-P for the present invention.
Fig. 2 is the surface topography map of Pd-Co-P composite membranes in the present invention.
Embodiment
With reference to embodiment, the invention will be further described.
Step 1, as shown in Figure 1, graphite cake matrix is subjected to the pretreatment procedures such as alkaline degreasing, pickling, washing, drying
Depositing base is used as afterwards, takes 250mL ionic liquid 1-butyl-3-methyl imidazolium chlorine (BMIMCl) to be put into coating bath, Ran Houxiang
10g liquid containing cobalt ions [BMIM] CoCl is separately added into ionic liquid3, 3g sodium hypophosphites NaH2PO2And 0.5 gram of dimethyl
Glycolylurea (DMH), ultrasonic wave disperses, and mixing speed is 300 rpms, and temperature is kept for 85 DEG C carry out chemical plating 30 minutes；Take out
Plating piece uses ethanol and deionized water rinsing successively, drying, produces Co-P alloy layers.
Step 2, in inert-gas environment, take 300mL Choline Chloride and urea (mol ratio 1:2) anhydrous low melting point mixing
Solvent is put into displacement reaction vessel, is then separately added into 1.5g Ch containing palladium ionic liquids to low melting point in the mixed solvent2PdCl4,
The alloy plating piece that step 1 obtains is put into displacement liquid, temperature is kept for 85 DEG C, and mixing speed control is in 150rm, immersion
4h, Pd-Co-P composite membranes are made.Using cyclic voltammetric technology, to prepared catalyst in alkaline environment to the electricity of methanol
Oxidation catalytic activity is tested, and Methanol Anode oxidative peak current density reaches 98mA/cm-2, and show preferably stable
Property.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (3)
- A kind of 1. method that Pd-Co-P composite membranes are prepared using chemical plating-displacement, it is characterised in that：In electroless plating tank, add Ionic liquid 1-butyl-3-methyl imidazolium chlorine (BMIMCl), liquid containing cobalt ions [BMIM] CoCl3, sodium hypophosphite NaH2PO2With And DMH (DMH) is used as chemical plating fluid, the scattered stirring of ultrasonic wave, chemical plating is carried out on graphite cake, obtains Co-P alloys Plating piece；Choline Chloride and urea (mol ratio 1 are added in reaction vessel is replaced:2) anhydrous low melting point mixed solvent, containing palladium from Sub- liquid Ch2PdCl4As displacement liquid, Co-P alloy plating pieces are put into displacement liquid and soak a period of time, obtained Pd-Co-P is answered Close film.
- 2. the method according to claim 1 that Pd-Co-P composite membranes are prepared using chemical plating-displacement, it is characterised in that： Component composition of the Co-P chemical plating fluids based on mass volume ratio：Liquid containing cobalt ions [BMIM] CoCl3For 6~30g/L, hypophosphorous acid Sodium NaH2PO2It is 0~5g/L for 1.5~6g/L, DMH (DMH).Chemical plating fluid temperature is 70-100 DEG C, mixing speed For 200-400 rpms (rm), electroless plating time 20-40 minutes.
- 3. the method according to claim 1 that Pd-Co-P composite membranes are prepared using chemical plating-displacement, it is characterised in that：Put Change Ch containing palladium ionic liquids in liquid2PdCl4For 3~8g/L, alloy plating piece soaks 3-8h in displacement liquid, and temperature keeps 80~100 DEG C, mixing speed is controlled in 150rm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710487486.XA CN107447209B (en) | 2017-06-23 | 2017-06-23 | Method for preparing Pd-Co-P composite membrane by utilizing chemical plating-displacement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710487486.XA CN107447209B (en) | 2017-06-23 | 2017-06-23 | Method for preparing Pd-Co-P composite membrane by utilizing chemical plating-displacement |
Publications (2)
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| CN107447209A true CN107447209A (en) | 2017-12-08 |
| CN107447209B CN107447209B (en) | 2020-08-14 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
| CN114425332A (en) * | 2022-02-24 | 2022-05-03 | 河南科技大学 | Preparation method and application of Au-Pd micro-flowers constructed by ultrathin nanosheets |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409745A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Preparation method of high-performance superlow-palladium-capacity anode electrocatalyst Pd-CoP/C of direct formic acid fuel cell |
| US20150203968A1 (en) * | 2014-01-17 | 2015-07-23 | National Central University | Method for treating metal surface |
| CN106521581A (en) * | 2016-10-12 | 2017-03-22 | 安庆师范大学 | Method for preparing Ni-Cr-P alloy clad layer through ionic liquid electroplating technology |
-
2017
- 2017-06-23 CN CN201710487486.XA patent/CN107447209B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150203968A1 (en) * | 2014-01-17 | 2015-07-23 | National Central University | Method for treating metal surface |
| CN104409745A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Preparation method of high-performance superlow-palladium-capacity anode electrocatalyst Pd-CoP/C of direct formic acid fuel cell |
| CN106521581A (en) * | 2016-10-12 | 2017-03-22 | 安庆师范大学 | Method for preparing Ni-Cr-P alloy clad layer through ionic liquid electroplating technology |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
| CN114425332A (en) * | 2022-02-24 | 2022-05-03 | 河南科技大学 | Preparation method and application of Au-Pd micro-flowers constructed by ultrathin nanosheets |
| CN114425332B (en) * | 2022-02-24 | 2023-07-25 | 河南科技大学 | Preparation method and application of Au-Pd micron flower constructed by ultrathin nanosheets |
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| Publication number | Publication date |
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| CN107447209B (en) | 2020-08-14 |
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