CN105688935A - Preparation method of Pt/Cu-Ni catalyst and method and application of catalyst for catalyzing and oxidizing alcohols - Google Patents
Preparation method of Pt/Cu-Ni catalyst and method and application of catalyst for catalyzing and oxidizing alcohols Download PDFInfo
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- 229910002482 Cu–Ni Inorganic materials 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 title abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000004070 electrodeposition Methods 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 230000003197 catalytic effect Effects 0.000 claims description 39
- 230000003647 oxidation Effects 0.000 claims description 35
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 238000000151 deposition Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 30
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000002060 nanoflake Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 229910021607 Silver chloride Inorganic materials 0.000 description 19
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 19
- 210000001787 dendrite Anatomy 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000002135 nanosheet Substances 0.000 description 10
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- -1 platinum ion Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910002677 Pd–Sn Inorganic materials 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- 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
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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
Abstract
The invention discloses a preparation method of a Pt/Cu-Ni catalyst and a method and application of the catalyst for catalyzing and oxidizing alcohols. The preparation method comprises the steps that a Cu-Ni bimetallic alloy which is subjected to electrodeposition in advance serves as a heterogeneous template, chloroplatinic acid serves as a platinum source, and a nano flake Pt/Cu-Ni catalyst with a dendritic structure is obtained. The preparation method is simple, the condition is mild and controllable, high temperature and strict equipment requirements are not needed, environmental friendliness is achieved, pollution does not exist, and the prepared Pt/Cu-Ni catalyst has a larger specific surface area and can efficiently catalyze and oxidize alcoholic solutions, specially a monohydric alcohol solution, in acid solutions.
Description
Technical field
The invention belongs to method for preparing catalyst and application, be specifically related to a kind of preparation method of Pt/Cu-Ni catalyst and the method for catalytic oxidation of alcohol thereof and application。
Background technology
Along with society is fast-developing, energy demand is the subject matter that the mankind are badly in need of solving。Methanol fuel cell (DAFCs) is the energy of a kind of cleaning, thus being also considered as the most promising energy。In the catalytic oxidation of methanol, Pt demonstrates higher catalysis activity, but, Pt is not only expensive but also poor stability, thus hindering methanol fuel cell extensive use commercially。
Therefore, current substantial amounts of research is intended to the material finding a kind of novelty to replace part Pt and to improve its catalytic capability, and this has just had Pt bimetallic the catalyst even development of three-way catalyst。This is because alloy material can cause series of effects, the change (increasing the d electron orbit room of Pt) of the isolation of such as surface-element, the change (further Pt-Pt spacing) of geometric configuration and Pt electronic structure, thus improve the electro catalytic activity of Pt。In these catalyst, Pt base transition metal nano material has attracted to pay close attention to widely, owing to their excellent properties, such as optics, electricity, magnetic force, catalytic performance, with the Pt bimetallic catalyst being bonded, there is bimetallic synergy and then substantially increase the electrocatalysis characteristic of Pt。Pt bimetallic alloy film (Ni, Co) that Moffat seminar presents electro-deposition prepared compares with the pure Pt catalyst of electro-deposition, Pt bimetallic alloy film significantly improves redox speed (referring to Electrochem.Soc., 2009,156, B238-B251)。
Recently, the catalyst based material of Pt is because between its atom, coordination is low and its site defect in nanoparticle surface, thus being conducive to the electroxidation of organic molecule and the decomposition of water, therefore start an alloy particle with the controlled micro nano structure of multi phase interface structure and surface becomes the hot topic of research always。But the Pt catalyst being made up of two or more metals has fabulous catalytic performance and good stability rarely has report simultaneously。
Compared with business Pt/C catalyst, the redox ability of bimetallic Pt-M (M=Fe, Ni etc.) catalyst is obviously enhanced (referring to ACSAppl.Mater.Interfaces, 2014,6,12046-12061)。2011, ChunhuaCui et al. reports and adopts electro-deposition method under-1.2V constant voltage in DMSO solvent, obtain the porous Pt-Ni nanoparticle tubes that large scale builds, the electrocatalytic oxidation of methanol is shown high catalysis activity and stability (referring to Chem.Sci. by it, 2011,2,1611-1614)。2012, JoshuaSnyder et al. reported and uses the synthesizing porous Ni/Pt nanoparticle of solvothermal, and it presents significantly high active area compared with business Pt/C, and then deduce it and there is fine redox ability (referring to J.Am.Chem.Soc., 2012,134,8633-8645)。2013, LiangxinDing et al. reported Pd-Sn alloy nano lamellar dendrite prepared by a step electrodeposition process, and the catalytic oxidation of ethanol presents significant catalytic performance (referring to Sci.Rep., 2013,3,1181-1187) in alkaline solution。2015, PengfangZhang et al. was reported the octahedra nanocrystalline electrocatalytic oxidation to methanol and formic acid of Pt-Ni-Cu prepared by solvent-thermal method and presents good catalytic performance (referring to Chem.Mater., 2015,27,6402-6410)。
The above preparation method condition harsh and synthetic material component and size are difficult to control to。
Summary of the invention
In order to overcome above deficiency, the preparation method that the invention provides a kind of Pt/Cu-Ni catalyst, the Cu-Ni bimetallic alloy gone out with electro-deposition in advance, for foreign template, using chloroplatinic acid as platinum source, prepares the nano-sheet Pt/Cu-Ni catalyst of a kind of pine-tree structure, this preparation method is simple, mild condition is controlled, it is not necessary to too high temperature and strict equipment requirements, and environmental friendliness, pollution-free, and the Pt/Cu-Ni catalyst prepared has relatively larger specific surface area。
Present invention also offers the application in alcohols catalytic oxidation of the Pt/Cu-Ni catalyst, when it is used to the catalytic oxidation to Organic Alcohol, there is good catalytic oxidation effect。
A kind of method that present invention also offers catalytic oxidation of alcohol, has certain catalysed oxidn in an acidic solution with the working electrode that Pt/Cu-Ni catalyst covers to alcohols。
The technical solution used in the present invention is:
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A mantoquita, nickel salt and boric acid are dissolved in deionized water by (), adopt electrochemical deposition method, deposit Cu-Ni bimetallic alloy at working electrode surface；
B platinum salt or chlordene are closed platinic acid and are dissolved in deionized water and form platinum ion solution by (), have the working electrode of Cu-Ni bimetallic alloy for working electrode with deposition, adopt electrochemical deposition method, can obtain depositing the working electrode of Pt/Cu-Ni product。
C working electrode is washed, dries, collects the product on surface by (), can obtain Pt/Cu-Ni catalyst。
When the surface area of working electrode is 1cm2Time, the arbitrary value between the desirable 0.1～10mmol of amount of substance of described mantoquita, nickel salt and boric acid；The ratio of the amount of substance between mantoquita, nickel salt and boric acid three is preferably 1:9:1。
Described mantoquita includes copper chloride, copper sulfate, Schweinfurt green。
The concentration of described nickel salt is 0.3M, and described nickel salt includes Nickel dichloride., nickel sulfate。
The concentration of described platinum ion solution is 0.0193M, and volume is 8～15mL。。
Described electrochemical deposition three-electrode system, make auxiliary electrode with Pt silk, Ag/AgCl makes reference electrode, working electrode made by ITO electro-conductive glass, its operating current is the constant current of 5～20mA, and electrodeposition time is 1～10 minute, it is preferable that electro-deposition 5min under the constant current of 10mA。
Present invention also offers the application preparing Pt/Cu-Ni catalyst that above-mentioned preparation method prepares in alcohols catalytic oxidation。
A kind of method that present invention also offers catalytic oxidation of alcohol; glass-carbon electrode covers the alcohol dispersion liquid of the Pt/Cu-Ni catalyst that preparation method according to claim 1 prepares; after drying; cover naphthol solution more herein above as protecting film, in an acidic solution as working electrode catalytic oxidation of alcohol solution after after drying。
Said method specifically includes: Pt/Cu-Ni catalyst ultrasonic disperse preparation method according to claim 1 prepared is in alcohol solvent; form the dispersion liquid of 2～10mg/mL; take the dispersant liquid drop of 3～6ul on glass-carbon electrode; treating that it takes concentration after drying is that 0.5% naphthol solution 3～6ul drips above as protecting film, adopts electrochemical method catalytic oxidation of alcohol solution after drying in an acidic solution as working electrode。
Described acid solution is sulfuric acid solution, and its concentration is 0.5M, and the effect of acid solution makes the part Pt in Pt/Cu-Ni catalyst activate, there is evolving hydrogen reaction, thus catalytic oxidation of alcohol solution。
The concentration of described alcohol solution is 0.1～2M, it is preferred to 1～2M。
The method of above-mentioned catalytic oxidation of alcohol is particularly suited for the catalytic oxidation to monohydric alcohol solution。
Compared with prior art, advantage for present invention is:
1. the nano-sheet Pt/Cu-Ni catalyst of the pine-tree structure prepared by the present invention, its preparation method is novel, simple, do not report before this and used the nano-sheet Pt/Cu-Ni catalyst preparing pine-tree structure in this way, and its novel in shape, having very big specific surface area, product is magnetic recovery conveniently。
2. condition prepared by the present invention is simple, gentle controlled, it is not necessary to too high temperature and strict equipment requirements, consuming time short, and environmental friendliness, it is not necessary to be still further processed。
3. the nano-sheet Pt/Cu-Ni catalyst of the pine-tree structure prepared by the present invention, owing to having bigger specific surface area, is therefore better than general Pt/C catalyst, can be used in actual life, to solve energy problem alcohols catalytic oxidation effect。
Accompanying drawing explanation
Fig. 1 is copper source is CuCl2Time gained micron order Cu-Ni dendrite scanning electron micrograph；
Fig. 2 is copper source is CuSO4Time gained micron order Cu-Ni dendrite scanning electron micrograph；
Fig. 3 is copper source is CuAc2Time gained micron order Cu-Ni dendrite scanning electron micrograph；
Fig. 4 is nickel source is NiSO4Time gained micron order Cu-Ni dendrite scanning electron micrograph；
Gained micron order Cu-Ni dendrite scanning electron micrograph when Fig. 5 is raw material not boronic acid containing；
The scanning electron micrograph of the Pt/Cu-Ni catalyst of the pine-tree structure of gained when Fig. 6 is different electrodeposition time；
Fig. 7 is the X-ray powder diffraction figure of the Pt/Cu-Ni catalyst of products therefrom Cu-Ni dendrite and different sedimentation time；
Fig. 8 is the transmission electron micrograph of the nano-sheet Pt/Cu-Ni catalyst of gained pine-tree structure；
Fig. 9 is the Energy Dispersive X-ray figure of the nano-sheet Pt/Cu-Ni catalyst of gained pine-tree structure；
Figure 10 is that nano-sheet Pt/Cu-Ni catalyst and the business Pt/C of gained pine-tree structure are at 0.5MH2SO4CV curve chart in solution；
Figure 11 is nano-sheet Pt/Cu-Ni catalyst and the business Pt/C CV curve chart to methanol catalytic oxidation of gained pine-tree structure；
Figure 12 is the nano-sheet Pt/Cu-Ni catalyst of the gained gained pine-tree structure CV curve chart to Catalytic oxidation of ethanol；
Figure 13 is the gained nano-sheet Pt/Cu-Ni pine-tree structure CV curve chart to propanol catalytic oxidation。
Detailed description of the invention
Reagent used by the present invention and experiment material is all commercially available obtains。
The surface area of ITO electro-conductive glass used in the present invention is 1cm2。
Embodiment 1
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 1mmolCuCl2、9mmolNiCl2Being placed in beaker with 1mmol boric acid, it is dissolved by the deionized water adding 30mL。30min is stirred at room temperature, forms uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as it is shown in figure 1, it can be seen that Cu-Ni product presents the microstructure of dendrite。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 10mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 1min under the constant current of 10mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Adopt the method identical with step (b), electro-deposition 3min, 5min under the constant current of 10mA respectively, then, has the ITO taking-up deionized water wash of Pt/Cu-Ni product for several times by deposition, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Pt/Cu-Ni catalyst electro-deposition 1min, 3min, 5min obtained is put and is observed under a scanning electron microscope, the SEM of three schemes as shown in Figure 6, find along with the increase of electrodeposition time, the Pt content on Cu-Ni surface adds, having finally given the dendrite that surface has flaky crystal to cover, this point can be confirmed from the transmission electron microscope figure of the Pt/Cu-Ni catalyst shown in Fig. 8。
In addition, never the X-ray diffractogram (as shown in Figure 7) of the Pt/Cu-Ni catalyst product that the synsedimentary time obtains can be seen that, increase along with sedimentation time, the intensity at Pt peak is gradually increased, Cu, Ni two the intensity at peak weaken gradually, explanation increases over time, and the Pt cumulative amount on Cu-Ni surface is gradually increased, and namely the Pt content on Cu-Ni surface is gradually increased。The Energy Dispersive X-ray figure of the Pt/Cu-Ni catalyst that Fig. 9 is sedimentation time to be obtained when being 5min, has a large amount of Pt to be deposited from figure it can also be seen that in product。
Embodiment 2
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 1mmolCuSO4、9mmolNiCl2Being placed in beaker with 1mmol boric acid, it is dissolved by the deionized water adding 30mL。30min is stirred at room temperature, forms uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 2。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 10mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 5min under the constant current of 10mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 3
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 1mmolCu (CH3COO)2、9mmolNiCl2Being placed in beaker with 1mmol boric acid, it is dissolved by the deionized water adding 30mL。Stir 30min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 3。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 10mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 5min under the constant current of 10mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 4
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 1mmolCuCl2、9mmolNiSO4Being placed in beaker with 1mmol boric acid, it is dissolved by the deionized water adding 30mL。Stir 30min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 4。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 10mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 5min under the constant current of 10mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 5
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 0.6mmolCuCl2、0.6mmolNiSO4Being placed in beaker with 0.6mmol boric acid, it is dissolved by the deionized water adding 2mL。Stir 10min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 10min under the constant current of 15mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 4。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 8mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 10min under the constant current of 15mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 6
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 0.6mmolCuCl2、9mmolNiCl2Being placed in beaker with 10mmol boric acid, it is dissolved by the deionized water adding 30mL。Stir 20min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 3min under the constant current of 20mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 4。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 15mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 3min under the constant current of 15mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 7
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 0.6mmolCuSO4、6mmolNiSO4Being placed in beaker with 9mmol boric acid, it is dissolved by the deionized water adding 20mL。Stir 30min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 10min under the constant current of 5mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 4。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 12mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 10min under the constant current of 5mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Embodiment 8
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () weighs 5mmolCu (CH3COO)2、3mmolNiSO4Being placed in beaker with 10mmol boric acid, it is dissolved by the deionized water adding 10mL。Stir 30min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as shown in Figure 4。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 15mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 10min under the constant current of 5mA。Then, deposition is had the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO。
Comparative example 1
A kind of preparation method of Pt/Cu-Ni catalyst, described preparation method comprises the following steps:
A () takes 1mmolCuCl2And 9mmolNiCl2Being placed in beaker, it is dissolved by the deionized water adding 30ml。Stir 30min under room temperature, form uniform solution。Then three-phase electrode (auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode, ITO makes working electrode) is inserted in mixed solution, electro-deposition 5min under the constant current of 10mA。Afterwards, deposition is had the ITO taking-up deionized water wash of Cu-Ni product for several times, put into thermostatic drying chamber freeze-day with constant temperature standby。The SEM of Cu-Ni product schemes as it is shown in figure 5, as can be seen from the figure when not containing boric acid in raw material, can be only formed a small amount of dendrite product, and what boric acid was described has the formation being beneficial to dendrite。
B () weighs 1.93mmol (1g) H2PtCl6·6H2O is placed in the volumetric flask of 100mL, adds deionized water constant volume, and mixing takes this solution of 10mL in electrolysis bath after shaking up。Choosing deposition has the ITO electro-conductive glass of Cu-Ni product to make working electrode, and just submerge solution by the area at product place, and auxiliary electrode made by Pt silk, Ag/AgCl makes reference electrode in employing, electro-deposition 5min under the constant current of 10mA。Then, deposition having the ITO taking-up deionized water wash of Pt/Cu-Ni catalyst product for several times, after putting into thermostatic drying chamber freeze-day with constant temperature, collect the end product on ITO, final product also cannot present the structure of dendrite。
Embodiment 9
A kind of method of catalytic oxidation methanol, comprises the following steps:
Weigh a certain amount of Pt/Cu-Ni catalyst prepared by the preparation method of embodiment 1; put in centrifuge tube; add a certain amount of ethanol as solvent; the concentration being made into is 4mg/ml; after ultrasonic disperse; the dispersion soln taking 5 μ L drops on the glass-carbon electrode (GEC) handled well, waits taking after drying the naphthol solution that concentration is 0.5% again and drop in and make protecting film above。Make working electrode after drying, after making it activate with electrochemical workstation CV test in 0.5M sulfuric acid solution solution (as shown in Figure 10), adding a certain amount of absolute methanol, in final solution, the concentration of methanol is 1M, and last CV tests the effect of its catalytic oxidation。Its CV schemes as shown in figure 11, it can be seen that the catalytic oxidation performance of methanol is better than business Pt/C by Pt/Cu-Ni catalyst。
Embodiment 10
A kind of method of catalytic oxidation of alcohol, comprises the following steps:
Weigh a certain amount of Pt/Cu-Ni catalyst prepared by the preparation method of embodiment 1; put in centrifuge tube; add a certain amount of ethanol as solvent; the concentration being made into is 8mg/ml; after ultrasonic disperse; the dispersion soln taking 6 μ L drops on the glass-carbon electrode (GCE) handled well, waits taking after drying the naphthol solution 6 μ L that concentration is 0.5% again and drop in and make protecting film above。Making working electrode after drying, test with electrochemical workstation CV in 0.5M sulfuric acid solution solution after making it activate, add a certain amount of dehydrated alcohol, in final solution, the concentration of ethanol is 1.5M, and last CV tests the effect of its catalytic oxidation。Its CV schemes as shown in figure 12, it can be seen that ethanol is had certain catalytic oxidation effect by Pt/Cu-Ni catalyst。
Embodiment 11
A kind of method of catalytic oxidation propanol, comprises the following steps:
Weigh a certain amount of Pt/Cu-Ni catalyst prepared by the preparation method of embodiment 1; put in centrifuge tube; add a certain amount of ethanol as solvent; the concentration being made into is 10mg/ml; after ultrasonic disperse; the dispersion soln taking 3 μ L drops on the glass-carbon electrode (GCE) handled well, waits taking after drying the naphthol solution 3 μ L that concentration is 0.5% again and drop in and make protecting film above。Making working electrode after drying, test with electrochemical workstation CV in 0.5M sulfuric acid solution solution after making it activate, add a certain amount of anhydrous propanol, in final solution, the concentration of propanol is 2M, and last CV tests the effect of its catalytic oxidation。Its CV schemes as shown in figure 13, it can be seen that propanol is had certain catalytic oxidation effect by Pt/Cu-Ni catalyst。
The above-mentioned detailed description preparation method of Pt/Cu-Ni catalyst and the method for catalytic oxidation of alcohol thereof and application carried out with reference to embodiment; it is illustrative rather than determinate; can according to restriction scope list several embodiments; therefore without departing from changing and modifications under present general inventive concept, should belong within protection scope of the present invention。
Claims (10)
1. the preparation method of a Pt/Cu-Ni catalyst, it is characterised in that described preparation method comprises the following steps:
A mantoquita, nickel salt and boric acid are dissolved in deionized water by (), adopt electrochemical deposition method, deposit Cu-Ni bimetallic alloy at working electrode surface；
B platinum salt or chlordene are closed platinic acid and are dissolved in deionized water and form platinum ion solution by (), have the working electrode of Cu-Ni bimetallic alloy for working electrode with deposition, adopt electrochemical deposition method, can obtain depositing the working electrode of Pt/Cu-Ni product。
C working electrode is washed, dries, collects the product on surface by (), can obtain Pt/Cu-Ni catalyst。
2. preparation method according to claim 1, it is characterised in that: the surface area of working electrode is 1cm2Time, the arbitrary value between the desirable 0.1～10mmol of amount of substance of described mantoquita, nickel salt and boric acid。
3. preparation method according to claim 1 and 2, it is characterised in that: the ratio of the amount of substance of described mantoquita, nickel salt and boric acid is 1:9:1。
4. preparation method according to claim 3, it is characterised in that the concentration of described nickel salt is 0.3M。
5. preparation method according to claim 2, it is characterised in that the concentration of described platinum ion solution is 0.0193M。
6. preparation method according to claim 5, it is characterised in that described platinum ion liquor capacity is 8～15mL。
7. the preparation method according to claim 1 or 2 or 4 or 5 or 6, it is characterised in that the operating current of described electrochemical deposition method is the constant current of 5～20mA, and electrodeposition time is 1～10 minute。
8. the Pt/Cu-Ni catalyst that preparation method according to claim 1 prepares application in alcohols catalytic oxidation。
9. the method for a catalytic oxidation of alcohol; it is characterized in that: on glass-carbon electrode, cover the alcohol dispersion liquid of the Pt/Cu-Ni catalyst that preparation method according to claim 1 prepares; after drying; cover naphthol solution more herein above as protecting film, in an acidic solution as working electrode catalytic oxidation of alcohol solution after after drying。
10. the method for catalytic oxidation of alcohol according to claim 9, it is characterised in that the concentration of described alcohol solution is 0.1～2M。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106525948A (en) * | 2016-10-31 | 2017-03-22 | 扬州大学 | Preparation method and application of sensor for molecular imprinting detection of 2,4-d |
| CN107331874A (en) * | 2017-06-16 | 2017-11-07 | 江汉大学 | NiCu films load the preparation method of Pt nano particle electroxidation ethanol composite catalyst |
| CN107732263A (en) * | 2017-09-26 | 2018-02-23 | 天津工业大学 | A kind of preparation method of the ethanol oxidation catalyst of efficent electronic transmission structure |
| CN108247080A (en) * | 2018-02-08 | 2018-07-06 | 厦门大学 | A kind of platinoid nickel ternary alloy nano material and preparation method thereof |
| CN110735152A (en) * | 2019-10-25 | 2020-01-31 | 燕山大学 | Ni-Cu-C electrocatalyst, and preparation method and application thereof |
| CN113130916A (en) * | 2019-12-30 | 2021-07-16 | 大连大学 | Preparation method of lactose fuel cell based on PdNPs/NiNPs/ITO electrode |
| CN113140740A (en) * | 2021-06-22 | 2021-07-20 | 成都大学 | Pd @ Ni0.7Cu0.3/NiOOH/CuO mixed crystal methanol oxidation composite electrode and preparation method thereof |
| CN114420956A (en) * | 2021-11-19 | 2022-04-29 | 东北电力大学 | Preparation method of anode electrocatalyst CuNi/C of direct methanol fuel cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337193A (en) * | 2008-08-04 | 2009-01-07 | 山东大学 | Method of surface nano-crystallization of noble metal catalyst |
| CN101362094A (en) * | 2008-09-25 | 2009-02-11 | 同济大学 | No-Pt catalyst for fuel cell, preparation method and use thereof |
| CN101635315A (en) * | 2009-08-18 | 2010-01-27 | 郑直 | Chemical method for preparing three-dimensional dendritic copper selenide nano-crystalline photoelectric film material |
| EP2378597A1 (en) * | 2005-11-21 | 2011-10-19 | Nanosys, Inc. | Nanowire structures comprising carbon |
| CN102925923A (en) * | 2012-10-26 | 2013-02-13 | 复旦大学 | Preparation method of nano-palladium or palladium-nickel alloy catalyst having three-dimensional porous structure |
-
2016
- 2016-01-13 CN CN201610025501.4A patent/CN105688935B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2378597A1 (en) * | 2005-11-21 | 2011-10-19 | Nanosys, Inc. | Nanowire structures comprising carbon |
| CN101337193A (en) * | 2008-08-04 | 2009-01-07 | 山东大学 | Method of surface nano-crystallization of noble metal catalyst |
| CN101362094A (en) * | 2008-09-25 | 2009-02-11 | 同济大学 | No-Pt catalyst for fuel cell, preparation method and use thereof |
| CN101635315A (en) * | 2009-08-18 | 2010-01-27 | 郑直 | Chemical method for preparing three-dimensional dendritic copper selenide nano-crystalline photoelectric film material |
| CN102925923A (en) * | 2012-10-26 | 2013-02-13 | 复旦大学 | Preparation method of nano-palladium or palladium-nickel alloy catalyst having three-dimensional porous structure |
Non-Patent Citations (2)
| Title |
|---|
| HUYING ZHANG ET AL: "Fast electrodeposition, influencing factors and catalytic properties of dendritic Cu-M(M=Ni,Fe,Co) microstructures", 《RSC ADVANCES》 * |
| YONGMEI ZHANG ET AL: "Polycrystalline Cu7Te4 Dendritic Microstructures Constructed by Spherical Nanoparticles: Fast Electrodeposition, Influencing Factors,and the Shape Evolution", 《CRYSTAL GROWTH & DESIGN》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106525948A (en) * | 2016-10-31 | 2017-03-22 | 扬州大学 | Preparation method and application of sensor for molecular imprinting detection of 2,4-d |
| CN106525948B (en) * | 2016-10-31 | 2019-04-19 | 扬州大学 | A kind of preparation method and application of molecular engram detection 2,4-d sensor |
| CN107331874A (en) * | 2017-06-16 | 2017-11-07 | 江汉大学 | NiCu films load the preparation method of Pt nano particle electroxidation ethanol composite catalyst |
| CN107732263A (en) * | 2017-09-26 | 2018-02-23 | 天津工业大学 | A kind of preparation method of the ethanol oxidation catalyst of efficent electronic transmission structure |
| CN108247080A (en) * | 2018-02-08 | 2018-07-06 | 厦门大学 | A kind of platinoid nickel ternary alloy nano material and preparation method thereof |
| CN110735152A (en) * | 2019-10-25 | 2020-01-31 | 燕山大学 | Ni-Cu-C electrocatalyst, and preparation method and application thereof |
| CN113130916A (en) * | 2019-12-30 | 2021-07-16 | 大连大学 | Preparation method of lactose fuel cell based on PdNPs/NiNPs/ITO electrode |
| CN113130916B (en) * | 2019-12-30 | 2022-06-14 | 大连大学 | Method for constructing lactose fuel cell based on PdNPs/NiNPs/ITO electrode |
| CN113140740A (en) * | 2021-06-22 | 2021-07-20 | 成都大学 | Pd @ Ni0.7Cu0.3/NiOOH/CuO mixed crystal methanol oxidation composite electrode and preparation method thereof |
| CN113140740B (en) * | 2021-06-22 | 2021-08-17 | 成都大学 | Pd @ Ni0.7Cu0.3/NiOOH/CuO mixed crystal methanol oxidation composite electrode and preparation method thereof |
| CN114420956A (en) * | 2021-11-19 | 2022-04-29 | 东北电力大学 | Preparation method of anode electrocatalyst CuNi/C of direct methanol fuel cell |
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