CN105688935B - A kind of preparation method of Pt/Cu Ni catalyst and its method and the application of catalytic oxidation of alcohol - Google Patents
A kind of preparation method of Pt/Cu Ni catalyst and its method and the application of catalytic oxidation of alcohol Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000243 solution Substances 0.000 claims abstract description 63
- 238000004070 electrodeposition Methods 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 102
- 238000001035 drying Methods 0.000 claims description 31
- 238000000151 deposition Methods 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 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
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 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
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 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
- 239000002135 nanosheet Substances 0.000 abstract description 12
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 61
- 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
- 210000004027 cell Anatomy 0.000 description 11
- 239000012467 final product Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 230000005611 electricity Effects 0.000 description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910052802 copper Inorganic materials 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
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 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
- -1 platinum ion Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation 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
- 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
- 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 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
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003760 hair shine Effects 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
- 229910001092 metal group alloy Inorganic materials 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
- 238000004626 scanning electron microscopy 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
-
- 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
-
- 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 method and the application of a kind of preparation method of Pt/Cu Ni catalyst and its catalytic oxidation of alcohol.The Cu Ni bimetallic alloys gone out using advance electro-deposition is foreign templates, platinum source is used as using chloroplatinic acid, a kind of nano-sheet Pt/Cu Ni catalyst of pine-tree structure is prepared, the preparation method is simple, and mild condition is controllable, too high temperature and strict equipment requirement are not needed, and it is environment-friendly, pollution-free, the Pt/Cu Ni catalyst prepared has bigger specific surface area, being capable of efficiently catalyzing and oxidizing alcohol solution, especially unitary alcoholic solution in an acidic solution.
Description
Technical field
The invention belongs to method for preparing catalyst and application field, and in particular to a kind of preparation side of Pt/Cu-Ni catalyst
The method and application of method and its catalytic oxidation of alcohol.
Background technology
With the rapid development of society energy demand is the subject matter that the mankind are badly in need of solution.Methanol fuel cell (DAFCs)
It is a kind of energy of cleaning, so as to be also considered as the most promising energy.In the catalytic oxidation of methanol, Pt is shown
Higher catalytic activity, however, Pt is not only expensive but also stability is poor, so as to hinder methanol fuel cell commercially
Extensive use.
Therefore, substantial amounts of research at present is intended to find a kind of novel material to replace part Pt and improve its catalysis energy
Power, this just has Pt bimetallics the catalyst even development of three-way catalyst.Because alloy material can trigger a system
Column effect, such as isolation, the change (further Pt-Pt spacing) of geometric configuration and the change of Pt electronic structures of surface-element
(increase Pt d electron orbits room), so as to improve Pt electro catalytic activity.In these catalyst, Pt base transition metal
Nano material has attracted extensive concern, is attributed to their excellent properties, such as optics, electricity, magnetic force, catalytic performance, with Pt
The bimetallic catalyst being bonded has bimetallic synergy and then substantially increases Pt electrocatalysis characteristic.Moffat classes
Topic group presents Pt bimetallic alloys film (Ni, Co) made from electro-deposition compared with the pure Pt catalyst of electro-deposition, and Pt bases are double
Metal alloy film significantly improves redox speed (referring to Electrochem.Soc., 2009,156, B238-B251).
Recently, Pt bases catalyst material is because being coordinated low and its site defect in nanoparticle surface between its atom, from
And be advantageous to the electroxidation of organic molecule and the decomposition of water, therefore starting one has multi phase interface structure and surface controllable
The alloy particle of micro nano structure turns into the hot topic of research always.But the Pt catalyst being made up of two or more metals is same
Catalytic performance fabulous Shi Yongyou and good stability are rarely reported.
Compared with business Pt/C catalyst, the redox ability of bimetallic Pt-M (M=Fe, Ni etc.) catalyst significantly increases
By force (referring to ACS Appl.Mater.Interfaces, 2014,6,12046-12061).2011, Chunhua Cui et al. reports
Road using electro-deposition method under -1.2V constant voltages in DMSO solvents, obtain the porous Pt-Ni nanoparticles of large scale structure
Son pipe, its electrocatalytic oxidation to methanol show high catalytic activity and stability (referring to Chem.Sci., 2011,2,
1611-1614).2012, Joshua Snyder et al. were reported with the synthesizing porous Ni/Pt nano-particles of solvothermal, its
Very high active area is showed compared with business Pt/C, so deduce its have fine redox ability (referring to
J.Am.Chem.Soc., 2012,134,8633-8645).2013, Liangxin Ding et al. reported a step electrodeposition process
The Pd-Sn alloy nano sheet dendrite of preparation, shows significant catalytic performance in alkaline solution to the catalysis oxidation of ethanol
(referring to Sci.Rep., 2013,3,1181-1187).2015, Pengfang Zhang et al. were reported by solvent heat legal system
The octahedra nanocrystalline electrocatalytic oxidation to methanol and formic acid of standby Pt-Ni-Cu show preferable catalytic performance (referring to
Chem.Mater., 2015,27,6402-6410).
The above preparation method condition is harsh and the component and size of synthetic material are difficult to control.
The content of the invention
It is heavy with advance electricity the invention provides a kind of preparation method of Pt/Cu-Ni catalyst in order to overcome the above insufficient
The Cu-Ni bimetallic alloys that product goes out are foreign template, using chloroplatinic acid as platinum source, prepare a kind of nano-sheet of pine-tree structure
Pt/Cu-Ni catalyst, the preparation method is simple, and mild condition is controllable, it is not necessary to too high temperature and strict equipment requirement,
And it is environment-friendly, it is pollution-free, and the Pt/Cu-Ni catalyst prepared has bigger specific surface area.
Present invention also offers application of the Pt/Cu-Ni catalyst in alcohols catalysis oxidation, when it is used for Organic Alcohol
Catalysis oxidation when, there is good catalytic oxidation effect.
Present invention also offers a kind of method of catalytic oxidation of alcohol, is existed with the working electrode that Pt/Cu-Ni catalyst covers
There is certain catalysed oxidn in acid solution to alcohols.
The technical solution adopted by the present invention is：
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) mantoquita, nickel salt and boric acid are dissolved in deionized water, using electrochemical deposition method, sunk in working electrode surface
Product goes out Cu-Ni bimetallic alloys；
(b) platinum salt or chlordene are closed into platinic acid and is dissolved in formation platinum ion solution in deionized water, there are Cu-Ni bimetallics with deposition
The working electrode of alloy is working electrode, using electrochemical deposition method, you can obtaining deposition has the work electricity of Pt/Cu-Ni products
Pole.
(c) working electrode is washed to, dried, collected the product on surface, you can obtain Pt/Cu-Ni catalyst.
When the surface area of working electrode is 1cm2When, the amount of the material of the mantoquita, nickel salt and boric acid desirable 0.1~
Arbitrary value between 10mmol；The ratio between amount of material between mantoquita, nickel salt and boric acid three is preferably 1：9：1.
The mantoquita includes copper chloride, copper sulphate, copper acetate.
The concentration of the nickel salt is 0.3M, and the nickel salt includes nickel chloride, nickel sulfate.
The concentration of the platinum ion solution is 0.0193M, and volume is 8~15mL..
The electrochemical deposition uses three-electrode system, makees auxiliary electrode with Pt silks, Ag/AgCl makees reference electrode, ITO is led
Electric glass makees working electrode, and its operating current is 5~20mA constant current, and electrodeposition time is 1~10 minute, preferably in 10mA
Constant current under electro-deposition 5min.
Present invention also offers prepare Pt/Cu-Ni catalyst that above-mentioned preparation method is prepared in alcohols catalysis oxidation
The application of aspect.
Present invention also offers a kind of method of catalytic oxidation of alcohol, covered on glass-carbon electrode according to claim 1
The alcohol dispersion liquid for the Pt/Cu-Ni catalyst that preparation method is prepared, after drying, then naphthol solution conduct is being covered above
Diaphragm, working electrode catalytic oxidation of alcohol solution is used as in an acidic solution after drying again.
The above method specifically includes：The Pt/Cu-Ni catalyst that preparation method according to claim 1 is prepared is surpassed
Sound is dispersed in alcohol solvent, is formed 2~10mg/mL dispersion liquid, is taken 3~6ul dispersant liquid drop to treat it on glass-carbon electrode
It is 0.5% 3~6ul of naphthol solution drops above as diaphragm that concentration is taken after drying, and working electrode is used as after drying in acidity
Electrochemical method catalytic oxidation of alcohol solution is used in solution.
The acid solution is sulfuric acid solution, and its concentration is 0.5M, and the effect of acid solution makes in Pt/Cu-Ni catalyst
Part Pt activation, so that evolving hydrogen reaction occurs, so as to catalytic oxidation of alcohol solution.
The concentration of the alcohol solution is 0.1~2M, preferably 1~2M.
The method of above-mentioned catalytic oxidation of alcohol is particularly suitable for use in the catalysis oxidation to unitary alcoholic 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,
Before this without reporting the used nano-sheet Pt/Cu-Ni catalyst that pine-tree structure is prepared in this way, and its shape
Looks are novel, have very big specific surface area, and product is magnetic recovery conveniently.
2. condition prepared by the present invention is simple, gentle controllable, it is not necessary to too high temperature and strict equipment requirement, takes
It is short and environment-friendly, 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, due to larger ratio surface
Product, therefore in general Pt/C catalyst is better than to alcohols catalytic oxidation effect, available in actual life, asked with solving the energy
Topic.
Brief description of the drawings
Fig. 1 is that copper source is CuCl2When gained micron order Cu-Ni dendrite scanning electron micrographs；
Fig. 2 is that copper source is CuSO4When gained micron order Cu-Ni dendrite scanning electron micrographs；
Fig. 3 is that copper source is CuAc2When gained micron order Cu-Ni dendrite scanning electron micrographs；
Fig. 4 is that nickel source is NiSO4When gained micron order Cu-Ni dendrite scanning electron micrographs；
Fig. 5 be raw material not boronic acid containing when gained micron order Cu-Ni dendrite scanning electron micrographs；
The scanning electron microscopy of the Pt/Cu-Ni catalyst of pine-tree structure obtained by when Fig. 6 is different electrodeposition times shines
Piece；
Fig. 7 is the X-ray powder diffraction of the Pt/Cu-Ni catalyst of products therefrom Cu-Ni dendrite and different sedimentation times
Figure；
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 nano-sheet Pt/Cu-Ni catalyst and the business Pt/C of gained pine-tree structure in 0.5M H2SO4In solution
CV curve maps；
Figure 11 is nano-sheet Pt/Cu-Ni catalyst and the business Pt/C of gained pine-tree structure to methanol catalytic oxidation
CV curve maps；
Figure 12 is CV curve of the nano-sheet Pt/Cu-Ni catalyst to Catalytic oxidation of ethanol of gained gained pine-tree structure
Figure；
Figure 13 is CV curve map of the gained nano-sheet Pt/Cu-Ni pine-tree structures to propyl alcohol catalysis oxidation.
Embodiment
Reagent and experiment material used in the present invention are commercially available to be obtained.
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, the preparation method comprise the following steps：
(a) 1mmol CuCl are weighed2、9mmol NiCl2It is placed in 1mmol boric acid in beaker, adds 30mL deionized water pair
It is dissolved.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electrode, Ag/AgCl
Make reference electrode, ITO makees working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.Afterwards, will be heavy
The ITO that product has Cu-Ni products, which takes out, to be washed with deionized for several times, and it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.Cu-Ni products
SEM scheme as shown in figure 1, it can be seen that Cu-Ni products show the microstructure of dendrite.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 10mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 10mA perseverance
Electro-deposition 1min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Using with step (b) identical method, electro-deposition 3min, 5min under 10mA constant current respectively then, will be heavy
The ITO that product has Pt/Cu-Ni products, which takes out, to be washed with deionized for several times, after being put into thermostatic drying chamber freeze-day with constant temperature, collects ITO
On final product.
The Pt/Cu-Ni catalyst that electro-deposition 1min, 3min, 5min are obtained is put and observed under a scanning electron microscope,
The SEM figures of three are final as shown in fig. 6, find to add with the increase of electrodeposition time, the Pt contents on Cu-Ni surfaces
The dendrite that surface has flaky crystal to cover is arrived, this point can be from the transmission electron microscope of the Pt/Cu-Ni catalyst shown in Fig. 8
It is confirmed in figure.
In addition, never the X-ray diffractogram (as shown in Figure 7) for the Pt/Cu-Ni catalyst products that the synsedimentary time obtains can
To find out, with the increase of sedimentation time, the intensity at Pt peaks gradually increases, and the intensity at the peak of Cu, Ni two gradually weakens, illustrate with
The increase of time, cumulative amounts of the Pt on Cu-Ni surfaces gradually increase, i.e. the Pt contents on Cu-Ni surfaces gradually increase.Fig. 9 is heavy
The Energy Dispersive X-ray figure for the Pt/Cu-Ni catalyst that the product time obtains when being 5min, it can also be seen that having in product from figure
A large amount of Pt are deposited.
Embodiment 2
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 1mmol CuSO are weighed4、9mmol NiCl2It is placed in 1mmol boric acid in beaker, adds 30mL deionized water pair
It is dissolved.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electrode, Ag/AgCl
Make reference electrode, ITO makees working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.Afterwards, will be heavy
The ITO that product has Cu-Ni products, which takes out, to be washed with deionized for several times, and it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.Cu-Ni products
SEM figures it is as shown in Figure 2.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 10mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 10mA perseverance
Electro-deposition 5min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 3
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 1mmol Cu (CH are weighed3COO)2、9mmol NiCl2Be placed in 1mmol boric acid in beaker, add 30mL go from
Sub- water dissolves to it.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electricity
Reference electrode is made in pole, Ag/AgCl, ITO makees working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.
Afterwards, the ITO that deposition there are Cu-Ni products is taken out and be washed with deionized for several times, it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.
The SEM figures of Cu-Ni products are as shown in Figure 3.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 10mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 10mA perseverance
Electro-deposition 5min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 4
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 1mmol CuCl are weighed2、9mmol NiSO4It is placed in 1mmol boric acid in beaker, adds 30mL deionized water pair
It is dissolved.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electrode, Ag/
AgCl makees reference electrode, ITO makees working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.Afterwards,
The ITO that deposition there are Cu-Ni products is taken out and is washed with deionized for several times, it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.Cu-Ni
The SEM figures of product are as shown in Figure 4.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 10mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 10mA perseverance
Electro-deposition 5min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 5
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 0.6mmol CuCl are weighed2、0.6mmol NiSO4Be placed in 0.6mmol boric acid in beaker, add 2mL go from
Sub- water dissolves to it.10min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electricity
Reference electrode is made in pole, Ag/AgCl, ITO makees working electrode) insert in mixed solution, the electro-deposition under 15mA constant current
10min.Afterwards, the ITO that deposition there are Cu-Ni products is taken out and be washed with deionized for several times, be put into thermostatic drying chamber constant temperature and do
It is dry standby.The SEM figures of Cu-Ni products are as shown in Figure 4.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 8mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode, will
Area where product just submerges solution, makees auxiliary electrode using Pt silks, Ag/AgCl makees reference electrode, in 15mA perseverance electricity
Flow down electro-deposition 10min.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and be washed with deionized for several times, put
After entering thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 6
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 0.6mmol CuCl are weighed2、9mmol NiCl2It is placed in 10mmol boric acid in beaker, adds 30mL deionization
Water dissolves to it.20min is stirred at room temperature, forms uniform solution.Then by three-phase electrode (Pt silks make auxiliary electrode,
Ag/AgCl makees reference electrode, ITO makees working electrode) insert in mixed solution, the electro-deposition 3min under 20mA constant current.It
Afterwards, the ITO that deposition there are Cu-Ni products is taken out and be washed with deionized for several times, it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.
The SEM figures of Cu-Ni products are as shown in Figure 4.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 15mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 15mA perseverance
Electro-deposition 3min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 7
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 0.6mmol CuSO are weighed4、6mmol NiSO4It is placed in 9mmol boric acid in beaker, adds 20mL deionized water
It is dissolved.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electrode, Ag/
AgCl makees reference electrode, ITO makees working electrode) insert in mixed solution, the electro-deposition 10min under 5mA constant current.Afterwards,
The ITO that deposition there are Cu-Ni products is taken out and is washed with deionized for several times, it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.Cu-Ni
The SEM figures of product are as shown in Figure 4.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 12mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 5mA perseverance electricity
Flow down electro-deposition 10min.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and be washed with deionized for several times, put
After entering thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Embodiment 8
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 5mmol Cu (CH are weighed3COO)2、3mmol NiSO4It is placed in 10mmol boric acid in beaker, adds going for 10mL
Ionized water dissolves to it.30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electricity
Reference electrode is made in pole, Ag/AgCl, ITO makees working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.
Afterwards, the ITO that deposition there are Cu-Ni products is taken out and be washed with deionized for several times, it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.
The SEM figures of Cu-Ni products are as shown in Figure 4.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 15mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 5mA perseverance electricity
Flow down electro-deposition 10min.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and be washed with deionized for several times, put
After entering thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected.
Comparative example 1
A kind of preparation method of Pt/Cu-Ni catalyst, the preparation method comprise the following steps：
(a) 1mmol CuCl are taken2With 9mmol NiCl2It is placed in beaker, adds 30ml deionized water to dissolve it.
30min is stirred at room temperature, forms uniform solution.Then by three-phase electrode, (Pt silks make auxiliary electrode, Ag/AgCl makees reference electricity
Pole, ITO make working electrode) insert in mixed solution, the electro-deposition 5min under 10mA constant current.Afterwards, deposition there is into Cu-Ni
The ITO of product takes out and is washed with deionized for several times, and it is standby to be put into thermostatic drying chamber freeze-day with constant temperature.The SEM figures of Cu-Ni products are such as
Shown in Fig. 5, as can be seen from the figure when not containing boric acid in raw material, a small amount of dendrite product is can be only formed, illustrates boric acid
It there are the formation beneficial to dendrite.
(b) 1.93mmol (1g) H is weighed2PtCl6·6H2O is placed in 100mL volumetric flask, adds deionized water constant volume,
Mixing takes the 10mL solution in electrolytic cell after shaking up.The ITO electro-conductive glass that choosing deposition has Cu-Ni products makees working electrode,
Area where product is just submerged into solution, auxiliary electrode is made using Pt silks, Ag/AgCl makees reference electrode, in 10mA perseverance
Electro-deposition 5min under electric current.Then, the ITO that deposition there are Pt/Cu-Ni catalyst products is taken out and is washed with deionized for several times,
After being put into thermostatic drying chamber freeze-day with constant temperature, the final product on ITO is collected, final product can not also show the knot of dendrite
Structure.
Embodiment 9
A kind of method of catalysis oxidation methanol, comprises the following steps：
The a certain amount of Pt/Cu-Ni catalyst as made from the preparation method of embodiment 1 is weighed, is put into centrifuge tube, adds one
For quantitative ethanol as solvent, the concentration being made into is 4mg/ml, after ultrasonic disperse, takes 5 μ L dispersion soln to drop in what is handled well
On glass-carbon electrode (GEC), wait the naphthol solution for taking concentration to be 0.5% after drying again to drop in and make diaphragm above.Workmanship after drying
Make electrode, CV tests make after its activation (as shown in Figure 10), to add in 0.5M sulfuric acid solution solution with electrochemical workstation
A certain amount of absolute methanol, the concentration of methanol is 1M in final solution, and last CV tests the effect of its catalysis oxidation.Its CV schemes such as
Shown in Figure 11, it can be seen that Pt/Cu-Ni catalyst is better than business Pt/C to the catalytic oxidation performance of methanol.
Embodiment 10
A kind of method of catalytic oxidation of alcohol, comprises the following steps：
The a certain amount of Pt/Cu-Ni catalyst as made from the preparation method of embodiment 1 is weighed, is put into centrifuge tube, adds one
For quantitative ethanol as solvent, the concentration being made into is 8mg/ml, after ultrasonic disperse, takes 6 μ L dispersion soln to drop in what is handled well
On glass-carbon electrode (GCE), wait the μ L of naphthol solution 6 for taking concentration to be 0.5% after drying again to drop in and make diaphragm above.Make after drying
Working electrode, with electrochemical workstation in 0.5M sulfuric acid solution solution CV test make its activate after, add a certain amount of nothing
Water-ethanol, the concentration of ethanol is 1.5M in final solution, and last CV tests the effect of its catalysis oxidation.Its CV is schemed such as Figure 12 institutes
Show, it can be seen that Pt/Cu-Ni catalyst has certain catalytic oxidation effect to ethanol.
Embodiment 11
A kind of method of catalysis oxidation propyl alcohol, comprises the following steps：
The a certain amount of Pt/Cu-Ni catalyst as made from the preparation method of embodiment 1 is weighed, is put into centrifuge tube, adds one
For quantitative ethanol as solvent, the concentration being made into is 10mg/ml, after ultrasonic disperse, takes 3 μ L dispersion soln to drop in what is handled well
On glass-carbon electrode (GCE), wait the μ L of naphthol solution 3 for taking concentration to be 0.5% after drying again to drop in and make diaphragm above.Make after drying
Working electrode, with electrochemical workstation in 0.5M sulfuric acid solution solution CV test make its activate after, add a certain amount of nothing
Water propyl alcohol, the concentration of propyl alcohol is 2M in final solution, and last CV tests the effect of its catalysis oxidation.Its CV figures are as shown in figure 13,
It can be seen that Pt/Cu-Ni catalyst has certain catalytic oxidation effect to propyl alcohol.
Above-mentioned reference embodiment is to the preparation method of Pt/Cu-Ni catalyst and its method for catalytic oxidation of alcohol and application
The detailed description of progress, it is illustrative rather than limited, several embodiments can be included according to limited scope, because
This changing and modifications in the case where not departing from present general inventive concept, should belong within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Pt/Cu-Ni catalyst, it is characterised in that the preparation method comprises the following steps：
（a）Mantoquita, nickel salt and boric acid are dissolved in deionized water, using electrochemical deposition method, deposited in working electrode surface
Cu-Ni bimetallic alloys；
（b）Platinum salt or chlordene are closed into platinic acid and are dissolved in formation platinum ion solution in deionized water, there are Cu-Ni bimetallic alloys with deposition
Working electrode be working electrode, using electrochemical deposition method, you can obtaining deposition has the working electrodes of Pt/Cu-Ni products；
（c）Working electrode is washed to, dried, collected the product on surface, you can obtain Pt/Cu-Ni catalyst；
The surface area of working electrode is 1cm2When, the amount of the material of the mantoquita, nickel salt and boric acid three's any of which
Take the arbitrary value between 0.1~10mmol.
2. preparation method according to claim 1, it is characterised in that：The amount of the material of the mantoquita, nickel salt and boric acid it
Than for 1:9:1.
3. preparation method according to claim 2, it is characterised in that the concentration of the nickel salt is 0.3M.
4. preparation method according to claim 1, it is characterised in that the concentration of the platinum ion solution is 0.0193M.
5. preparation method according to claim 4, it is characterised in that the platinum ion liquor capacity is 8 ~ 15mL.
6. according to the preparation method described in claim 1 or 3 or 4 or 5, it is characterised in that the work of the electrochemical deposition method
Electric current is 5~20 mA constant current, and electrodeposition time is 1~10 minute.
7. the Pt/Cu-Ni catalyst that preparation method according to claim 1 is prepared is in terms of alcohols catalysis oxidation
Using.
A kind of 8. method of catalytic oxidation of alcohol, it is characterised in that：Preparation side according to claim 1 is covered on glass-carbon electrode
The alcohol dispersion liquid for the Pt/Cu-Ni catalyst that method is prepared, after drying, then naphthol solution is being covered above as diaphragm,
Working electrode catalytic oxidation of alcohol solution is used as in an acidic solution after drying again.
9. the method for catalytic oxidation of alcohol according to claim 8, it is characterised in that the concentration of the alcohol solution is 0.1
~2M.
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| 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 |
| CN108247080B (en) * | 2018-02-08 | 2020-09-11 | 厦门大学 | Platinum-copper-nickel ternary alloy nano material and preparation method thereof |
| CN110735152B (en) * | 2019-10-25 | 2021-02-05 | 燕山大学 | Ni-Cu-C electrocatalyst and preparation method and application thereof |
| CN113130916B (en) * | 2019-12-30 | 2022-06-14 | 大连大学 | Method for constructing lactose fuel cell based on PdNPs/NiNPs/ITO electrode |
| 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 |
| CN114420956B (en) * | 2021-11-19 | 2024-03-29 | 东北电力大学 | Preparation method of direct methanol fuel cell anode electrocatalyst CuNi/C |
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