CN108336375A - A kind of serrated metal nano wire-carbon-based fuel cell catalyst and preparation method - Google Patents
A kind of serrated metal nano wire-carbon-based fuel cell catalyst and preparation method Download PDFInfo
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- CN108336375A CN108336375A CN201810076743.5A CN201810076743A CN108336375A CN 108336375 A CN108336375 A CN 108336375A CN 201810076743 A CN201810076743 A CN 201810076743A CN 108336375 A CN108336375 A CN 108336375A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000000446 fuel Substances 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 239000002070 nanowire Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- 150000002815 nickel Chemical class 0.000 claims abstract description 25
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 238000001962 electrophoresis Methods 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 230000005684 electric field Effects 0.000 claims description 14
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical group [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- JIJAYWGYIDJVJI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 JIJAYWGYIDJVJI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- HIURFGKIUTXLCT-UHFFFAOYSA-N propyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OCCC)=CC=CC2=C1 HIURFGKIUTXLCT-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 32
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 229910052697 platinum Inorganic materials 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910000905 alloy phase Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- -1 molybdenum ion Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001474977 Palla Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 description 1
- WAUIPKMDSHEJSA-UHFFFAOYSA-N copper palladium platinum Chemical compound [Cu][Pd][Pt] WAUIPKMDSHEJSA-UHFFFAOYSA-N 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of serrated metal nano wire carbon-based fuel cell catalyst and preparation methods.Mantoquita is soluble in water with nickel salt, reducing agent, complexant and surfactant is added after adjusting acid-base value, corronil nano wire is made, tetraphenylporphyrin association reaction is added ,/nanowire composite is made, carbon structure is calcined in vacuum environment high temperature, and clad alloy skeleton, and electrophoresis leaches nickel, obtains serrated metal nano wire carbon-based fuel cell catalyst.Composite catalyst made from this method possesses more active site with zigzag skeleton, large specific surface area, good dispersion, surface, catalytic activity is high, and catalytic performance is good, and preparation process is simple, raw material is easy to get, and manufacturing cost is cheap, is expected to catalyst choice of the substitution noble metal platinum as fuel cell.
Description
Technical field
The present invention relates to fuel cell fields, and in particular to the technology of preparing of catalyst, more particularly to a kind of zigzag
Metal nanometer line-carbon-based fuel cell catalyst and preparation method.
Background technology
Fuel cell be it is a kind of it is clean, with consume renewable small-molecule substance supplying power for outside high efficient energy sources convert dress
It sets.Different from traditional to consume the one-shot battery and secondary cell that itself chemical energy externally energizes, fuel cell is one and opens
The system put, it is the reaction by being catalyzed between foreign substance and isothermal is low will be stored in the chemistry between fuel and oxidant
Electric energy can be converted into provide to external circuit acting.Fuel cell be it is a kind of without burning directly in a manner of electrochemical reaction
The chemical energy of fuel is changed into the power generator of electric energy, is that a high efficiency utilizes the energy and new skill free from environmental pollution
Art is widely used to the every field such as fuel cell plant, electric vehicle, high effective portable power supply, has extremely wide
Application prospect.
The building block of fuel cell mainly have catalyst, dielectric film, gas diffusion layers, membrane electrode assembly, bipolar plates,
Fuel cell pile etc..Wherein catalyst is one of critical material of fuel cell, and effect is to reduce the activation energy of reaction, is promoted
Into oxidation-reduction process, the raising reaction rate of hydrogen, oxygen on the electrode.Currently, catalyst is mainly carbon supported platinum-based catalyst.
But platinum based catalyst is existed simultaneously stability problem by cost and resource restriction, by fuel cell decay Analysis on Mechanism it is found that
Under running conditions of vehicle, catalyst can decay fuel cell, and Pt nanoparticle such as can occur under electrokinetic potential effect
Reunite, migration, be lost in, high potential leads to catalyst carbon support caused by generating hydrogen sky interface in open circuit, idling and shutdown process
Corrosion, so as to cause catalyst loss.Therefore, for cost and endurance issues existing for current commercial catalyst, research
Novel high-stability, the low platinum of high activity or non-platinum catalyst are current hot spots.
Chinese invention patent application number 201210120922.7 discloses a kind of fuel cell carbon supported core-shell copper palladium-platinum
Catalyst and preparation method thereof.Carrier is made by conductive carbon black, active component is the copper pallas with coreshell type structure, wherein
Copper palladium is core, and platinum is shell, and mass percentage composition is：Conductive carbon black 70 ~ 91%, copper 2 ~ 10%, palladium 2 ~ 10%,：5 ~ 10%.
Chinese invention patent application number 201210296525.5 discloses a kind of system of catalyst of nanometer carbon-base fuel cell
Carbon nanotube or graphene are mainly positioned over stirring in the container for containing dimethylformamide first, disperseed by Preparation Method, then into
Row mechanical lapping is washed respectively to remove dimethylformamide with ethyl alcohol and distilled water after the product filtering after grinding, is done
Up to catalyst of nanometer carbon-base fuel cell after dry.
Chinese invention patent application number 201410832089.8 discloses a kind of carbon-based composite fuel battery negative pole oxygen also
Raw catalyst and preparation method thereof, the invention carbon-based composite fuel battery negative pole oxygen reduction catalyst are Jie of molybdenum ion doping
Hole carbon-graphite alkene complex first uses the synthesising mesoporous carbon-graphite alkene precursor of soft template method, and adulterates molybdenum ion in situ, then exists
It is calcined under argon gas atmosphere, obtains carbon-based composite fuel battery negative pole oxygen reduction catalyst.
It is anode-catalyzed that Chinese invention patent application number 201610901142.4 discloses a kind of load type carbon base fuel battery
Agent material, the invention use two-step method technology of preparing, first with organic ligand trimesic acid and copper acetate in N, N- diformazans
Base formamide, second alcohol and water mixed solution in self assembly obtain porous metals organic framework materials, by it is a series of carbonization and
Meso-porous carbon material is obtained after acid etch processing, ultrasonic assisted technique is then utilized, noble metal Pt nanoparticle is loaded to mesoporous
On carbon material, finally prepare that nano platinum particle is evenly distributed, particle size is uniform, the catalyst material of a diameter of 2 ~ 3 nm
Material.
According to above-mentioned, for the platinum based catalyst of fuel cell there are of high cost in existing scheme, durability is poor, stability
The problems such as poor, and the non-platinum based catalyst studied and applied at present is serious there are reuniting in preparation process, specific surface area is low, catalysis
The defects such as activity is low, and catalytic efficiency is low, and preparation process is complicated, and cost is still higher.
Invention content
Of high cost for the wider platinum based catalyst of current application, durability is poor, and stability is poor, and specific surface area is low, catalysis
The problems such as activity is low, a kind of serrated metal nano wire-carbon-based fuel cell catalyst of present invention proposition and preparation method, to
The catalytic activity of non-platinum based catalyst is effectively increased, while cheap, is expected to substitution noble metal platinum as fuel cell
Catalyst choice.
Specific technical solution of the present invention is as follows：
A kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst, preparation process are：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with corronil nano wire, inhibit
Nanowire composite is made in the reunion of corronil nano wire；
（3）By step（2）Composite material obtained is placed in vacuum environment, and high-temperature calcination carbonization forms carbon coating alloy skeleton；
（4）By step（3）Obtained carbon coating alloy skeleton is placed in progress electrophoresis in low voltage electric field and leaches, and makes nickle atom from alloy
It is detached from phase, remaining copper-carbon skeleton is serrated structure, obtains serrated metal nano wire-carbon-based fuel cell catalysis
Agent.
Preferably, a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst, each raw material are pressed
Parts by weight are calculated as：15 ~ 20 parts of mantoquita, 12 ~ 15 parts of nickel salt, 28 ~ 47.5 parts of water, 3 ~ 5 parts of reducing agent, 2 ~ 3 parts of complexant, surface are lived
0.5 ~ 1 part of agent of property, 20 ~ 28 parts of tetraphenylporphyrin.
Preferably, the mantoquita is at least one of copper chloride, copper nitrate or copper sulphate.
Preferably, the nickel salt is at least one of nickel chloride, nickel sulfate, nickel nitrate or nickel acetate.
Preferably, the reducing agent is one kind in propylene glycol, ethyl alcohol or oxalic acid.
Preferably, the complexant is at least one of citric acid, succinic acid, glycine or malic acid.
Preferably, the surfactant is one kind in propyl naphthalene sulfonate, butyl naphthalene sulfonate or alkyl sulfate.
Preferably, the pH value of the mixed solution is 7.5 ~ 8.5；
Preferably, the temperature of the high-temperature calcination is 400 ~ 600 DEG C, and the time is 2 ~ 3h；
Preferably, the voltage of electric field that the electrophoresis leaches is 150 ~ 200V.
A kind of serrated metal nano wire-carbon-based fuel cell catalyst being prepared by the above method.
The preparation method of the present invention is combined by corronil with organic phase, is formed reticular structure by organic phase, is inhibited
Nano metal is reunited, and improves its specific surface area and active site, the carbon structure after high temperature cabonization is evenly coated at outside metallic framework
Layer, is leached by electrophoresis, the nickle atom in copper-nickel alloy is made to be detached from from alloy, remaining copper skeleton is serrated, table later
Face forms the unsaturated defect of many coordinations, can improve catalytic performance.
New catalyst proposed by the present invention has the catalytic performance similar with platinum base, and manufacturing cost is cheap, is expected to
Replace catalyst choice of the noble metal platinum as fuel cell.
It is and existing the present invention provides a kind of serrated metal nano wire-carbon-based fuel cell catalyst and preparation method
Technology is compared, and the feature and excellent effect protruded is：
1, it proposes progress high temperature cabonization after being combined with organic phase using corronil and prepares serrated metal nano wire-carbon-based combustion
Expect the method for cell catalyst.
2, reticular structure is formed through organic phase by corronil, then high temperature cabonization rear electrophoresis leaches, and obtains zigzag
Remaining copper skeleton, large specific surface area, good dispersion, catalytic performance is good.
3, the more active site formed by dentalation copper-carbon composite catalytic agent surface has been obviously improved catalysis and has lived
Property and catalytic efficiency.
4, preparation process of the invention is relatively simple, and using base metal, raw material is easy to get, and manufacturing cost is cheap, is expected to take
Catalyst choice for noble metal platinum as fuel cell.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Raw material is calculated as by weight：18 parts of mantoquita, 13 parts of nickel salt, 38 parts of water, 4 parts of reducing agent, 2 parts of complexant, surfactant 1
Part, 24 parts of tetraphenylporphyrin；Mantoquita is copper chloride；Nickel salt is nickel chloride；Reducing agent is propylene glycol；Complexant is citric acid；Table
Face activating agent is propyl naphthalene sulfonate；Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 8；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with nano wire, inhibit nanometer
Nanowire composite is made in the reunion of alloy；
（3）By step（2）Composite material obtained is placed in vacuum environment, high-temperature calcination carbonization, and clad alloy skeleton；High temperature
The temperature of calcining is 500 DEG C, time 2.5h；
（4）It is placed in progress electrophoresis in low voltage electric field to leach, so that nickle atom is detached from from alloy phase, remaining copper-carbon skeleton is in saw
Dentalation obtains serrated metal nano wire-carbon-based fuel cell catalyst；The heating temperature of drying is 130 DEG C, the time
For 5h；The voltage of electric field that electrophoresis leaches is 180V.
Laciniation copper-carbon composite catalytic agent prepared by embodiment 1, specific surface area, catalytic efficiency are as shown in table 1.
Embodiment 2
Raw material is calculated as by weight：15 parts of mantoquita, 12 parts of nickel salt, 47.5 parts of water, 3 parts of reducing agent, 2 parts of complexant, surface-active
0.5 part of agent, 20 parts of tetraphenylporphyrin；Mantoquita is copper nitrate；Nickel salt is nickel sulfate；Reducing agent is ethyl alcohol；Complexant is succinic acid；
Surfactant is butyl naphthalene sulfonate；
Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 7.5；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with nano wire, inhibit nanometer
Nanowire composite is made in the reunion of alloy；
（3）By step（2）Composite material obtained is placed in vacuum environment, high-temperature calcination carbonization, and clad alloy skeleton；High temperature
The temperature of calcining is 400 DEG C, time 3h；
（4）It is placed in progress electrophoresis in low voltage electric field to leach, so that nickle atom is detached from from alloy phase, remaining copper-carbon skeleton is in saw
Dentalation obtains serrated metal nano wire-carbon-based fuel cell catalyst；The heating temperature of drying is 120 DEG C, the time
For 6h；The voltage of electric field that electrophoresis leaches is 150V.
Laciniation copper-carbon composite catalytic agent prepared by embodiment 2, specific surface area, catalytic efficiency are as shown in table 1.
Embodiment 3
Raw material is calculated as by weight：20 parts of mantoquita, 15 parts of nickel salt, 28 parts of water, 5 parts of reducing agent, 3 parts of complexant, surfactant 1
Part, 28 parts of tetraphenylporphyrin；Mantoquita is copper sulphate；Nickel salt is nickel nitrate；Reducing agent is oxalic acid；Complexant is glycine；Surface
Activating agent is alkyl sulfate；
Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 8.5；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with nano wire, inhibit nanometer
Nanowire composite is made in the reunion of alloy；
（3）By step（2）Composite material obtained is placed in vacuum environment, high-temperature calcination carbonization, and clad alloy skeleton；High temperature
The temperature of calcining is 600 DEG C, time 2h；
（4）It is placed in progress electrophoresis in low voltage electric field to leach, so that nickle atom is detached from from alloy phase, remaining copper-carbon skeleton is in saw
Dentalation obtains serrated metal nano wire-carbon-based fuel cell catalyst；The heating temperature of drying is 140 DEG C, the time
For 4h；The voltage of electric field that electrophoresis leaches is 200V.
Laciniation copper-carbon composite catalytic agent prepared by embodiment 3, specific surface area, catalytic efficiency are as shown in table 1.
Embodiment 4
Raw material is calculated as by weight：16 parts of mantoquita, 13 parts of nickel salt, 42.4 parts of water, 3 parts of reducing agent, 3 parts of complexant, surface-active
0.6 part of agent, 22 parts of tetraphenylporphyrin；Mantoquita is copper chloride；Nickel salt is nickel acetate；Reducing agent is propylene glycol；Complexant is apple
Acid；Surfactant is propyl naphthalene sulfonate；Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 8；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with nano wire, inhibit nanometer
Polymer/nano line composite material is made in the reunion of alloy；
（3）By step（2）Composite material obtained is placed in vacuum environment, high-temperature calcination carbonization, and clad alloy skeleton；High temperature
The temperature of calcining is 450 DEG C, time 3h；
（4）It is placed in progress electrophoresis in low voltage electric field to leach, so that nickle atom is detached from from alloy phase, remaining copper-carbon skeleton is in saw
Dentalation obtains serrated metal nano wire-carbon-based fuel cell catalyst；The heating temperature of drying is 125 DEG C, the time
For 6h；The voltage of electric field that electrophoresis leaches is 160V.
Laciniation copper-carbon composite catalytic agent prepared by embodiment 4, specific surface area, catalytic efficiency are as shown in table 1.
Embodiment 5
Raw material is calculated as by weight：18 parts of mantoquita, 14 parts of nickel salt, 34.2 parts of water, 4 parts of reducing agent, 3 parts of complexant, surface-active
0.8 part of agent, 26 parts of tetraphenylporphyrin；Mantoquita is copper nitrate；Nickel salt is nickel chloride；Reducing agent is ethyl alcohol；Complexant is citric acid；
Surfactant is butyl naphthalene sulfonate；
Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 8.5；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with nano wire, inhibit nanometer
Nanowire composite is made in the reunion of alloy；
（3）By step（2）Composite material obtained is placed in vacuum environment, high-temperature calcination carbonization, and clad alloy skeleton；High temperature
The temperature of calcining is 550 DEG C, time 2h；
（4）It is placed in progress electrophoresis in low voltage electric field to leach, so that nickle atom is detached from from alloy phase, remaining copper-carbon skeleton is in saw
Dentalation obtains serrated metal nano wire-carbon-based fuel cell catalyst；The heating temperature of drying is 135 DEG C, the time
For 4.5h；The voltage of electric field that electrophoresis leaches is 180V.
Laciniation copper-carbon composite catalytic agent prepared by embodiment 5, specific surface area, catalytic efficiency are as shown in table 1.
Comparative example 1
Raw material is calculated as by weight：18 parts of mantoquita, 14 parts of nickel salt, 34.2 parts of water, 4 parts of reducing agent, 3 parts of complexant, surface-active
0.8 part of agent, 26 parts of carbon dust；Mantoquita is copper nitrate；Nickel salt is nickel chloride；Reducing agent is ethyl alcohol；Complexant is citric acid；It lives on surface
Property agent be butyl naphthalene sulfonate；
Preparation process is：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；The pH value of mixed solution is 8.5；
（2）Step is added in carbon dust（1）System in, so that carbon dust is combined with nano wire, nano wire composite catalyst be made.
Laciniation copper nano-wire catalyst prepared by comparative example 1, specific surface area, catalytic efficiency are as shown in table 1.
The catalyst that embodiment 1-5, comparative example 1 obtain is dispersed in respectively in perfluorocarbon sulfonate resin and water, is coated on
On the two sides of perfluorocarbon sulfonate resin film, current density test is carried out in oxygen-hydrogen fuel cell under same coating layer thickness.Such as
Shown in table 1.
Table 1：
Claims (10)
1. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst, preparation process are：
（1）Mantoquita is soluble in water with nickel salt, and the acid-base value for adjusting mixed solution is alkalinity, and solution is placed in nitrogen atmosphere,
Reducing agent, complexant and surfactant is added, reacts and corronil nano wire is made；
（2）Step is added in tetraphenylporphyrin（1）System in, so that tetraphenylporphyrin is combined with corronil nano wire, inhibit
Nanowire composite is made in the reunion of corronil nano wire；
（3）By step（2）Composite material obtained is placed in vacuum environment, and high-temperature calcination carbonization forms carbon coating alloy skeleton；
（4）By step（3）Obtained carbon coating alloy skeleton is placed in progress electrophoresis in low voltage electric field and leaches, and makes nickle atom from alloy
It is detached from phase, remaining copper-carbon skeleton is serrated structure, obtains serrated metal nano wire-carbon-based fuel cell catalysis
Agent.
2. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：A kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst, each raw material is by weight
For：15 ~ 20 parts of mantoquita, 12 ~ 15 parts of nickel salt, 28 ~ 47.5 parts of water, 3 ~ 5 parts of reducing agent, 2 ~ 3 parts of complexant, surfactant 0.5 ~
1 part, 20 ~ 28 parts of tetraphenylporphyrin.
3. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The mantoquita is at least one of copper chloride, copper nitrate or copper sulphate.
4. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The nickel salt is at least one of nickel chloride, nickel sulfate, nickel nitrate or nickel acetate.
5. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The reducing agent is one kind in propylene glycol, ethyl alcohol or oxalic acid.
6. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The complexant is at least one of citric acid, succinic acid, glycine or malic acid；The surfactant is
One kind in propyl naphthalene sulfonate, butyl naphthalene sulfonate or alkyl sulfate.
7. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The pH value of the mixed solution is 7.5 ~ 8.5.
8. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The temperature of the high-temperature calcination is 400 ~ 600 DEG C, and the time is 2 ~ 3h.
9. a kind of preparation method of serrated metal nano wire-carbon-based fuel cell catalyst according to claim 1, special
Sign is：The voltage of electric field that the electrophoresis leaches is 150 ~ 200V.
10. a kind of serrated metal nano wire-carbon-based fuel cell that any one of claim 1-9 the methods are prepared is urged
Agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904000A (en) * | 2019-04-10 | 2019-06-18 | 蚌埠学院 | A kind of preparation method and application of nanowire nickel-based complex electrode material |
| CN111627724A (en) * | 2020-04-22 | 2020-09-04 | 上海工程技术大学 | Carbon-coated nickel-based film electrode material and preparation method and application thereof |
| CN112614699A (en) * | 2020-11-03 | 2021-04-06 | 宁波工程学院 | Zigzag nitrogen-doped SiC nanowire-based high-temperature supercapacitor |
| US20220029173A1 (en) * | 2020-07-22 | 2022-01-27 | Rutgers, The State University Of New Jersey | Carbon Nanomaterial Supported Single Atom Catalysts and Methods of Preparing Same |
-
2018
- 2018-01-26 CN CN201810076743.5A patent/CN108336375A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904000A (en) * | 2019-04-10 | 2019-06-18 | 蚌埠学院 | A kind of preparation method and application of nanowire nickel-based complex electrode material |
| CN111627724A (en) * | 2020-04-22 | 2020-09-04 | 上海工程技术大学 | Carbon-coated nickel-based film electrode material and preparation method and application thereof |
| CN111627724B (en) * | 2020-04-22 | 2022-02-08 | 上海工程技术大学 | Carbon-coated nickel-based film electrode material and preparation method and application thereof |
| US20220029173A1 (en) * | 2020-07-22 | 2022-01-27 | Rutgers, The State University Of New Jersey | Carbon Nanomaterial Supported Single Atom Catalysts and Methods of Preparing Same |
| US12308444B2 (en) * | 2020-07-22 | 2025-05-20 | Rutgers, The State University Of New Jersey | Carbon nanomaterial supported single atom catalysts and methods of preparing same |
| CN112614699A (en) * | 2020-11-03 | 2021-04-06 | 宁波工程学院 | Zigzag nitrogen-doped SiC nanowire-based high-temperature supercapacitor |
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