CN106816614A - Preparation and electrode and application that fuel cell is catalyzed with fine and close platinum monoatomic layer - Google Patents
Preparation and electrode and application that fuel cell is catalyzed with fine and close platinum monoatomic layer Download PDFInfo
- Publication number
- CN106816614A CN106816614A CN201510864125.3A CN201510864125A CN106816614A CN 106816614 A CN106816614 A CN 106816614A CN 201510864125 A CN201510864125 A CN 201510864125A CN 106816614 A CN106816614 A CN 106816614A
- Authority
- CN
- China
- Prior art keywords
- npg
- electrode
- platinum
- monoatomic layer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- 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
- H01M4/88—Processes of manufacture
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of fuel cell fine and close platinum monoatomic layer catalysis electrode and preparation method thereof.Nanoporous gold thin film is obtained using de- alloyage as raw material with goldleaf (Au/Ag films) first, then by this film transfer in glassy carbon electrode surface or the side of PEM.Platinum is deposited in mixed electrolytic solution using the method that electrochemistry and chemistry are combined in this, as substrate, the fine and close platinum individual layer catalysis electrode based on nano-porous gold is formed.The method applied in the present invention has the advantages that an environment-friendly, step is completed, catalyst loading is controllable, monoatomic layer is fine and close.Constructed can be used for fuel cell and other batteries and electrochemical reactor based on nano-porous gold densification platinum individual layer catalysis electrode.
Description
Technical field
The present invention relates to a kind of fine and close platinum monoatomic layer catalysis electrode for catalytic fuel cell electrode reaction
And preparation method thereof.
Background technology
Fuel cell is a kind of clean, efficient energy conversion device, at present in electric automobile, distribution
The multiple fields such as power station, aviation, submarine achieve application.Wherein Proton Exchange Membrane Fuel Cells is with its power
Density is high, toggle speed is fast, high conversion efficiency, advantages of environment protection are of great interest.Electrode
It is the core component of fuel cell, is the place that electrochemical reaction occurs.In order to realize the business of fuel cell
It is the noble metal platinum in electrode is reduced on the premise of ensureing activity to change one of application, current problem demanding prompt solution
Consumption so that reduces cost.
Nano-porous gold (NPG, Nanoporous Gold)) thickness of film can be in the model of 100nm~1 μm
Interior modulation is enclosed, it also has three-dimensional continuous insertion pore passage structure, good electric conductivity, larger ratio in addition
Surface area, can be used to prepare fuel cell thin layer electrode.
Prior art mainly prepares low platinum carrying capacity using the method for electronation and the method for electrochemical deposition
Catalysis electrode.
Patent WO2004021481-A1 describes a kind of nano-porous gold (NPG, nanoporous gold)
The method that carried metal Pt is used for Proton Exchange Membrane Fuel Cells.First, using going alloyage to be prepared for receiving
Meter Duo Kong gold；Then, nano-porous gold is placed in the solution containing Pt presomas, puts down nano-porous gold
Liquid level is laid on, then to hydrazine steam is passed through in reactor, the presoma of Pt is reduced the table in nano-porous gold
On face, NPG load~3nmPt layers of catalysis electrode is ultimately formed.
Patent CN101332425-A describes a kind of inner surface uniform fold platinum metal in nano-porous gold
The method of atomic layer.The method principle is underpotential deposition.It is specific as follows：1) goldleaf is carried out with nitric acid
Removal alloying treatment, obtains nano-porous gold；2) with it is porous gold as working electrode, graphite flake be to electrode,
SCE is reference electrode, in the acid solution containing 0.01~100mM copper, silver or lead ion of abundant deoxygenation
Owe potential deposition copper, silver or lead, potential range (- 0.5V, -0.3V) vs.SCE of deposition, sedimentation time
1~10min；3) working electrode is transferred to displacement in the platinum metal cationic solution of 0.01~100mM
5~30min.Catalyst prepared by the patent is mainly used in the Electrocatalytic Oxidation of organic molecule.
Patent WO2012102712-A1 and WO2012102714-A1 describe a kind of nanoporous gold surface and repair
The method of Pt layers of decorations.The method of nano-porous gold surface modification Pt is dipping-electrochemical reducing.Specifically
Method is：1) alloyage is gone to prepare nano-porous gold；2) nano-porous gold be impregnated in into chloroplatinic acid or chlorine
In platinic acid salting liquid；3) nano-porous gold for being adsorbed with presoma is embathed with deionized water, to control platinum layer
Thickness；3) three-electrode system is used, nano-porous gold is used as working electrode, 0.5M H2SO4 conducts
Electrolyte；Platinum layer is deposited in nanoporous gold surface using potentiostatic method or cyclic voltammetric electrodeposition process；4)
Repeat 2), 3) to control platinum layer thickness.
Chemical reduction method refer to by using appropriate reducing agent, surfactant etc. under certain conditions
Make reactant that specific reduction reaction to occur and prepare platinum layer catalysis electrode.Preparation process as described in above-mentioned patent
Used as reducing agent, this has potentially hazardous to middle use hydrazine to environment and human body, and this electronation side
Method inconvenience control Pt thickness degree.The method that electrochemical deposition combines displacement reaction can prepare uniform Pt originals
Sublayer catalysis electrode, but preparation process point multistep carries out, and monoatomic layer is easily aoxidized in electrode transfer process.
Present invention is generally directed to solve problem present in above-mentioned prior art or preparation method, there is provided Yi Zhongji
In the preparation method of the fine and close platinum monoatomic layer catalysis electrode of nano-porous gold, the step of the method preparation process one is complete
Into, platinum monoatomic layer, Pt layer of covering densification etc. can be realized.
The content of the invention
The principle of preparation method of the present invention is：Bivalent cupric ion in specific potential region, it is specific
Substrate surface can occur underpotential deposition (Underpotential Deposition, UPD), i.e., in height
In Cu2+Certain of/Cu balance sedimentation potentials is specific interval interior, and copper ion will be deposited in the form of monoatomic layer
In substrate surface, at the end of UPD processes, the Cu of monoatomic layer takes surface, now only by current potential
The body deposition that Cu occurs just is may proceed to when being reduced to balance sedimentation potential.After the Cu of monoatomic layer is formed,
It is different from the movable metallic order of Pt using Cu, reacted by displacement, copper puts platinum from its presoma
Swap out and, so as to obtain the monoatomic layer of platinum.From unlike current all technologies, the process is in a mixing
Carried out in electrolyte solution, a step is completed, underpotential deposition and displacement reaction are carried out continuously successively, it is to avoid
The oxidation of copper atom in electrode transfer process.The mixed solution is the sulfuric acid that with the addition of platinum presoma and citric acid
Copper solution.The addition of citric acid can prevent the undercurrent potential that copper occurs again on the monatomic platinum layer for being formed from sinking
Product, thus formed platinum cluster and un-densified smooth platinum monoatomic layer.
To achieve these goals, the present invention is adopted the following technical scheme that：With potassium chloroplatinite, dilute sulfuric acid,
Copper sulphate, the mixed solution of citric acid are used as electrolyte solution.In three-electrode system using platinum plate electrode as
To electrode, used as reference electrode, nanoporous gold electrode is used as working electrode for saturated calomel electrode.In electrolysis
Argon gas to saturation is passed through in matter solution, it is interval fast with scanning by controlling potential then using cyclic voltammetry
Degree a, step realizes the reduction of the Atomic layer deposition and platinum presoma of copper ion.Finally, with deionized water pair
Electrode surface is cleaned.
Fine and close platinum monoatomic layer catalysis electrode preparation process based on nano-porous gold is as follows：
1) nano-porous gold is prepared using de- alloyage：First by goldleaf (Au/Ag films；12-carat,
Sepp LeafProducts, New York) small pieces that are cut to certain area are placed in deionized water, so
After be transferred into dense HNO3In, in corroding 10min-2h under 10 DEG C of -60 DEG C of temperature conditionss.Removing Ag with
Nano-porous gold (NPG) is obtained, is cleaned repeatedly in deionized water several times, it is stand-by.
2) preparation of NPG working electrodes：NPG working electrodes are divided into area for 0.1256cm2With 2 × 2cm2Two
Kind.1) NPG prepared in is transferred to glass carbon (glass carbon, GC) electrode surface, waits to fill
Divide after drying, the NPG to electrode surface is modified, final is only to cover glass carbon part, a diameter of 4mm
GC/NPG electrodes；1) NPG prepared in is transferred in mica sheet or metallic substrates first, is used
NPG films are transferred to amberplex surface by pressure sintering from substrate surface, and (amberplex used includes matter
Proton exchange and anion-exchange membrane), the pressure size applied during hot pressing be 2~10MPa, the time be 0.5~
30min, temperature is 50~200 DEG C, prepares the NPG electrodes of 2cm × 2cm.
3) electrolyte solution is prepared：The electrolyte solution that preparation method described in this patent is used is：50mM
H2SO4+50mM CuSO4Middle addition concentration is the K of 0.01-10mM2PtCl4Solution and concentration are the lemon of 5-50mM
The mixed solution of lemon acid solution.
4) densification Pt monoatomic layer catalysis electrodes are prepared：Electrolyte solution is placed in tri- mouthfuls of electrolytic cells of 100ml
In, it is passed through Ar about 30min -1h to saturation.Using three-electrode system, using cyclic voltammetric technology by electricity
On certain interval between -0.2-0.6V (vs.SCE), sweep speed selection exists for position control
1mV/s -50mV/s carries out the monoatomic layer displacement of the underpotential deposition and platinum of copper.
Monoatomic layer is controllable, cladding is fine and close, and the step of preparation process one is completed.
There is the method applied in the present invention an environment-friendly, step to complete, catalyst loading is controllable, monatomic
The advantages of layer is fine and close.Constructed can be used for fuel cell based on nano-porous gold densification platinum individual layer catalysis electrode
And other batteries and electrochemical reactor.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of nano-porous gold micromorphology.
Fig. 2 is that nano-porous gold is the stereoscan photograph of surface topography after carrier cladding platinum layer.
Fig. 3 is the CV curves of the naked surface of nano-porous gold (not carrying out Pt layers of cladding).
Fig. 4 is the CV curves that underpotential deposition Cu is carried out in nanoporous gold surface.
Fig. 5 is schematic diagram of the Pt monoatomic layers dense arrangement in nanoporous gold surface.
Fig. 6 is the CV curves after nano-porous gold and Surface coating platinum monoatomic layer.
Fig. 7 is the stability curve after the interval sign nano-porous gold Surface coating platinum monoatomic layer of high potential.
Fig. 8 is the Pt monoatomic layer catalyst for being commercialized PtC and being prepared using the method for the invention
CV curve control figures.
Fig. 9 is the Pt monoatomic layer catalyst for being commercialized PtC and being prepared using the method for the invention
ORR curve control figures.
Specific embodiment
Below in conjunction with the accompanying drawings with embodiment to fine and close platinum monoatomic layer catalysis electrode of the present invention and its system
Preparation Method is described further.
Embodiment 1
Specific preparation process：
1) by goldleaf (Au/Ag films；12-carat, Sepp LeafProducts, New York) it is placed in
In dense HNO3, corrode 1 hour under the conditions of 50 DEG C, removing Ag is with prepared nano-porous gold (NPG).；
2) by step 1) in NPG working electrodes be divided into area for 0.1256cm2 is circular and 2 × 2cm2 square two
Kind.；The circular NPG that will be prepared is transferred to glassy carbon electrode surface, is then modified to diameter 4mm layers
Folded GC/NPG electrodes；The NPG that will be prepared is transferred in mica sheet substrate, using pressure sintering (pressure
It is 2MPa, the time is 25min, and temperature is 80 DEG C) NPG films are transferred to ion exchange from substrate surface
Film surface, prepares the square NPG electrodes of 2cm × 2cm；
3) added in the 50mM H2SO4, the 50mM CuSO4 that prepare 100mL 2mL concentration be 10mM K2PtCl4,
5mL concentration is the mixed solution of 10mM citric acid solutions as electrolyte solution；
4) electrolyte solution is placed in tri- mouthfuls of electrolytic cells of 100ml, is passed through Ar to saturation.Using three electrode bodies
System, respectively with circular and square NPG as working electrode, with platinized platinum be to electrode, saturated calomel electrode be join
The use of cyclic voltammetric technical controlling potential region is -0.2-0.6V than electrode, sweep speed is 30mV/s
Carry out the monoatomic layer displacement of the underpotential deposition and platinum of copper.
Nano-porous gold and the microcosmic knot of Supported Pt Nanoparticles monoatomic layer catalyst material prepared by the method for the invention
Structure morphology characterization.
The nano-porous gold prepared by taking off alloyage has three-dimensional continuous insertion pore structure, and stephanoporate framework is clear
Clear, in the range of 30-50nm, size is homogeneous, be evenly distributed in aperture, the microcosmic surface shape of nano-porous gold
Looks refer to Figure of description 1.The nano-porous gold Supported Pt Nanoparticles list prepared using experimental technique of the present invention
The micromorphology of atomic layer catalyst refers to Figure of description 2.It is porous from the point of view of the contrast of two width figures
The surface topography of gold there occurs substantially change, but its structural intergrity is not destroyed, simply original
Golden skeleton on coated densification platinum atomic layer.
Embodiment 2
The theoretical meter of the nanoporous auri Pt monoatomic layer catalysis electrodes to being prepared using this patent methods described
Calculate result.
Figure of description 3 be NPG bare electrodes CV curves (electrolyte solution be 0.1M HClO4, scanning
Speed is 100mV/s), according to the reduction peak (dash area in accompanying drawing 3) at 1.2V, by following formula meters
Calculate the active area of NPG：
S is the integral area (AV) of dash area in figure, and ν is the sweep speed of CV curves, Qref tables
Show absorption electricity (the 400 μ Ccm in NPG surface unit areas-2).Thus the NPG being calculated lives
Property area ECSA be 0.6125cm2。
Assuming that Pt atoms (a diameter of 0.225nm) according to individual layer dense arrangement on the surface of NPG, such as explanation
Shown in book accompanying drawing 5, Red diamonds (area S in figure is takenIRepresent) shown in atom be elementary cell.Therefore,
Amount (the n of the Pt atom species required for occupying completely above-mentioned active area in theory1) be：
n1=ECSA/ (SI×N)
Calculate n1=0.201 × 10-8Mol, N take 6.02 × 1023。
Figure of description 4 is the underpotential deposition curve of Cu, and current potential shown in arrow is the UPD of Cu in figure
Terminate current potential, the dash area integral area in figure can indirectly be calculated transfer during UPD
Electron number and Cu individual layer atomicities, according to Cu2+Displacement one-to-one with Pt and then try to achieve and be actually coated on NPG
Amount (the n of the Pt atom species on surface2) be：
n2=Q/ (2e × N)
It is calculated n2=0.204 × 10-8Mol, Q are the device electricity of dash area in Fig. 4, and e is single
Electron charge 1.6 × 10-19C。
To n1And n2Contrasted, n1≈n2, therefore can to a certain extent think that Pt atoms are fine and close in individual layer
It is coated on NPG surfaces.
Embodiment 3
Nano-porous gold and the nano-porous gold Supported Pt Nanoparticles monoatomic layer catalysis prepared using this patent methods described
The cyclic voltammetric of agent is characterized.
It is electric as work to be loaded with the glass-carbon electrode of nano-porous gold and nanoporous auri platinum single-layer catalyst respectively
Pole, with saturated calomel electrode as reference electrode, platinum plate electrode be to electrode constitute three-electrode system, with lead to N2
The HClO of the 0.1M of saturation4It is electrolyte solution, connects electrochemical workstation selection cyclic voltammetric technology,
In potential region 0.05-1.7V, sweep test, acquired results are circulated with the sweep speed of 50mV/s
As shown in Figure of description 6.
Accompanying drawing 6 is interval interior high potential, the CV curves of nano-porous gold and nano-porous gold Supported Pt Nanoparticles monoatomic layer.
Wherein, square curve is CV curve of the nano-porous gold in 0.05-1.7V potential ranges, and the curve exists
1.4V or so starts to terminate to 1.6V, continuously goes out three oxidation peaks of cash, and current potential is born during sweeping low
Occurs an obvious reduction peak when 1.2V, the curve is the CV curves of typical nano-porous gold.Through
CV curves there occurs substantially change after this patent methods described prepares platinum monoatomic layer, and such as figure intermediate cam shape is bent
Shown in line, the curve loses the typical oxidation peak of nano-porous gold and goes back completely under identical testing conditions
Parent peak, especially obvious in 1.2V, the covered disappearance of reduction peak of gold, this explanation passes through the party
The platinum monoatomic layer of method preparation is fine and close to be covered on the skeleton of nano-porous gold.
Accompanying drawing 7 is that nano-porous gold and nano-porous gold Supported Pt Nanoparticles are monatomic in the 0.7V-1.6V of high potential interval
Layer catalyst electrode accelerates attenuation test (attenuation test current potential respectively through 100,200,500,1000 circles
Interval 0.6V-1.2V, sweep speed 100mV/s) after CV curves.Wherein square curve is typical
, there is obvious reduction peak in 1.2V or so in the CV curves of nano-porous gold.After being coated through Pt atomic layers,
This reduction peak disappear, respectively through 100,200,500 and 1000 cyclical acceleration attenuation tests after,
Reduction peak current at 1.2V gradually increases, and this shows gradually to have the signal of NPG to occur.But by 500
After 1000 circle loop tests, the increase of reduction peak current is not obvious, it is meant that Pt monoatomic layers are still
Can be finer and close envelope NPG skeletons.After accelerating decay, start to engender NPG on CV curves
Signal, think：When volt-ampere be circulated in 0.7V-1.6V this potential region testing, because
The dissolution potential that interval high potential has exceeded Pt is tested, so the dissolving of Pt is inevitably had, and
Pt is again monoatomic layer arrangement, therefore the reduction peak of NPG occurs.But the electricity in actual application
Electrode potential can't reach it is so high, therefore Pt atomic layers be densification be coated on NPG surfaces.
Embodiment 4
The Pt monoatomic layers catalysis electrode based on NPG to being prepared using this patent methods described carries out CV and ORR
Characterize.
The glass-carbon electrode of NPG base Pt monoatomic layers (NPG/Pt) is loaded with as working electrode, saturated calomel electrode
For reference electrode, platinum plate electrode are to constitute three-electrode system to electrode, electrochemical workstation selection circulation is connected
Volt-ampere technology, to lead to N2The HClO of the 0.1M of saturation4It is electrolyte solution, in 0.05-1.2V potential regions
It is interior, voltammetric scan is circulated with the sweep speed of 50mV/s and is tested, as a result as shown in Figure of description 8；
Selection linear scan technique, to lead to O2The HClO of the 0.1M of saturation4It is electrolyte solution, in 0.2-1.0V
In potential region, linear scan test is carried out with the sweep speed of 10mV/s, acquired results such as specification is attached
Shown in Fig. 9.
Fig. 8 is NPG, NPG/Pt, the CV curves of commercialization PtC catalyst, with square curve (NPG)
Compare, CV curves occur substantially to change after being modified by the monoatomic layer of Pt, such as circular curve in figure
(NPG/Pt) shown in, either in the adsorption desorption area (0.05-0.3V) of H or going back in 0.8V or so
CV curves at parent peak all substantially to PtC catalyst are similar, shown in figure intermediate cam shape curve.Illustrate that Pt is former
Sub- densification is coated on the skeleton of NPG.
Fig. 9 is nanoporous auri Pt monoatomic layers catalyst (NPG/Pt) and commercialization PtC catalyst
ORR curves, be intuitively demonstrated by two kinds of active sizes of catalyst, from the point of view of half wave potential, NPG/Pt
Relatively commercialization PtC is higher by~50mV；And the hydrogen reduction take-off potential of NPG/Pt catalysis electrodes is close to~1.0V,
Show that the platinum monoatomic layer catalysis electrode based on nano-porous gold prepared by this patent methods described can use
In fuel cell, and improve platinum utilization.
Claims (7)
1. a kind of fuel cell preparation method of fine and close platinum monoatomic layer catalysis electrode, its step is：
1) nano-porous gold is prepared using de- alloyage：By goldleaf (Au/Ag films；12-carat,
Sepp LeafProducts, New York) it is placed in dense HNO3Middle corrosion, removing Ag is more so that nanometer is obtained
Kong Jin (NPG)；
2) preparation of NPG working electrodes：By step 1) in NPG working electrodes be divided into area and be
0.1256cm2Circular and 2 × 2cm2Square two kinds；The circular NPG that will be prepared is transferred to glass carbon (glass
Carbon, GC) electrode surface, then it is modified to the GC/NPG electrodes of diameter 4mm stackings；Will
1) NPG prepared in is transferred in mica sheet or metallic substrates first, using pressure sintering that NPG is thin
Film is transferred to amberplex surface from substrate surface, prepares the square NPG electrodes of 2cm × 2cm；
3) electrolyte solution is prepared：The electrolyte solution for using is：H2SO4、CuSO4、K2PtCl4、
The mixed solution of citric acid solution；
4) densification Pt monoatomic layer catalysis electrodes are prepared：Electrolyte solution is placed in tri- mouthfuls of electricity of 100ml
Xie Chizhong, is passed through Ar to saturation；Using three-electrode system, using cyclic voltammetric technical controlling current potential and
Sweep speed carries out the monoatomic layer displacement of the underpotential deposition and platinum of copper.
2. preparation method according to claim 1, it is characterised in that：De- alloyage prepares nanometer
The condition of porous gold is to corrode 10min-2h under 10 DEG C of -60 DEG C of temperature conditionss.
3. preparation method according to claim 1, it is characterised in that：By modification, make circle
0.1256cm2Electrode be completely covered on the glassy carbon electrode surface of a diameter of 4mm just for NPG；Pressure sintering
Prepare the square NPG electrodes of 2cm × 2cm, condition is 2~10Mpa of pressure size, 0.5~30min of time,
50~200 DEG C of temperature.
4. preparation method according to claim 1, it is characterised in that：The electrolyte solution is
The 50mM H of 100mL2SO4+50mM CuSO4200 μ L-2mL concentration of middle addition are 0.01-10mM's
K2PtCl4Solution and 1-5mL concentration are the mixed solution of the citric acid solution of 5-50mM.
5. preparation method according to claim 1, it is characterised in that：The cyclic voltammetry is
On certain interval using cyclic voltammetric technology by control of Electric potentials between -0.2-0.6V (vs.SCE),
Sweep speed selection carries out the monoatomic layer displacement of the underpotential deposition and platinum of copper in 1-50mV/s.
6. a kind of fuel cell of any preparations of claim 1-5 is with fine and close platinum monoatomic layer catalysis electrode.
7. the platinum monoatomic layer catalysis electrode described in a kind of claim 6 can be used for catalytic fuel cell electricity
React or other batteries or electrochemical reactor pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510864125.3A CN106816614B (en) | 2015-11-27 | 2015-11-27 | The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510864125.3A CN106816614B (en) | 2015-11-27 | 2015-11-27 | The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106816614A true CN106816614A (en) | 2017-06-09 |
| CN106816614B CN106816614B (en) | 2019-07-05 |
Family
ID=59107268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510864125.3A Active CN106816614B (en) | 2015-11-27 | 2015-11-27 | The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106816614B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109326799A (en) * | 2018-09-19 | 2019-02-12 | 伊犁师范学院 | A kind of preparation method of nanoporous platinum ruthenium catalyst |
| CN109599580A (en) * | 2018-12-24 | 2019-04-09 | 天津理工大学 | A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell |
| CN112774697A (en) * | 2020-09-07 | 2021-05-11 | 南京大学 | Monoatomic metal-molybdenum sulfide nano-composite and preparation method and application thereof |
| CN114583194A (en) * | 2022-03-01 | 2022-06-03 | 天津理工大学 | Large porosity catalyst layer suitable for proton exchange membrane fuel cell |
| CN114772682A (en) * | 2022-03-31 | 2022-07-22 | 北京化工大学 | Gold-based modified electrode, method for removing glycerol oxychloride and application of gold-based modified electrode |
| TWI787322B (en) * | 2017-08-14 | 2022-12-21 | 美商蘭姆研究公司 | Selective electroless electrochemical atomic layer deposition in an aqueous solution without external voltage bias |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070031722A1 (en) * | 2004-12-22 | 2007-02-08 | Radoslav Adzic | Electrocatalysts having platinum monolayers on palladium, palladium alloy, and gold alloy nanoparticle cores, and uses thereof |
| CN101332425A (en) * | 2008-08-04 | 2008-12-31 | 山东大学 | Nano porous gold-loaded ultrathin platinum metallic film catalyst and preparation method thereof |
| CN103402631A (en) * | 2011-02-22 | 2013-11-20 | Utc电力公司 | Method of forming a catalyst with an atomic layer of platinum atoms |
| CN104001525A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院长春应用化学研究所 | Preparation method for PtCu/C catalyst |
-
2015
- 2015-11-27 CN CN201510864125.3A patent/CN106816614B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070031722A1 (en) * | 2004-12-22 | 2007-02-08 | Radoslav Adzic | Electrocatalysts having platinum monolayers on palladium, palladium alloy, and gold alloy nanoparticle cores, and uses thereof |
| CN101332425A (en) * | 2008-08-04 | 2008-12-31 | 山东大学 | Nano porous gold-loaded ultrathin platinum metallic film catalyst and preparation method thereof |
| CN103402631A (en) * | 2011-02-22 | 2013-11-20 | Utc电力公司 | Method of forming a catalyst with an atomic layer of platinum atoms |
| CN104001525A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院长春应用化学研究所 | Preparation method for PtCu/C catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI787322B (en) * | 2017-08-14 | 2022-12-21 | 美商蘭姆研究公司 | Selective electroless electrochemical atomic layer deposition in an aqueous solution without external voltage bias |
| CN109326799A (en) * | 2018-09-19 | 2019-02-12 | 伊犁师范学院 | A kind of preparation method of nanoporous platinum ruthenium catalyst |
| CN109326799B (en) * | 2018-09-19 | 2022-08-26 | 伊犁师范学院 | Preparation method of nano porous platinum ruthenium catalyst |
| CN109599580A (en) * | 2018-12-24 | 2019-04-09 | 天津理工大学 | A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell |
| CN112774697A (en) * | 2020-09-07 | 2021-05-11 | 南京大学 | Monoatomic metal-molybdenum sulfide nano-composite and preparation method and application thereof |
| CN114583194A (en) * | 2022-03-01 | 2022-06-03 | 天津理工大学 | Large porosity catalyst layer suitable for proton exchange membrane fuel cell |
| CN114772682A (en) * | 2022-03-31 | 2022-07-22 | 北京化工大学 | Gold-based modified electrode, method for removing glycerol oxychloride and application of gold-based modified electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106816614B (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Park et al. | Ultra-low loading of IrO2 with an inverse-opal structure in a polymer-exchange membrane water electrolysis | |
| CN109449466B (en) | Preparation method of membrane electrode and preparation method of anode catalyst layer of membrane electrode | |
| CN106816614A (en) | Preparation and electrode and application that fuel cell is catalyzed with fine and close platinum monoatomic layer | |
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN106498434B (en) | The preparation method of the Ni-based porous nickel phosphide hydrogen-precipitating electrode of integration | |
| CN105734606B (en) | A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application | |
| CN108075144B (en) | Core-shell structure catalyst for fuel cell and preparation and application thereof | |
| CN107858701A (en) | A kind of titanium-based hydrogen-precipitating electrode for solid polymer water electrolyzer and preparation method thereof | |
| CN103280583B (en) | Method for preparing catalytic layer structure of proton exchange membrane fuel cell | |
| CN106887598A (en) | A kind of ordering membrane electrode and its preparation and application | |
| CN105633420B (en) | A kind of nano-porous gold is used for the preparation method of fuel cell thin layer electrode | |
| CN104218250A (en) | PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell | |
| CN110556546B (en) | Nitrogen and oxygen co-doped hierarchical porous carbon material and preparation method thereof | |
| Adilbish et al. | Effect of the Nafion content in the MPL on the catalytic activity of the Pt/C-Nafion electrode prepared by pulsed electrophoresis deposition | |
| JP2018529516A (en) | Electrocatalyst on carbonitride matrix | |
| US7625659B2 (en) | Fuel cell, membrane electrode assembly, catalyst used therefor, and method of producing catalyst | |
| CN111545227A (en) | 3D nanosheet network structure bimetallic phosphorus oxide electrocatalyst and preparation method and application thereof | |
| CN103409780B (en) | A kind of method of nano-porous gold being carried out to surface alloy modification | |
| Jia et al. | In situ synthesis of nanorod arrays of nickel–molybdenum nitrides as stable electrocatalysts for hydrogen evolution reactions | |
| Chabi et al. | Electrocatalysis of oxygen reduction reaction on Nafion/platinum/gas diffusion layer electrode for PEM fuel cell | |
| CN104701549B (en) | A carbon-free membrane electrode assembly | |
| Yang et al. | Au-and Pd-modified porous Co film supported on Ni foam substrate as the high performance catalysts for H2O2 electroreduction | |
| CN103579639A (en) | Cathode catalyst for fuel cell and preparation method thereof | |
| Xu et al. | Electrosynthesis of dendritic palladium supported on Ti/TiO2NTs/Ni/CeO2 as high-performing and stable anode electrocatalyst for methanol electrooxidation | |
| TW201020205A (en) | Electroplating solution for manufacturing nanometer platinum and platinum based alloy particles and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |