CN106328960A - ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell - Google Patents
ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell Download PDFInfo
- Publication number
- CN106328960A CN106328960A CN201610881979.7A CN201610881979A CN106328960A CN 106328960 A CN106328960 A CN 106328960A CN 201610881979 A CN201610881979 A CN 201610881979A CN 106328960 A CN106328960 A CN 106328960A
- Authority
- CN
- China
- Prior art keywords
- zif
- catalyst
- solution
- porous carbon
- composite material
- 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.)
- Pending
Links
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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/9041—Metals or alloys
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses application of a nitrogen-doped porous carbon fixed Co@Pt nano-particle composite material, prepared by taking ZIF-67 as a template, as an efficient catalyst for oxygen reduction catalytic reaction of a cathode of a fuel cell. The application has the superiorities that (1) a synthetic method of the catalyst is simple and feasible, the shape of the catalyst is controllable, batch preparation can be realized, and the catalytic performance is very stable; (2) the oxygen reduction catalytic reaction of nitrogen-doped porous carbon fixed cobalt-platinum core-shell nano-particles in the cathode of the fuel cell shows that the nano-particles have good catalytic activity and excellent methanol poisoning resistance stability, and compared with traditional commercial Pt/C, the nano-particles have relatively high take-off potentials and half-wave-peak potentials (nano-particles: 0.99V and 0.87V, and Pt/C: 0.98V and 0.83V); and (3) metal organic frameworks (MOFs) for preparing the catalyst have sequential microcellular structures and relatively large specific surface areas and can be widely applied to the storage and conversion of energy sources. Therefore, a method for simply and directly preparing cheap and efficient cathode oxygen reduction electro-catalyst is provided for the fuel cell and has a wide application prospect.
Description
Technical field
The Co@Pt nano particle composite material that present invention application N doping porous carbon is fixed is efficient for fuel battery negative pole
Hydrogen reduction catalytic reaction, belongs to catalyst and novel energy resource material technology field.It is related specifically to a kind of noble metal nucleocapsid structure receive
The preparation of rice grain catalyst, and the application in terms of fuel battery negative pole hydrogen reduction electro-catalysis.
Background technology
Fuel cell (Fuel Cell) is a kind of the chemical energy of storage in fuel and oxidant can be converted into electric energy
Device.Fuel cell can be divided into following five types by the difference according to its electrolyte: 1) alkaline fuel cell
(Alkaline Fuel Cell, AFC)；2) polymer dielectric film fuel cell (Polymer Electrolyte
Membrane Fuel Cell, PEMFC)；3) phosphoric acid fuel cell (Phosphoric Acid Fuel Cell, PAFC)；4) molten
Melt carbonate fuel battery (Molten Carbonate Fuel Cell, MCFC)；5) SOFC (Solid
Oxide Fuel Cell, SOFC).Owing to PEMFC has, required operating ambient temperature is relatively low, it is very fast to start, have higher ratio
Power, simple in construction, the advantage such as easy to operate, therefore suffer from the extensive concern of insider, is acknowledged as electric automobile, fixing
The first-selected energy of the equipment such as electric station.PEMFC monocell is to be made up of negative electrode, anode and PEM, and negative electrode happens is that
The reduction reaction of oxygen, anode happens is that the oxidation reaction of hydrogen fuel, and negative and positive two-stage all contains eelctro-catalyst to add simultaneously
Speed electrode electro Chemical reaction；Comparing anode reaction, cathode reaction speed is lower, therefore cathode reaction is rate-determing step.At present
The business Pt/C catalyst that one of Main Bottleneck of PEMFC large-scale commercial application is used exactly with high costs, performance
Stability is strong, and precious metals pt content in the earth's crust is relatively low and skewness.In order to reduce the cost of fuel cell, reduce Pt
Load capacity, improve Pt mass activity, improve activity and the service life of catalyst simultaneously, have highly important reality meaning
Justice.Therefore, development cost is low, and activity is high, the low-platinum catalyst that stability is strong, can be that the large-scale commercial of fuel cell should
By the condition of offer.
MOFs material is a kind of supermolecule hybrid material by inorganic metal ion and organic ligand self assembly, by
In alternative metal ion and organic ligand huge number, this is that the multiformity of MOFs kind and structure thereof has established base
Plinth.Along with the research to MOFs and derived material thereof progressively deeply, MOFs material this within several years, obtained fast development.One side
Face, MOFs derived material has conventional porous materials and does not has the advantage that, as structure and properties is adjustable, uncommon hole shape
Shape, functionalization is simple, various, and synthesis is simple.On the other hand, these materials itself have big specific surface area, high porosity,
The features such as structure diversification, available metal active centres, uncommon photo effect.Therefore, MOFs and derivant thereof are at gas
Body stores, is selectively adsorbing and separating, optical, electrical, magnetic, catalysis and the field such as chiral separation, thin-film material and fluorescent probe have
Wide application prospect.
Owing to it has orderly microcellular structure and bigger specific surface area, MOFs class material is much investigated as
Preferably template, i.e. by the method with inert atmosphere protection at high temperature dinectly bruning carbonization, thus synthesis has porous carbon solid
Fixed metal particle composite media.
According to existing research report, Pt alloy (such as PtNi, PtCo, PtCu, PtFe, PtCr etc.) is as main
Low Pt class catalyst in hydrogen reduction electrocatalytic reaction, demonstrated the strongest electrocatalysis characteristic.Another kind of low Pt class catalysis
The synthetic method of agent is that the Pt of several atomic layers thick is deposited on another kind of metal (M) surface, forms the nucleocapsid knot of a M@Pt
Structure, is possible not only to reduce the consumption of Pt, it is possible to make more active site be exposed to oxygen molecule, simultaneously between nucleocapsid
Mutually synergism can also promote the absorption to oxygen by the control of electronics and surface strain effect.Hence with ZIF-
67 make template, by the Co nanometer fixing with the method for inert atmosphere protection at high temperature dinectly bruning carbonization synthesis porous carbon
Grain, then by K2PtCl4Formed the nucleocapsid structure with Co@Pt by Galvanic displacement with the Co granule in this composite
Composite.The most direct and the easy large batch of preparation of the method, aobvious in the hydrogen reduction electrocatalytic reaction of fuel battery negative pole
Show that abundant active site and stronger methanol tolerance poison stability, and there is higher take-off potential and half-wave
Spike potential (0.99 V and 0.87 V) is compared to traditional business Pt/C(0.98 V and 0.83 V).Therefore, this material is combustion
Material battery provides the electrocatalyst for cathode of a kind of new Cheap highly effective, has a good application prospect.
The present invention, there is not yet disclosed document or patent report.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides the Co@Pt nano-particles reinforcement material that N doping porous carbon is fixing
Material is for the research of fuel battery negative pole efficient hydrogen reduction catalytic reaction.
The present invention is achieved by the following technical solutions, specifically includes following step:
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, cobalt nitrate is first dissolved in water, and to make A molten
Liquid, then 2-methylimidazole is dissolved in water makes B solution；Mixed for two kinds of solution being incorporated under 800 rpm is stirred 6 h, the most again from
The heart, washing and methanol are washed repeatedly thus are obtained purple precipitation；Gained purple precipitation is positioned over 60oC vacuum drying oven is dried
24 h, it is thus achieved that ZIF-67 nanocrystal.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned in the tube furnace with argon shield, with 1oThe speed of C/min
Rate is heated to 600oC is also incubated 2 h, the i.e. available Co nano particle composite material (Co-fixed by N doping porous carbon
NC).
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By a certain amount of potassium chloroplatinite (K2PtCl4) aqueous solution instills in above-mentioned solution, pass through
Galvanic displacement obtains the core shell nanoparticles of Co@Pt.
Step (1) described solution A concentration is formulated as 1.8 g Co (NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is joined
It is made as 22 g 2-methylimidazoles to be dissolved in the deionized water of 80 mL；After mixing, gained blue precipitate should be centrifuged successively, wash three
Secondary and methanol cleans three times, then is positioned over 60oC vacuum drying oven is dried 24 h.
Step (2) described ZIF-67 must calcine under noble gas (Ar gas) is protected, and diamond heating speed needs control
It is made as 1oC/min, temperature retention time is 2 h.
Step (3) is described there is Galvanic displacement under noble gas (Ar) is protected, and prepared catalyst is used for oxygen
During reduction reaction, the load capacity being coated on glassy carbon working electrode is 320 μ g cm-2, the load capacity of business Pt/C is 160 μ
g cm-2。
In sum, compared with existing research, the invention have benefit that:
(1) this eelctro-catalyst synthetic method is simple, morphology controllable, can realize large batch of preparation, and the catalysis of this material
Performance is relatively stable.
(2) the Co@Pt nano-particle fixed by N doping porous carbon is at the hydrogen reduction electrocatalytic reaction of fuel battery negative pole
Show that abundant active site and stronger methanol tolerance poison stability, and compared to traditional business Pt/C
(0.98V and 0.83V), it has higher take-off potential and half-peak potential (0.99V and 0.87V).
(3) metal organic frame (Metal Organic Frameworks, MOFs) preparing this eelctro-catalyst has
Orderly microcellular structure and bigger specific surface area, MOFs class material is much investigated as preferable template, is i.e. passed through
With the at high temperature dinectly bruning carbonization of the method for inert atmosphere protection, thus synthesis has the compound of the fixing metallic particles of porous carbon
Material, and in being widely used in energy storage and converting.
Accompanying drawing explanation
Fig. 1 be example 1 preparation ZIF-67 SEM figure (Figure 1A and Figure 1B), Co-NC SEM figure (Fig. 1 C and Fig. 1 D) and
SEM figure (Fig. 1 E and Fig. 1 F) of Co@Pt-NC.
Fig. 2 is the linear scanning figure of the Co@Pt-NC of example 1 preparation.
Fig. 3 is the Co@Pt-NC of example 1 and business Pt/C is at N2And O2The most saturated circulation in 0.1 M KOH solution
Volt-ampere curve figure.
Fig. 4 is that NC and Co-NC of example 1 preparation is at N2And O2The most saturated cyclic voltammetric in 0.1 M KOH solution is bent
Line chart.
Fig. 5 be example 1 preparation NC, Co-NC, Co@Pt-NC and business Pt/C at O2In 0.1 saturated M KOH solution
The linear polarisation curves figure of rotating disk electrode (r.d.e).
Fig. 6 is that the Co@Pt-NC-2 and Co@Pt-NC-3 of example 4-5 are at N2And O2In 0.1 the most saturated M KOH solution
Cyclic voltammetry curve figure.
Fig. 7 is that the Co@Pt-NC-2 for preparing of example 4-5 and Co@Pt-NC-3 is at O2The saturated rotation in 0.1 M KOH solution
Turn the linear polarisation curves figure of disk electrode.
Fig. 8 is NC, Co-NC, Co@Pt-NC and business Pt/C electron transfer number and the hydrogen peroxide productivity curve of example 1 preparation
Figure.
Fig. 9 be the Co@Pt-NC of example 2 preparation and business Pt/C with the speed of 50 mV/S at 0.6 V-1.0 V(vs.
RHE) the durability line figure after cyclic voltammetry scan 5000 times is done in electromotive force interval.
Figure 10 is the Co@Pt-NC of example 3 preparation and the i-t stability test of business Pt/C and methanol tolerance poison ability
Curve chart.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but the present invention is not limited to following example.
Embodiment 1.
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, solution A concentration is formulated as 1.8
g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is formulated as 22 g 2-methylimidazoles and is dissolved in the deionized water of 80 mL
In；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, and gained blue precipitate should be centrifuged successively, wash three times, first
Alcohol cleans three times, then is positioned over 60oC vacuum drying oven is dried 24 h, it is thus achieved that ZIF-67 nanocrystal.Fig. 1 (A, B) institute
Show that this ZIF-67 nanocrystal is the multiaspect solid of a size of 160-400 nm.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned over (Ar gas gas flow rate is about with in the tube furnace of argon shield
It is 350 sccm), with 1oThe speed of C/min is heated to 600oC is also incubated 2 h, the most again with 5oThe rate of temperature fall fall of C/min
Temperature, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon.Fig. 1 (C, D) has shown Co
The porous carbon of the irregular geometry that metallic particles embeds, metal particle size is about 7 nm.
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By the potassium chloroplatinite (K of 10 mg2PtCl4) deionized water that is dissolved in 2 mL is made into potassium chloroplatinite
Aqueous solution, obtains the core shell nanoparticles composite (Co@Pt-NC) of Co@Pt by Galvanic displacement.At Co@shown in Fig. 2
In Pt granule, the content of Co is about 8 times of Pt content.
(4) Co-NC of above-mentioned gained is taken 100 mg and adds the polytetrafluoroethyl-ne alkene reaction inside liner that volume is 50 mL, add
The HCl/water solution of 10 wt% of 30 mL；Use stainless steel outer sleeve sealed liner, be placed on 170oIn the air dry oven of C, constant temperature adds
Heat 12 h, clean products therefrom repeatedly to pH=7, and by secondary processing procedure in triplicate, i.e. can obtain without Co granule is pure
N doping porous carbon (NC).
Catalytic performance is tested:
It is to have three electrode body on the CHI 750E electrochemical workstation that Shanghai Chen Hua company produces that electro-chemical test characterizes
The test pond of system is carried out.Wherein, platinum filament is to electrode, and Ag/AgCl electrode is reference electrode, is loaded with the glass carbon of catalyst
Electrode is working electrode.5 % Nafion ethanol solution of 5 mg catalyst and 10 μ L are separately added into the anhydrous second of 1 mL
In alcohol, ultrasonic disperse 30 minutes is so that catalyst and Nafion fully mix formation ink solution；The ink dripping 16 μ L is molten
Liquid coats on the working electrode (s uniformly, and obtaining catalyst loadings knowable to calculating is 320 μ g/cm-2.Working electrode is placed in
The 0.1 M KOH solution that oxygen is saturated carries out volt-ampere scan round and the test of linear voltammetric scan.Test result such as Fig. 3,4,
5, shown in 8.
Fig. 3 is the Co@Pt-NC of example 1 and business Pt/C is at N2And O2The most saturated circulation in 0.1 M KOH solution
Volt-ampere curve figure.As seen from the figure, at N2Time saturated, the voltammogram of all catalyst does not has any oxidoreduction peak；And at O2
Time saturated, the voltammogram of each catalyst occurs in that obvious oxidoreduction peak, illustrates that catalyst towards oxygen reduction reaction has significantly
Catalysis activity.The reduction peak position of the electrode being loaded with Co Pt-NC is 0.87 V, relatively business Pt/C(0.83 V) value corrigendum.
Fig. 4 is that NC and Co-NC of example 1 preparation is at N2And O2The most saturated cyclic voltammetric in 0.1 M KOH solution is bent
Line chart.As seen from the figure, at N2Time saturated, the voltammogram of all catalyst does not has any oxidoreduction peak；And at O2Saturated
Time, the voltammogram of each catalyst occurs in that obvious oxidoreduction peak, illustrates that catalyst towards oxygen reduction reaction has significantly catalysis
Activity.The reduction peak position of the electrode being loaded with Co-NC is 0.85 V, and the reduction peak position being loaded with NC electrode is (0.78 V).
Fig. 5 be example 1 preparation NC, Co-NC, Co@Pt-NC and business Pt/C at O2In 0.1 saturated M KOH solution
The linear polarisation curves figure of rotating disk electrode (r.d.e).It can be seen that Co@Pt-NC initial electricity in the polarization curve that ORR reacts
Position relative standard hydrogen electeode be+0.99 V, the most just in business Pt/C(+0.98 V), NC (+0.88 V) and Co-NC(+0.95
V)；At+0.50 V, the limiting current density of Co@Pt-NC is 5.99 mA/cm2。
Fig. 8 is NC, Co-NC, Co@Pt-NC and business Pt/C electron transfer number and the hydrogen peroxide productivity curve of example 1 preparation
Figure.In the 0.40-0.80 V of electromotive force interval, the electron transfer number of Co@Pt-NC is 3.93 ~ 3.97, and hydrogen peroxide yield is
3.1 % ~ 3.6 %.The oxygen reduction reaction understanding Co@Pt-NC catalysis is 4 electron transfer reactions；With business Pt/C(3.92-
3.97) electron transfer number is close, and is better than NC(3.31-3.50) and Co-NC(3.60-3.85).Hydrogen peroxide is as oxygen also
By-product in former reaction, its productivity is the smaller the better, and the hydrogen peroxide yield of Co@Pt-NC is close with business Pt/C.
Embodiment 2.
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, solution A concentration is formulated as
1.8g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is formulated as 22 g 2-methylimidazoles and is dissolved in the deionization of 80 mL
In water；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, gained blue precipitate should be centrifuged successively, wash three times,
Methanol cleans, then is positioned over 60oC vacuum drying oven is dried 24 h, it is thus achieved that ZIF-67 nanocrystal.Shown in Fig. 1 (A, B)
This ZIF-67 nanocrystal is the multiaspect solid of a size of 160-400 nm.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned over (Ar gas velocity is about with in the tube furnace of argon shield
350 sccm), with 1oThe speed of C/min is heated to 600oC is also incubated 2 h, the most again with 5oThe rate of temperature fall fall of C/min
Temperature, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon.Fig. 1 (C, D) has shown Co
The porous carbon of the irregular geometry that metallic particles embeds, metal particle size is about 7 nm.
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By the potassium chloroplatinite (K of 10 mg2PtCl4) deionized water that is dissolved in 2 mL is made into potassium chloroplatinite
Aqueous solution, obtains the core shell nanoparticles composite (Co@Pt-NC) of Co@Pt by Galvanic displacement.At Co@shown in Fig. 2
In Pt granule, the content of Co is about 8 times of Pt content.
Catalytic performance is tested:
It is to have three electrode body on the CHI 750E electrochemical workstation that Shanghai Chen Hua company produces that electro-chemical test characterizes
The test pond of system is carried out.Wherein, platinum filament is to electrode, and Ag/AgCl electrode is reference electrode, is loaded with the glass carbon of catalyst
Electrode is working electrode.5 % Nafion ethanol solution of 5 mg catalyst and 10 μ L are separately added into the anhydrous second of 1 mL
In alcohol, ultrasonic disperse 30 minutes is so that catalyst and Nafion fully mix formation ink solution；The ink dripping 16 μ L is molten
Liquid coats on the working electrode (s uniformly, and obtaining catalyst loadings knowable to calculating is 320 μ g/cm-2.Working electrode is placed in
Carrying out a volt-ampere scan round in the 0.1 M KOH solution that oxygen is saturated, sweep interval is 0.60-1.0 V(vs. RHE), scanning
Speed is 50 mV/s, and scanning times is 5000 circles.Test result is as shown in Figure 9.
Fig. 9 be the Co@Pt-NC of example 2 preparation and business Pt/C with the speed of 50 mV/s at 0.6 V-1.0 V(vs.
RHE) the durability line figure after cyclic voltammetry scan 5000 times is done in electromotive force interval.As seen from the figure, the work of Co@Pt-NC it is coated with
Make electrode carried out 5000 circle circulation after, its E1/2Current potential is only negative 17 mV that moved before comparing circulation, and the E of business Pt/C1/2
Current potential is negative have been moved more than 26 mV, illustrates that the catalytic stability of Co@Pt-NC is more preferable.
Embodiment 3.
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, solution A concentration is formulated as
1.8g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is formulated as 22 g 2-methylimidazoles and is dissolved in the deionization of 80 mL
In water；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, gained blue precipitate should be centrifuged successively, wash three times,
Methanol cleans three times, then is positioned over 60oC vacuum drying oven is dried 24 h, it is thus achieved that ZIF-67 nanocrystal.Fig. 1 (A, B)
This ZIF-67 nanocrystal shown is the multiaspect solid of a size of 160-400 nm.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned over (Ar gas velocity is about with in the tube furnace of argon shield
350 sccm), with 1oThe speed of C/min is heated to 600oC is also incubated 2 h, the most again with 5oThe rate of temperature fall fall of C/min
Temperature, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon.Fig. 1 (C, D) has shown Co
The porous carbon of the irregular geometry that metallic particles embeds, metal particle size is about 7 nm.
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By the potassium chloroplatinite (K of 10 mg2PtCl4) deionized water that is dissolved in 2 mL is made into potassium chloroplatinite
Aqueous solution, obtains the core shell nanoparticles composite (Co@Pt-NC) of Co@Pt by Galvanic displacement.At Co@shown in Fig. 2
In Pt granule, the content of Co is about 8 times of Pt content.
Catalytic performance is tested:
It is to have three electrode body on the CHI 750E electrochemical workstation that Shanghai Chen Hua company produces that electro-chemical test characterizes
The test pond of system is carried out.Wherein, platinum filament is to electrode, and Ag/AgCl electrode is reference electrode, is loaded with the glass carbon of catalyst
Electrode is working electrode.5 % Nafion ethanol solution of 5 mg catalyst and 10 μ L are separately added into the anhydrous second of 1 mL
In alcohol, ultrasonic disperse 30 minutes is so that catalyst and Nafion fully mix formation ink solution；The ink dripping 16 μ L is molten
Liquid coats on the working electrode (s uniformly, and obtaining catalyst loadings knowable to calculating is 320 μ g/cm-2.Working electrode is placed in
In the 0.1 M KOH solution that oxygen is saturated, under the conditions of the constant voltage of 0.60 V in the aqueous solution containing 0.1 M KOH continuous work
Make 40000 seconds, test the decline of its current value；In containing 0.1 M KOH and the water of 1 M methanol under the conditions of the constant voltage of 0.60 V
Solution works 2500 seconds continuously, tests the decline of its current value；Test result is as shown in Figure 10.
Figure 10 is the Co@Pt-NC of example 3 preparation and the i-t stability test of business Pt/C and methanol tolerance poison ability
Curve chart.As it can be seen, work 40000 seconds continuously in the aqueous solution containing 0.1 M KOH under the conditions of the constant voltage of 0.60 V,
What test was coated with the current value of Co@Pt-NC electrode drops to about 12%, and the current value of business Pt/C declines and becomes apparent from,
It is about 45 %；Testing its methanol when poisoning experiment, the current value change being coated with Co@Pt-NC electrode is inconspicuous, does not the most do
Disturb, and and there is substantially fluctuation in the current value of business Pt/C, the most serious by methanol poisoning effect.
Embodiment 4.
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, solution A concentration is formulated as 1.8
g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is formulated as 22 g 2-methylimidazoles and is dissolved in the deionized water of 80 mL
In；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, and gained blue precipitate should be centrifuged successively, wash three times, first
Alcohol cleans three times, then is positioned over 60oC vacuum drying oven is dried 24 h, it is thus achieved that ZIF-67 nanocrystal.Fig. 1 (A, B) institute
Show that this ZIF-67 nanocrystal is the multiaspect solid of a size of 160-400 nm.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned over (Ar gas velocity is about with in the tube furnace of argon shield
350 sccm), with 1oThe speed of C/min is heated to 600oC is also incubated 2 h, the most again with 5oThe rate of temperature fall fall of C/min
Temperature, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon.Fig. 1 (C, D) has shown Co
The porous carbon of the irregular geometry that metallic particles embeds, metal particle size is about 7 nm.
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By the potassium chloroplatinite (K of 5 mg2PtCl4) deionized water that is dissolved in 2 mL is made into potassium chloroplatinite water
Solution, obtains the core shell nanoparticles composite (Co@Pt-NC) of Co@Pt by Galvanic displacement.
Catalytic performance is tested:
It is to have three electrode body on the CHI 750E electrochemical workstation that Shanghai Chen Hua company produces that electro-chemical test characterizes
The test pond of system is carried out.Wherein, platinum filament is to electrode, and Ag/AgCl electrode is reference electrode, is loaded with the glass carbon of catalyst
Electrode is working electrode.5 % Nafion ethanol solution of 5 mg catalyst and 10 μ L are separately added into the anhydrous second of 1 mL
In alcohol, ultrasonic disperse 30 minutes is so that catalyst and Nafion fully mix formation ink solution；The ink dripping 16 μ L is molten
Liquid coats on the working electrode (s uniformly, and obtaining catalyst loadings knowable to calculating is 320 μ g/cm-2.Working electrode is placed in
The 0.1 M KOH solution that oxygen is saturated carries out volt-ampere scan round and the test of linear voltammetric scan.Test result such as Fig. 6,7 institutes
Show.
Fig. 6 is that the Co@Pt-NC-2 of example 4 is at N2And O2The most saturated cyclic voltammetry curve in 0.1 M KOH solution
Figure.As seen from the figure, at N2Time saturated, the voltammogram of all catalyst does not has any oxidoreduction peak；And at O2Time saturated,
The voltammogram of each catalyst occurs in that obvious oxidoreduction peak, illustrates that catalyst towards oxygen reduction reaction has and is significantly catalyzed work
Property.
Fig. 7 is that the Co@Pt-NC-2 of example 4 preparation is at O2The line of the saturated rotating disk electrode (r.d.e) in 0.1 M KOH solution
Property polarization curve.It can be seen that Co@Pt-NC take-off potential relative standard hydrogen electeode in the polarization curve that ORR reacts is
+0.97 V。
Embodiment 5.
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, solution A concentration is formulated as 1.8
g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, and B solution is formulated as 22 g 2-methylimidazoles and is dissolved in the deionized water of 80 mL
In；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, and gained blue precipitate should be centrifuged successively, wash three times, first
Alcohol cleans three times, then is positioned over 60oC vacuum drying oven is dried 24 h, it is thus achieved that ZIF-67 nanocrystal.Fig. 1 (A, B) institute
Show that this ZIF-67 nanocrystal is the multiaspect solid of a size of 160-400 nm.
(2) above-mentioned gained ZIF-67 nanocrystal is positioned over (Ar gas velocity is about with in the tube furnace of argon shield
350 sccm), with 1oThe speed of C/min is heated to 600oC is also incubated 2 h, the most again with 5oThe rate of temperature fall fall of C/min
Temperature, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon.Fig. 1 (C, D) has shown Co
The irregular geometry porous carbon mechanism that metallic particles embeds, metal particle size is about 7 nm.
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and use Ar atmosphere protection
Prevent Co granule oxidized；By the potassium chloroplatinite (K of 15 mg2PtCl4) deionized water that is dissolved in 2 mL is made into potassium chloroplatinite
Aqueous solution, obtains the core shell nanoparticles composite (Co@Pt-NC) of Co@Pt by Galvanic displacement.
Catalytic performance is tested:
It is to have three electrode body on the CHI 750E electrochemical workstation that Shanghai Chen Hua company produces that electro-chemical test characterizes
The test pond of system is carried out.Wherein, platinum filament is to electrode, and Ag/AgCl electrode is reference electrode, is loaded with the glass carbon of catalyst
Electrode is working electrode.5% Nafion ethanol solution of 5 mg catalyst and 10 μ L is separately added into the dehydrated alcohol of 1 mL
In, ultrasonic disperse 30 minutes is so that catalyst and Nafion fully mix formation ink solution；Drip the ink solution of 16 μ L
On the working electrode (s, obtaining catalyst loadings knowable to calculating is 320 μ g/cm in uniform coating-2.Working electrode is placed in oxygen
The 0.1 M KOH solution that gas is saturated carries out volt-ampere scan round and the test of linear voltammetric scan.Test result such as Fig. 6,7 institutes
Show.
Fig. 6 is that the Co@Pt-NC-3 of example 5 is at N2And O2The most saturated cyclic voltammetry curve in 0.1 M KOH solution
Figure.As seen from the figure, at N2Time saturated, the voltammogram of all catalyst does not has any oxidoreduction peak；And at O2Time saturated,
The voltammogram of each catalyst occurs in that obvious oxidoreduction peak, illustrates that catalyst towards oxygen reduction reaction has and is significantly catalyzed work
Property.
Fig. 7 is that the Co@Pt-NC-3 of example 5 preparation is at O2The line of the saturated rotating disk electrode (r.d.e) in 0.1 M KOH solution
Property polarization curve.It can be seen that Co@Pt-NC take-off potential relative standard hydrogen electeode in the polarization curve that ORR reacts is
+0.96 V。
Above-described embodiment is the present invention preferably detailed description of the invention, and wherein the catalytic effect of example 1 is optimal, but the present invention
Protection domain be not limited thereto, the change made under other any spirit without departing from the present invention and principle, repair
Adorn, substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (5)
1.ZIF-67 template prepares cobalt platinum nucleocapsid particles/porous carbon composite and the catalysis in fuel battery negative pole should
With, it is characterised in that: comprise the steps:
(1) according to Co2+: Hmim: H2The ratio of O=1:58: 1100, at room temperature, is first dissolved in water by cobalt nitrate and makes A
Solution, then 2-methylimidazole is dissolved in water makes B solution；Mixed for two kinds of solution of A and B being incorporated under 800 rpm is stirred 6 h, so
After centrifugal, washing three times again, methanol clean three times thus obtain purple precipitation；Gained purple precipitation is positioned over 60oC vacuum
Drying baker is dried 24 h, it is thus achieved that ZIF-67 nanocrystal；
(2) above-mentioned gained ZIF-67 nanocrystal is placed in the tube furnace with argon shield, with 1oThe speed of C/min is heated to
600 oC is also incubated 2 h, the i.e. available cobalt nano-particle composite (Co-NC) fixed by N doping porous carbon；
(3) Co-NC of above-mentioned gained is taken 50 mg ultrasonic disperse in the deionized water of 8 mL, and prevent with Ar atmosphere protection
Co granule is oxidized；By a certain amount of potassium chloroplatinite (K2PtCl4) aqueous solution instilled in above-mentioned solution, put by Galvanic
Get the core shell nanoparticles of Co@Pt in return, and use it for, in hydrogen reduction catalytic reaction, obtaining being better than the hydrogen reduction of business Pt/C
Electrocatalysis characteristic.
2. the Co used according to claim 12+Source is Co (NO3)2 • 6 H2O, Hmim are 2-methylimidazole, H2O for go from
Sub-water, Pt2+Source is K2PtCl4。
The preparation method of ZIF-67 the most according to claim 1, it is characterised in that: step (1) described solution A concentration is formulated as
1.8 g Co(NO3)2 • 6 H2O is dissolved in 12 mL water, B solution be formulated as 22 g 2-methylimidazoles be dissolved in 80 mL go from
In sub-water；After mixing gained blue precipitate should be centrifuged successively, wash three times, methanol clean three times, then be positioned over 60oC vacuum is done
Dry case is dried 24 h.
Prepare, for template, the Co Pt nanometer that N doping porous carbon is fixing for 1. 1 kinds the most according to claim 1 with ZIF-67
The preparation method of granules composite material, it is characterised in that: step (2) described ZIF-67 must be under noble gas (Ar gas) be protected
Calcining, diamond heating speed need to control to be 1oC/min, temperature retention time is 2 h.
Prepare, for template, the Co Pt nanometer that N doping porous carbon is fixing for 1. 1 kinds the most according to claim 1 with ZIF-67
The preparation method of granules composite material, it is characterised in that: step (3) is described occurs Galvanic to put under noble gas (Ar) is protected
Changing, prepared catalyst is when oxygen reduction reaction, and the load capacity being coated on glassy carbon working electrode is 320 μ g cm-2,
The load capacity of business Pt/C is 160 μ g cm-2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881979.7A CN106328960A (en) | 2016-10-08 | 2016-10-08 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881979.7A CN106328960A (en) | 2016-10-08 | 2016-10-08 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106328960A true CN106328960A (en) | 2017-01-11 |
Family
ID=57821353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610881979.7A Pending CN106328960A (en) | 2016-10-08 | 2016-10-08 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106328960A (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916110A (en) * | 2017-03-10 | 2017-07-04 | 国家纳米科学中心 | A kind of carried noble metal nano composition and preparation method thereof |
| CN106915776A (en) * | 2017-03-30 | 2017-07-04 | 中南大学 | A kind of solvent-free method for preparing rich nitrogen carbon coating cobalt compound |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN107262052A (en) * | 2017-07-21 | 2017-10-20 | 福建农林大学 | A kind of konjaku glucomannan Dye Adsorption cotton and preparation method thereof |
| CN107694592A (en) * | 2017-09-28 | 2018-02-16 | 华南理工大学 | Monatomic noble metal catalyst and its method prepared by ultrasonic wave added displacement reaction |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
| CN108176396A (en) * | 2017-12-07 | 2018-06-19 | 广东省石油与精细化工研究院 | A kind of formaldehyde remover and its preparation method and application |
| CN108598390A (en) * | 2018-03-29 | 2018-09-28 | 武汉新能源研究院有限公司 | A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery |
| CN108736031A (en) * | 2018-05-21 | 2018-11-02 | 同济大学 | A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof |
| CN109860629A (en) * | 2018-12-27 | 2019-06-07 | 南京理工大学 | The brewed Preparation Method of Co/N doped carbon nanometer is classified derived from phenolic aldehyde/resin auxiliary MOFs |
| CN109962246A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application |
| CN110336048A (en) * | 2019-06-12 | 2019-10-15 | 青岛科技大学 | A kind of low-load amount ruthenium cladding ZIF-67 derivative and preparation method thereof and the application in lithium-air battery |
| CN110479224A (en) * | 2019-07-31 | 2019-11-22 | 同济大学 | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application |
| CN110501397A (en) * | 2019-08-30 | 2019-11-26 | 济南大学 | A kind of preparation method of chirality MOF supermolecule composite material and its application for identifying penicillamine enantiomer |
| CN110649273A (en) * | 2019-09-12 | 2020-01-03 | 华南理工大学 | Method for synthesizing small-size high-dispersion intermetallic compound catalyst material and application |
| CN110783577A (en) * | 2019-10-08 | 2020-02-11 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| CN111244481A (en) * | 2020-01-24 | 2020-06-05 | 西安科技大学 | Preparation method of fulvic acid lamella-based MOFs-derived electrocatalyst material |
| CN111710878A (en) * | 2020-05-29 | 2020-09-25 | 新疆大学 | Preparation method of metal organic framework derived Co embedded nitrogen-doped carbon nanotube modified mesoporous carbon supported platinum catalyst |
| CN111933960A (en) * | 2020-08-18 | 2020-11-13 | 哈尔滨工业大学（深圳） | PtCo @ N-GNS catalyst and preparation method and application thereof |
| CN111987322A (en) * | 2020-08-11 | 2020-11-24 | 广东能创科技有限公司 | Novel Pt-Co/NC catalyst and preparation method and application thereof |
| CN112164809A (en) * | 2020-10-06 | 2021-01-01 | 青岛蓝创科信新能源科技有限公司 | Preparation method of PtCo @ NC catalyst for direct methanol fuel cell |
| CN112397736A (en) * | 2020-12-10 | 2021-02-23 | 福州大学 | FePt @ C composite nano material prepared based on MOF and application thereof |
| CN112436158A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| CN112436159A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
| CN113130923A (en) * | 2021-04-15 | 2021-07-16 | 北京师范大学 | Preparation method and application of two-dimensional porous carbon supported catalyst |
| CN113571714A (en) * | 2021-07-26 | 2021-10-29 | 山东能源集团有限公司 | Carbon-based platinum-iron alloy material and application thereof |
| CN113698617A (en) * | 2021-08-25 | 2021-11-26 | 福州大学 | Synthesis method of ultrathin two-dimensional hierarchical porous ZIF-67 |
| CN114171747A (en) * | 2021-10-12 | 2022-03-11 | 南京林业大学 | Hollowed-out polyhedral cobaltosic oxide/carbon-based composite carrier anchoring palladium nano material and preparation method and application thereof |
| WO2021262323A3 (en) * | 2020-05-04 | 2022-04-28 | Tda Research, Inc. | Electrocatalysts and electrolyzers |
| WO2022111008A1 (en) * | 2020-11-26 | 2022-06-02 | 中国科学院大连化学物理研究所 | Platinum-and-cobalt-based alloy encapsulated with nitrogen-and-phosphorus-co-doped metal organic framework, preparation method therefor and use thereof |
| CN115074773A (en) * | 2022-07-12 | 2022-09-20 | 重庆师范大学 | Sandwich-shaped M x Co 9-x Se 8 @ NC core-shell nano cubic box electrocatalyst and preparation and application thereof |
| CN115117373A (en) * | 2022-05-13 | 2022-09-27 | 北京化工大学 | Nitrogen-doped carbon-based oxygen reduction reaction catalyst and preparation method and application thereof |
| CN115125579A (en) * | 2022-05-19 | 2022-09-30 | 上海理工大学 | Preparation method and application of platinum monoatomic coordination cobalt-platinum alloy in limitation of nitrogen-doped porous carbon |
| CN116435528A (en) * | 2023-06-14 | 2023-07-14 | 长春黄金研究院有限公司 | Preparation method of Pt-supported ZIF-67-based hydrogen fuel cell catalyst |
| CN117161374A (en) * | 2023-09-07 | 2023-12-05 | 苏州大学 | Nitrogen-doped porous carbon-loaded multielement ordered metal alloy nanoparticle and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227000A (en) * | 2008-01-21 | 2008-07-23 | 重庆大学 | Process for preparation of gas perforated electrode catalyst of nucleus-shell structure |
| CN101359744A (en) * | 2008-09-08 | 2009-02-04 | 重庆大学 | Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit |
| CN102500365A (en) * | 2011-10-19 | 2012-06-20 | 华南理工大学 | Preparation method of catalyst with core-shell structure for low-temperature fuel cell |
| CN103537299A (en) * | 2013-10-29 | 2014-01-29 | 常州大学 | Carbon-loaded Co core-Pt shell nanoparticle catalyst as well as preparation method thereof |
-
2016
- 2016-10-08 CN CN201610881979.7A patent/CN106328960A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227000A (en) * | 2008-01-21 | 2008-07-23 | 重庆大学 | Process for preparation of gas perforated electrode catalyst of nucleus-shell structure |
| CN101359744A (en) * | 2008-09-08 | 2009-02-04 | 重庆大学 | Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit |
| CN102500365A (en) * | 2011-10-19 | 2012-06-20 | 华南理工大学 | Preparation method of catalyst with core-shell structure for low-temperature fuel cell |
| CN103537299A (en) * | 2013-10-29 | 2014-01-29 | 常州大学 | Carbon-loaded Co core-Pt shell nanoparticle catalyst as well as preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KUI SHEN等: ""MOFs-Templated Co@Pd Core−Shell NPs Embedded in N‑Doped Carbon Matrix with Superior Hydrogenation Activities"", 《ACS CATALYSIS》 * |
| NOEL KRISTIAN等: ""Synthesis and characterization of Cocore–Ptshell electrocatalyst prepared by spontaneous replacement reaction for oxygen reduction reaction"", 《ELECTROCHIMICA ACTA》 * |
Cited By (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916110B (en) * | 2017-03-10 | 2020-03-24 | 国家纳米科学中心 | Supported noble metal nanoparticle composite material and preparation method thereof |
| CN106916110A (en) * | 2017-03-10 | 2017-07-04 | 国家纳米科学中心 | A kind of carried noble metal nano composition and preparation method thereof |
| CN106915776A (en) * | 2017-03-30 | 2017-07-04 | 中南大学 | A kind of solvent-free method for preparing rich nitrogen carbon coating cobalt compound |
| CN106915776B (en) * | 2017-03-30 | 2018-09-14 | 中南大学 | A kind of solvent-free method for preparing rich nitrogen carbon coating cobalt compound |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN107262052A (en) * | 2017-07-21 | 2017-10-20 | 福建农林大学 | A kind of konjaku glucomannan Dye Adsorption cotton and preparation method thereof |
| CN107694592A (en) * | 2017-09-28 | 2018-02-16 | 华南理工大学 | Monatomic noble metal catalyst and its method prepared by ultrasonic wave added displacement reaction |
| CN107694592B (en) * | 2017-09-28 | 2020-08-18 | 华南理工大学 | Monatomic noble metal catalyst prepared by ultrasonic-assisted displacement reaction and method thereof |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
| CN108176396B (en) * | 2017-12-07 | 2021-02-09 | 广东省石油与精细化工研究院 | Formaldehyde remover and preparation method and application thereof |
| CN108176396A (en) * | 2017-12-07 | 2018-06-19 | 广东省石油与精细化工研究院 | A kind of formaldehyde remover and its preparation method and application |
| CN109962246A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application |
| CN108598390A (en) * | 2018-03-29 | 2018-09-28 | 武汉新能源研究院有限公司 | A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery |
| CN108736031B (en) * | 2018-05-21 | 2021-09-03 | 同济大学 | Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof |
| CN108736031A (en) * | 2018-05-21 | 2018-11-02 | 同济大学 | A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof |
| CN109860629A (en) * | 2018-12-27 | 2019-06-07 | 南京理工大学 | The brewed Preparation Method of Co/N doped carbon nanometer is classified derived from phenolic aldehyde/resin auxiliary MOFs |
| CN110336048A (en) * | 2019-06-12 | 2019-10-15 | 青岛科技大学 | A kind of low-load amount ruthenium cladding ZIF-67 derivative and preparation method thereof and the application in lithium-air battery |
| CN110479224A (en) * | 2019-07-31 | 2019-11-22 | 同济大学 | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application |
| CN110501397A (en) * | 2019-08-30 | 2019-11-26 | 济南大学 | A kind of preparation method of chirality MOF supermolecule composite material and its application for identifying penicillamine enantiomer |
| CN110649273A (en) * | 2019-09-12 | 2020-01-03 | 华南理工大学 | Method for synthesizing small-size high-dispersion intermetallic compound catalyst material and application |
| CN110649273B (en) * | 2019-09-12 | 2021-09-14 | 华南理工大学 | Method for synthesizing small-size high-dispersion intermetallic compound catalyst material and application |
| CN110783577A (en) * | 2019-10-08 | 2020-02-11 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| CN110783577B (en) * | 2019-10-08 | 2021-05-18 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| CN111244481A (en) * | 2020-01-24 | 2020-06-05 | 西安科技大学 | Preparation method of fulvic acid lamella-based MOFs-derived electrocatalyst material |
| WO2021262323A3 (en) * | 2020-05-04 | 2022-04-28 | Tda Research, Inc. | Electrocatalysts and electrolyzers |
| CN111710878A (en) * | 2020-05-29 | 2020-09-25 | 新疆大学 | Preparation method of metal organic framework derived Co embedded nitrogen-doped carbon nanotube modified mesoporous carbon supported platinum catalyst |
| CN111987322A (en) * | 2020-08-11 | 2020-11-24 | 广东能创科技有限公司 | Novel Pt-Co/NC catalyst and preparation method and application thereof |
| CN111933960A (en) * | 2020-08-18 | 2020-11-13 | 哈尔滨工业大学（深圳） | PtCo @ N-GNS catalyst and preparation method and application thereof |
| CN111933960B (en) * | 2020-08-18 | 2022-01-18 | 哈尔滨工业大学（深圳） | PtCo @ N-GNS catalyst and preparation method and application thereof |
| CN112164809A (en) * | 2020-10-06 | 2021-01-01 | 青岛蓝创科信新能源科技有限公司 | Preparation method of PtCo @ NC catalyst for direct methanol fuel cell |
| CN112164809B (en) * | 2020-10-06 | 2021-12-24 | 江西东醇新能源科技有限公司 | Preparation method of PtCo @ NC catalyst for direct methanol fuel cell |
| CN112436159B (en) * | 2020-11-06 | 2022-09-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
| CN112436159A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
| CN112436158A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| WO2022111008A1 (en) * | 2020-11-26 | 2022-06-02 | 中国科学院大连化学物理研究所 | Platinum-and-cobalt-based alloy encapsulated with nitrogen-and-phosphorus-co-doped metal organic framework, preparation method therefor and use thereof |
| CN112397736A (en) * | 2020-12-10 | 2021-02-23 | 福州大学 | FePt @ C composite nano material prepared based on MOF and application thereof |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
| CN113130923A (en) * | 2021-04-15 | 2021-07-16 | 北京师范大学 | Preparation method and application of two-dimensional porous carbon supported catalyst |
| CN113571714A (en) * | 2021-07-26 | 2021-10-29 | 山东能源集团有限公司 | Carbon-based platinum-iron alloy material and application thereof |
| CN113698617A (en) * | 2021-08-25 | 2021-11-26 | 福州大学 | Synthesis method of ultrathin two-dimensional hierarchical porous ZIF-67 |
| CN114171747A (en) * | 2021-10-12 | 2022-03-11 | 南京林业大学 | Hollowed-out polyhedral cobaltosic oxide/carbon-based composite carrier anchoring palladium nano material and preparation method and application thereof |
| CN115117373A (en) * | 2022-05-13 | 2022-09-27 | 北京化工大学 | Nitrogen-doped carbon-based oxygen reduction reaction catalyst and preparation method and application thereof |
| CN115125579B (en) * | 2022-05-19 | 2023-05-12 | 上海理工大学 | Preparation method and application of platinum monoatomic synergistic cobalt-platinum alloy limited in nitrogen-doped porous carbon |
| CN115125579A (en) * | 2022-05-19 | 2022-09-30 | 上海理工大学 | Preparation method and application of platinum monoatomic coordination cobalt-platinum alloy in limitation of nitrogen-doped porous carbon |
| CN115074773A (en) * | 2022-07-12 | 2022-09-20 | 重庆师范大学 | Sandwich-shaped M x Co 9-x Se 8 @ NC core-shell nano cubic box electrocatalyst and preparation and application thereof |
| CN115074773B (en) * | 2022-07-12 | 2023-10-27 | 重庆师范大学 | Sandwich-shaped M x Co 9-x Se 8 Nano cubic box electrocatalyst with @ NC core-shell, preparation and application thereof |
| CN116435528A (en) * | 2023-06-14 | 2023-07-14 | 长春黄金研究院有限公司 | Preparation method of Pt-supported ZIF-67-based hydrogen fuel cell catalyst |
| CN116435528B (en) * | 2023-06-14 | 2023-09-05 | 长春黄金研究院有限公司 | Preparation method of Pt-supported ZIF-67-based hydrogen fuel cell catalyst |
| CN117161374A (en) * | 2023-09-07 | 2023-12-05 | 苏州大学 | Nitrogen-doped porous carbon-loaded multielement ordered metal alloy nanoparticle and preparation method thereof |
| CN117161374B (en) * | 2023-09-07 | 2024-06-14 | 苏州大学 | Nitrogen-doped porous carbon-loaded multielement ordered metal alloy nanoparticle and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106328960A (en) | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell | |
| Guo et al. | Rational design of electrocatalysts and photo (electro) catalysts for nitrogen reduction to ammonia (NH 3) under ambient conditions | |
| Hanif et al. | ZIF derived PtNiCo/NC cathode catalyst for proton exchange membrane fuel cell | |
| Chen et al. | From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis | |
| CN104681823B (en) | A kind of nitrogen-doped graphene and Co3O4 hollow nano-sphere composites and its preparation method and application | |
| Sun et al. | Palladium-coated manganese dioxide catalysts for oxygen reduction reaction in alkaline media | |
| Kang et al. | Moderate oxophilic CoFe in carbon nanofiber for the oxygen evolution reaction in anion exchange membrane water electrolysis | |
| Ghoshal et al. | ZIF 67 based highly active electrocatalysts as oxygen electrodes in water electrolyzer | |
| CN104624190B (en) | Cobalt-based transition metal oxygen reduction catalyst, preparation method and application thereof | |
| Zhang et al. | Hierarchical architecture of well‐aligned nanotubes supported bimetallic catalysis for efficient oxygen redox | |
| WO2017123289A2 (en) | Membraneless direct liquid fuel cells | |
| Yang et al. | PdBi bimetallic catalysts including polyvinylpyrrolidone surfactant inducing excellent formic acid oxidation reaction and direct formic acid fuel cell performance | |
| Anderson et al. | Establishing performance baselines for the oxygen evolution reaction in alkaline electrolytes | |
| Sun et al. | Manganese dioxide-supported silver bismuthate as an efficient electrocatalyst for oxygen reduction reaction in zinc-oxygen batteries | |
| Wang et al. | Bioethanol as a new sustainable fuel for anion exchange membrane fuel cells with carbon nanotube supported surface dealloyed PtCo nanocomposite anodes | |
| Hu et al. | Synthesis of anti-poisoning spinel Mn–Co–C as cathode catalysts for low-temperature anion exchange membrane direct ammonia fuel cells | |
| Beydaghi et al. | Preparation and characterization of electrocatalyst nanoparticles for direct methanol fuel cell applications using β-D-glucose as a protection agent | |
| CN1990101B (en) | Electrocatalyst for proton exchange film fuel cell | |
| Cao et al. | N-doped ZrO2 nanoparticles embedded in a N-doped carbon matrix as a highly active and durable electrocatalyst for oxygen reduction | |
| Glass et al. | Optimization of platinum loading on partially fluorinated carbon catalysts for enhanced proton exchange membrane fuel cell performance | |
| Wang et al. | A Highly Active Bifunctional Catalyst of Mn–Co–Fe–N/S@ CNT for Rechargeable Zinc-Air Batteries | |
| Tian et al. | PtTiO x/C Electrocatalysts with Improved Durability in H2/O2 PEMFCs without External Humidification | |
| Yang et al. | Thiocyanate Ion Ligand-Induced Atomically Dispersed Fe–N–S Tridoped Hollow Catalyst for High-Performance Zinc–Air Rechargeable Batteries | |
| CN106887602B (en) | A kind of Ag-CuO/C catalyst and its preparation and application | |
| Zhang et al. | An Ultrastable Rechargeable Zinc–Air Battery Using a Janus Superwetting Air Electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170111 |