CN107754795B - Composite catalyst and preparation method and application thereof - Google Patents

Composite catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN107754795B
CN107754795B CN201610692984.3A CN201610692984A CN107754795B CN 107754795 B CN107754795 B CN 107754795B CN 201610692984 A CN201610692984 A CN 201610692984A CN 107754795 B CN107754795 B CN 107754795B
Authority
CN
China
Prior art keywords
composite catalyst
palladium
catalyst according
mno
preparing
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.)
Active
Application number
CN201610692984.3A
Other languages
Chinese (zh)
Other versions
CN107754795A (en
Inventor
胡赏
***
孙予罕
张豪杰
林超
杜福平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Advanced Research Institute of CAS
Original Assignee
Shanghai Advanced Research Institute of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Advanced Research Institute of CAS filed Critical Shanghai Advanced Research Institute of CAS
Priority to CN201610692984.3A priority Critical patent/CN107754795B/en
Publication of CN107754795A publication Critical patent/CN107754795A/en
Application granted granted Critical
Publication of CN107754795B publication Critical patent/CN107754795B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a composite catalyst and a preparation method and application thereof, wherein the composite catalyst at least comprises the following components in molar ratio: MnO20.008 to 0.08 wt%, 0.00005 to 0.0005 wt% of carbon source, and 0.0001 to 0.0012 wt% of palladium. The composite catalyst prepared by the method has excellent electrochemical performance, excellent charge and discharge stability and 2mg/cm of load capacity2The discharge power of the catalyst used for the metal-air battery under the air condition can reach 274mW/cm2The process is simple and practical.

Description

Composite catalyst and preparation method and application thereof
Technical Field
The invention relates to a composite catalyst and a preparation method and application thereof.
Background
Today, fossil energy still dominates the energy market, but the increasing environmental pollution and the gradual depletion of fossil energy compel us to find a new clean renewable energy to replace the dominance of fossil energy, so that the realization of efficient energy conversion and storage by electrochemical reaction becomes a hot spot of current research. The metal-air battery is concerned by researchers because of the easily available raw materials, simple equipment, easy reaction, good safety, environmental friendliness and extremely high theoretical current density. The electrocatalytic Oxygen Evolution Reaction (OER) and the Oxygen Reduction Reaction (ORR) limit the efficiency of metal-air batteries by involving the transfer of four electrons and the adsorption and desorption processes of various intermediates, and are the biggest obstacles to the development of metal-air batteries. At present, noble metals such as platinum and iridium and oxide catalysts thereof are still considered to have the best reaction activity and reaction stability for electrocatalysis of OER or ORRQualitatively, its expensive price and low reserves in the crust prevent its large-scale industrial production. Therefore, it is urgently required to develop a catalyst which is inexpensive and highly active and can be used in a metal-air battery. MnO2It is of great interest to scientists because of its abundance, low cost, environmental friendliness and its ability to exhibit superior catalytic performance to both OER and ORR. But MnO2Is poor in conductivity and is not favorable for the OER and ORR reactions. Compounding or doping with other materials is considered to be a good improvement for MnO2A method of electrocatalytic performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a highly efficient and stable composite catalyst, a method for its preparation and its use.
To achieve the above and other related objects, the present invention provides, in one aspect, a composite catalyst comprising at least the following components in a molar ratio:
MnO20.008～0.08
C 0.00005～0.0005
0.0001 to 0.0012 of palladium.
In order to further optimize the design scheme, the C is selected from any one or more of carbon nanotubes, graphene or graphene oxide.
To further optimize the design, the palladium is distributed in MnO2On the carbon neutralized by the crystal lattice, or distributed in MnO2In the crystal lattice; the MnO2C and the mass ratio of palladium in the catalyst is not less than 70%.
To further optimize the design, the MnO2Is α -MnO2The nano-wire has a diameter of 5-20nm and a length of 10 nm-10 μm.
Another embodiment of the present invention provides a method for preparing a composite catalyst, comprising the steps of:
(1) respectively weighing reactant divalent manganese salt, reaction auxiliary agent, oxidant, carbon source and palladium source;
(2) dissolving the reactant in the step (1) in water, and stirring;
(3) and carrying out hydrothermal reaction for 4-24 h at the temperature of 90-250 ℃, cooling to room temperature, cleaning, drying and grinding to obtain the catalyst.
The hydrothermal reaction refers to a chemical reaction in a fluid such as water (aqueous solution) or steam under high temperature and high pressure
In order to further optimize the design scheme, the divalent manganese salt is selected from any one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
More preferably, the divalent manganese salt is manganese sulfate.
In order to further optimize the design scheme, the reaction auxiliary agent is sulfate, preferably any one or more of ammonium sulfate, sodium sulfate or potassium sulfate.
More preferably, the reaction aid is ammonium sulfate.
In order to further optimize the design scheme, the oxidant is persulfate, preferably any one or more of potassium persulfate, sodium persulfate or ammonium persulfate.
More preferably, the oxidizing agent is ammonium persulfate.
For further optimization of the design, the palladium source is a palladium-containing salt, preferably palladium nitrate and/or palladium chloride.
More preferably, the palladium source is palladium nitrate.
In order to further optimize the design scheme, the carbon source is selected from one or more of carbon nanotubes, graphene or graphene oxide, and the hydrothermal reaction in the step (3) is carried out for 12 hours.
In order to further optimize the design scheme, the molar ratio of the reactants in the step (1) is as follows:
Figure BDA0001084158150000021
further, in the present invention,
Figure BDA0001084158150000022
since different palladium sources may contain different amounts of palladium, what is needed in the present invention is the amount of molar ratio of palladium in the palladium source.
In another aspect of the present invention, there is provided a use of the composite catalyst in a metal-air battery.
In order to further optimize the design scheme, the metal-air battery is any one of a zinc-air battery, a lithium-air battery, an aluminum-air battery or a magnesium-air battery.
As described above, the composite catalyst and the preparation method thereof of the present invention have the following beneficial effects:
the composite catalyst synthesized by the invention can catalyze oxygen reduction reaction and oxygen evolution reaction, has excellent catalytic performance, can be applied to metal-air batteries, and has excellent charge and discharge performance. The initial potential and the limiting current are better than 10 wt% Pt/C in the catalytic oxygen reduction reaction, and the catalyst loading is 2mg/cm under the condition of air2When the catalyst is used in a metal-air battery, the discharge power can reach 274mW/cm2。
Meanwhile, the invention has the advantages of environmental protection, easily obtained raw materials, relatively low price, mild reaction conditions, simple experimental steps, simple process, practicality and the like, is easy to amplify and further produce in a large scale, and is a good catalyst which can be applied to metal-air batteries.
Drawings
FIG. 1 Pd-MnO prepared in example 52Scanning electron microscope image of carbon nano tube
FIG. 2 Pd-MnO prepared in example 52XRD patterns of/carbon nanotubes and Carbon Nanotubes (CNTs)
FIG. 3 polarization curves of catalysts prepared in examples 1-4 in the oxygen reduction reaction zone
FIG. 4 Pd-MnO prepared in example 52Polarization curve of carbon nanotube, carbon nanotube and 10 wt% Pt/C in oxygen reduction reaction region
FIG. 5 Pd-MnO prepared in example 52Polarization curve of carbon nano tube in oxygen evolution reaction zone
FIG. 6 Pd-MnO prepared in example 52Carbon nanotube as air for metal-air batteryGraph of power generation of electrode
FIG. 7 graph of power generation of Pd-MnO 2/graphene composite material prepared by the invention in example 6 as an air electrode of a metal-air battery
FIG. 8 graph of power generation of Pd-MnO 2/graphene oxide composite material prepared in example 7 as an air electrode of a metal-air battery
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
MnO2The preparation of (1): respectively weighing 0.02mol of manganese sulfate, 0.02mol of ammonium persulfate and 0.08mol of ammonium sulfate, adding 75mL of ultrapure water, and magnetically stirring for 15-20 min to ensure thatThe raw materials are completely dissolved, transferred into a hydrothermal kettle and reacted for 12 hours at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is approximately equal to 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain MnO2。
Example 2
Pd-MnO2The preparation of (1): 0.02mol of manganese sulfate, 0.02mol of ammonium persulfate, 0.08mol of ammonium sulfate and 0.00012mol of palladium nitrate are respectively weighed, and the content of palladium element in the obtained catalyst is 1 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 12h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is about 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain Pd-MnO2。
Example 3
Pd-MnO2The preparation of (1): 0.02mol of manganese nitrate, 0.02mol of ammonium persulfate, 0.08mol of sodium sulfate and 0.00012mol of palladium chloride are respectively weighed, and the content of palladium element in the obtained catalyst is 1 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 12h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is about 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain Pd-MnO2。
Example 4
Pd-MnO2The preparation of (1): respectively weighing 0.02mol of manganese acetate, 0.02mol of potassium persulfate, 0.08mol of potassium sulfate and 0.0012mol of palladium nitrate, wherein the content of palladium element in the obtained catalyst is 10 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 12h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH value of the effluent waste liquid is approximately equal to 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain the catalystPd-MnO2A nanowire.
Example 5
Pd-MnO2Preparation of carbon nanotubes: 0.02mol of manganese sulfate, 0.02mol of sodium persulfate, 0.08mol of ammonium sulfate, 0.00012mol of palladium nitrate and 0.00005mol of carbon nano tube are respectively weighed, and the content of palladium element in the obtained catalyst is 1 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 12h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is about 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain Pd-MnO2A carbon nanotube composite catalyst.
Example 6
Pd-MnO2Preparation of graphene: 0.05mol of manganese nitrate, 0.06mol of sodium persulfate, 0.05mol of potassium sulfate, 0.0009mol of palladium chloride and 0.00015mol of graphene are respectively weighed, wherein the content of palladium element in the obtained catalyst is 3 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 8h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is about 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain Pd-MnO2A graphene composite catalyst.
Example 7
Pd-MnO2Preparation of graphene oxide: 0.03mol of manganese chloride, 0.035mol of potassium persulfate, 0.1mol of sodium sulfate, 0.0008mol of palladium nitrate and 0.00045mol of graphene oxide are respectively weighed, and the content of palladium element in the obtained catalyst is 5 wt%. Adding 75mL of ultrapure water, magnetically stirring for 15-20 min to completely dissolve the raw materials, transferring the raw materials into a hydrothermal kettle, and reacting for 12h at 140 ℃. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, washing the obtained catalyst with a large amount of clear water until the pH of the effluent waste liquid is about 7, transferring the sample into a vacuum drying oven, and performing vacuum drying at 60 ℃ overnight to obtain Pd-MnO2A graphene oxide composite catalyst.
Example 8
5mg of the catalyst powder prepared in examples 1 to 5 was dispersed in 1mL of ethanol and 45. mu. Lnafion solution, and the solution was sonicated for 1 to 3 hours to uniformly disperse the catalyst in the solution to form a uniform slurry, the catalyst content dropped on the rotating disk electrode was 0.2mg/cm2And naturally drying. The polarization curve of the catalyst was tested with an electrochemical workstation. Oxygen was introduced into 0.1M KOH solution for 30min, and then the polarization curves of the catalysts prepared in examples 1 to 5 were measured in this order using a disk electrode on which the catalyst was dropped as a working electrode, a Pt wire as a counter electrode, and a reference electrode as an Ag/AgCl electrode (see FIGS. 1 to 5). Pd-MnO on ORR2The/carbon nano tube composite catalyst shows excellent catalytic performance which is far higher than 10 wt% of Pt/C.
Example 9
5mg of the catalyst powder prepared in examples 5, 6 and 7 was dispersed in 1mL of ethanol and 45. mu. Lnafion solution, and the solution was sonicated for 1-3h to uniformly disperse the catalyst in the solution to form a uniform slurry, which was dropped onto a home-made carbon paper electrode (catalyst content: 2 mg/cm)2) And naturally drying. The test was performed with an electrochemical workstation. A home-made carbon paper electrode is used as a working electrode, a counter electrode is a zinc sheet with the same area as the carbon paper, and a two-electrode system is adopted to carry out the performance test of the zinc-air battery in 6MKOH solution under the condition of air.
The results are shown in FIGS. 6-8, which show that the composite catalyst prepared by the present invention has a loading of 2mg/cm2The discharge power of the catalyst used for the metal-air battery under the air condition can reach 274mW/cm2。
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.

Claims (14)

1. A composite catalyst is characterized by comprising at least the following components in a molar ratio:
MnO20.008～0.08
C 0.00005～0.0005
0.0001 to 0.0012 of palladium;
the palladium is palladium ion.
2. The composite catalyst according to claim 1, characterized in that: the C is selected from any one or more of carbon nano tube, graphene or graphene oxide.
3. The composite catalyst according to claim 2, characterized in that: the palladium ions are distributed in MnO2The crystal lattice is neutralized on C, or distributed on MnO2In the crystal lattice; the MnO2And the mass ratio of the carbon and the palladium in the catalyst is not less than 70%.
4. The composite catalyst according to claim 1, characterized in that: the MnO2Is α -MnO2The nano-wire has a diameter of 5-20nm and a length of 10 nm-10 μm.
5. The method for preparing a composite catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) respectively weighing reactant divalent manganese salt, reaction auxiliary agent, oxidant, carbon source and palladium source;
(2) dissolving the reactant in the step (1) in water, and stirring;
(3) carrying out hydrothermal reaction for 4-24 h at 90-250 ℃, cooling to room temperature, cleaning, drying and grinding to obtain the product;
the reaction auxiliary agent is sulfate; the oxidant is persulfate;
the molar ratio of the reactants in the step (1) is as follows:
Figure FDA0002441952990000011
6. the method for preparing a composite catalyst according to claim 5, characterized in that: the divalent manganese salt is selected from any one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
7. The method for preparing a composite catalyst according to claim 5, characterized in that: the sulfate is selected from one or more of ammonium sulfate, sodium sulfate and potassium sulfate.
8. The method for preparing a composite catalyst according to claim 5, characterized in that: the persulfate is selected from any one or more of potassium persulfate, sodium persulfate or ammonium persulfate.
9. The method for preparing a composite catalyst according to claim 5, characterized in that: the palladium source is a palladium-containing salt.
10. The method for preparing a composite catalyst according to claim 9, characterized in that: the salt containing palladium is palladium nitrate and/or palladium chloride.
11. The method for preparing a composite catalyst according to claim 5, characterized in that: the carbon source is selected from any one or more of carbon nano tube, graphene or graphene oxide, and the hydrothermal reaction in the step (3) is carried out for 12 hours.
12. The method for preparing a composite catalyst according to claim 5, characterized in that: the molar ratio of the reactants in the step (1) is as follows:
Figure FDA0002441952990000021
13. use of the composite catalyst according to any one of claims 1 to 4 in a metal-air battery.
14. The use of the composite catalyst as set forth in claim 13, wherein the metal-air battery is any one of a zinc-air battery, a lithium-air battery, an aluminum-air battery or a magnesium-air battery.
CN201610692984.3A 2016-08-19 2016-08-19 Composite catalyst and preparation method and application thereof Active CN107754795B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610692984.3A CN107754795B (en) 2016-08-19 2016-08-19 Composite catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610692984.3A CN107754795B (en) 2016-08-19 2016-08-19 Composite catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107754795A CN107754795A (en) 2018-03-06
CN107754795B true CN107754795B (en) 2020-06-16

Family

ID=61262086

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610692984.3A Active CN107754795B (en) 2016-08-19 2016-08-19 Composite catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107754795B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113611884A (en) * 2021-08-03 2021-11-05 中国科学技术大学 Ruthenium-doped alpha-manganese dioxide composite material, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593472A (en) * 2011-01-13 2012-07-18 三星电子株式会社 Catalyst including active particles, method of preparing the catalyst, fuel cell, electrode and lithium air battery
CN102814178A (en) * 2012-08-23 2012-12-12 南京理工大学 Palladium-transition metal oxide-graphene ternary composite catalyst and preparation method thereof
CN103887528A (en) * 2014-03-04 2014-06-25 成都达艾斯电子有限公司 MnO2-RuO2/C catalyst for lithium-air battery and preparation method of MnO2-RuO2/C catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593472A (en) * 2011-01-13 2012-07-18 三星电子株式会社 Catalyst including active particles, method of preparing the catalyst, fuel cell, electrode and lithium air battery
CN102814178A (en) * 2012-08-23 2012-12-12 南京理工大学 Palladium-transition metal oxide-graphene ternary composite catalyst and preparation method thereof
CN103887528A (en) * 2014-03-04 2014-06-25 成都达艾斯电子有限公司 MnO2-RuO2/C catalyst for lithium-air battery and preparation method of MnO2-RuO2/C catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mesoporous α-MnO2/Pd catalyst air electrode for rechargeable lithium-air battery;Arjun Kumar Thapa et al.;《Journal of Power Sources》;20101007;第196卷;第7016页摘要 *

Also Published As

Publication number Publication date
CN107754795A (en) 2018-03-06

Similar Documents

Publication Publication Date Title
Wu et al. A metal-organic framework-derived bifunctional catalyst for hybrid sodium-air batteries
Fang et al. Prussian blue analog-derived 2D ultrathin CoFe 2 O 4 nanosheets as high-activity electrocatalysts for the oxygen evolution reaction in alkaline and neutral media
Guo et al. Carbon nanosheets containing discrete Co-N x-B y-C active sites for efficient oxygen electrocatalysis and rechargeable Zn–Air batteries
Su et al. CoO-Mo2N hollow heterostructure for high-efficiency electrocatalytic hydrogen evolution reaction
Qian et al. Co3O4 nanoparticles on porous bio-carbon substrate as catalyst for oxygen reduction reaction
Ma et al. Hierarchically porous Co3C/Co-NC/G modified graphitic carbon: a trifunctional corrosion-resistant electrode for oxygen reduction, hydrogen evolution and oxygen evolution reactions
US9797052B2 (en) Electrolytic water splitting using a carbon-supported MnOx-composite
Li et al. Graphene confined MoS2 particles for accelerated electrocatalytic hydrogen evolution
Dinari et al. Construction of Ce-doped NiCo-LDH@ CNT nanocomposite electrodes for high-performance supercapacitor application
Lin et al. Hierarchical iron-doped nickel diselenide hollow spheres for efficient oxygen evolution electrocatalysis
Yuan et al. Silicon oxide-protected nickel nanoparticles as biomass-derived catalysts for urea electro-oxidation
CN110292939B (en) Double-carbon-limited-domain iridium nanocluster and preparation method and application thereof
Song et al. Synthesis and electrocatalytic activities of Co 3 O 4 nanocubes
Lei et al. S-doping promotes pyridine nitrogen conversion and lattice defects of carbon nitride to enhance the performance of Zn–Air batteries
Meng et al. A novel cobalt and nitrogen co-doped mesoporous hollow carbon hemisphere as high-efficient electrocatalysts for oxygen reduction reaction
CN110690425B (en) Boron-doped reduced carbon nanotube-loaded ferric oxide composite material and preparation method thereof
CN114628696B (en) Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst
Sun et al. Novel transition-metal phosphides@ N, P-codoped carbon electrocatalysts synthesized via a universal strategy for overall water splitting
Hayat et al. Electrocatalytic activity of Cu MOF and its g-C3N4-based composites for oxygen reduction and evolution reaction in metal-air batteries
Salarizadeh et al. Comparison of methanol oxidation reaction process for NiCo2O4/X (X= rGO, MWCNTs, HCNs) nanocatalyst
Ren et al. N-doped carbon nanotubes as an efficient electrocatalyst for O 2 conversion to H 2 O 2 in neutral electrolyte
CN110586127A (en) Preparation method and application of platinum-cobalt bimetallic hollow nanospheres
Trivedi et al. Enhanced electrocatalytic performance of CuxNi1-xS Nanoflakes for overall water splitting
Guangzhi et al. Three-dimensional crumpled reduced graphene oxide/Co9S8 nanocomposites as efficient electrocatalyst for oxygen evolution reaction
CN107754795B (en) Composite catalyst and preparation method and application 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