CN102867965A - Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof - Google Patents
Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN102867965A CN102867965A CN2012103723022A CN201210372302A CN102867965A CN 102867965 A CN102867965 A CN 102867965A CN 2012103723022 A CN2012103723022 A CN 2012103723022A CN 201210372302 A CN201210372302 A CN 201210372302A CN 102867965 A CN102867965 A CN 102867965A
- Authority
- CN
- China
- Prior art keywords
- manganese
- porous microsphere
- carbonate
- type calcium
- ore type
- 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
Images
Classifications
-
- 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 relates to a porous microsphere perovskite type calcium manganese oxide compound. The compound has a porous two-stage micro-nano structure, the chemical formula is CaMnO3, the element ratio of Ca to Mn is 1: 1.08, the diameter of microspheres is 1-3mu m, and the compound is formed by accumulating secondary nano-particles with the particle sizes of 100-400nm; a solid solution precursor calcination method is adopted for preparation; and the material can constitute a three-electrode system for testing hydrogen reduction performance. The compound disclosed by the invention has the advantages that the preparation method is simple to operate, low in price of raw materials, rich in sources, high in purity of a product, good in crystallinity and capable of controlling appearance, the porous network structure which is formed by accumulating nano-particles or nanorods is conductive to electrode gas-liquid-solid three-phase interface contact, a better substance transmission channel can be provided, the electrocatalytic activity can be further effectively improved, the product simultaneously has higher electrochemical activity and good stability, and the compound can be used as a novel catalyst for being applied to metal air batteries, fuel batteries and the like.
Description
Technical field
The present invention relates to the preparation of oxygen reduction electro-catalyst, particularly a kind of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and its preparation method and application.
Background technology
Along with the active demand to extensive energy storage of the day by day in short supply and modern society of fossil energy, the mechanism of new electrochemical power sources of application high-efficiency cleaning, significant to the sustainable development of modern society undoubtedly.Metal-air cell and fuel cell have very high theoretical specific energy, and energy conversion efficiency is high, cleanliness without any pollution, and cathode active material oxygen can derive from air, resource is inexhaustible, is the direction that new energy field is given priority to, and is subject to national governments and scientist's great attention.
Yet Cathodic oxygen reduction dynamics is slow, has determined to a great extent to comprise the performance of the electrochemical appliances such as fuel cell and metal-air cell.Noble metal-based catalysts such as Pt or Pt alloy have excellent catalytic performance to oxygen reduction reaction, but such catalyst is expensive, scarcity of resources, greatly limited its large-scale practical application (Y.H.Bing, H.S.Liu, L.Zhang, et al.Chem.Soc.Rev.2010,39,2184-2202).Therefore, developing non-precious metal catalyst cheap, excellent performance substitutes platinum based catalyst and has important scientific meaning and using value (F.Jaouen, E.Proietti, M.Lefevre, et al.Energy Environ.Sci.2011,4,114-130).Wherein, Mn oxide and manganese base composite oxidate more and more receive researcher's concern because the manganese valence state is numerous, raw material sources are extensive, cheap, asepsis environment-protecting and the excellent advantages such as electrocatalysis characteristic.For example, the people such as Mao (L.Mao, T Sotomura, K Nakatsu, et al.J.Electrochem.Soc.2002,149, A504-A507) utilize cyclic voltammetry to further investigate the catalytic activity of different Mn oxides, result's demonstration, MnOOH has shown best electrochemical catalysis performance; The people such as Cheng (F.Y.Cheng, J Shen, B Peng, et al.Nat Chem.2011,3,79-84) reported the room temperature synthetic method of a dvimanganese system spinel nano material, the compound manganese oxide nano-material specific area of synthetic spinel-type is large and defective abundant, has a good electrochemical catalysis as eelctro-catalyst active.The present invention has developed a kind of novel cheap, porous microsphere high active calcium manganese oxygen eelctro-catalyst.Adopt simple and easy to do solid solution precursor process, obtained the calcium manganese oxygen composite oxide of a class porous microsphere, and be applied to first catalytic oxidation-reduction reaction, wherein porous microsphere Ca-Ti ore type CaMnO
3At aspect advantages such as limiting current density, initial reduction potential, half wave potential and mistake electron transfer numbers, shown its potential application at aspects such as fuel cell, metal-air cells.
Summary of the invention
The object of the invention is to for above-mentioned technical Analysis; a kind of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and preparation method thereof is provided; this porous microsphere Ca-Ti ore type calcium manganese and oxygen compound is the porous microsphere type; the loose structure that forms is piled up mutually by nano particle by system, and for oxygen provides the good passage that transports, product purity is high, good crystallinity, active high; the preparation method is simple; raw material resources are abundant, and production cost is low, use as eelctro-catalyst to have higher catalytic efficiency.
Technical scheme of the present invention:
A kind of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound has porous secondary micro-nano structure, and chemical formula is CaMnO
3, its Ca:Mn element is than being 1:1.08, the micron ball diameter is 1-3 μ m, is piled up by the secondary nano particle of 100-400nm to form.
A kind of preparation method of described porous microsphere Ca-Ti ore type calcium manganese and oxygen compound adopts solid solution presoma calcination method, and step is as follows:
1) soluble manganese source and carbonic acid raw material are dissolved in respectively deionized water, solution concentration is 0.05-0.40mol/L solution, the carbonic acid material solution is added drop-wise in the solution of manganese source under constantly stirring, the mol ratio of soluble manganese source and carbonic acid raw material is 1:5-10, after stirring 30min, centrifugal, washing, 60 ℃ of vacuumize 5h obtain manganese carbonate;
2) freshly prepd manganese carbonate and calcium carbonate are dissolved in the dilute nitric acid solution that concentration is 0.1-0.5mol/L, the total amount of manganese carbonate and calcium carbonate and the mol ratio of nitric acid are 1:2.2-3.0, constantly stir, until fully dissolving, the mol ratio of manganese carbonate and calcium carbonate is 1:1;
3) under constantly stirring, mentioned solution is added in the sal volatile that concentration is 0.1-0.5mol/L, the total amount of manganese carbonate and calcium carbonate and the mol ratio of ammonium carbonate are 1:2.5-3.0, and be centrifugal after precipitation is complete, washing, 80 ℃ of vacuumize 5h;
4) dried powder is placed the alundum (Al2O3) crucible, calcine in high temperature and air atmosphere, design parameter is: 900 ℃ of calcining heats, calcination time 5h namely make porous microsphere Ca-Ti ore type calcium manganese and oxygen compound.
Described soluble manganese salt is manganese chloride, manganese nitrate or manganese sulfate, and the carbonic acid raw material is ammonium carbonate, carbonic hydroammonium, sodium carbonate or potash.
A kind of application of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound of described method preparation, consist of the test that three-electrode system is used for its hydrogen reduction catalytic performance as eelctro-catalyst, namely with the active material component of this porous microsphere Ca-Ti ore type calcium manganese and oxygen compound as work electrode, take saturated calomel electrode (SCE) as reference electrode, 6cm
2Platinized platinum be that the KOH solution of auxiliary electrode, 0.1mol/L is that electrolyte forms three-electrode system, described active material as work electrode is comprised of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and the active carbon that plays electric action, and the mass ratio of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and active carbon is 3:7.
Advantage of the present invention is: this porous microsphere Ca-Ti ore type calcium manganese and oxygen compound is the porous microsphere type, the loose structure that forms is piled up mutually by nano particle by system, being conducive to electrode surface gas-liquid-solid three-phase interface better contacts, for mass transfer provides the good passage that transports, be convenient to contacting of active material and oxygen molecule, be beneficial to the generation of oxygen reduction reaction, can effectively improve electro catalytic activity as eelctro-catalyst; Product purity is high, good crystallinity, active high, the preparation method is simple, raw material resources are abundant, production cost is low, use as eelctro-catalyst and to have higher catalytic efficiency, the field such as electro-catalysis has important value and realistic meaning on development of new catalyst and metal-air cell thereof, fuel cell.
Description of drawings
Fig. 1 is this porous microsphere Ca-Ti ore type CaMnO
3XRD figure.
Fig. 2 is this porous microsphere Ca-Ti ore type CaMnO
3SEM figure.
Fig. 3 is this porous microsphere Ca-Ti ore type CaMnO
3TEM figure.
Fig. 4 is this porous microsphere Ca-Ti ore type CaMnO
3As eelctro-catalyst linear scan polarization curve under 900rpm in 0.1mol/L KOH.
Fig. 5 is this porous microsphere Ca-Ti ore type CaMnO
3As the K-L curve of eelctro-catalyst under 0.5V.
Fig. 6 is this porous microsphere Ca-Ti ore type CaMnO
3As eelctro-catalyst under 0.4V-0.8V electron transfer number n and course of reaction in the growing amount of intermediate product hydrogen peroxide.
Fig. 7 is this porous microsphere Ca-Ti ore type CaMnO
3As the chronoa mperometric plot of eelctro-catalyst under 0.8V.
Embodiment
Embodiment:
1) preparation of fresh manganese carbonate
Respectively the 2mmol manganese chloride is dissolved in 20ml distilled water, 10mmol carbonic hydroammonium is dissolved in 40ml distilled water, after the dissolving, the 0.25mol/L ammonium bicarbonate soln is added drop-wise in the manganese chloride solution of 0.1mol/L under constantly stirring, after being added dropwise to complete fully, continue to stir a moment, stop to stir, centrifugal, washing, be dried overnight under the 0.1MPa at 80 ℃, vacuum degree, for subsequent use.
2) porous microsphere Ca-Ti ore type CaMnO
3Preparation
With 2mmolCaCO
3With 2mmol according to 1) the fresh MnCO of described method preparation
3Be dissolved in rare nitric acid, constantly stir, fully after the dissolving, the excessive 0.5mol/L sal volatile for preparing in advance dropwise is added drop-wise in the above-mentioned salting liquid, after being added dropwise to complete, continues to stir 20-30min, centrifugal, product is with deionized water washing 3 times, and absolute ethanol washing 2 times is dry 5h under the 0.1MPa at 80 ℃, vacuum degree.Dried powder is placed the alundum (Al2O3) crucible, and 900 ℃ of calcining 5h in the Muffle furnace naturally cool to room temperature under the air atmosphere.
This porous microsphere Ca-Ti ore type CaMnO
3XRD figure as shown in Figure 1, calculate cell parameter according to characteristic peak positions in the spectrogram and intensitometer and be
Be perovskite structure, belong to rhombic system, with JCPDS standard card No.76-1132 CaMnO
3Match.Scanning electron microscope (SEM) photograph as shown in Figure 2, the micron ball diameter is at 1-3 μ m, piled up by the secondary nano particle of 100-400nm to form; Pore structure wherein can significantly be found out by transmission electron microscope picture, as shown in Figure 3.
3) porous microsphere Ca-Ti ore type CaMnO
3Performance test as eelctro-catalyst
The preparation of eelctro-catalyst work electrode:
Work electrode is prepared as follows: mixed serum is comprised of 30wt% porous microsphere calcium manganese oxygen composite oxide, 70wt% carbon black and Nafion solution, isopropyl alcohol, after the ultrasonic dispersion an amount of finely dispersed slurries is applied on the glass-carbon electrode and at room temperature more than the dry 5h of alcohol atmosphere.Three-electrode system is adopted in electrocatalysis characteristic test, take the calcium manganese electrode that makes as work electrode, and 6cm
2The Pt sheet be auxiliary electrode, saturated calomel electrode (SCE) is work electrode, electrolyte is alkalescent 0.1MKOH solution.Tester adopts Parstat 263 electrochemical workstations (Princeton Applied Research﹠amp; AMTECT Company).
Electrochemical Properties:
Fig. 4 is this porous microsphere Ca-Ti ore type CaMnO
3As eelctro-catalyst linear scan polarization curve under 900rpm in 0.1mol/L KOH.Show among the figure: this porous microsphere Ca-Ti ore type CaMnO
3Has good hydrogen reduction catalytic performance, the chemistry titration result shows that the Mn valence state is+3.8 in this compound, the mixed valence that shows activated centre Mn plays an important role in the hydrogen reduction high-performance, and the octahedra passage of the Mn-O of perovskite structure 1x1 is conducive to contacting of oxygen molecule and activated centre.
Fig. 5 is this porous microsphere Ca-Ti ore type CaMnO
3As the K-L curve of eelctro-catalyst under 0.5V.Show among the figure: this porous microsphere perovskite structure CaMnO
3Have larger limiting diffusion current and higher electron transfer number.
Fig. 6 is this porous microsphere Ca-Ti ore type CaMnO
3As eelctro-catalyst under 0.4V-0.8V electron transfer number n and course of reaction in the growing amount of intermediate product hydrogen peroxide.What from Fig. 6 a, can find out in the 0.4V-0.8V scope as catalyst electron transfer number in the catalytic oxidation-reduction process, the growing amount that from Fig. 6 b, can find out simultaneously product hydrogen peroxide in the middle of it lower (approximately 1%), show that it has preferably hydrogen reduction electrocatalysis characteristic, fuel cell, the exploitation that can fill the metal-air cell non noble metal catalyst for cathode are had important using value.
Fig. 7 is this porous microsphere Ca-Ti ore type CaMnO
3As the chronoa mperometric plot of eelctro-catalyst under 0.8V.In the process of (0.8V vs RHE) continuous polarization 1h, the polarization current conservation rate illustrates this multi-pore micron ball Ca-Ti ore type CaMnO more than 96% under constant voltage
3In weakly alkaline solution, have simultaneously high electrochemical activity and stable preferably, be of very high actual application value.
Claims (4)
1. porous microsphere Ca-Ti ore type calcium manganese and oxygen compound, it is characterized in that: have porous secondary micro-nano structure, chemical formula is CaMnO
3, its Ca:Mn element is than being 1:1.08, the micron ball diameter is 1-3 μ m, is piled up by the secondary nano particle of 100-400nm to form.
2. preparation method of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound as claimed in claim 1, it is characterized in that: adopt solid solution presoma calcination method, step is as follows:
1) soluble manganese source and carbonic acid raw material are dissolved in respectively deionized water, solution concentration is 0.05-0.40mol/L solution, the carbonic acid material solution is added drop-wise in the solution of manganese source under constantly stirring, the mol ratio of soluble manganese source and carbonic acid raw material is 1:5-10, after stirring 30min, centrifugal, washing, 60 ℃ of vacuumize 5h obtain manganese carbonate;
2) freshly prepd manganese carbonate and calcium carbonate are dissolved in the dilute nitric acid solution that concentration is 0.1-0.5mol/L, the total amount of manganese carbonate and calcium carbonate and the mol ratio of nitric acid are 1:2.2-3.0, constantly stir, until fully dissolving, the mol ratio of manganese carbonate and calcium carbonate is 1:1;
3) under constantly stirring, mentioned solution is added in the sal volatile that concentration is 0.1-0.5mol/L, the total amount of manganese carbonate and calcium carbonate and the mol ratio of ammonium carbonate are 1:2.5-3.0, and be centrifugal after precipitation is complete, washing, 80 ℃ of vacuumize 5h;
4) dried powder is placed the alundum (Al2O3) crucible, calcine in high temperature and air atmosphere, design parameter is: 900 ℃ of calcining heats, calcination time 5h namely make porous microsphere Ca-Ti ore type calcium manganese and oxygen compound.
3. the preparation method of described porous microsphere Ca-Ti ore type calcium manganese and oxygen compound according to claim 2, it is characterized in that: described soluble manganese salt is manganese chloride, manganese nitrate or manganese sulfate, the carbonic acid raw material is ammonium carbonate, carbonic hydroammonium, sodium carbonate or potash.
4. as claimed in claim 2 application of the porous microsphere Ca-Ti ore type calcium manganese and oxygen compound of method preparation, it is characterized in that: consist of the test that three-electrode system is used for its hydrogen reduction catalytic performance as eelctro-catalyst, namely with the active material component of this porous microsphere Ca-Ti ore type calcium manganese and oxygen compound as work electrode, take saturated calomel electrode (SCE) as reference electrode, 6cm
2Platinized platinum be that the KOH solution of auxiliary electrode, 0.1mol/L is that electrolyte forms three-electrode system, described active material as work electrode is comprised of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and the active carbon that plays electric action, and the mass ratio of porous microsphere Ca-Ti ore type calcium manganese and oxygen compound and active carbon is 3:7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103723022A CN102867965A (en) | 2012-09-29 | 2012-09-29 | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103723022A CN102867965A (en) | 2012-09-29 | 2012-09-29 | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102867965A true CN102867965A (en) | 2013-01-09 |
Family
ID=47446670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103723022A Pending CN102867965A (en) | 2012-09-29 | 2012-09-29 | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102867965A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543210A (en) * | 2016-02-26 | 2016-05-04 | 河北工业大学 | Method for preparing porous enzyme microspheres |
| CN107469818A (en) * | 2017-09-14 | 2017-12-15 | 利民化工股份有限公司 | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application |
| CN107986324A (en) * | 2017-11-17 | 2018-05-04 | 河北工业大学 | A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure |
| CN108080000A (en) * | 2016-11-22 | 2018-05-29 | 天津大学 | A kind of hollow porous micro sphere catalysis material and preparation method thereof and degradation NO applications |
| CN109473682A (en) * | 2018-12-28 | 2019-03-15 | 宁波石墨烯创新中心有限公司 | A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst, preparation method and application |
| CN110416560A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of calcium Mn oxide material and its preparation method and application |
| CN111320211A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | Perovskite type calcium manganate material, preparation method thereof and application thereof in wide-temperature-zone lithium ion battery |
| CN111994959A (en) * | 2020-07-17 | 2020-11-27 | 中山大学 | CaMnO3Perovskite material and preparation method and application thereof |
| CN114210338A (en) * | 2021-12-20 | 2022-03-22 | 河北科技大学 | Perovskite-like catalyst for catalyzing ozone oxidation and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101716A (en) * | 1977-08-15 | 1978-07-18 | Exxon Research & Engineering Co. | Use of high surface area mixed metal oxides of manganese and calcium in electrochemical processes |
-
2012
- 2012-09-29 CN CN2012103723022A patent/CN102867965A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101716A (en) * | 1977-08-15 | 1978-07-18 | Exxon Research & Engineering Co. | Use of high surface area mixed metal oxides of manganese and calcium in electrochemical processes |
Non-Patent Citations (1)
| Title |
|---|
| XIAOPENG HAN ET AL: "Porous calcium–manganese oxide microspheres for electrocatalytic oxygen reduction with high activity(Electronic Supplementary Information)", 《CHEMICAL SCIENCE》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543210A (en) * | 2016-02-26 | 2016-05-04 | 河北工业大学 | Method for preparing porous enzyme microspheres |
| CN108080000A (en) * | 2016-11-22 | 2018-05-29 | 天津大学 | A kind of hollow porous micro sphere catalysis material and preparation method thereof and degradation NO applications |
| CN107469818A (en) * | 2017-09-14 | 2017-12-15 | 利民化工股份有限公司 | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application |
| CN107469818B (en) * | 2017-09-14 | 2020-05-29 | 利民化学有限责任公司 | CaZrO3Preparation method of carrier, catalyst with noble metal loaded on carrier, preparation method and application thereof |
| CN107986324A (en) * | 2017-11-17 | 2018-05-04 | 河北工业大学 | A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure |
| CN110416560A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of calcium Mn oxide material and its preparation method and application |
| CN110416560B (en) * | 2018-04-26 | 2022-05-20 | 天津大学 | Calcium manganese oxide material and preparation method and application thereof |
| CN109473682A (en) * | 2018-12-28 | 2019-03-15 | 宁波石墨烯创新中心有限公司 | A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst, preparation method and application |
| CN111320211A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | Perovskite type calcium manganate material, preparation method thereof and application thereof in wide-temperature-zone lithium ion battery |
| CN111994959A (en) * | 2020-07-17 | 2020-11-27 | 中山大学 | CaMnO3Perovskite material and preparation method and application thereof |
| CN114210338A (en) * | 2021-12-20 | 2022-03-22 | 河北科技大学 | Perovskite-like catalyst for catalyzing ozone oxidation and preparation method and application thereof |
| CN114210338B (en) * | 2021-12-20 | 2023-11-10 | 河北科技大学 | Perovskite-like catalyst for catalyzing ozone oxidation and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102867965A (en) | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof | |
| Wu et al. | Role of flower-like ultrathin Co 3 O 4 nanosheets in water splitting and non-aqueous Li–O 2 batteries | |
| CN109759077B (en) | Perovskite oxide catalyst and preparation method and application thereof | |
| CN108579751B (en) | Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis | |
| CN104773764B (en) | A kind of preparation method of three-dimensional flower-shaped cobalt acid nickel nano film mesoporous microsphere | |
| CN105618060A (en) | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN104993159A (en) | Dual-function catalyst and preparation thereof and application in metal-air battery | |
| CN104157858B (en) | Classifying porous ferroso-ferric oxide/graphene nano line and its preparation method and application | |
| CN111634954B (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| CN111244470B (en) | Nano composite cathode and preparation and application thereof | |
| CN107792884B (en) | A kind of air electrode catalyst material nano hexagon ZnMnO3Preparation method and application | |
| Sennu et al. | Exceptional catalytic activity of hollow structured La 0.6 Sr 0.4 CoO 3− δ perovskite spheres in aqueous media and aprotic Li–O 2 batteries | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN113611881B (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| CN110451489A (en) | A kind of cobalt nitride is embedded in porous nitrogen-doped graphene material and preparation method and application | |
| CN110098410A (en) | A kind of synthetic method of nanostructure composite cathode material containing cobalt | |
| CN105742646A (en) | Positive electrode material provided with pomegranate fruit structure for solid-oxide fuel cell and preparation of positive electrode material | |
| CN104810518A (en) | Cobalt-manganese-based spinel nano material as well as preparation method and application thereof | |
| CN112968184A (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN109755600A (en) | The application of carbon cloth nickel-loaded cobalt oxide nano-sheet composite material and preparation method and electrode | |
| Yu et al. | A multi-shelled CeO 2/Co@ N-doped hollow carbon microsphere as a trifunctional electrocatalyst for a rechargeable zinc–air battery and overall water splitting | |
| CN102867966A (en) | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130109 |