CN113201749A - Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst - Google Patents
Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst Download PDFInfo
- Publication number
- CN113201749A CN113201749A CN202110342467.4A CN202110342467A CN113201749A CN 113201749 A CN113201749 A CN 113201749A CN 202110342467 A CN202110342467 A CN 202110342467A CN 113201749 A CN113201749 A CN 113201749A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- sulfur
- electrode catalyst
- modified carbon
- doped copper
- 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.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst, and a preparation method thereof comprises the following steps: dispersing cobalt chloride hexahydrate and copper chloride in a solution of mixed ammonia water and absolute ethyl alcohol, adding a hydroxylated carbon nanotube, continuing to perform ultrasonic treatment to uniformly disperse the hydroxylated carbon nanotube, and adding the hydroxylated carbon nanotube to obtain a dispersed precursor mixed solution; then, two-step heat treatment is carried out, wherein the first-time thermal reaction condition is a reflux method; and the second thermal reaction condition is a hydrothermal method, thiourea is added and transferred to a hydrothermal reaction kettle, and after the reaction, the product after the heat treatment is filtered to obtain a solid. The electrode catalyst has a one-dimensional tubular structure, is loaded with nano particles with high intrinsic activity, and simultaneously has excellent dual-functional catalytic performance of oxygen reduction and oxygen precipitation. The preparation method is simple, low in cost and easy to popularize.
Description
Technical Field
The invention belongs to the technical field of new energy and new material application, and particularly relates to a preparation method and application of a sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst.
Background
Under the alkaline condition, the copper cobaltate catalyst is expected to be the choice for replacing a noble metal ORR/OER bifunctional electrode catalyst due to the unique d electronic structure and crystal structure of the copper cobaltate catalyst; however, pure-phase copper cobaltate has poor conductivity due to its semiconductor properties, and is difficult to be commercially produced. Research is conducted on constructing an electron transmission channel by coupling the hydroxyl carbon nanotube with the copper cobaltate and increasing the number of active sites, but the intrinsic activity of the catalyst needs to be improved. Therefore, how to realize the further bifunctional application of the copper cobaltate modified carbon nanotube catalyst needs to be deeply researched.
Disclosure of Invention
Aiming at some defects in the prior art, the invention provides a preparation method of a sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst. The method comprises the following steps:
(1) dispersing 0.05-1 mmol of cobalt chloride hexahydrate and 0.025-0.5 mmol of copper chloride in a solution of 0.8ml of ammonia water and 70ml of absolute ethanol, wherein the molar ratio of cobalt chloride hexahydrate to copper chloride is 2: 1, adding a hydroxylated carbon nanotube, continuing to perform ultrasonic treatment to uniformly disperse the hydroxylated carbon nanotube, and adding 50mg of the hydroxylated carbon nanotube to obtain a dispersed precursor mixed solution;
(2) carrying out two-step heat treatment on the precursor mixed solution in the step (1), wherein the first thermal reaction condition is a reflux method, the reaction temperature is 80 ℃, and the reaction time is 16 hours; and (3) adding thiourea and transferring to a hydrothermal reaction kettle under the condition of a hydrothermal method as a second thermal reaction condition, wherein the molar ratio of the thiourea to the copper chloride in the step (1) is (1-2): (1-2), reacting at 140 ℃ for 3 hours, filtering the heat-treated product, and drying the obtained solid, namely the sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst.
Preferably, 0.2mmol of cobalt chloride hexahydrate and 0.1mmol of copper chloride are used in step (1) of the above preparation method.
Preferably, the thiourea in step (2) is 0.1 mmol.
As another object of the invention, the invention provides an application of the sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst in electrochemical oxygen reduction reaction and oxygen precipitation reaction.
As another object of the invention, the invention provides a sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst which can be used for a rechargeable zinc-air battery cathode.
The invention has the beneficial effects that:
1. according to the invention, a hydroxyl carbon nanotube material is used as a carrier, and is coupled with a sulfur-doped copper cobaltate spinel material with high intrinsic activity to construct a heterogeneous interface, so that the material has the dual-functional properties of catalyzing oxygen reduction and oxygen precipitation reaction. Compared with noble metals, the sulfur-doped copper cobaltate modified carbon nanotube is a catalyst with excellent performance and has lower cost.
2. The electronegativity of the sulfur negative ions is lower than that of the oxygen negative ions, the polarization is easier, more dispersed electrons can balance the strong positive dipole of the metal ions, therefore, the proper sulfur doping degree ensures that the spinel structure of the copper cobaltate is maintained, more active sites are generated, and the electrochemical catalytic reaction activity is further improved.
3. The sulfur-doped copper cobaltate modified carbon nanotube is applied to a rechargeable zinc-air battery, the open-circuit potential is 1.45V, and the power density is 89.4mW/cm-2。
Drawings
FIG. 1 is a linear voltammogram for oxygen reduction reaction of the electrode catalysts of examples 1 to 3 and comparative examples 1 to 3.
FIG. 2 is a linear voltammogram of oxygen evolution reaction of the electrode catalysts of examples 1 to 3 and comparative examples 1 to 2 and 4.
Fig. 3 is a topographical characterization of example 2 and comparative example 1. Wherein FIG. 3a is comparative example 1CuCo2O4-oCNT scanning Electron microscopy, FIG. 3b is CuCo of example 22O4-xSx-scanning electron micrograph of oCNT-2.
FIG. 4 is a structure-characterizing X-ray diffraction pattern of example 2 and comparative example 1.
FIG. 5 is an open circuit potential diagram applied to the air cathode of the zinc-air battery in example 2.
Fig. 6 is a charge-discharge curve diagram of the air cathode of the zinc-air battery applied in example 2.
Fig. 7 is a graph of the discharge curve and power density of the air cathode of the zinc-air battery applied in example 2.
Detailed Description
The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst comprises the following steps:
(1) 0.05g of hydroxyl carbon nanotube oCNT, 0.0476g (0.2mmol) of cobalt chloride hexahydrate and 0.0170g (0.1mmol) of copper chloride are weighed and placed in a 100mL round-bottom flask, 0.8mL of ammonia water and 70mL of absolute ethyl alcohol are added, and then ultrasonic treatment is carried out for 30min for dispersion and mixing.
(2) The round-bottomed flask was put in an 80 ℃ oil bath to reflux for 16 hours for the first heat treatment, and then 0.0038g (0.05mmol) of thiourea was added, and the mixed liquid was transferred to a 100mL hydrothermal reaction vessel and further reacted in an oven at 140 ℃ for 3 hours. Filtering and washing at normal temperature, drying in a 50 ℃ oven for 4 hours, collecting a sample, and marking the sample as CuCo2O4-xSx-oCNT-1。
Example 2
Thiourea was added at 0.0076g (0.10 mmol); other preparation processes and parameters are the same as those of the example 1; the resulting sample was labeled CuCo2O4-xSx-oCNT-2。
Example 3
Thiourea was added at 0.0114g (0.15 mmol); other preparation processes and parameters are the same as those of the example 1; the resulting sample was labeled CuCo2O4-xSx-oCNT-3。
Comparative example 1
The procedure in comparative example 1 was substantially the same as in example 1 above, except that: no sulfur source, i.e. no thiourea, was introduced between the two heat treatments. Sample designation CuCo2O4-oCNT。
Comparative example 2
The hydroxyl carbon nanotube otcnt is commonly used on the market.
Comparative example 3
Pt/C platinum carbon catalyst is commonly used on the market.
Comparative example 4
IrO commonly used in the market2A catalyst.
Example 4 electrochemical Performance characterization test
(1) And (3) researching the ORR performance of the carbon nano tube modified by sulfur-doped copper cobaltate with different degrees.
Redox performance analysis was performed on the samples obtained in examples 1 to 3 and comparative examples 1 to 3, and the ORR performance of the sulfur-doped copper cobaltate modified carbon nanotubes of different degrees was studied.
Preparing a working electrode: weighing 3mg of catalyst sample, adding the catalyst sample into a mixed solution of 0.5mL of deionized water, 0.5mL of isopropanol and 20 mu L of Nafion, carrying out ultrasonic treatment for 15min to uniformly disperse the catalyst sample and prepare catalyst ink, using a liquid transfer gun to transfer 5 mu L of catalyst ink, dropwise adding the catalyst ink on the surface of a glassy carbon working electrode, and drying.
Linear sweep voltammetry: a standard three-electrode system is adopted, a glassy carbon electrode dripped with a catalyst is used as a working electrode, a spectral pure graphite carbon rod is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode. The electrolyte solution was 0.1M KOH. The Hg/HgO electrode reference electrode was at a voltage of 0.85V relative to the RHE electrode in 0.1M KOH. Introducing oxygen for 30 minutes before testing, testing an LSV curve after waiting for oxygen saturation, and scanning at a speed of 10mV s-1The rotation speed is 1600rpm, the voltage interval of ORR reaction is 0.2-1.0V vs. RHE, and the data is recorded, and the specific results are shown in Table 1 and figure 1.
TABLE 1 electrochemical ORR data for sulfur-doped copper cobaltate-modified carbon nanotubes of different degrees and comparative examples
As can be seen from Table 1, the initial potential and the limiting current density of all the sulfur-doped copper cobaltate modified carbon nanotube catalysts are better than those of CuCo which is not doped with sulfur2O4-oCNT (comparative example 1), better than unmodified oCNT (comparative example 2). It can therefore be concluded that: the sulfur element doping can promote the catalytic efficiency of copper cobaltate modified carbon nanotubes on ORR, and effectively increase the number of active sites of the catalyst. The more positive the oxygen reduction potential, the lower the overpotential, O2The more readily electrons are received to cause an oxygen reduction reaction, and therefore, when the cathode catalyst is used, the more likely the electric power generation performance of the air fuel cell is improved. FIG. 1 is a linear sweep voltammogram of different sulfur-doped copper cobaltate-modified carbon nanotubes, in which CuCo is2O4-xSx-oCNT-1And CuCo2O4-xSx-oCNT-2 has an initial potential greater than CuCo2O4-xSx-oCNT-3, which may be too much introduction of a sulfur source affecting the material's OH-pair-Adsorption of (3); and CuCo2O4-xSx-oCNT-2 and CuCo2O4-xSxThe limiting current densities of-oCNT-3 were all higher than Pt/C (comparative example 3), which illustrates CuCo2O4-xSx-oCNT-2 possesses the best ORR properties.
(2) And (3) researching the OER performance of the carbon nano tube modified by the sulfur-doped copper cobaltate with different degrees.
And (3) analyzing the oxygen precipitation reaction performance of the samples in the examples 1-3, the comparative examples 1-2 and the comparative example 4, and researching the OER performance of the sulfur-doped copper cobaltate modified carbon nano tube in different degrees.
Preparing a working electrode: weighing 3mg of catalyst sample, adding the catalyst sample into a mixed solution of 0.5mL of deionized water, 0.5mL of isopropanol and 20 mu L of Nafion, carrying out ultrasonic treatment for 15min to uniformly disperse the catalyst sample and prepare catalyst ink, using a liquid transfer gun to transfer 5 mu L of catalyst ink, dropwise adding the catalyst ink on the surface of a glassy carbon working electrode, and drying.
Linear sweep voltammetry: a standard three-electrode system is adopted, a glassy carbon electrode dripped with a catalyst is used as a working electrode, a spectral pure graphite carbon rod is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode. The standard potential of the Hg/HgO electrode reference electrode was 0.098V. The electrolyte solution was 0.1M KOH. Testing LSV curve, scanning speed 10mV s-1The rotation speed is 1600rpm, the voltage interval of OER reaction is 1.2-1.65V vs. RHE, the data is recorded, and the specific results are shown in Table 2 and figure 2.
TABLE 2 electrochemical OER data for sulfur-doped copper cobaltate-modified carbon nanotubes of varying degrees and comparative examples
As can be seen from Table 2 and FIG. 2, all the sulfur-doped copper cobaltate-modified carbon nanotube catalysts have a current density of 5mA cm-2The corresponding potentials are all less than that of CuCo without doping sulfur2O4-oCNT (comparative example 1), better than IrO2(comparative example 4). This shows that the sulfur-doped copper cobaltate modified carbon nanotube has extremely excellent OER catalytic performance. Wherein, CuCo2O4-xSx-oCNT-2 at a current density of 5mA cm-2The corresponding potential is the lowest, which also just indicates that the oxygen evolution performance of the catalyst cannot be optimized to the maximum extent of too little or too much sulfur doping for the copper cobaltate modified carbon nanotube system. Current density 5mA cm-2The activity of the oxygen electrode is generally evaluated according to the difference value between the corresponding potential and the ORR half-wave potential, and the smaller the potential difference value is, the larger the bifunctional catalytic activity of the oxygen electrode is. CuCo2O4-xSx-oCNT-2 has a minimal potential difference even compared to the noble metal IrO2Current density 5mA cm-2The difference between the corresponding potential and the Pt/C half-wave potential combination is smaller by 0.01V. It can therefore be concluded that: sulfur-doped copper cobaltate modified carbon nanotube catalyst CuCo2O4-xSx-oCNT-2 has excellent catalytic performance for reversible oxygen reaction.
Example 5 CuCo2O4-oCNT and CuCo2O4-xSx-structural morphology characterization of oCNT-2
Modification of carbon nanotube CuCo by Scanning Electron Microscope (SEM) copper cobaltate2O4-oCNT and sulfur-doped copper cobaltate modified carbon nanotube CuCo2O4-xSx-oCNT-2, see FIG. 3. The tubular morphology of CuCo can be clearly seen in FIG. 3a2O4-oCNT are randomly dispersed and stacked together, and CuCo with different sizes is dispersed on the tube wall2O4Nanoparticles. FIG. 3b vulcanized CuCo2O4-xSxThe tubular morphology of-oCNT-2 is basically maintained, and small particles distributed on the surface of the carbon tube wall are also retained, which indicates that the introduction of the sulfur source is applied to CuCo2O4-the morphological structure of the otcnt has little influence.
FIG. 4 shows CuCo2O4-oCNT and CuCo2O4-xSx-X-ray diffraction pattern of otnt-2. From FIG. 4, CuCo can be seen2O4-oCNT and CuCo2O4-xSxThe presence of characteristic diffraction peaks attributed to carbon nanotubes at 26.2 ° and 44.4 ° for the-oCNT-2 catalyst, corresponding to the (002) and (101) crystallographic planes of graphitic carbon. In addition, whether CuCo or CuCo2O4-oCNT is also CuCo2O4-xSx-oCNT-2, all of which can find the characteristic diffraction peak corresponding to CuCo at 36.7 DEG2O4The (311) crystal face of (A), which further proves that sulfur doping does not influence the original CuCo2O4The spinel structure of (1).
Example 6 CuCo2O4-xSx-oCNT-2 is applied to air cathode analysis of zinc-air battery
Selecting CuCo in example 22O4-xSx-oCNT-2 was used for analysis in air cathode of zinc-air battery. The performance of the open circuit potential, charge and discharge power density of the material was studied.
Assembling a zinc-air battery device: a single chamber reactor of 28mL capacity was used. The anode is a polished zinc sheet with the thickness of 0.5mm, the electrolyte is a mixed solution of 6mol/L potassium hydroxide and 0.2mol/L zinc acetate, the cathode substrate is hydrophobic carbon cloth, and the loading amount of the hydrophobic carbon cloth is 4.5mg/cm2Of CuCo2O4-xSx-oCNT-2 catalyst.
FIG. 5 shows CuCo2O4-xSx-oCNT-2 is applied to a battery open-circuit potential-time diagram of an air cathode of a zinc-air battery, the battery open-circuit potential is stable to 1.45V, and the higher open-circuit potential proves that CuCo2O4-xSx-oCNT-2 is an ideal material as an air cathode catalyst. FIG. 6 is a graph showing the charge/discharge characteristics of the battery at 50mA/cm2The corresponding charging and discharging voltages are respectively 2.27V and 1.05V, the voltage window is 1.22V, and the CuCo is shown2O4-xSxApplication potential of oCNT-2 in a high-current use scene. FIG. 7 is a graph showing the discharge curve to calculate CuCo2O4-xSxThe power density of the-oCNT-2 air cathode zinc-air battery is 89.4mW/cm2High power density further proves CuCo2O4-xSx-the feasibility of applying otcnt-2 to an air cathode of a zinc-air battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. The sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst is characterized in that the preparation method comprises the following steps:
(1) dispersing 0.05-1 mmol of cobalt chloride hexahydrate and 0.025-0.5 mmol of copper chloride in a solution of 0.8ml of ammonia water and 70ml of absolute ethanol, wherein the molar ratio of cobalt chloride hexahydrate to copper chloride is 2: 1, adding a hydroxylated carbon nanotube, continuing to perform ultrasonic treatment to uniformly disperse the hydroxylated carbon nanotube, and adding 50mg of the hydroxylated carbon nanotube to obtain a dispersed precursor mixed solution;
(2) carrying out two-step heat treatment on the precursor mixed solution in the step (1), wherein the first thermal reaction condition is a reflux method, the reaction temperature is 80 ℃, and the reaction time is 16 hours; and (3) adding thiourea and transferring to a hydrothermal reaction kettle under the condition of a hydrothermal method as a second thermal reaction condition, wherein the molar ratio of the thiourea to the copper chloride in the step (1) is (1-2): (1-2), reacting at 140 ℃ for 3 hours, filtering the heat-treated product, and drying the obtained solid, namely the sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst.
2. The sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst of claim 1, wherein the cobalt chloride hexahydrate used in the step (1) is 0.2mmol, and the copper chloride is 0.1 mmol.
3. The sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst of claim 1, wherein the thiourea in the step (2) is 0.1 mmol.
4. The use of the sulfur-doped copper cobaltate-modified carbon nanotube electrode catalyst of claim 1 in electrochemical oxygen reduction reactions and oxygen evolution reactions.
5. The sulfur-doped copper cobaltate modified carbon nanotube electrode catalyst as claimed in claim 1, which can be used in a rechargeable zinc-air battery cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110342467.4A CN113201749A (en) | 2021-03-30 | 2021-03-30 | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110342467.4A CN113201749A (en) | 2021-03-30 | 2021-03-30 | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113201749A true CN113201749A (en) | 2021-08-03 |
Family
ID=77025887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110342467.4A Withdrawn CN113201749A (en) | 2021-03-30 | 2021-03-30 | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113201749A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066249A (en) * | 2013-01-25 | 2013-04-24 | 浙江大学 | Cobalt-based complex oxide/graphene composite material as well as preparation method and application thereof |
| CN105244183A (en) * | 2015-10-23 | 2016-01-13 | 中南民族大学 | Preparation method for super capacitor obtained by carbon nanotube yarn compositing cobaltates metallic oxide nanowire |
| CN106082349A (en) * | 2016-06-20 | 2016-11-09 | 济南大学 | A kind of spinel-type sulfur doping Co ferrite Nano powder and preparation method |
| CN106531988A (en) * | 2016-10-21 | 2017-03-22 | 吉林大学 | N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof |
| CN109103027A (en) * | 2018-07-09 | 2018-12-28 | 江苏大学 | Solvent-thermal method prepares the method and its application of cobalt acid copper combination electrode material |
| CN112903779A (en) * | 2021-03-10 | 2021-06-04 | 东北电力大学 | Foam nickel loaded CuCo2O4Non-enzymatic glucose electrochemical sensor |
-
2021
- 2021-03-30 CN CN202110342467.4A patent/CN113201749A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066249A (en) * | 2013-01-25 | 2013-04-24 | 浙江大学 | Cobalt-based complex oxide/graphene composite material as well as preparation method and application thereof |
| CN105244183A (en) * | 2015-10-23 | 2016-01-13 | 中南民族大学 | Preparation method for super capacitor obtained by carbon nanotube yarn compositing cobaltates metallic oxide nanowire |
| CN106082349A (en) * | 2016-06-20 | 2016-11-09 | 济南大学 | A kind of spinel-type sulfur doping Co ferrite Nano powder and preparation method |
| CN106531988A (en) * | 2016-10-21 | 2017-03-22 | 吉林大学 | N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof |
| CN109103027A (en) * | 2018-07-09 | 2018-12-28 | 江苏大学 | Solvent-thermal method prepares the method and its application of cobalt acid copper combination electrode material |
| CN112903779A (en) * | 2021-03-10 | 2021-06-04 | 东北电力大学 | Foam nickel loaded CuCo2O4Non-enzymatic glucose electrochemical sensor |
Non-Patent Citations (6)
| Title |
|---|
| CHENG CHEN 等，: ""Sufur-doped copper cobalt bimetallic oxides with abundant Cu(I):A novel peroxymonosulfate activator for chloromphenicol degradation"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| J.H.LIN 等，: ""S doped NiCo2O4 nanosheet arrays by Ar plasma and bifunctional for overall water splitting"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| MEI-LING LI 等，: ""CuCo2o4 nanosheets coupled with carbon nanotube heterostructures for highly efficient capacitive energy storage"", 《CHEMELECTROCHEM》 * |
| WEIJIN 等，: ""Encapsulated spinel CuXCo3-XO4 in carbon nanotubes as efficient and stable oxygen electrocatalysts"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| XUEQING LI 等，: ""One-step fabrication of bimetallic CuCoOS as an efficient catalyst for Cr(VI) reduction"", 《ENVIRONMENTAL SCIENCE：NANO》 * |
| 赵良凤等: "锌-空气电池阴极纳米Co_3O_4@rGO催化剂研究", 《电源技术》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110911697B (en) | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof | |
| CN108448117B (en) | Oxygen defect-rich ultrathin nickel-cobalt oxide nanosheet electrode array and preparation method thereof | |
| CN108963282A (en) | A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction | |
| CN110451489B (en) | Cobalt nitride embedded porous nitrogen-doped graphene material, and preparation method and application thereof | |
| CN110247068B (en) | Preparation method and application of iron/copper aza graphene zinc air battery cathode catalyst | |
| CN109279600B (en) | Multi-doped carbon material and preparation method and application thereof | |
| CN109659570B (en) | Application of metal organic framework compound hollow microspheres loaded with iron cobalt sulfide | |
| CN112138697B (en) | Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst | |
| CN112103518B (en) | Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material | |
| CN114068963B (en) | Preparation method and application of transition metal and compound thereof anchored nitrogen-doped carbon catalyst | |
| CN111013631A (en) | Novel three-dimensional grading porous composite material, preparation method and application thereof | |
| CN110756188A (en) | Preparation method of three-dimensional carbon network supported FeCo bifunctional oxygen catalyst | |
| CN112002915B (en) | Oxygen electrode bifunctional catalyst, preparation method and application | |
| CN114477163B (en) | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof | |
| CN113652708B (en) | Pt/Ni alloy 3 N@Mo 2 Preparation method of C hydrogen hydroxide precipitation electrocatalyst | |
| CN113839058B (en) | Carbon-based oxygen reduction reaction catalyst and preparation method thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN114400340A (en) | Nitrogen-sulfur co-doped carbon nanotube composite material and preparation method and application thereof | |
| CN113201746A (en) | Fluorine modified nickel cobaltate modified carbon nanotube electrode catalyst | |
| CN113201750A (en) | Fluorine modified copper cobaltate modified carbon nanotube electrode catalyst | |
| CN113629261B (en) | Morphology-controllable pentairon di-carbide/ferric oxide/iron-nitrogen-carbon electrocatalyst and preparation method thereof | |
| CN115172781A (en) | Carbon-based Fe/Co/P/N Co-doped bifunctional catalyst, and preparation method and application thereof | |
| CN113201749A (en) | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst | |
| CN116417626A (en) | Dendritic structure's NiS 2 Preparation and application of @ Co-N-C/CNF zinc-air battery catalyst | |
| CN111244472A (en) | Carbon material composite nickel-iron-manganese metal catalyst, preparation method and application |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210803 |