CN114759203A - Fex-Co3S4Nanosheet and preparation method and application thereof - Google Patents
Fex-Co3S4Nanosheet and preparation method and application thereof Download PDFInfo
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Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
Abstract
The invention provides Fex‑Co3S4Nanosheets, the main elements of which are Co, S, O and C, and Fe doped into Co3S4In the crystal lattice, the nano-sheet particles are thin, have a porous structure and have more dislocation and step defect sites. The invention also discloses the Fex‑Co3S4A preparation method and application of the nano-sheet. Fe produced in the present inventionx‑Co3S4The nanosheet has excellent OER performance, and can efficiently catalyze the OER reaction in the fuel cell. The invention has simple process, low reaction temperature and short time, is suitable for batch production, and can be used for the technical development of renewable energy sourcesHas important guiding significance.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to Fex-Co3S4Nanosheet and preparation method and application thereof.
Background
Hydrogen is considered a promising alternative energy source to fossil fuels, and can alleviate energy crisis and environmental pollution. Research shows that the hydrogen production by water electrolysis is widely concerned due to high efficiency and environmental protection. The water electrolysis process involves two half-reactions, the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER), which, since OER involves a four-electron coupling process, is slow in reaction kinetics and becomes the rate-determining step of the reaction. The high-efficiency catalyst can reduce the OER energy barrier, so that the development of a proper catalyst for reducing the overpotential and accelerating the oxidation process of water is urgently needed. To date, noble metal catalysts such as IrO 2And RuO2It is considered to be effective in catalyzing OER, but its wide use is limited due to its high cost, scarce resources, and poor long-term stability. Therefore, it is a hot spot of researchers to find an electrocatalyst with low price, high efficiency and stability.
Literature studies have shown that transition metal chalcogenides exhibit superior performance due to their rich composition, unique lattice structure, excellent electron transport capabilities, and the like. Recent reports have demonstrated that sulfides may be converted to oxyhydroxides during OER, but to oxyhydroxidesThe subsequent trace amount of S can still improve the OER performance of the catalyst, because the electronegativity of the S atom is less than that of the O atom, the electronic structure of the catalyst can be adjusted during introduction, and the adsorption energy of an intermediate is optimized. However, developing new electrocatalysts with controllable defects to improve their electrocatalytic activity and stability is an effective strategy, but precise design of these catalysts on an atomic scale remains very difficult. For example, Shenyang industry university Wuxiang and Jilin university Baifu et al prepared several kinds of CoZn with vacancy dependence by adjusting the concentration of doped Zn ionxMn2-xO4The catalyst can raise the efficiency of water decomposing to produce hydrogen. Zn ion doping can cause the change of geometric structure and electronic structure, the in-situ activation in the OER process accelerates the formation of active substances and is beneficial to surface reconstruction, and the intrinsic activity of the catalyst can be further improved by forming (Co, Mn) OOH active substances. Currently, cobalt sulfide exhibits potential utility values in the fields of energy storage and energy conversion. But the catalytic activity and stability performance of the catalyst are far inferior to those of commercial catalysts, so that the practical application of the catalyst is limited. Therefore, how to synthesize cobalt sulfide materials with high activity and stability remains a great challenge for its wide application.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides Fex-Co3S4The nano-sheet, the preparation method and the application thereof have the characteristics of novelty, high efficiency, low price and stability.
The technical scheme adopted by the invention for overcoming the technical problems is as follows: fex-Co3S4Nanosheets, the main elements of which are Co, S, O and C, Fe being doped into Co3S4In the crystal lattice, the nano-sheet particles are thin, have a porous structure and have more dislocation and step defect sites.
The invention also discloses the Fex-Co3S4The preparation method of the nano-sheet takes Co-MOF, a sulfur source, ammonium ferrous sulfate hexahydrate and a solvent as raw materials, and Fe is prepared by adopting a hydrothermal methodx-Co3S4Nanosheets.
Preferably, the hydrothermal method comprises two heat preservation reactions, wherein the temperature of the first heat preservation reaction is 180-220 ℃ and the time is 10-30min, and the temperature of the second heat preservation reaction is 280-320 ℃ and the time is 20-40 min.
Preferably, the sulfur source is n-dodecyl mercaptan.
Preferably, the solvent is dodecylamine.
Preferably, each part of Fex-Co3S4The addition proportion of each raw material of the nano sheet is as follows: 0.2655g of Co-MOF, 0.1g of ammonium ferrous sulfate hexahydrate, 5ml of sulfur source and 3ml of solvent.
Preferably, the preparation method of the Co-MOF is as follows: mixing cobalt nitrate hexahydrate, formic acid and N, N-dimethylformamide, heating, and carrying out heat preservation reaction to obtain Co-MOF.
Preferably, the temperature of the heat preservation reaction is 80-120 ℃, and the time is 22-26 h.
Preferably, the addition ratio of each raw material of each part of Co-MOF is as follows: 1.75g of cobalt nitrate hexahydrate, 1.5ml of formic acid and 5ml of N, N-dimethylformamide.
The invention also discloses the Fex-Co3S4Nanosheet or Fe prepared by the preparation methodx-Co3S4The nanosheet is used as a fuel cell reaction catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts Fe to effectively regulate Co3S4Nanosheets, Fe doped into Co3S4In the crystal lattice, adjusting Co3S4The electronic structure of the nanosheet has more dislocation and step defect sites, enhances the adsorption of Co sites on the surface and reduces the dissociation energy of water, thereby improving the Co3S4Activity of nanosheet, Fex-Co3S4The nanosheet has excellent OER performance, and can efficiently catalyze the OER in the fuel cell. The performance of the product is detected to be superior to that of the RuO which is commercially available at present2The method has important guiding significance for the development of renewable energy development technology.
2. The invention adopts solid-liquid phase chemical reaction at normal pressure and low temperatureControllably synthesize Fex-Co3S4Nanosheets; meanwhile, Fe is obtained by adopting a one-pot boiling mode and a program temperature control modex-Co3S4The nano-sheet has simple process, low reaction temperature and short time, is suitable for batch production, and has important guiding significance for the development of renewable energy technology.
Drawings
FIG. 1 shows Co in comparative example of the present invention3S4TEM images of the nanoplates.
FIG. 2 shows Fe in the example of the present inventionx-Co3S4TEM images of the nanoplates.
FIG. 3 shows Co in an embodiment of the present invention3S4Nanosheet, Fex-Co3S4XRD pattern of nanoplatelets.
FIG. 4 shows a Co-MOF and Co3S4Nanosheet, Fex-Co3S4XPS comparison of nanoplates.
FIG. 5 shows Co-MOF and Co in an example of the present invention3S4Nanosheet, Fex-Co3S4EPR comparison of nanoplates.
FIG. 6 shows Co in an embodiment of the present invention3S4Nanosheet, Fex-Co3S4BET comparison of nanoplates.
FIG. 7 shows Co-MOF and Co in an example of the present invention3S4Nanosheet, Fex-Co3S4And (3) an OER performance test chart of the nanosheet.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
Example 1
Preparation of Co-MOF: weighing 1.75g of cobalt nitrate hexahydrate at room temperature, transferring 1.5ml of formic acid and 5ml of N, N-dimethylformamide, mixing the mixed raw materials into a dry reaction kettle with the capacity of 50ml, transferring the reaction kettle into an oven, raising the temperature to 100 ℃ at the rate of 1.7 ℃/min under program control, preserving the temperature for 24 hours, naturally cooling the reaction kettle to the room temperature after the reaction is finished, washing with N, N-dimethylformamide to obtain a product Co-MOF, and drying in vacuum at 60 ℃ for analytical characterization.
The analysis of the Co-MOF product using XPS testing is shown in FIG. 4. From the analysis of the characterization result of XPS, it can be seen from the general spectrum of FIG. 4a that Co-MOF is mainly composed of Co, C and O elements, and the Co 2p orbit has poor signal because of the low content of Co.
Comparative example
Preparation of Co3S4Nanosheet: 0.2655g of Co-MOF (prepared in example 1), 5ml of n-dodecyl mercaptan and 3ml of dodecylamine are weighed and added into a three-necked flask to be uniformly mixed, then the three-necked flask is transferred into a sand bath, the temperature is raised to 200 ℃ at the speed of 7 ℃/min under the programmed temperature control for 20min, the temperature is raised to 300 ℃ for 30min, after the reaction is finished, when the reactor is naturally cooled to the room temperature, a proper amount of the mixture is added, wherein the volume ratio is 1: 3, dispersing the n-heptane and the ethanol, centrifugally separating the solid, and washing the solid to obtain a product Co3S4The nanosheets were dried at 60 ℃ in vacuo for analytical characterization.
Respectively testing Co by adopting TEM, XRD and XPS3S4Analysis of the nanosheet product, Co can be seen in the TEM image of FIG. 13S4The nano-sheet is very thin nano-sheet small particles, and the lattice spacing of the nano-sheet is measured to be 0.283nm and is Co3S4The type 311 crystal plane of (1); the synthesized Co can be seen from the XRD pattern of FIG. 33S4The crystal phase of (A) is cubic phase (JCPDS # 3-731); from the analysis of the characterization results of XPS of FIG. 4, the general spectrum of FIG. 4a is mainly composed of Co, S, O, C elements, and the Co 2p orbital is composed of three groups of peaks, the first group is composed of peaks at 780.50eV and 795.65eV, and is attributed to Co 2+The second group of peaks consists of peaks at 782.17eV and 798.45eV, and is assigned to Co3+The third group of peaks consists of satellite peaks at 785.94eV, 803.84 eV; the S2 p orbital mainly consists of 4 peaks, wherein two main peaks are respectively located at 163.29eV and 164.44eV and belong to S2-Peaks at 165.99eV and 170.66eV are assigned to the S-O bond and the satellite peak, respectively.
Example 2
Preparation of Fex-Co3S4Nanosheet: 0.2655g of Co-MOF (prepared in example 1), 0.1g of ammonium ferrous sulfate hexahydrate, 5ml of n-dodecyl mercaptan and 3ml of dodecylamine are weighed and added into a three-neck flask for uniform mixing, then the three-neck flask is transferred into a sand bath, the temperature is raised to 200 ℃ at the rate of 7 ℃/min under the programmed temperature control for 20min, the temperature is raised to 300 ℃ for 30min, after the reaction is finished, the reactor is naturally cooled to room temperature, and the mixture is added into the reactor in a volume ratio of 1: 3, dispersing the n-heptane and the ethanol, centrifugally separating the solid, and washing the solid to obtain a product Fex-Co3S4The nanosheets were dried at 60 ℃ in vacuo for analytical characterization.
The TEM, XRD, XPS, EPR and BET tests are adopted to respectively test Fex-Co3S4Analysis of the nanosheet product, Fe can be seen from TEM in fig. 2x-Co3S4Is compared with Co3S4The nanometer sheet particle is even finer, and the synthesized matter is cubic Co as can be seen from the XRD pattern in figure 3 3S4(JCPDS # 3-731), cubic phase Co3S4Are located at 26.71 °, 31.46 °, 38.09 °, 50.26 ° and 55.10 ° belonging to the (220), (311), (400), (511) and (440) crystal planes, respectively. From the analysis of the XPS characterization results of FIG. 4, the general spectrum of FIG. 4a is mainly composed of Co, S, O, C elements, and the Co 2p orbital of FIG. 4b is composed of three sets of peaks, the first set is composed of peaks at 780.98eV and 795.02eV, and is attributed to Co2+The second group of peaks consists of peaks at 782.60eV and 798.04eV, and is assigned to Co3+The third group of peaks consists of satellite peaks at 785.80eV and 803.30 eV; the S2 p orbital of FIG. 4c is mainly composed of 4 peaks, two of which are located at 164.29eV and 165.45eV, respectively, and are assigned to S2-Peaks at 166.83eV and 171.26eV are assigned to the S-O bond and satellite peak, respectively; the Fe 2p orbital of FIG. 4d consists of 3 sets of peaks, the first consisting of peaks at 713.81eV, 721.95eV, assigned to Fe2+The second group of peaks consists of peaks at 717.24 eV and 729.58eV, and is assigned to Fe3+The third group of peaks consists of satellite peaks at 721.95eV, 735.06 eV.Can observe Fex-Co3S4Nanosheet and Co3S4In contrast, both the Co 2p and S2 p orbitals move in the high wave direction, indicating that the Co and S electron transfer is to the Fe site. As can be seen from the EPR chart of FIG. 5, Co 3S4、Fex-Co3S4G values of (a) are 2.004, corresponding to S vacancies and O vacancies, while a g value of Co-MOF of 2.004, corresponding to O vacancies, and Fe can be observedx-Co3S4Peak intensity ratio of Co3S4Slightly larger, so it can be concluded that Fe was successfully doped into S and O vacancies. Co can be seen from the BET characterization of FIG. 63S4Has a specific surface area of 29.60m2g-1And is of Fex-Co3S4Has a specific surface area of 43.24m2g-1The corresponding pore diameters are all mesoporous.
Test examples
The electrochemical properties of the samples are respectively tested by cyclic voltammetry and polarization curve methods in a three-electrode system, wherein the samples are Co-MOF obtained in example 1 and Co obtained in comparative example3S4Nanosheet, Fe obtained in example 2x-Co3S4Nanosheet, commercial IrO2And commercial RuO2The specific process is as follows:
electrochemical experiments were performed on the Shanghai Chenhua CHI760E electrochemical workstation using a standard three-electrode test system, the corresponding working electrode being a glassy carbon electrode modified with the sample obtained herein, the counter electrode being a platinum sheet, and the reference electrode being mercury oxide (HgO). All potentials in this experiment were relative to HgO, electrolyte 0.1M KOH solution, and all electrochemical tests were performed at 25 ℃. At each experiment, all modified electrodes were tested in 0.1M KOH solution.
The preparation method of the sample modified electrode comprises the following steps:
before each experiment, a rotating disk electrode with a diameter of 5mm was used with 1.0 μm, 0.3 μm and 0.05 μm of Al in this order2O3Grinding to mirror surface, ultrasonic cleaning, rinsing with secondary distilled water, and standing at room temperature N2Drying under atmosphere for later use. 5mg of the product were dispersed in 0.25ml of ethanol and then 0.7ml of water and 0.25ml of 1% naphthol solution were added to obtain a suspension of 5mg/ml of the product. 10 mul of the suspension and 5 mul of 0.1% naphthol solution were dispersed successively on the surface of a rotating disk electrode N2And drying in the atmosphere to obtain the sample modified electrode.
Before OER test, high-purity O is firstly introduced into the solution2For 30min to remove dissolved other gases in the solution and continue to pass O during the experiment2To maintain O of the solution2And (4) atmosphere. LSV is also at O2The electrochemical scanning speed is 10mV/s, the rotating speed is set to 1600rpm, and the scanning range is 0V-1.0V.
OER performance testing with reference to FIG. 7a can result in a current density of 10mA/cm in 0.1M KOH solution2Of (i) Fex-Co3S4Nanosheet, Co3S4The overpotential of Co-MOF is 300mV, 321mV, 437mV, Fex-Co3S4The overpotential of the nanosheet at the current density is lower than that of commercial IrO2382mV of catalyst is slightly higher than commercial RuO 2297mV of the catalyst. From FIG. 7b, Fe can be seenx-Co3S4Nanosheet, Co3S4Co-MOF, commercial RuO2Catalyst, commercial IrO2The Taffel slopes of the catalyst are respectively 59mV/dec, 68mV/dec, 95mV/dec, 68mV/dec and 90mV/dec, and Fex-Co3S4Tafel slopes of nanoplates are lower than commercial RuO268mV/dec of catalyst and commercial IrO290mV/dec for the catalyst, indicating that it has a faster reaction rate than the commercial catalyst. From the impedance property test of FIG. 7c, it can be seen that Fex-Co3S4The nanosheet has the smallest charge transfer resistance, and Co after Fe doping can also be seen3S4The electrochemical performance of the nano-sheet is greatly improved. The results of electrochemical tests show that the performance of the product in 0.1M KOH is better than that of commercial IrO2And commercial RuO2Catalyst, indicating its substituted commercial IrO2And RuO2Potential of the catalyst.
Example 3
Fex-Co3S4A method of making nanoplatelets comprising the steps of: weighing 1.75g of cobalt nitrate hexahydrate at room temperature, transferring 1.5ml of formic acid and 5ml of N, N-dimethylformamide, mixing, adding the mixed raw materials into a dry reaction kettle with the capacity of 50ml, transferring the reaction kettle into an oven, raising the temperature to 80 ℃ at the rate of 1.7 ℃/min under the programmed temperature control, preserving the temperature for 22 hours, after the reaction is finished, naturally cooling the reaction kettle to the room temperature, and washing with N, N-dimethylformamide to obtain a product Co-MOF; 0.2655g of Co-MOF, 0.1g of ferrous ammonium sulfate hexahydrate, 5ml of n-dodecyl mercaptan and 3ml of dodecylamine are weighed and added into a three-neck flask for uniform mixing, then the three-neck flask is transferred into a sand bath, the temperature is raised to 180 ℃ at the speed of 7 ℃/min under the programmed temperature control for 10min, the temperature is raised to 280 ℃ for 20min, after the reaction is finished, the reactor is naturally cooled to the room temperature, and the mixture is added with the components in the volume ratio of 1: 3, dispersing the n-heptane and the ethanol, centrifugally separating the solid, and washing the solid to obtain a product Fe x-Co3S4Nanosheets.
Example 4
Fex-Co3S4A method of making nanoplatelets comprising the steps of: weighing 1.75g of cobalt nitrate hexahydrate at room temperature, transferring 1.5ml of formic acid and 5ml of N, N-dimethylformamide, mixing, adding the mixed raw materials into a dry reaction kettle with the capacity of 50ml, transferring the reaction kettle into an oven, raising the temperature to 120 ℃ at the rate of 1.7 ℃/min under the programmed temperature control, preserving the temperature for 26 hours, naturally cooling the reaction kettle to the room temperature after the reaction is finished, and washing with N, N-dimethylformamide to obtain a product Co-MOF; 0.2655g of Co-MOF, 0.1g of ammonium ferrous sulfate hexahydrate, 5ml of n-dodecyl mercaptan and 3ml of dodecylamine are weighed and added into a three-necked flask for uniform mixing, then the three-necked flask is transferred into a sand bath, the temperature is raised to 220 ℃ at the rate of 7 ℃/min under the programmed temperature control for 30min, then the temperature is raised to 320 ℃ for 40min, after the reaction is finished, the reactor is naturally cooled to the room temperature, and the materials are added into the three-necked flask in the volume ratio of 1: 3, dispersing the n-heptane and the ethanol, centrifugally separating the solid, and washing the solid to obtain a product Fex-Co3S4Nanosheets.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Fex-Co3S4The nano-sheet is characterized in that the main elements are Co, S, O and C, and Fe is doped into Co3S4In the crystal lattice, the nano-sheet particles are thin and have a porous structure.
2. Fe as defined in claim 1x-Co3S4The preparation method of the nano-sheet is characterized in that Co-MOF, a sulfur source, ammonium ferrous sulfate hexahydrate and a solvent are used as raw materials, and Fe is prepared by adopting a hydrothermal methodx-Co3S4Nanosheets.
3. The preparation method as claimed in claim 2, wherein the hydrothermal method comprises two thermal insulation reactions, wherein the temperature of the first thermal insulation reaction is 220 ℃ at 180 ℃ for 10-30min, and the temperature of the second thermal insulation reaction is 320 ℃ at 280 ℃ for 20-40 min.
4. The production method according to claim 2 or 3, wherein the sulfur source is n-dodecyl mercaptan.
5. The production method according to claim 2 or 3, characterized in that the solvent is dodecylamine.
6. A method according to claim 2 or 3, characterized in that each portion of Fex-Co3S4Addition of raw materials for nanosheetsThe proportion is as follows: 0.2655g of Co-MOF, 0.1g of ammonium ferrous sulfate hexahydrate, 5ml of sulfur source and 3ml of solvent.
7. A method of preparation according to claim 2 or 3, wherein the Co-MOF is prepared as follows: mixing cobalt nitrate hexahydrate, formic acid and N, N-dimethylformamide, heating, and carrying out heat preservation reaction to obtain Co-MOF.
8. The preparation method of claim 7, wherein the temperature of the incubation reaction is 80-120 ℃ and the time is 22-26 h.
9. The preparation method according to claim 7 or 8, wherein the raw materials are added in the following ratio per part of Co-MOF: 1.75g of cobalt nitrate hexahydrate, 1.5ml of formic acid and 5ml of N, N-dimethylformamide.
10. Fe of claim 1x-Co3S4Nanoplatelets or Fe prepared by the preparation method of any of claims 2-9x-Co3S4The nanosheet is used as a fuel cell reaction catalyst.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176360A (en) * | 2019-04-22 | 2019-08-27 | 山东大学 | A kind of hollow core-shell structure super capacitor material Fe-Co-S/NF and its preparation method and application |
| CN113235128A (en) * | 2021-04-25 | 2021-08-10 | 北京师范大学 | Triangular nano array assembled by iron-doped cobalt sulfide and molybdenum sulfide nanosheets and preparation method and application thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176360A (en) * | 2019-04-22 | 2019-08-27 | 山东大学 | A kind of hollow core-shell structure super capacitor material Fe-Co-S/NF and its preparation method and application |
| CN113235128A (en) * | 2021-04-25 | 2021-08-10 | 北京师范大学 | Triangular nano array assembled by iron-doped cobalt sulfide and molybdenum sulfide nanosheets and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JIANKANG WANG等: ""Metal-organic framework-derived Ni doped Co3S4 hierarchical nanosheets as a monolithic electrocatalyst for highly efficient hydrogen evolution reaction in alkaline solution"", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
| LEI ZHONG等: ""Fe-doping effect on CoTe catalyst with greatly boosted intrinsic activity for electrochemical oxygen evolution reaction"", 《ELECTROCHIMICA ACTA》 * |
| WEN LU等: ""Synergistic effects of Fe and Mn dual-doping in Co3S4 ultrathin nanosheets for high-performance hybrid supercapacitors"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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