CN113249754A - Preparation method and application of Co/Fe-MOF LDHs composite material - Google Patents
Preparation method and application of Co/Fe-MOF LDHs composite material Download PDFInfo
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- CN113249754A CN113249754A CN202110546690.0A CN202110546690A CN113249754A CN 113249754 A CN113249754 A CN 113249754A CN 202110546690 A CN202110546690 A CN 202110546690A CN 113249754 A CN113249754 A CN 113249754A
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Abstract
A preparation method and application of a Co/Fe-MOF LDHs composite material belong to the technical field of metal organic framework materials. Mixing a cobalt and iron double-metal salt aqueous solution, a 4, 4-bipyridyl ethanol solution and pyridine for hydrothermal reaction, washing and drying the obtained precipitate to obtain the Co/Fe-MOF LDHs composite material. The compound not only has large electrochemical specific surface area and abundant metal active centers, but also has strong coupling effect between the two, and has high electron transfer speed and reaction activity. The Co/Fe-MOF LDHs composite material and the Nafion solution are mixed under the ultrasonic condition and then are modified on the surface of the glassy carbon electrode, so that the test electrode for the electro-catalytic oxygen evolution reaction is prepared, the overpotential of the OER reaction can be reduced, and the electro-catalytic performance is improved.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials.
Background
Metal Organic Frameworks (MOFs) are a common class of porous crystalline materials that have received a great deal of attention since their discovery. It is different from inorganic porous material and common organic complex, and has the rigidity of inorganic material and the flexibility of organic material. And because the structure of the pores can be controlled and the specific surface area is large, the MOFs has wider application prospect than other porous materials, such as gas separation, catalysts, energy storage materials and the like.
The two-dimensional layered material can be used as a good electrode material due to the high specific surface area and the unique electronic characteristic, and is widely applied to electrocatalysis and energy storage. The Layered Double Hydroxides (LDHs) have good development prospects in the preparation of electrocatalysis and catalysis materials due to the advantages of typical layered structure characteristics, low price, simple synthesis method, easy functionalization, easy composition regulation, tailorable structure and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a Co/Fe-MOF LDHs composite material, which comprises the following steps:
1) dissolving cobalt salt and ferric salt in deionized water to prepare a double-metal salt water solution;
2) dissolving 4, 4-bipyridine in ethanol to prepare a 4, 4-bipyridine ethanol solution;
3) and mixing the aqueous solution of the bimetallic salt, the 4, 4-bipyridyl ethanol solution and pyridine for hydrothermal reaction, washing and drying the obtained precipitate to obtain the Co/Fe-MOF LDHs composite material.
The composite of MOFs and LDHs not only has large electrochemical specific surface area and abundant metal active centers, but also has strong coupling effect between the MOFs and the LDHs, and has high electron transfer speed and reaction activity. Therefore, it has excellent OER activity. This study will provide valuable guidance for designing MOF-based materials with optimized electrochemical properties.
Further, the cobalt salt is CoSO4·7H2O, iron salt being FeSO4·7H2O, since acid groups carried by these salts participate in coordination synthesis of the material, and play a role in balancing electrons, and a desired product is more easily obtained, it is preferable to use these salts.
Further, the feeding molar ratio of the cobalt salt to the iron salt is 30: 1. The use of this ratio allows the synthesis of the composite material as much as possible while preserving the MOF structure.
Further, the feeding molar ratio of the total amount of the cobalt salt and the iron salt to the 4, 4-bipyridine is 1: 1. The proportion is selected to ensure that the reaction between the metal salt and the organic ligand is more complete and the utilization rate is improved.
Furthermore, the temperature of the hydrothermal reaction is 100 ℃, the time is 24 h, and the obtained Co/Fe-MOF LDHs composite material has a good appearance under the condition.
The invention also aims to provide the application of the Co/Fe-MOF LDHs composite material prepared by the preparation method in electrocatalytic oxygen evolution.
Mixing the Co/Fe-MOF LDHs composite material with a Nafion solution under an ultrasonic condition, and then modifying the mixture on the surface of a glassy carbon electrode to prepare a test electrode for electrocatalytic oxygen evolution reaction.
The electrode prepared by adding the Co/Fe-MOF LDHs composite material can reduce the overpotential during the OER reaction and improve the electrocatalytic performance.
Repeated experiments prove that the Co/Fe-MOF LDHs composite material with uniform appearance and high purity can be synthesized under the condition, and the method is the optimal process condition. The preparation method is simple to operate, does not need complex equipment, is mild in condition, and is easy to obtain precursor materials and controllable in process.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of the prepared Co/Fe-MOF LDHs composite material.
FIG. 2 is an X-ray diffraction pattern (XRD) of the Co/Fe-MOF LDHs composite material prepared by the invention.
FIG. 3 is an Infrared (IR) spectrum of the Co/Fe-MOF LDHs composite material prepared by the present invention.
FIG. 4 is a graph comparing oxygen evolution performance of Co/Fe-MOF LDHs composite material prepared by the present invention and comparative example 1.
Detailed Description
Firstly, preparing materials.
Example 1:
0.2719 g of cobalt sulfate heptahydrate (CoSO)4·7H2O), 0.009 g ferrous sulfate heptahydrate (FeSO)4·7H2O) was dissolved in 16 ml of deionized water to give a double metal salt solution.
1 mmol of 4, 4-bipyridine was dissolved in 8 ml of ethanol to obtain an ethanol solution of 4, 4-bipyridine.
Mixing the bimetallic salt solution and 4, 4-bipyridyl ethanol solution, adding 2 ml pyridine, stirring at room temperature for 25 min, and finally carrying out hydrothermal treatment on the solution at 100 ℃ for 24 h to obtain brown precipitate. And washing the product with deionized water and ethanol for three times respectively, and drying at room temperature to obtain the Co/Fe-MOF LDHs nano composite material.
Comparative example 1:
referring to example 1, FeSO was not added during the synthesis of the material4·7H2O pure Co-MOF nanocomposites were obtained, and the synthesis method, synthesis conditions and pyridine addition were all the same as in example 1.
And secondly, preparing an electrode material.
5 mg of the samples prepared in example 1 and comparative example 1 were ultrasonically mixed with 100. mu.L of Nafion solution (concentration: 1%), 300. mu.L of ethanol and 600. mu.L of deionized water, respectively, to prepare mixed solutions.
And (3) taking 5 mu L of mixed solution, coating the mixed solution on the surface of a clean glassy carbon electrode with the diameter of 3 mm, and naturally airing to obtain two working electrode samples.
And thirdly, testing the electrochemical performance.
And respectively carrying out linear volt-ampere scanning on the two working electrode samples under 0-0.8V, wherein the test methods and test conditions of the two samples are completely the same.
As can be clearly seen in FIG. 4, for the OER reaction, the Co/Fe-MOF LDHs nanocomposites are at 10mA cm-2The overpotential at (A) is 325mV, which is significantly lower than 379mV for pure Co-MOF nanocomposites. The undaria-shaped Co/Fe-MOF LDHs nanocomposite prepared by the invention also has good stability and wide application prospect in the field of energy storage and conversion.
Claims (6)
1. A preparation method of a Co/Fe-MOF LDHs composite material is characterized by comprising the following steps:
1) dissolving cobalt salt and ferric salt in deionized water to prepare a double-metal salt water solution;
2) dissolving 4, 4-bipyridine in ethanol to prepare a 4, 4-bipyridine ethanol solution;
3) and mixing the aqueous solution of the bimetallic salt, the 4, 4-bipyridyl ethanol solution and pyridine for hydrothermal reaction, washing and drying the obtained precipitate to obtain the Co/Fe-MOF LDHs composite material.
2. The method of claim 1, wherein the cobalt salt is CoSO4·7H2O, iron salt being FeSO4·7H2O。
3. The method according to claim 1, wherein the molar ratio of cobalt salt to iron salt is 30: 1.
4. The process of claim 1, wherein the molar ratio of the total amount of cobalt and iron salts to the charge of 4, 4-bipyridine is 1: 1.
5. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 100 ℃ for a period of 24 hours.
6. The application of the Co/Fe-MOF LDHs composite material prepared by the method of claim 1 in testing electrodes is characterized in that the Co/Fe-MOF LDHs composite material and Nafion solution are mixed under an ultrasonic condition and then are modified on the surface of a glassy carbon electrode, so that the testing electrode for electrocatalytic oxygen evolution reaction is prepared.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
| CN111995760A (en) * | 2020-07-17 | 2020-11-27 | 扬州大学 | Cobalt-metal organic framework nanosheet and preparation method and application thereof |
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- 2021-05-19 CN CN202110546690.0A patent/CN113249754A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995760A (en) * | 2020-07-17 | 2020-11-27 | 扬州大学 | Cobalt-metal organic framework nanosheet and preparation method and application thereof |
| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZEHUA ZOU ET. AL.: "Expediting in-Situ Electrochemical Activation of Two-Dimensional Metal−Organic Frameworks for Enhanced OER Intrinsic Activity by Iron Incorporation", 《ACS CATAL.》, vol. 9, pages 7356 * |
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