CN112481639A - Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material - Google Patents
Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
本发明提供了一种分等级多孔镍基金属有机骨架电催化材料的制备方法及应用，在低温下通过控制液相界面分层，调整不同层之间的溶液密度，在扩散控制的作用下，使得上层金属离子和底层配体分子于中间层界面处发生配位反应，反应产物沉淀在最底层，随后采用简单的离心收集即得到镍基金属有机骨架电催化材料（Ni‑M‑MOFs,M=Fe,Co,Cu,Mn,Zn),其可以直接作为碱性环境中高效的电解水阳极析氧反应（OER）电催化剂。该制备方法操作简便，成本低廉且具有一定的普适性，对于推动清洁和可再生能源的高效利用以及合理设计燃料电池、金属空气电池、水电解槽等装置具有重要意义。
The invention provides a preparation method and application of a graded porous nickel-based metal-organic framework electrocatalytic material. By controlling the liquid phase interface layering at low temperature, the solution density between different layers is adjusted, and under the action of diffusion control, The upper-layer metal ions and the bottom-layer ligand molecules undergo a coordination reaction at the interface of the intermediate layer, and the reaction products are precipitated at the bottom layer, and then simple centrifugal collection is used to obtain nickel-based metal-organic framework electrocatalytic materials (Ni‑M‑MOFs, M =Fe, Co, Cu, Mn, Zn), which can be directly used as an efficient electrocatalyst for the anodic oxygen evolution reaction (OER) of water electrolysis in an alkaline environment. The preparation method is easy to operate, low in cost, and has certain universality, which is of great significance for promoting the efficient utilization of clean and renewable energy and rationally designing devices such as fuel cells, metal-air batteries, and water electrolyzers.
Description
Technical Field
The invention belongs to the field of chemical energy materials, particularly relates to preparation of a metal organic framework electro-catalytic material, and particularly relates to a preparation method of a hierarchical porous nickel-based metal organic framework electro-catalytic material for catalyzing an anodic oxygen evolution reaction of electrolyzed water.
Background
With the increasing environmental pollution caused by the exhaustion of fossil fuels, the development of a new alternative clean energy is urgent. Hydrogen is a sustainable and environmentally friendly clean energy with a top combustion value and energy density and is favored by researchers, and how to efficiently produce hydrogen has become a research focus in recent years. The water electrolysis hydrogen production technology has become an ideal way for preparing hydrogen energy in the future because of the advantages of rich raw materials, good storability, high purity of products, strong adjustability and the like; however, in the technology, the anodic oxygen evolution reaction involves a complex four-electron reaction process, and the kinetics is very slow, so that the anodic oxygen evolution reaction becomes one of the main limiting factors for improving the hydrogen production efficiency of the electrolyzed water. In order to effectively improve the anode reaction kinetics, Ru and Ir-based catalysts are considered to be the most effective oxygen evolution reaction catalysts at present, but cannot realize the development and application of large-scale electrolytic water due to the influence of the factors such as high cost, scarcity, poor long-term stability and the like. Therefore, the search for efficient, inexpensive and earth-resource-abundant catalysts is currently a major research task.
Due to the periodicity of the nanoscale, the higher porosity and the adjustable chemical environment, the Metal Organic Framework (MOF) has an excellent application prospect in the aspects of gas storage, separation, drug delivery and the like, and is widely applied to the field of electrocatalysis in recent years. Among them, nickel-based MOF catalysts are receiving more and more attention due to their excellent activity and wide source, but single nickel metal materials cannot be directly used as anode oxygen evolution reaction electrocatalysts due to limited number of catalytic active sites, undesirable nano-morphology and extremely low conductivity, and cannot reach industrial production standards (current density of 500mA cm)-2And the overpotential is less than 300 mV). In order to effectively improve the catalytic activity of the oxygen evolution reaction, some traditional two-dimensional flaky nickel-based metal organic framework electrocatalytic materials prepared at present need to be compounded with carbon materials such as high-conductivity graphene or carbon black. Therefore, how to rationally develop a new catalyst material of low cost and high activity nickel-based MOF that can be directly used is still a very serious challenge.
Disclosure of Invention
In view of the above problems, the technical problem to be solved by the present invention is to provide a method for preparing a nickel-based metal organic framework electrocatalyst with low cost, high performance and high stability, which can be directly used. The method has the advantages of abundant raw material reserves, low price and simple preparation process, and the obtained nickel-based metal organic framework electro-catalysis material has a hierarchical porous structure, has excellent oxygen precipitation electro-catalysis performance, and has certain guiding significance for the commercial application of electrolyzed water.
In order to solve the problem, the invention prepares the bimetallic organic framework electro-catalytic material Ni-M-MOFs (M = Fe, Co, Cu, Mn, Zn), on one hand, the bimetallic synergistic effect is beneficial to increasing the number of active sites and improving the activity of the catalytic active sites; on the other hand, the doping of the metal element can effectively adjust the active site Ni2+With 3d orbital electron arrangement, via bridge O2-Realize the electron transfer of Ni-O-M, thereby improving the activity of the active site. Meanwhile, the formation of a graded porous structure is beneficial to enhancing the adsorption of oxygen-containing intermediates (OH, O and OOH) and oxygen (O)2) The releasing capacity of the catalyst can effectively improve the oxygen evolution reaction performance and the catalytic stability.
In particular, the invention successfully synthesizes a series of nickel-based metal organic framework electrocatalysis materials by adopting a simple interface induction strategy, so that the nickel-based metal organic framework electrocatalysis materials can be directly used as an efficient oxygen precipitation reaction electrocatalyst in an alkaline solution. The technical solution we have designed is mainly based on the following considerations: firstly, the metal organic framework electro-catalytic material has the advantages of higher specific surface area, adjustable chemical environment, abundant active sites, higher porosity and the like; secondly, a simple interface induction synthesis strategy is adopted, different solutions are utilized to have different densities, the diffusion directions of metal ions on the upper layer and ligand molecules on the bottom layer in the solutions on the different layers are different, the diffusion direction of the metal ions on the upper layer is from top to bottom, the diffusion direction of the ligand molecules on the bottom layer is from bottom to top, the metal ions and the ligand molecules are in coordination reaction after being contacted with each other on the middle layer, and the generated metal organic framework electrocatalytic material is precipitated on the bottommost layer by means of gravity. Meanwhile, in the process of further centrifugal collection, redundant ligand molecules and solvent molecules remained in pores of the metal organic framework electro-catalysis material can be removed through the cleaning action of the N, N-dimethylformamide and the trichloromethane, and the formation of a hierarchical pore structure (comprising micropores less than or equal to 2nm, mesopores of 2-50nm and macropores) is facilitated>50 nm) nickel-based metal organic framework electrocatalysisMaterial is changed; the formation of the hierarchical porous morphology is beneficial to the material transmission between the catalyst surface and the electrolyte, enhances the adsorption of oxygen-containing intermediates in the process of the anodic oxygen evolution reaction, obviously reduces the Gibbs free energy of the oxygen evolution reaction, and can accelerate the product (O)2) Thereby improving the catalytic activity and stability of the catalyst. In the process of the anodic oxygen evolution reaction of electrolyzed water, catalysts such as NiFe-MOF, NiCo-MOF and the like prepared by the method show unusual catalytic activity in an alkaline electrolyte system, which is obviously superior to commercial Ru-based catalysts and sheet nickel-based metal organic framework electrocatalytic materials prepared by most of traditional methods, and provides a new concept and approach for rational design and development of novel high-efficiency oxygen evolution reaction electrocatalysts.
Different from the traditional manufacturing method of the sheet nickel-based metal organic framework electro-catalytic material, the hierarchical porous nickel-based metal organic framework electro-catalytic material prepared in the invention enables metal ions on the upper layer and ligand molecules on the bottom layer to perform coordination reaction at the interface of the middle layer by controlling the layering of a liquid phase interface at low temperature and adjusting the solution density between different layers under the action of diffusion control, a reaction product is precipitated at the bottommost layer, and then the metal organic framework electro-catalytic material (Ni-M-MOFs, M = Fe, Co, Cu, Mn and Zn) is obtained by adopting simple centrifugal collection.
By using mixed solvents with different volume ratios, the solution density is different, and the solvent density of the upper layer, the middle layer and the lower layer is different. According to the diffusion law, the solute diffuses from a high-density position to a low-density position under the action of a chemical gradient, so that the diffusion direction of the solute between different layers is adjusted. In order to ensure that the formed porous structure is more uniform and ordered, and the formed porous structure is beneficial to the adsorption and desorption of an oxygen-containing intermediate in the process of anodic oxygen evolution reaction, the diffusion speed of solute is reasonably controlled. Researches find that under different temperatures of low temperature, room temperature, 50 ℃ and 100 ℃, the reaction speed is accelerated when the temperature is too high, which is not beneficial to the coordination reaction between metal ions and ligands; the diffusion speed is slowed down under the low temperature condition, and the formation of the hierarchical porous morphology is facilitated, so that the coordination reaction is carried out under the specific low temperature of-25 ℃. In addition, if the nickel-based metal organic framework electro-catalytic material is prepared in a mode of not adding an intermediate mixed solvent layer, the coordination reaction speed is remarkably increased, and the hierarchical porous morphology is difficult to form. Therefore, the method of adding the intermediate mixed solvent layer can slow down the diffusion speed, and is very favorable for forming the graded porous morphology.
The technical scheme adopted by the invention is as follows: dissolving a proper amount of 1, 4-terephthalic acid ligand powder and metal salt in a mixed solvent of N, N-dimethylformamide and acetonitrile respectively; respectively dripping the prepared solutions with different densities into a glass bottle to form a clear layered interface, standing for reaction to generate a sediment substance at the bottommost layer; and centrifuging the obtained precipitate, drying the precipitate at room temperature, and collecting the precipitate to obtain the nickel-based metal-organic framework electrocatalyst. In particular to a preparation method of a graded porous nickel-based metal organic framework electro-catalytic material, which comprises the following steps:
a) the pretreatment process comprises the following steps: weighing a certain amount of dicarboxylic acid ligand powder, dissolving the dicarboxylic acid ligand powder in a mixed solvent consisting of N, N-dimethylformamide and acetonitrile in a fixed proportion, stirring at room temperature at a certain rotating speed until the dicarboxylic acid ligand powder is completely dissolved, and preparing a solution A with a certain concentration; measuring N, N dimethylformamide and acetonitrile in a fixed proportion, stirring at room temperature at a certain rotating speed, and preparing a solution B; weighing a proper amount of bimetallic salt in proportion, dissolving the bimetallic salt in a mixed solvent consisting of N, N dimethylformamide and acetonitrile, stirring at room temperature at a certain rotating speed until the bimetallic salt is completely dissolved, and preparing a solution C with a certain concentration;
b) and (3) interface induction process: forming a layered solution with a clear interface by controlling the liquid phase density of the solution A, the solution B and the solution C at a low temperature, and precipitating a product at the bottom layer after reaction;
c) and (3) centrifugal collection process: and (c) placing the whole substance after the step (b) in a centrifuge tube, repeatedly centrifuging by using an organic solvent, collecting the centrifuged substance, and placing the centrifuge tube containing the centrifuged substance in a room-temperature environment for standing and drying for a period of time.
Further, in the step (B), a proper amount of the solution A is placed at the bottom of the glass bottle to form a solution bottom layer, a proper amount of the solution B is slowly dripped along the wall of the glass bottle to serve as an intermediate layer solution, a proper amount of the solution C is slowly dripped along the wall of the glass bottle to serve as an upper layer solution to form a layered solution with a clear interface, and the glass bottle is placed at a low temperature and stands for a period of time.
Further, in the step (b), the liquid phase density is controlled at low temperature to form a three-layer solution, the solution density between different layers is adjusted, under the action of diffusion control, ligand molecules on the upper layer and metal ions on the lower layer are subjected to coordination reaction at the interface, and reaction products are precipitated at the bottommost layer.
Further, the volume ratio of the solution A, the solution B and the solution C in the step (B) is 3: 2: 3 respectively; the standing time is 24h, and the standing temperature is-25 ℃.
Further, in the step (a), the volume ratio of N, N-dimethylformamide to acetonitrile in the solution A is 2: 1, the volume ratio of N, N-dimethylformamide to acetonitrile in the solution B is 1: 1, the volume ratio of N, N-dimethylformamide to acetonitrile in the solution C is 1: 2, and the stirring rotation speed is 800 rpm.
Further, in the step (a), the dicarboxylic acid ligand powder is 1, 4-terephthalic acid; the double metal salt is the combination of nickel acetate tetrahydrate and another substance, and the another substance is any one of ferrous acetate, cobalt acetate tetrahydrate, copper acetate monohydrate, manganese acetate tetrahydrate and zinc acetate dihydrate.
Further, in the step (c), the organic solvent is N, N-dimethylformamide and chloroform.
Further, in the step (c), centrifuging three times respectively by using N, N-dimethylformamide and chloroform, wherein the volume of the solvent used in each time is 3 mL; the standing and drying time is 12 h.
Furthermore, the preparation method can obtain NiFe-MOF, NiCo-MOF, NiCu-MOF, NiMn-MOF or NiZn-MOF with graded porous morphology.
Furthermore, the hierarchical porous nickel-based metal organic framework electrocatalysis material prepared by the method can be applied to the anodic oxygen evolution reaction of catalytic electrolysis water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method is simple and efficient, layering is carried out at a low temperature by controlling a liquid phase interface, solution density between different layers is adjusted, ligand molecules on an upper layer and metal ions on a bottom layer are diffused to an intermediate layer to carry out a coordination reaction under the action of diffusion control, a reaction product is precipitated on the bottom layer, and then the nickel-based metal organic framework electrocatalytic material (Ni-M-MOFs, M = Fe, Co, Cu, Mn and Zn) can be obtained by adopting simple centrifugal collection and can be directly used as an efficient oxygen evolution reaction electrocatalyst in an alkaline environment.
(2) The nickel-based metal organic framework electrocatalysis material with the hierarchical pore structure promotes the adsorption of oxygen-containing intermediates (OH, O and OOH) in the oxygen evolution reaction process, can realize rapid electron transfer and material transmission in an alkaline environment when being applied to the electrolytic water anodic oxygen evolution reaction, reduces the overpotential of the oxygen evolution reaction, and further shows excellent electrocatalysis performance.
(3) The invention has the advantages of low price of raw materials, low production cost and simple preparation process, and is a low-cost preparation method. The Ni-M-MOFs catalyst prepared by the method has the advantages of high specific surface area, excellent hierarchical porous structure and fully exposed active sites, and shows excellent oxygen evolution electrocatalytic activity and stability. The preparation method is simple and convenient to operate, low in cost and universal, and has important significance for promoting high-efficiency utilization of clean and renewable energy sources and reasonably designing devices such as fuel cells, metal-air cells and water electrolysis cells.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) and High Resolution Transmission Electron Microscope (HRTEM) image of a NiFe-MOF catalyst;
FIG. 2 shows Ni-MOF, NiFe-MOF and RuO2Linear Sweep Voltammetric (LSV) contrast images of the catalyst;
FIG. 3 is an X-ray diffraction (XRD) pattern of a Ni-M-MOFs (M = Fe, Co, Cu, Mn, Zn) catalyst;
FIG. 4 is an infrared (FT-IR) spectrum of a Ni-M-MOFs (M = Fe, Co, Cu, Mn, Zn) catalyst;
fig. 5 is a Raman spectroscopy (Raman) image of Ni-M-MOFs (M = Fe, Co, Cu, Mn, Zn) catalysts.
Detailed Description
The invention will now be described with reference to the following specific examples, but is not limited to the examples.
Example 1: preparation of NiFe-MOF oxygen evolution catalyst
Weighing 80 mg of 1, 4-terephthalic acid powder, dissolving in a mixed solvent consisting of 16mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring and dissolving at room temperature for 2 hours to obtain a solution A; measuring 8mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring at room temperature for 2h to obtain a solution B; weighing a proper amount of nickel acetate tetrahydrate and ferrous acetate, dissolving the nickel acetate tetrahydrate and the ferrous acetate in a mixed solvent consisting of 8mL of N, N-dimethylformamide and 16mL of acetonitrile, and fully stirring the mixture for 2 hours at room temperature to obtain a solution C. And then in the stirring process, 3mL of the solution A is dripped into the bottom of a glass bottle, 2mL of the solution B is placed on the upper layer of the solution A to form a middle layer solution, 3mL of the solution C is placed on the upper layer of the solution B, and the glass bottle which is obviously layered is placed in a low-temperature environment and is kept stand to react for 24 hours. And then centrifuging at 10000 rpm for 20min, repeatedly washing with N, N dimethylformamide/chloroform solvent for 3 times, and drying the obtained precipitate at room temperature for 12h to obtain NiFe-MOF powder which can be used as an oxygen evolution reaction electrocatalyst.
Example 2: preparation of NiCo-MOF oxygen evolution catalyst
Weighing 80 mg of 1, 4-terephthalic acid powder, dissolving in a mixed solvent consisting of 16mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring and dissolving at room temperature for 2 hours to obtain a solution A; measuring 8mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring at room temperature for 2h to obtain a solution B; weighing a proper amount of nickel acetate tetrahydrate and cobalt acetate tetrahydrate, dissolving the nickel acetate tetrahydrate and the cobalt acetate tetrahydrate in a mixed solvent consisting of 8mL of N, N-dimethylformamide and 16mL of acetonitrile, and fully stirring the mixture for 2 hours at room temperature to obtain a solution C. And then in the stirring process, 3mL of the solution A is dripped into the bottom of a glass bottle, 2mL of the solution B is placed on the upper layer of the solution A to form a middle layer solution, 3mL of the solution C is placed on the upper layer of the solution B, and the glass bottle which is obviously layered is placed in a low-temperature environment and is kept stand to react for 24 hours. And then centrifuging at 10000 rpm for 20min, repeatedly washing with N, N dimethylformamide/chloroform solvent for 3 times, and drying the obtained precipitate at room temperature for 12h to obtain NiCo-MOF powder which can be used as an oxygen evolution reaction electrocatalyst.
Example 3: preparation of NiCu-MOF oxygen evolution catalyst
Weighing 80 mg of 1, 4-terephthalic acid powder, dissolving in a mixed solvent consisting of 16mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring and dissolving at room temperature for 2 hours to obtain a solution A; measuring 8mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring at room temperature for 2h to obtain a solution B; weighing a proper amount of nickel acetate tetrahydrate and copper acetate monohydrate, dissolving in a mixed solvent consisting of 8mL of N, N-dimethylformamide and 16mL of acetonitrile, and fully stirring for 2h at room temperature to obtain a solution C. And then in the stirring process, 3mL of the solution A is dripped into the bottom of a glass bottle, 2mL of the solution B is placed on the upper layer of the solution A to form a middle layer solution, 3mL of the solution C is placed on the upper layer of the solution B, and the glass bottle which is obviously layered is placed in a low-temperature environment and is kept stand to react for 24 hours. And then centrifuging at 10000 rpm for 20min, repeatedly washing with N, N dimethylformamide/chloroform solvent for 3 times, and drying the obtained precipitate at room temperature for 12h to obtain NiCu-MOF powder which can be used as an oxygen evolution reaction electrocatalyst.
Example 4: preparation of NiMn-MOF oxygen evolution catalyst
Weighing 80 mg of 1, 4-terephthalic acid powder, dissolving in a mixed solvent consisting of 16mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring and dissolving at room temperature for 2 hours to obtain a solution A; measuring 8mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring at room temperature for 2h to obtain a solution B; weighing a proper amount of nickel acetate tetrahydrate and manganese acetate tetrahydrate, dissolving the nickel acetate tetrahydrate and the manganese acetate tetrahydrate in a mixed solvent consisting of 8mL of N, N-dimethylformamide and 16mL of acetonitrile, and fully stirring the mixture for 2 hours at room temperature to obtain a solution C. And then in the stirring process, 3mL of the solution A is dripped into the bottom of a glass bottle, 2mL of the solution B is placed on the upper layer of the solution A to form a middle layer solution, 3mL of the solution C is placed on the upper layer of the solution B, and the glass bottle which is obviously layered is placed in a low-temperature environment and is kept stand to react for 24 hours. And then centrifuging at 10000 rpm for 20min, repeatedly washing with N, N dimethylformamide/chloroform solvent for 3 times, and drying the obtained precipitate at room temperature for 12h to obtain NiMn-MOF powder which can be used as an oxygen evolution reaction electrocatalyst.
Example 5: preparation of NiZn-MOF oxygen evolution catalyst
Weighing 80 mg of 1, 4-terephthalic acid powder, dissolving in a mixed solvent consisting of 16mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring and dissolving at room temperature for 2 hours to obtain a solution A; measuring 8mL of N, N-dimethylformamide and 8mL of acetonitrile, and fully stirring at room temperature for 2h to obtain a solution B; weighing a proper amount of nickel acetate tetrahydrate and zinc acetate dihydrate, dissolving the nickel acetate tetrahydrate and the zinc acetate dihydrate in a mixed solvent consisting of 8mL of N, N-dimethylformamide and 16mL of acetonitrile, and fully stirring the mixture for 2 hours at room temperature to obtain a solution C. And then in the stirring process, 3mL of the solution A is dripped into the bottom of a glass bottle, 2mL of the solution B is placed on the upper layer of the solution A to form a middle layer solution, 3mL of the solution C is placed on the upper layer of the solution B, and the glass bottle which is obviously layered is placed in a low-temperature environment and is kept stand to react for 24 hours. And then centrifuging at 10000 rpm for 20min, repeatedly washing with N, N dimethylformamide/chloroform solvent for 3 times, and drying the obtained precipitate at room temperature for 12h to obtain NiZn-MOF powder which can be used as an oxygen evolution reaction electrocatalyst.
Application example 1
Before use, the carbon cloth is firstly respectively subjected to ultrasonic treatment for 20min by acetone (30 ml), deionized ethanol (30 ml) and deionized water (30 ml) in an ultrasonic instrument, and then is placed in a vacuum oven at 50 ℃ for 24 h. Simultaneously, catalyst ink was prepared according to the following steps: 5 mg of the prepared MOF powder in the solution was dispersed in a mixed solvent of water/isopropanol/Nafion in a volume ratio of 4/1/0.1, and uniformly dispersed ink was obtained by ultrasonic treatment. Finally, will50 μ L of the above catalyst suspension was dropped onto the surface of a carbon cloth electrode, and then dried at room temperature using an infrared lamp, followed by conducting an oxygen evolution reaction test. The mass loading was calculated to be 1 mg/cm for all samples2. Then, taking the prepared Fe/Ni-MOF catalyst as an example, the performance of the oxygen evolution catalytic reaction was tested on the catalyst modified electrode by using the NiFe-MOF catalyst obtained in example 1 as a working electrode, a saturated Hg/HgO electrode as a reference electrode, a carbon rod as a counter electrode, and a chenhua CHI-660E electrochemical workstation.
In 1.0M KOH alkaline solution, the modified electrode of the obtained NiFe-MOF catalyst has optimal oxygen evolution catalytic activity. At a current density of 10 mA/cm2When the overpotential is 217 mV, the Tafel slope is 50.5 mV dec-1While at a high current density of 500 mA/cm2When the overpotential is 297 mV, the standard of industrial application is met (the current density is 500 mA/cm)2Overpotential less than 300 mV), far beyond commercial RuO2The performance of the catalyst and the performance of most sheet-shaped transition metal-based metal organic framework catalysts prepared by the traditional method have important significance for promoting the commercialization process of hydrogen production by water electrolysis. Example 1 NiFe-MOF catalyst modified electrode at 10 mA/cm2Long-term stability test was performed, no significant performance degradation occurred after 40 h, whereas commercial RuO2The catalyst has obvious performance decay change, which shows that the NiFe-MOF catalyst prepared by the method has good stability.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113702472A (en) * | 2021-09-01 | 2021-11-26 | 吉林大学 | (Ni1-xFex) Mixed potential type room temperature NO sensor with-MOF as sensitive electrode and preparation method thereof |
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008020218A1 (en) * | 2006-08-17 | 2008-02-21 | The University Court Of The University Of St Andrews | Adsorption and release of nitric oxide in metal organic frameworks |
| CN106279053A (en) * | 2016-08-10 | 2017-01-04 | 大连理工大学 | A kind of preparation method of the MOFs with π activating catalytic effect |
| CN106582887A (en) * | 2016-12-12 | 2017-04-26 | 南京工业大学 | Novel catalyst based on metal organic framework material and preparation method and application thereof |
| CN108051418A (en) * | 2017-12-23 | 2018-05-18 | 福州大学 | A kind of fluorescent optical sensor for detecting inorganic pyrophosphatase and preparation method thereof |
| CN108080034A (en) * | 2017-12-29 | 2018-05-29 | 济南大学 | One kind is based on Ni-based 3-dimensional metal organic framework method for preparing catalyst and application |
| CN108187751A (en) * | 2018-01-11 | 2018-06-22 | 三峡大学 | A kind of preparation method and applications of isomorphism metal-organic framework material |
| CN108772103A (en) * | 2018-05-24 | 2018-11-09 | 南京工业大学 | Bimetallic MOF catalyst, preparation method and application |
| CN109126480A (en) * | 2018-09-04 | 2019-01-04 | 同济大学 | Modified forward osmosis membrane of a kind of metal organic frame nanometer sheet and its preparation method and application |
| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN110423356A (en) * | 2019-07-09 | 2019-11-08 | 漳州致一环保科技有限公司 | Detect the synthesis and application of hypoxanthic metal-organic framework materials in the flesh of fish |
| CN110449046A (en) * | 2019-08-07 | 2019-11-15 | 恩泰环保科技（常州）有限公司 | Modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof |
| CN110467731A (en) * | 2019-07-25 | 2019-11-19 | 北京科技大学 | A kind of preparation method for stablizing ultra-thin mesoporous metal organic framework materials |
| CN111044590A (en) * | 2019-11-26 | 2020-04-21 | 云南大学 | CuNi-MOF nano-material modified electrode and application thereof |
| CN111318305A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Non-noble metal bifunctional catalyst and preparation method and application thereof |
| CN111905818A (en) * | 2020-07-13 | 2020-11-10 | 苏州科技大学 | A MOF-based two-dimensional ultrathin electrocatalyst and its preparation method and application |
| US20200354845A1 (en) * | 2019-05-10 | 2020-11-12 | Bin Mu | Two-dimensional metal-organic framework alloy photocatalysts |
-
2020
- 2020-12-01 CN CN202011375604.6A patent/CN112481639B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008020218A1 (en) * | 2006-08-17 | 2008-02-21 | The University Court Of The University Of St Andrews | Adsorption and release of nitric oxide in metal organic frameworks |
| CN106279053A (en) * | 2016-08-10 | 2017-01-04 | 大连理工大学 | A kind of preparation method of the MOFs with π activating catalytic effect |
| CN106582887A (en) * | 2016-12-12 | 2017-04-26 | 南京工业大学 | Novel catalyst based on metal organic framework material and preparation method and application thereof |
| CN108051418A (en) * | 2017-12-23 | 2018-05-18 | 福州大学 | A kind of fluorescent optical sensor for detecting inorganic pyrophosphatase and preparation method thereof |
| CN108080034A (en) * | 2017-12-29 | 2018-05-29 | 济南大学 | One kind is based on Ni-based 3-dimensional metal organic framework method for preparing catalyst and application |
| CN108187751A (en) * | 2018-01-11 | 2018-06-22 | 三峡大学 | A kind of preparation method and applications of isomorphism metal-organic framework material |
| CN108772103A (en) * | 2018-05-24 | 2018-11-09 | 南京工业大学 | Bimetallic MOF catalyst, preparation method and application |
| CN109126480A (en) * | 2018-09-04 | 2019-01-04 | 同济大学 | Modified forward osmosis membrane of a kind of metal organic frame nanometer sheet and its preparation method and application |
| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN111318305A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Non-noble metal bifunctional catalyst and preparation method and application thereof |
| US20200354845A1 (en) * | 2019-05-10 | 2020-11-12 | Bin Mu | Two-dimensional metal-organic framework alloy photocatalysts |
| CN110423356A (en) * | 2019-07-09 | 2019-11-08 | 漳州致一环保科技有限公司 | Detect the synthesis and application of hypoxanthic metal-organic framework materials in the flesh of fish |
| CN110467731A (en) * | 2019-07-25 | 2019-11-19 | 北京科技大学 | A kind of preparation method for stablizing ultra-thin mesoporous metal organic framework materials |
| CN110449046A (en) * | 2019-08-07 | 2019-11-15 | 恩泰环保科技（常州）有限公司 | Modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof |
| CN111044590A (en) * | 2019-11-26 | 2020-04-21 | 云南大学 | CuNi-MOF nano-material modified electrode and application thereof |
| CN111905818A (en) * | 2020-07-13 | 2020-11-10 | 苏州科技大学 | A MOF-based two-dimensional ultrathin electrocatalyst and its preparation method and application |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113702472A (en) * | 2021-09-01 | 2021-11-26 | 吉林大学 | (Ni1-xFex) Mixed potential type room temperature NO sensor with-MOF as sensitive electrode and preparation method thereof |
| CN113754894A (en) * | 2021-09-01 | 2021-12-07 | 华中科技大学 | Asymmetric coordination double-site metal organic framework nano material and preparation method and application thereof |
| CN114540831A (en) * | 2021-11-30 | 2022-05-27 | 上海科技大学 | Nickel-iron bimetal coordination polymer catalyst for water electrolysis and preparation method thereof |
| CN114540831B (en) * | 2021-11-30 | 2023-08-04 | 上海科技大学 | A nickel-iron bimetallic coordination polymer catalyst for electrolysis of water and preparation method thereof |
| CN114438516A (en) * | 2022-02-16 | 2022-05-06 | 中国海洋大学 | Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction |
| CN114438516B (en) * | 2022-02-16 | 2023-12-19 | 中国海洋大学 | Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction |
| CN114752071A (en) * | 2022-05-17 | 2022-07-15 | 安徽师范大学 | Cobalt-manganese bimetal organic framework material, preparation method thereof and application thereof in ethylbenzene C-H bond selective oxidation reaction |
| CN114752071B (en) * | 2022-05-17 | 2023-12-19 | 安徽师范大学 | Cobalt-manganese bimetal organic framework material, preparation method thereof and application thereof in ethylbenzene C-H bond selective oxidation reaction |
| CN115044940A (en) * | 2022-05-31 | 2022-09-13 | 重庆大学溧阳智慧城市研究院 | Method for producing hydrogen by electrocatalytic oxidation of ammonia by bimetallic NiCu-MOF anode |
| CN114892184A (en) * | 2022-06-11 | 2022-08-12 | 蚌埠学院 | Preparation method of MOFs derivative electrocatalyst |
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