CN111320759B - Environment-friendly two-dimensional nanowall MOF material and preparation method thereof - Google Patents
Environment-friendly two-dimensional nanowall MOF material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon material preparation, and particularly relates to an environment-friendly method for preparing a terpyridine Metal Organic Framework (MOF) two-dimensional nano wall array structure. The preparation method comprises the following steps: (1) immersing the three-dimensional porous foamed nickel material substrate into a hydrochloric acid solution to obtain an activated three-dimensional porous foamed nickel material substrate (2), dispersing copper metal salt, cobalt metal salt and a certain amount of terpyridine ligand in deionized water according to a certain proportion, and transferring the mixture to a polytetrafluoroethylene hydrothermal reaction kettle inner container; then, the substrate is immersed into the solution for hydrothermal reaction, and the two-dimensional MOF material with the nanowall array-like structure is prepared. The bimetallic MOF material synthesized by the method has a large-current effect, and meanwhile, the copper-cobalt MOF material with a two-dimensional nanowall array structure provided by the invention takes water as a solvent, and the pH value of the solution before and after reaction is neutral, so that the material is harmless to the environment.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to an environment-friendly method for preparing a terpyridine Metal Organic Framework (MOF) two-dimensional nano wall array structure.
Background
The first class of MOFs was synthesized as early as the 90's of the 20 th century, but its porosity and chemical stability were not high. Thus, scientists have begun investigating novel cationic, anionic and neutral ligand-forming coordination polymers. At present, a large number of metal organic framework materials are synthesized, mainly by carboxyl-containing organic anionic ligands or by using nitrogen-containing heterocyclic organic neutral ligands together. Many of these metal-organic frameworks have high porosity and good chemical stability. In recent years, Metal Organic Framework (MOF) and its derivative nano-materials have the characteristics of high porosity, large specific surface area, regular periodic structure, diversity of metal center and ligand, adjustable functionalization and the like, and have attracted the research interest of broad researchers in the fields of catalysis, energy storage, conversion and the like.
Today, there are many methods for making MOF materials, mainly:
(1) a solvent method: in the presence of water or organic solvent, a stainless steel high-pressure reaction kettle or a glass test tube with a polytetrafluoroethylene lining is used for heating a raw material mixture, and a high-quality single crystal is obtained by reaction under the self pressure;
(2) liquid phase diffusion method: mixing metal salt, organic ligand and proper solvent according to a certain proportion, putting the mixture into a small glass bottle, putting the small glass bottle into a large bottle, putting a protonized solvent into the large glass bottle, sealing the bottle cap, standing, and generating MOFs crystals after a period of time;
(3) other methods are as follows: many new production methods have been developed in recent years, including sol-gel method, stirring synthesis method, solid phase synthesis method, microwave, ultrasonic wave, and ion thermal method.
However, there are many reports on the preparation method of two-dimensional MOF material, most of which are that three-dimensional layered structure is peeled by chemical or physical method to obtain two-dimensional material, but the method is difficult to control, and the thickness of the peeled material is not uniform and the efficiency is low. In addition, most of the traditional synthetic methods use organic solvents, which causes great pollution to the environment; in addition, the reaction process is complex and long in time consumption and high in cost.
Aiming at the defects of the traditional synthetic method, it is necessary to develop an environment-friendly, simple and economic preparation method of the two-dimensional material.
Disclosure of Invention
Aiming at the defects of the existing method, the invention provides an environment-friendly method for preparing a terpyridine Metal Organic Framework (MOF) two-dimensional nanowall array structure, the method improves the preparation process of the material in a pertinence manner, and selects and optimizes key process parameters and raw material types in the preparation process, so that a copper-cobalt MOF new material with excellent two-dimensional nanowall array structure and better comprehensive properties such as conductivity, stability and the like than common MOF materials is obtained correspondingly. The technical scheme of the method is realized in water, and the method provides a new direction for green preparation of the MOF material. The technical scheme of the invention is realized as follows:
the invention provides a two-dimensional copper-cobalt MOF material with a nano-wall array structure and a preparation method thereof, and the preparation method comprises the following procedures and steps:
a first step: preparing a porous nickel foam material: the invention is prepared from the commercial foam three-dimensional porous nickel foam material
Composition of the foamed nickel: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
the formula of the activating solution is as follows: HCL with a concentration of 1-10 mol/L
The activation process comprises the following steps: the temperature is 25-60 ℃ and the time is 15-45 min.
And (3) activating the three-dimensional porous foamed nickel material according to the formula and the process, removing oxide skin on the surface of the three-dimensional porous foamed nickel material, taking out and drying to obtain the activated three-dimensional porous foamed nickel material substrate.
A third step of: a one-step synthesis method is used for preparing the copper-cobalt bimetallic MOF material,
the working procedure is that the copper-cobalt bimetallic MOF material is prepared by one-step synthesis in a high-pressure reaction kettle by a hydrothermal method on the activated three-dimensional porous foamed nickel material substrate prepared in the working procedure (II).
Further, the process comprises the following 4 steps:
step 1: raw material preparation
Taking copper sulfate pentahydrate and cobalt chloride hexahydrate as analytically pure, wherein the copper sulfate pentahydrate: 10-50 mg, cobalt chloride hexahydrate: 10-50 mg of a surfactant, in an amount of 10-50 mg,
taking deionized water: 20ml of each experiment
Step 2: preparing reaction equipment: high-pressure reactor, specification and model: 25ml, polytetrafluoroethylene inner container.
And step 3: synthesis of 4-phenyl terpyridine ligand:
further, step 3 comprises
(1) Preparing synthetic raw materials: the 2-acetylpyridine, the benzaldehyde and the absolute ethyl alcohol are analytically pure, wherein 4.8456g of the 2-acetylpyridine and 2.2122g of the benzaldehyde are taken and stirred and dispersed in 100ml of the absolute ethyl alcohol to prepare solution A;
taking potassium hydroxide and 30% ammonia water as analytical reagents, wherein 3.08g of potassium hydroxide and 60ml of ammonia water are taken, and the potassium hydroxide is ultrasonically dissolved in the ammonia water to prepare solution B;
(2) synthesis of
Slowly dripping the solution B into the solution A under the condition of strong stirring, wherein the reaction temperature is 34 ℃, and the reaction time is 24 hours; after the reaction is completed, the product is filtered and washed, wherein deionized water is used for washing for 3 times, and after ice ethanol is used for washing for three times, the product is dried for 12 hours at the temperature of 40 ℃; to obtain the 4-phenyl terpyridine ligand.
And 4, step 4: preparation of MOF material:
adding 20ml of deionized water into a high-pressure reaction kettle, then respectively weighing copper sulfate pentahydrate and cobalt chloride hexahydrate, and adding into the reaction kettle; and (3) adding a ligand (4-phenyl terpyridine), carrying out ultrasonic dissolution completely, then placing the activated three-dimensional porous foamed nickel material substrate obtained in the step (II) into a solution in a reaction kettle, and carrying out hydrothermal reaction for 24 hours at 150 ℃.
And taking out and naturally airing to obtain the environment-friendly bimetallic MOF material with the two-dimensional nano-wall array structure.
Electrochemical test results:
the prepared MOF material is used for a working electrode of an OER linear cyclic voltammetry test, and the purpose that the working electrode reaches 300mA/cm at 0.4-1V2The above current density. This demonstrates the excellent oxygen evolution properties of the present materials.
Compared with the prior art and the corresponding material, the technical scheme and the prepared catalytic material have the following beneficial effects:
1. the invention provides an environment-friendly method for preparing a terpyridine Metal Organic Framework (MOF) two-dimensional nano wall array structure.
2. According to the copper-cobalt MOF material with the two-dimensional nano-wall array structure, which is prepared by a hydrothermal method, the components of the material are combined by chemical bonds, so that the stability of the material is good.
3. According to the copper-cobalt MOF material with the two-dimensional nanowall array structure, water is used as a solvent, and the pH value of the solution before and after reaction is neutral, so that the copper-cobalt MOF material is harmless to the environment.
4. The hydrothermal method is simple, safe and environment-friendly, and the high-quality crystalline catalytic material is prepared.
5. The copper-cobalt MOF material with the two-dimensional nano wall array structure has a large-current effect, and can reach 300mA/cm in a voltage window of 0.4-1V in an OER test2The above current density.
In a word, the method is safe, rapid, simple and convenient, and the prepared material has good catalytic performance and does not need subsequent treatment. The invention provides a copper-cobalt MOF material with a two-dimensional nano wall array structure and a preparation method thereof, which have wide application prospects in the fields of catalysis, separation, sensing, microelectronic devices and the like.
Drawings
FIG. 1 is a schematic view of the preparation process
FIG. 2 photo picture of different samples during preparation
FIG. 3 is a Scanning Electron Microscope (SEM) image of a copper-cobalt bimetallic MOF material with a two-dimensional nano-wall array structure
FIG. 4 is a Transmission Electron Microscope (TEM) image of a copper-cobalt bimetallic MOF material with a two-dimensional nanowall array structure
FIG. 5 is an OER linear cyclic voltammogram of a copper-cobalt bimetallic MOF material with a two-dimensional nanowall array structure
Detailed description of the invention
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a two-dimensional copper-cobalt MOF material with a nano-wall array structure and a preparation method thereof, and the preparation method comprises the following procedures and steps:
a first step: preparing a porous nickel foam material: taking a commercially available foam three-dimensional porous nickel foam material, and comprising the following components: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
the formula of the activating solution is as follows: HCL with a concentration of 1-10 mol/L
The activation process comprises the following steps: the temperature is 25-60 ℃ and the time is 15-45 min.
And (3) activating the three-dimensional porous foamed nickel material according to the formula and the process, removing oxide skin on the surface of the three-dimensional porous foamed nickel material, taking out and drying to obtain the activated three-dimensional porous foamed nickel material substrate.
A third step of: the one-step synthesis method is used for preparing the copper-cobalt bimetallic MOF material, and comprises the following steps:
step 1: preparing raw materials:
taking copper sulfate pentahydrate: 10-50 mg, cobalt chloride hexahydrate: 10-50 mg of a surfactant, in an amount of 10-50 mg,
taking deionized water: 20ml of each experiment
Step 2: reaction equipment: high-pressure reactor, specification and model: 25ml, polytetrafluoroethylene inner container.
And step 3: synthesis of 4-phenyl terpyridine ligand:
4.8456g of 2-acetylpyridine and 2.2122g of benzaldehyde are taken, stirred and dispersed in 100ml of absolute ethyl alcohol to prepare solution A; taking 3.08g of potassium hydroxide and 60ml of 30% ammonia water, and ultrasonically dissolving the potassium hydroxide in the ammonia water to prepare solution B;
slowly dripping the solution B into the solution A under the condition of strong stirring, wherein the reaction temperature is 34 ℃, and the reaction time is 24 hours; after the reaction is completed, the product is filtered and washed, wherein deionized water is used for washing for 3 times, and after ice ethanol is used for washing for three times, the product is dried for 12 hours at the temperature of 40 ℃; to obtain the 4-phenyl terpyridine ligand.
And 4, step 4: preparation of MOF material:
adding 20ml of deionized water into a high-pressure reaction kettle, then respectively weighing copper sulfate pentahydrate and cobalt chloride hexahydrate, and adding into the reaction kettle; and (3) adding a ligand (4-phenyl terpyridine), carrying out ultrasonic dissolution completely, then placing the activated three-dimensional porous foamed nickel material substrate obtained in the step (II) into a solution in a reaction kettle, and carrying out hydrothermal reaction for 24 hours at 150 ℃.
And taking out and naturally airing to obtain the environment-friendly bimetallic MOF material with the two-dimensional nano-wall array structure.
The electrochemical test is carried out by using the material as a working electrode. The following are examples:
example 1:
taking a commercially available foam three-dimensional porous nickel foam material as a first step, wherein the first step comprises the following components: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
HCL with concentration of 1mol/L, temperature of 60 ℃ and time of 45 min.
A third step of: preparing a copper-cobalt bimetallic MOF material:
step 1: taking copper sulfate pentahydrate: 10mg, cobalt chloride hexahydrate: 50mg, deionized water: 20ml of each experiment
Step 2: the autoclave was prepared in accordance with the above-mentioned "detailed description".
And step 3: the 4-phenyl terpyridine ligand was synthesized as described above in "detailed description".
And 4, step 4: preparation of the MOF material synthesized as described above for the "detailed implementation method":
electrochemical test results:
when the prepared MOF material is used for a working electrode of an OER (organic electroluminescent) linear cyclic voltammetry test, as shown in figure 5, 350mA/cm can be reached2The required potential of the high current of (2) is 1.65V at a current density of 10mA/cm 2. This demonstrates the excellent OER performance of the present material.
Example 2:
taking a commercially available foam three-dimensional porous nickel foam material as a first step, wherein the first step comprises the following components: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
HCL, concentration 3mol/L, temperature 40 ℃, time 30 min.
A third step of: preparing a copper-cobalt bimetallic MOF material:
step 1: taking copper sulfate pentahydrate: 20mg, cobalt chloride hexahydrate: 30mg, taking deionized water: 20ml of each experiment
Step 2: the autoclave was prepared in accordance with the above-mentioned "detailed description".
And step 3: the 4-phenyl terpyridine ligand was synthesized as described above in "detailed description".
And 4, step 4: preparation of the MOF material synthesized as described above for the "detailed implementation method":
electrochemical test results:
when the prepared MOF material is used for a working electrode of an OER linear cyclic voltammetry test, a large current of 350mA/cm2 can be reached as shown in figure 5, and the required potential is 1.61V at a current density of 10mA/cm 2. This demonstrates the excellent OER performance of the present material.
Example 3:
taking a commercially available foam three-dimensional porous nickel foam material as a first step, wherein the first step comprises the following components: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
HCl with concentration of 7mol/L, temperature of 35 ℃ and time of 25 min.
A third step of: preparing a copper-cobalt bimetallic MOF material:
step 1: taking copper sulfate pentahydrate: 35mg, cobalt chloride hexahydrate: 20mg, taking deionized water: 20ml of each experiment
Step 2: the autoclave was prepared in accordance with the above-mentioned "detailed description".
And step 3: the 4-phenyl terpyridine ligand was synthesized as described above in "detailed description".
And 4, step 4: preparation of the MOF material synthesized as described above for the "detailed implementation method":
electrochemical test results:
when the prepared MOF material is used for a working electrode of an OER linear cyclic voltammetry test, a large current of 350mA/cm2 can be reached as shown in figure 5, and the required potential is 1.57V at a current density of 10mA/cm 2. This demonstrates the excellent OER performance of the present material.
Example 4:
taking a commercially available foam three-dimensional porous nickel foam material as a first step, wherein the first step comprises the following components: the nickel content is 99.8%; specification size: 10mm by 20mm by 1 mm;
a second step: preparing an activated three-dimensional porous foamed nickel material substrate:
HCL, concentration 10mol/L, temperature 25 ℃, time 15 min.
A third step of: preparing a copper-cobalt bimetallic MOF material:
step 1: taking copper sulfate pentahydrate: 50mg, cobalt chloride hexahydrate: 10mg, taking deionized water: 20ml of each experiment
Step 2: the autoclave was prepared in accordance with the above-mentioned "detailed description".
And step 3: the 4-phenyl terpyridine ligand was synthesized as described above in "detailed description".
And 4, step 4: preparation of the MOF material synthesized as described above for the "detailed implementation method":
electrochemical test results:
when the prepared MOF material is used for a working electrode of an OER linear cyclic voltammetry test, a large current of 350mA/cm2 can be reached as shown in figure 5, and the required potential is 1.6V at a current density of 10mA/cm 2. This demonstrates the excellent OER performance of the present material.
It is easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and all two-dimensional nanowall array structures formed by self-assembly of 4-phenyl terpyridine as ligand and water as solvent are included in the scope of the present invention; any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The preparation method of the environment-friendly two-dimensional copper-cobalt MOF material with the nano-wall array structure is characterized by comprising the following steps of:
step (I) and preparation of foamed nickel: taking a commercially available three-dimensional porous foamed nickel material;
step (II), preparing an activated three-dimensional porous foamed nickel material substrate:
activating the three-dimensional porous foamed nickel material in a hydrochloric acid solution to remove oxide skin on the surface of the three-dimensional porous foamed nickel material, and then taking out and drying to obtain an activated three-dimensional porous foamed nickel material substrate;
step (three), preparing the copper-cobalt bimetallic MOF material by a one-step synthesis method: the working procedure is that the activated three-dimensional porous foamed nickel material substrate prepared in the working procedure (II) is subjected to one-step synthesis in a high-pressure reaction kettle by a hydrothermal method to prepare the copper-cobalt bimetallic MOF material, and the preparation method for preparing the copper-cobalt bimetallic MOF material by the one-step synthesis method comprises the following 4 steps:
step 1: preparing raw materials: taking copper sulfate pentahydrate and cobalt chloride hexahydrate as analytically pure, wherein the copper sulfate pentahydrate: 10-50 mg, cobalt chloride hexahydrate: 10-50 mg, taking deionized water: 20ml of the test solution is used for each time;
step 2: preparing reaction equipment: high-pressure reactor, specification and model: 25ml of polytetrafluoroethylene inner container;
and step 3: synthesis of 4-phenyl terpyridine ligand: synthesizing 4-phenyl terpyridine ligand according to a method commonly used in the organic synthesis industry;
and 4, step 4: preparation of MOF material:
adding 20ml of deionized water into a high-pressure reaction kettle, then respectively weighing copper sulfate pentahydrate and cobalt chloride hexahydrate, and adding into the reaction kettle; and then adding 4-phenyl terpyridine as a ligand, after completely dissolving by ultrasonic wave, placing the activated three-dimensional porous foamed nickel material substrate obtained in the step (II) into the solution in a reaction kettle, and carrying out hydrothermal reaction for 24 hours at 150 ℃.
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| CN108315760A (en) * | 2018-03-29 | 2018-07-24 | 首都师范大学 | A kind of metal organic frame/foamed nickel electrode material and its preparation method and application |
| CN108492999A (en) * | 2018-02-01 | 2018-09-04 | 四川大学 | A method of three-dimensional structure Co-MOF/NF electrode material for super capacitor is prepared in situ based on nickel foam |
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| CN108492999A (en) * | 2018-02-01 | 2018-09-04 | 四川大学 | A method of three-dimensional structure Co-MOF/NF electrode material for super capacitor is prepared in situ based on nickel foam |
| CN108315760A (en) * | 2018-03-29 | 2018-07-24 | 首都师范大学 | A kind of metal organic frame/foamed nickel electrode material and its preparation method and application |
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