CN111822024A - Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof - Google Patents
Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- 239000012621 metal-organic framework Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 16
- FTMQVUCTIMHDLZ-UHFFFAOYSA-N 2-(4-phenylpyridin-2-yl)-3-pyridin-2-ylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC(C=2C(=CC=CN=2)C=2N=CC=CC=2)=C1 FTMQVUCTIMHDLZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 14
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
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- 239000006261 foam material Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 150000001879 copper Chemical class 0.000 claims 1
- 239000012085 test solution Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
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- 239000002184 metal Substances 0.000 abstract description 3
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- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
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- 239000011521 glass Substances 0.000 description 4
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention belongs to the technical field of carbon material preparation, and particularly relates to an environment-friendly copper-iron MOF material with a two-dimensional nanowall array structure and controllable iron content and a preparation method thereof. The preparation method comprises the following steps: (1) removing nickel oxide on the surface layer of the three-dimensional porous foamed nickel by using a hydrochloric acid soaking method, and improving the activity of the foamed nickel; (2) dispersing a certain amount of copper metal salt and a terpyridine ligand in deionized water, soaking activated foam nickel in the solution and carrying out hydrothermal reaction to prepare a two-dimensional MOF material with a nano-wall array structure; (3) carbonizing a two-dimensional MOF material at a certain temperature; (4) the carbonized MOF material is put in a certain concentrationDegree of Fe3+Soaking in the solution for different time to obtain the MOF materials with different Fe contents on the premise of not collapsing the material structure. The MOF material synthesized by the method has a large current effect, and meanwhile, the hydrothermal method for synthesizing the MOF material provided by the invention has the advantages that water is used as a solvent, no organic solvent is used, and the method 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 copper-iron MOF material with a two-dimensional nanowall array structure and controllable iron content and a preparation method thereof.
Background
The MOFs are coordination polymers that have been rapidly developed in recent decades and have a three-dimensional pore structure, and generally have metal ions as connection points and organic ligands as supports for spatial extension. MOFs have entered the field of vision as early as the mid-90 of the 20 th century, but are not highly porous and chemically stable. Thus, scientists have begun investigating novel cationic, anionic and neutral ligand-forming coordination polymers. At present, a large number of MOF materials are synthesized, mainly by using carboxyl-containing organic anion ligands or using the organic anion ligands together with nitrogen-containing heterocyclic ring organic neutral ligands. Most of these metal organic frameworks have high porosity and excellent chemical stability. In recent years, Metal Organic Framework (MOF) and a derivative nano material thereof have the characteristics of high porosity, large specific surface area, regular periodic structure, diversity of metal centers and ligands, adjustable functionalization and the like, and are widely applied to 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; the reaction process is complex and long in time consumption and high in cost. In addition, in the bimetallic material synthesized by the traditional method, the content ratio of the bimetallic material is difficult to control under the condition of ensuring good appearance.
Aiming at the defects of the traditional synthetic method, it is necessary to develop a preparation method of an environment-friendly, simple, convenient and economic two-dimensional material with controllable content.
Disclosure of Invention
Aiming at the defects of the existing method, the invention provides an environment-friendly copper-iron MOF material with a two-dimensional nano-wall array structure and a preparation method thereof, the invention improves the preparation process of the material in a targeted manner, and selects and optimizes key process parameters and raw material types in the preparation process, so that a copper-iron MOF new material with excellent two-dimensional nano-wall array structure and better comprehensive properties such as conductivity, stability and the like than the common MOF material is obtained correspondingly. The technical scheme of the invention 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 an environment-friendly copper-iron MOF material with a two-dimensional nano wall array structure and controllable iron content and a preparation method thereof, and the preparation method comprises the following steps:
a first step: preparing a porous nickel foam material: the method comprises the following steps of taking a commercially available foamed three-dimensional porous nickel material, wherein the foamed nickel 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:
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 synthesis method is used for preparing the copper MOF material:
the working procedure is that the activated three-dimensional porous foam 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 MOF material.
Further, the process comprises the following 4 steps:
step 1: raw material preparation
Taking copper sulfate pentahydrate, and analyzing and purifying, wherein the copper sulfate pentahydrate: 10 to 50mg
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, and then weighing copper sulfate pentahydrate 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 ℃.
Taking out and naturally drying. And obtaining the copper MOF material with a two-dimensional nano wall array structure. Step (iv): preparation of carbonized copper MOF material:
and (5) putting the copper MOF material prepared in the step (three) into a tube furnace, and carbonizing the material under the Ar atmosphere. The flow rate of argon gas is 20 ml/min; the carbonization temperature is 500-800 ℃.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 10-120s, taking out, washing with deionized water, and drying to obtain the environment-friendly copper-iron MOF material with a two-dimensional nano-wall array structure and controllable iron content.
Electrochemical test results:
the prepared MOF material is used for a working electrode of a linear cyclic voltammetry test, and the aim of reaching 300mA/cm at 0.4-1V is achieved2The above current density; meanwhile, in the HER test, 300mA/cm can be reached in a voltage window of (-0.85) - (-1.5) V2The above current density. This represents an excellent property of the present material.
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. The copper-iron MOF material with the two-dimensional nano wall array structure is prepared by a hydrothermal-soaking method, and the stability of the material is good because the components of the material are combined by chemical bonds.
3. According to the copper-iron 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-iron 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; and a subsequent soaking method is simple, convenient and quick, and the copper-iron bimetallic MOF material with the two-dimensional nano wall-shaped structure is obtained.
5. According to the invention, the iron element is embedded by using a soaking method, the content of the iron element is controlled by the length of the soaking time, and the iron doping is ensured not to influence the structure of the MOF material.
6. The copper-iron MOF material with the two-dimensional nanowall array structure has a large current effect, and can reach 300mA/cm in a voltage window of (-0.85) - (-1.5) V in an HER test2The above current density; in OER test, 300mA/cm can be reached in a voltage window of 0.4-1V2The above current density.
In a word, the method is safe, rapid, simple and convenient, and the prepared material has good catalytic performance. The invention provides a copper-iron 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 is a schematic diagram of a copper-iron bimetallic MOF material
FIG. 3 is a Scanning Electron Microscope (SEM) image of a Cu-Fe bimetallic MOF material with a two-dimensional nano-wall array structure
FIG. 4 is a Transmission Electron Microscope (TEM) image of a Cu-Fe bimetallic MOF material with a two-dimensional nanowall array structure
FIG. 5 is a HER linear cyclic voltammogram of a copper-iron bimetallic MOF material with a two-dimensional nanowall array structure
FIG. 6 is an OER linear cyclic voltammogram of a copper-iron 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 an environment-friendly copper-iron MOF material with a two-dimensional nano wall array structure and controllable iron content and a preparation method thereof, and the preparation method comprises the following 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: preparing a copper MOF material, the process comprising the steps of:
step 1: preparing raw materials:
taking copper sulfate pentahydrate: 10 to 50mg
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, and then weighing copper sulfate pentahydrate and adding into the reaction kettle; and then adding a ligand (4-phenyl terpyridine), and after completely dissolving by ultrasonic, 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 ℃.
Taking out and naturally drying. And obtaining the copper MOF material with a two-dimensional nano wall array structure. Step (iv): preparation of carbonized copper MOF material:
and (5) putting the copper MOF material prepared in the step (three) into a tube furnace, and carbonizing the material under the Ar atmosphere. The flow rate of argon gas is 20 ml/min; the carbonization temperature is 500-800 ℃.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 10-120s, taking out, washing with deionized water, and drying to obtain the environment-friendly copper-iron bimetallic MOF material with a two-dimensional nanowall array structure.
The electrochemical test is carried out by using the material as a working electrode. The following are specific examples:
example 1:
taking a commercially available three-dimensional porous foamed nickel material, and preparing 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: preparation of copper MOF materials:
step 1: taking copper sulfate pentahydrate: 10mg, taking deionized water: 20ml of each experiment
Step 2: a high-pressure reactor was prepared in accordance with the above-mentioned "method of carrying out the invention".
And step 3: the 4-phenyl terpyridine ligand was synthesized as described above in "detailed description".
And 4, step 4: preparation of the synthetic MOF materials according to the "detailed description" above.
Step (iv): preparation of carbonized copper MOF material:
the carbonization temperature was 600 ℃ and the argon flow rate was 20 ml/min.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 10s, taking out, washing with deionized water, and drying.
Electrochemical test results:
when the prepared MOF material is used for a working electrode of a linear cyclic voltammetry test, 350mA/cm can be reached as shown in figure 52The required potential of the high current of (2) is-0.26V at a current density of 10mA/cm 2. This demonstrates the excellent HER performance of the present material; can reach 350mA/cm as shown in figure 62The required potential of the high current of (2) is 1.539V 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: preparation of copper MOF materials:
step 1: taking copper sulfate pentahydrate: 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 synthetic MOF materials according to the "detailed description" above.
Step (iv): preparation of carbonized copper MOF material:
the carbonization temperature was 700 ℃ and the argon flow rate was 20 ml/min.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 30s, taking out, washing with deionized water, and drying.
Electrochemical test results:
when the prepared MOF material is used for a working electrode of a linear cyclic voltammetry test, 350mA/cm can be reached as shown in figure 52The required potential of the high current of (2) is-0.22V at a current density of 10mA/cm 2. This demonstrates the excellent HER performance of the present material; the required potential was 1.569V at a current density of 10mA/cm2 as shown in FIG. 6. 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: preparation of copper MOF materials:
step 1: taking copper sulfate pentahydrate: 35mg, 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 synthetic MOF materials according to the "detailed description" above.
Step (iv): preparation of carbonized copper MOF material:
the carbonization temperature was 500 ℃ and the argon flow rate was 20 ml/min.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 60s, taking out, washing with deionized water, and drying.
Electrochemical test results:
when the prepared MOF material is used for a working electrode of a linear cyclic voltammetry test, 350mA/cm can be reached as shown in figure 52The required potential of the high current of (2) is-0.19V at a current density of 10mA/cm 2. This demonstrates the excellent HER performance of the present material; the required potential was 1.547V at a current density of 10mA/cm2 as shown in FIG. 6. 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: preparation of copper MOF materials:
step 1: taking copper sulfate pentahydrate: 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 synthetic MOF materials according to the "detailed description" above.
Step (iv): preparation of carbonized copper MOF material:
the carbonization temperature was 800 ℃ and the argon flow rate was 20 ml/min.
A fifth step of: preparing a copper-iron bimetallic MOF material:
putting the copper carbide MOF material prepared in the step (IV) into 0.1M Fe3+Soaking in the solution for 120s, taking out, washing with deionized water, and drying.
Electrochemical test results:
when the prepared MOF material is used for a working electrode of a linear cyclic voltammetry test, 350mA/cm can be reached as shown in figure 52The required potential of the high current of (2) is-0.28V at a current density of 10mA/cm 2. This demonstrates the excellent HER performance of the present material; can reach 350mA/cm as shown in figure 62The required potential of the high current of (2) is 1.5V 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 (7)
1. An environment-friendly copper-iron MOF material with a two-dimensional nano wall array structure and controllable iron content and a preparation method thereof are characterized by comprising the following steps:
step (i) for preparing a porous nickel foam material: 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 (III), preparing the copper MOF material:
preparing a copper MOF material on an activated three-dimensional porous foam nickel material substrate prepared in the step (II) in a high-pressure reaction kettle by a hydrothermal method:
step (IV), preparing the carbonized copper MOF material:
the MOF material prepared in the step (three) is put into a tubular furnace for carbonization to obtain a carbonized copper MOF material:
step five, preparing the copper-iron bimetal MOF material:
the carbonized copper MOF material prepared in the step (IV) is placed in Fe3+Soaking in the solution, taking out, washing and drying to obtain the environment-friendly copper-iron MOF material with the two-dimensional nano-wall array structure and controllable iron content.
2. The method of claim 1, wherein the step (iii) of preparing the copper MOF material comprises the following 4 steps:
step 1: preparing raw materials:
taking copper sulfate pentahydrate as an analytical reagent, wherein the copper sulfate pentahydrate: 10 to 50mg
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, and then weighing copper sulfate pentahydrate 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 ℃.
3. A process for the preparation of "copper MOF material" according to claim 2, wherein the process uses raw materials: the copper salt is preferably copper sulfate pentahydrate, the ligand is 4-phenyl terpyridine, and the solvent is deionized water.
4. The process of claim 2, wherein the hydrothermal process temperature of step 4 is 150 ℃ and the hydrothermal time is 24 h.
5. The environment-friendly copper-iron MOF material with the two-dimensional nanowall array structure and the preparation method thereof according to claim 1, wherein the prepared two-dimensional MOF material with the nanowall array structure is a copper-iron bimetallic MOF material with the two-dimensional nanowall array structure; the preparation method is that the copper MOF material with a two-dimensional wall array structure grows on the surface of the activated three-dimensional porous foamed nickel material substrate.
6. The method according to claim 1, wherein the carbonization temperature in the step (IV) is 500-800 ℃, and Ar gas is introduced during the carbonization at a flow rate of 20 ml/min.
7. The method according to claim 1, wherein Fe in the step (V)3+The concentration of the solution is 0.1M; and the soaking time is 10-120 s.
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