CN113463110A - Preparation method of cobalt/cobalt oxide-loaded covalent organic framework - Google Patents
Preparation method of cobalt/cobalt oxide-loaded covalent organic framework Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 91
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 57
- 239000010941 cobalt Substances 0.000 title claims abstract description 57
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
- 239000011259 mixed solution Substances 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910020676 Co—N Inorganic materials 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 21
- 238000001075 voltammogram Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- -1 metal oxide ruthenium dioxide Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 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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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention belongs to the technical field of functional materials, and provides a preparation method of a covalent organic framework loaded with cobalt/cobalt oxide, which comprises the steps of preparing the covalent organic framework and inorganic Co (NO)3)2·6H2Mixing O in certain proportion and NaBH4The covalent organic framework loaded with cobalt/cobalt oxide is obtained through reduction, and N containing lone pair electrons in the covalent organic framework can be coordinated with cobalt to form a Co-N bond, so that the covalent organic framework loaded with cobalt/cobalt oxide has better electrocatalytic oxygen evolution activity and electrochemical stability in an alkaline environment. Meanwhile, the invention effectively solves the problem of slow reaction of OER in the water electrolysis technology, improves the electrochemical activity and stability of the water electrolysis oxygen evolution catalyst in the alkaline medium, has simple preparation process, and greatly improves the hydrogen production efficiency, thereby improving the effective benefit of hydrogen energyThe application is as follows.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a cobalt/cobalt oxide loaded covalent organic framework.
Background
Hydrogen energy is a recognized clean energy source, and hydrogen production by water electrolysis is a relatively promising hydrogen production technology. Since the hydrogen production by water electrolysis utilizes intermittent renewable energy sources for power generation, such as wind and solar energy, electrocatalytic conversion technology can apply electrical energy to drive specific chemical conversions. Therefore, the current method for producing hydrogen by electrolyzing water is widely applied. The hydrogen production by water electrolysis mainly comprises a cathodic Hydrogen Evolution Reaction (HER) and an anodic Oxygen Evolution Reaction (OER), however, the OER is a slow dynamic process and relates to multiple processes of multi-electron transfer and adsorption and desorption of intermediate substances, so that a large overpotential is generated, and the problem of low reaction efficiency is caused. The main way to solve the slow OER reaction is to reduce the reaction potential by using a catalyst, thereby promoting the rapid progress of the OER reaction. Noble metal oxide ruthenium dioxide (RuO)2) And the like are considered as the most effective OER electro-catalysts, but the large-scale application of the OER electro-catalysts is restricted by the problems of shortage of reserves in earth elements, high price, poor stability and the like.
Current OER electrocatalysts that can replace noble metal catalysts comprise a covalent organic framework. The covalent organic framework is an ordered porous crystalline organic polymer formed by accurately connecting organic building units through covalent bonds, and has the characteristics of order of a pore channel structure, low density, large specific surface area, easiness in surface modification and the like. However, covalent organic frameworks have poor conductivity and still suffer from high overpotentials.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for preparing a cobalt/cobalt oxide-supported covalent organic framework.
The invention provides a preparation method of a covalent organic framework loaded with cobalt/cobalt oxide, which is characterized by comprising the following steps: step 1, dispersing a covalent organic framework in methanol to obtain a dispersion liquid; step 2, adding Co (NO) into the dispersion liquid3)2·6H2After O, add NaBH4After the/methanol mixed solution is stirred and reacts for a period of time, the solution after the reaction is centrifugally washed to obtain a covalent organic framework loaded with cobalt/cobalt oxide; wherein, covalent organic framework, methanol, Co (NO)3)2·6H2O and NaBH4The feeding ratio of the mixed solution/methanol is 10mg:5 ml-20 ml: 0.025 mmol-0.075 mmol, 3 ml-10 ml.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein, the preparation steps of the covalent organic framework are as follows: step 1-1, adding 3, 3-diaminobenzidine and 1,3, 5-triphenylformaldehyde into 1, 4-dioxane, mixing and reacting for a period of time to obtain a mixed solution; step 1-2, adding an acetic acid/ethanol mixed solution into the mixed solution, and stirring for reaction to obtain a solution containing a crude product; step 1-3, a purification step, namely centrifuging a solution containing a crude product to obtain a solid product, washing and drying the solid product to obtain a covalent organic framework, wherein the feeding ratio of 3, 3-diaminobenzidine, 1,3, 5-triphenylformaldehyde, 1, 4-dioxane and an acetic acid/ethanol mixed solution is 1mmol:0.8 mmol-1.2 mmol: 1 ml-3 ml, 0.5 ml-1.5 ml.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein the methanol is deoxidized methanol.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein, in the step 1, the covalent organic framework is dispersed in methanol and then is subjected to ultrasonic treatment for 1 h-3 h.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein, in step 2, Co (NO) is added to the dispersion3)2·6H2And carrying out ultrasonic treatment for 1-3 h after O.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein, in step 2, NaB is addedH4The mixed solution of the methanol is stirred and reacted for 16 to 20 hours at room temperature.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can also have the following characteristics: wherein, in the step 2, the solid product is washed 3 to 5 times by using methanol, and then the washed solid product is dried for 8 to 10 hours in a vacuum drying oven at the temperature of between 50 and 70 ℃.
In the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention, the preparation method can have the following characteristics that: and 1-3, a purification step, wherein the covalent organic framework is washed by tetrahydrofuran for a plurality of times until the filtrate becomes colorless, and then the washed covalent organic framework is placed in a vacuum drying oven to be dried for 8-10 h at the temperature of 50-70 ℃.
Action and Effect of the invention
According to the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide, the covalent organic framework and inorganic Co (NO) are adopted3)2·6H2Mixing O in certain proportion and NaBH4The covalent organic framework loaded with cobalt/cobalt oxide is obtained through reduction, and N containing lone pair electrons in the covalent organic framework can be coordinated with cobalt to form a Co-N bond, so that the covalent organic framework loaded with cobalt/cobalt oxide has better electrocatalytic oxygen evolution activity and electrochemical stability in an alkaline environment. Meanwhile, the invention effectively solves the problem of slow reaction of OER in the water electrolysis technology, improves the electrochemical activity and stability of the water electrolysis oxygen evolution catalyst in the alkaline medium, has simple preparation process, and greatly improves the hydrogen production efficiency, thereby improving the effective utilization of hydrogen energy.
Drawings
FIG. 1 is a cobalt/cobalt oxide loaded covalent organic framework of example 1 of the invention13C solid nuclear magnetic map;
FIG. 2 is a Fourier infrared spectrum of a cobalt/cobalt oxide loaded covalent organic framework in example 1 of the present invention;
FIG. 3 is a linear sweep voltammogram of a cobalt/cobalt oxide loaded covalent organic framework in a 1MKOH solution in example 1 of the invention;
FIG. 4 shows examples 1-3 covalent organic frameworks loaded with cobalt/cobalt oxide by varying Co (NO)3)2·6H2Linear sweep voltammogram with molar amount of O in 1M KOH solution.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the following examples are combined with the accompanying drawings to specifically describe the preparation method of the cobalt/cobalt oxide loaded covalent organic framework of the invention.
The preparation method of the covalent organic framework loaded with cobalt/cobalt oxide provided by the invention comprises the following steps:
step 1, dispersing a covalent organic framework in methanol, and then carrying out ultrasonic treatment for 1-3 h to obtain a dispersion liquid;
step 2, adding Co (NO) into the dispersion liquid3)2·6H2Carrying out ultrasonic treatment for 1 h-3 h after O, and then adding NaBH4And after the methanol mixed solution is stirred and reacts for 16-20 h, centrifuging the solution of the reacted crude product to obtain a solid product, washing the solid product for 3-5 times by using methanol, and then drying the washed solid product in a vacuum drying oven at the temperature of 50-70 ℃ for 8-10 h to obtain the covalent organic framework.
Wherein, covalent organic framework, methanol, Co (NO)3)2·6H2O and NaBH4The feeding ratio of the mixed solution/methanol is 10mg:5 ml-20 ml: 0.025 mmol-0.075 mmol, 3 ml-10 ml.
The covalent organic framework used in the present invention is prepared by the following steps:
step 1-1, adding 3, 3-diaminobenzidine and 1,3, 5-triphenylformaldehyde into 1, 4-dioxane, mixing and reacting for a period of time to obtain a mixed solution;
step 1-2, adding an acetic acid/ethanol mixed solution into the mixed solution, and stirring for reaction to obtain a solution containing a crude product;
and 1-3, a purification step, namely washing the solution of the crude product with tetrahydrofuran for a plurality of times until the filtrate becomes colorless, and then drying the washed solid in a vacuum drying oven at the temperature of 50-70 ℃ for 8-10 h.
Wherein the feeding ratio of the 3, 3-diaminobenzidine, the 1,3, 5-triphenylformaldehyde, the 1, 4-dioxane and the acetic acid/ethanol mixed solution is 1mmol:0.8 mmol-1.2 mmol: 1 ml-3 ml, 0.5 ml-1.5 ml.
< example 1>
At room temperature, 1mmol of 3,3' -diaminobenzidine and 1mmol of 1,3, 5-triphenylformaldehyde are mixed and dissolved in 2ml of 1, 4-dioxane, and after 30mins, 0.5ml of 3M acetic acid/ethanol mixed solution is added into the mixed solution under the condition of vigorous stirring, and stirring is carried out for 1h, so as to obtain a solution containing orange solid. Then, the orange solid was collected by centrifugation of the solution and washed several times with tetrahydrofuran until the filtrate became colorless, and then the solid was dried in a vacuum oven at 60 ℃ for 8 hours to obtain a covalent organic framework.
And dispersing the prepared covalent organic framework in methanol, and performing ultrasonic treatment for 2 hours to obtain a dispersion liquid. Wherein the molar ratio of the covalent organic framework: methanol was dispersed at a ratio of 10mg to 10 ml. Followed by the addition of 0.05mmol Co (NO)3)2·6H2Continuing to perform ultrasonic treatment for 2h by O, and slowly dropwise adding 5ml of NaBH with the concentration of 0.3M4The/methanol mixed solution was stirred continuously at room temperature for 18 hours to obtain a solution containing the crude product. And (3) centrifugally separating the solution containing the crude product, collecting solid, washing the solid with methanol for 3-5 times, and drying the solid in a vacuum drying oven at the temperature of 60 ℃ for 8 hours to obtain the covalent organic framework loaded with the cobalt/cobalt oxide.
FIG. 1 is a representation of the cobalt/cobalt oxide loaded covalent organic frameworks (Co/CoO @ COF) in this example13C solid nuclear magnetic diagram. As shown in fig. 1, the signals appearing at chemical shifts around 112.83, 117.68, 123.51, 128.85, 132.25 and 134.67ppm for the cobalt/cobalt oxide loaded covalent organic framework correspond to the C atoms in positions 5, 8, 6, 1, 2 and 7 of the representation of fig. 1, respectively, due to resonance absorption of the benzene ring. The characteristic signature for the C-N bond corresponds to 146.83ppm of the C atom in position 4 in fig. 1, whereas the vibration of the C atom in position 3 around 152.63ppm should be assigned to the C ═ N bond, confirming the cobalt/cobalt oxide loaded covalent organic frameworkAnd generating a skeleton structure.
Figure 2 is a fourier infrared spectrum of the cobalt/cobalt oxide loaded covalent organic framework in this example. As shown in FIG. 2, it can be seen from FIG. 2(a) that the pure Covalent Organic Frameworks (COFs) are at 3363, 1697, 1612 and 1296cm-1The absorption peak has four characteristic absorption peaks, and is attributed to stretching vibration of-NH-, stretching vibration of H-C-O, stretching vibration of C-N and stretching vibration of C-N, wherein the edge of 1,3, 5-triphenylformaldehyde does not participate in Schiff base condensation reaction. The C ═ N bond is formed by the schiff base condensation reaction of 1,3, 5-triphenylformaldehyde and 3,3' -diaminobenzidine, demonstrating the formation of a covalent organic framework backbone. The cobalt/cobalt oxide loaded covalent organic framework inherits the fourier infrared spectra of the pure covalent organic framework, but there are also differences between them. Specifically, the introduction of cobalt/cobalt oxide resulted in a cobalt/cobalt oxide loaded covalent organic framework of 1049cm-1And a new peak appears (see fig. 2(b)), which indicates that N containing lone pair electrons in the covalent organic framework can coordinate with cobalt to form Co-N bond to promote charge transfer.
FIG. 3 is a linear sweep voltammogram of a cobalt/cobalt oxide loaded covalent organic framework in a 1M KOH solution in this example. As can be seen in FIG. 3, the covalent organic framework of the cobalt/cobalt oxide-loaded framework is 10mA cm-2The overpotential is 278mV, which is obviously superior to commercial ruthenium dioxide (RuO)2310 mV). Compared with the covalent organic framework with overpotential of 512mV when reaching the same current density, 234mV is obviously reduced, thereby proving that the covalent organic framework loaded with cobalt/cobalt oxide has higher catalytic activity to OER.
< example 2>
At room temperature, 1mmol of 3,3' -diaminobenzidine and 1mmol of 1,3, 5-triphenylformaldehyde are mixed and dissolved in 2ml of 1, 4-dioxane, and after 30mins, 0.5ml of 3M acetic acid/ethanol mixed solution is added into the mixed solution under the condition of vigorous stirring, and stirring is carried out for 1h, so as to obtain a solution containing orange solid. Then, the orange solid was collected by centrifugation of the solution and washed several times with tetrahydrofuran until the filtrate became colorless, and then the solid was dried in a vacuum oven at 60 ℃ for 8 hours to obtain a covalent organic framework.
And dispersing the prepared covalent organic framework in methanol, and performing ultrasonic treatment for 2 hours to obtain a dispersion liquid. Wherein the molar ratio of the covalent organic framework: methanol was dispersed at a ratio of 10mg to 10 ml. Followed by the addition of 0.025mmol Co (NO)3)2·6H2Continuing to perform ultrasonic treatment for 2h by O, and slowly dropwise adding 5ml of NaBH with the concentration of 0.3M4The/methanol mixed solution was stirred continuously at room temperature for 18 hours to obtain a solution containing the crude product. And (3) centrifugally separating the solution containing the crude product, collecting solid, washing the solid with methanol for 3-5 times, and drying the solid in a vacuum drying oven at the temperature of 60 ℃ for 8 hours to obtain the covalent organic framework loaded with the cobalt/cobalt oxide.
< example 3>
At room temperature, 1mmol of 3,3' -diaminobenzidine and 1mmol of 1,3, 5-triphenylformaldehyde are mixed and dissolved in 2ml of 1, 4-dioxane, and after 30mins, 0.5ml of 3M acetic acid/ethanol mixed solution is added into the mixed solution under the condition of vigorous stirring, and stirring is carried out for 1h, so as to obtain a solution containing orange solid. Then, the orange solid was collected by centrifugation of the solution and washed several times with tetrahydrofuran until the filtrate became colorless, and then the solid was dried in a vacuum oven at 60 ℃ for 8 hours to obtain a covalent organic framework.
And dispersing the prepared covalent organic framework in methanol, and performing ultrasonic treatment for 2 hours to obtain a dispersion liquid. Wherein the molar ratio of the covalent organic framework: methanol was dispersed at a ratio of 10mg to 10 ml. Followed by the addition of 0.075mmol Co (NO)3)2·6H2Continuing to perform ultrasonic treatment for 2h by O, and slowly dropwise adding 5ml of NaBH with the concentration of 0.3M4The/methanol mixed solution was stirred continuously at room temperature for 18 hours to obtain a solution containing the crude product. And (3) centrifugally separating the solution containing the crude product, collecting solid, washing the solid with methanol for 3-5 times, and drying the solid in a vacuum drying oven at the temperature of 60 ℃ for 8 hours to obtain the covalent organic framework loaded with the cobalt/cobalt oxide.
FIG. 4 shows examples 1-3 covalent organic frameworks loaded with cobalt/cobalt oxide by varying Co (NO)3)2·6H2Linear sweep voltammogram with molar amount of O in 1M KOH solution.
Co (NO) in example 13)2·6H2When the amount of O added is 0.05mmol, 10mA cm-2The overpotential is 278mV at the current density of (4); co (NO) in example 23)2·6H2The adding amount of O is 0.025mmol, and the overpotential is 400 mV; co (NO) in example 33)2·6H2The addition of O is 0.075mmol and the overpotential is 291 mV. As can be seen from FIG. 4, the overpotential of example 1 is lower than those of examples 2 and 3, thereby proving Co (NO)3)2·6H2The covalent organic framework with the addition of 0.05mmol of loaded cobalt/cobalt oxide has higher catalytic activity.
Effects and effects of the embodiments
According to the preparation method of the covalent organic framework loaded with cobalt/cobalt oxide, the covalent organic framework and inorganic Co (NO) are adopted3)2·6H2Mixing O in certain proportion and NaBH4The covalent organic framework loaded with cobalt/cobalt oxide is obtained through reduction, and N containing lone pair electrons in the covalent organic framework can be coordinated with cobalt to form a Co-N bond, so that the covalent organic framework loaded with cobalt/cobalt oxide has better electrocatalytic oxygen evolution activity and electrochemical stability in an alkaline environment. Meanwhile, the invention effectively solves the problem of slow reaction of OER in the water electrolysis technology, improves the electrochemical activity and stability of the water electrolysis oxygen evolution catalyst in the alkaline medium, has simple preparation process, and greatly improves the hydrogen production efficiency, thereby improving the effective utilization of hydrogen energy.
In addition, the method synthesizes the covalent organic framework by an impregnation method, and has simple operation and wide application range.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (8)
1. A preparation method of a covalent organic framework loaded with cobalt/cobalt oxide is characterized by comprising the following steps:
step 1, dispersing the covalent organic framework in methanol to obtain a dispersion liquid;
step 2, adding Co (NO) into the dispersion liquid3)2·6H2After O, add NaBH4After the/methanol mixed solution is stirred and reacts for a period of time, the solution after the reaction is centrifugally washed to obtain a covalent organic framework loaded with cobalt/cobalt oxide;
wherein the covalent organic framework, the methanol, the Co (NO)3)2·6H2O and the NaBH4The feeding ratio of the mixed solution/methanol is 10mg:5 ml-20 ml: 0.025 mmol-0.075 mmol, 3 ml-10 ml.
2. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein the preparation steps of the covalent organic framework are as follows:
step 1-1, adding 3, 3-diaminobenzidine and 1,3, 5-triphenylformaldehyde into 1, 4-dioxane, mixing and reacting for a period of time to obtain a mixed solution;
step 1-2, adding an acetic acid/ethanol mixed solution into the mixed solution, and stirring for reaction to obtain a solution containing a crude product;
step 1-3, centrifuging the solution containing the crude product to obtain a solid product, washing and drying the solid product to obtain the covalent organic framework,
wherein the feeding ratio of the 3, 3-diaminobenzidine, the 1,3, 5-tribenzaldehyde, the 1, 4-dioxane and the acetic acid/ethanol mixed solution is 1mmol:0.8 mmol-1.2 mmol: 1 ml-3 ml, 0.5 ml-1.5 ml.
3. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein the methanol is deoxygenated methanol.
4. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein, in the step 1, the covalent organic framework is dispersed in methanol and then is subjected to ultrasonic treatment for 1 h-3 h.
5. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein, in step 2, Co (NO) is added to the dispersion3)2·6H2And carrying out ultrasonic treatment for 1-3 h after O.
6. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein, in step 2, NaBH is added4The mixed solution of the methanol is stirred and reacted for 16 to 20 hours at room temperature.
7. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 1, characterized in that:
wherein, in the step 2, the solid product is washed 3 to 5 times by using the methanol, and then the washed solid product is placed in a vacuum drying oven to be dried for 8 to 10 hours at the temperature of between 50 and 70 ℃.
8. The method of preparing a cobalt/cobalt oxide loaded covalent organic framework of claim 2, characterized in that:
wherein, in the step 1-3, the solid product is washed by tetrahydrofuran for a plurality of times until the filtrate becomes colorless, and then the washed solid product is dried for 8-10 h in a vacuum drying oven at the temperature of 50-70 ℃.
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| CN108927224A (en) * | 2018-06-28 | 2018-12-04 | 福州大学 | A kind of covalent organic frame catalysis material and its preparation method and application of cobalt ions load |
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