CN111841645B - OER catalyst compounded by carbon nano tube and covalent organic framework - Google Patents

OER catalyst compounded by carbon nano tube and covalent organic framework Download PDF

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CN111841645B
CN111841645B CN202010895137.3A CN202010895137A CN111841645B CN 111841645 B CN111841645 B CN 111841645B CN 202010895137 A CN202010895137 A CN 202010895137A CN 111841645 B CN111841645 B CN 111841645B
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CN111841645A (en
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杜明亮
陆双龙
甘志健
朱罕
段芳
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Jiangnan University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
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    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses an OER catalyst compounded by carbon nano tubes and a common organic frame, belonging to the technical field of electrolytic water catalysis. The OER catalyst compounded by the carbon nano tube and the covalent organic framework consists of a molecular catalyst and a conductive carbon carrier, wherein the molecular catalyst is formed by the covalent organic framework COFs and metal ions through coordination, and the conductive carbon carrier is the carbon nano tube CNTs. The invention combines the high conductivity of CNTs and the synergistic effect of metal coordination COFs of surface active materials, greatly improves the catalytic conduction, mass transfer and accessibility of active sites, thereby improving the oxygen evolution catalytic activity of the carbon nanotubes. And the solvent thermal preparation method is adopted, so that the method is simple and safe.

Description

OER catalyst compounded by carbon nano tube and covalent organic framework
Technical Field
The invention relates to an OER catalyst compounded by a carbon nano tube and a common organic frame, belonging to the technical field of electrolytic water catalysis.
Background
With the development of the world economy, energy and environmental problems are becoming more serious. At present, the main energy used by human beings is still the traditional non-renewable energy such as coal, natural gas and petroleum. Depletion of limited resources has prompted research into a range of renewable energy sources as alternatives, with hydrogen energy being of great interest for its high efficiency, green color. Conversion systems such as fuel cells, metal-air cells, alkaline electrolysis water and the like designed based on energy conversion and storage are all double-electrode systems. The Oxygen Evolution Reaction (OER) of the anode part is a four electron-proton coupling reaction, which requires a higher overpotential than the two electron transfer reaction of the cathode part, the OER is a bottleneck to be broken through urgently as electrolyzed water, and the kinetic barrier of the electrode is a fatal disadvantage. Therefore, it is critical to find an OER catalyst with a low overpotential. Early stage, Ru02And Iro2Found to be the most effective OER catalysts, however, their widespread use is limited due to scarcity and high cost. Therefore, extensive attention has been paid to the development of efficient and economical OER catalysis.
To date, various abundant, inexpensive and effective OER catalysts have been developed, including metal phosphides, nitrides, sulfides, oxides, hydroxides, etc., but conventional metal catalysts have low atomic utilization and poor catalytic selectivity. Therefore, the molecular catalyst is concerned by researchers, and common porphyrin, phthalocyanine molecules and the like not only have definite active sites to fully exert the catalytic performance of metal, but also can be applied to different catalytic systems, and simultaneously can precisely customize the structure, and the transfer rate, steric hindrance, water solubility and the like of electrons are influenced by the type of a ligand, so that different catalytic activities are reflected.
The COFs are ordered structures constructed by organic monomers in an atomic precision mode, are connected by covalent bonds, have good thermal stability, larger specific surface area and lower framework density, are in a large pi-pi conjugated system and have open and regular pore channels, are beneficial to the transmission of electrons in materials, and can be applied to the aspects of gas storage and adsorption separation, catalysis, energy, chemical sensing, biomedicine and the like. However, the morphological structure of COF directly affects its catalytic performance by promoting mass transfer, but COF inevitably has poor conductivity as a polymer of organic molecules, which is also an important factor for limiting COF as an OER catalyst.
Disclosure of Invention
In order to solve at least one problem, the invention introduces carbon nano-tube CNTs with excellent electrical conductivity as a substrate of a catalyst, and combines the substrate with COFs to obtain a composite material, so that the electrical conductivity of the COFs is improved on the basis of ensuring the uniform and high-porosity distribution of the COFs. The 2D COF stack-up to form a layered overlapped structure shows a periodic ordered column structure, which is beneficial to the transport of charge carriers in the stacking direction, and the number of active sites and the electron transport efficiency of the material can be controlled by selecting different organic monomers to introduce a conjugated system, active functional groups and the like. In addition, the OER catalyst compounded by the carbon nano tube and the covalent organic framework has high catalytic activity, and the preparation method has simple process and low cost.
The invention aims to provide an OER catalyst compounded by carbon nanotubes and a covalent organic framework, the components of the OER catalyst comprise a molecular catalyst and a conductive carbon carrier, the molecular catalyst is formed by the coordination of Covalent Organic Frameworks (COFs) and metal ions, and the conductive carbon carrier is Carbon Nanotube (CNTs).
In one embodiment of the invention, the amount of metal ions is 1-7 times the mass of the covalent organic frameworks, COFs.
In one embodiment of the present invention, the CNTs have a diameter of about 11 nm.
In one embodiment of the invention, the mass ratio of the molecular catalyst to the conductive carbon support is 30:1 to 1: 20.
The second purpose of the invention is that the preparation method of the OER catalyst compounded by the carbon nano tube and the covalent organic framework comprises the following steps:
(1) weighing CNTs and a monomer composition containing polyamino COFs, and dissolving the CNTs and the monomer composition in a mixed solvent to form a monomer solution; then adding a catalyst, mixing uniformly, adding a solution containing the polyaldehyde COFs monomer, and mixing uniformly to obtain a mixed solution; freezing and vacuumizing the mixed solution, and then carrying out in-situ growth reaction; after the reaction is finished, washing, centrifuging and drying to obtain COF @ CNT powder;
(2) dispersing the COF @ CNT powder obtained in the step (1) in a solvent, adding a metal salt, and uniformly mixing for reaction; and after the reaction is finished, collecting, washing and drying to obtain the OER catalyst compounded by the carbon nano tube and the common organic frame.
Wherein the mass ratio of the CNTs to the monomers containing the polyamino COFs in the step (1) is 40: 1-1:20.
In one embodiment of the invention, the mixed solvent in the step (1) is n-butanol and o-dichlorobenzene, and the volume ratio of the n-butanol to the o-dichlorobenzene is 2:1-1: 2.
In one embodiment of the invention, the mass and volume ratio of the CNTs and the constituent monomers containing the polyamino COFs in the step (1) to the mixed solvent is 2-15 mg/mL.
In one embodiment of the present invention, the catalyst in step (1) is 3M acetic acid solution, and the amount of the catalyst is 0.05-0.4mL per mL of the mixed solvent.
In one embodiment of the present invention, the conditions of the in-situ growth reaction in step (1) are as follows: reacting at 90-130 ℃ for 60-80h, and specifically in-situ growing COFs on the CNTs.
In one embodiment of the present invention, the amount of the polyaldehyde COFs monomer solution in the step (1) is 20 to 400uL based on the mixed solvent.
In one embodiment of the present invention, the preparation method of the solution containing polyaldehyde COFs monomers in step (1) comprises: dissolving a multi-aldehyde COFs monomer in a mixed solvent, wherein the multi-aldehyde COFs monomer is one or two of terephthalaldehyde and trialdehyde phloroglucinol; the volume ratio of the mixed solvent is 2:1-1:2 of n-butyl alcohol and o-dichlorobenzene, and the mass volume ratio of the multi-aldehyde COFs monomer to the mixed solvent is 0.05-6 mg: 1 mL.
In one embodiment of the present invention, the polyamino-containing COFs monomer in step (1) is one or more selected from 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, 5' -diamino-2, 2' -bipyridine, p-diaminoazobenzene, and 3,3' -diaminobenzidine.
In an embodiment of the present invention, the polyaldehyde COFs monomers in step (1) are terephthalaldehyde.
In one embodiment of the present invention, the washing, centrifuging, and drying in step (1) specifically comprises: washing with cyclohexane/methanol mixed solution, centrifuging for 3-5 times, and vacuum drying at 60-80 deg.C for 12-24 hr.
In one embodiment of the present invention, the dissolution of the monomer solution in step (1) is: ultrasonic dissolving for 30-60min at 200W.
In one embodiment of the invention, the catalyst is added in the step (1) and continuously ultrasonically mixed for 5-15min, then the solution of the multi-aldehyde COFs monomer is added and continuously ultrasonically mixed for 15-30min to obtain the mixed solution.
In one embodiment of the present invention, the freezing and vacuuming process of the mixed solution in the step (1) may be repeated 3 times.
In one embodiment of the present invention, the freezing and vacuum-pumping process in step (1) is to freeze liquid by using liquid nitrogen and then pump vacuum by using a double row of pipes.
In one embodiment of the present invention, the mass-to-volume ratio of the COF @ CNT powder described in step (2) to the solvent is 0.05-0.5mg/mL, wherein the solvent is a methanol solution (95-100% by mass).
In one embodiment of the present invention, the metal salt in step (2) is one or more of acetate, chloride, nitrate and acetylacetonate.
In one embodiment of the present invention, the metal salt in step (2) is added in an amount of 0.1 to 5 times the saturated amount of the coordination sites of the COFs.
In one embodiment of the present invention, the reaction conditions during the preparation of step (2) are reflux at 70-90 ℃ for 6-12 h.
In one embodiment of the present invention, the washing and drying in step (2) are specifically centrifugal washing with methanol for 3-5 times, and vacuum drying at 60-80 ℃ overnight.
In an embodiment of the present invention, the specific preparation method of the OER catalyst is as follows:
(1) weighing constituent monomers of CNTs and COFs, dissolving the constituent monomers in a mixed solvent, adding an acetic acid solution serving as a catalyst, uniformly performing ultrasonic treatment in a glass bottle, transferring the mixture into a Pyrex bottle, freezing the liquid by using liquid nitrogen, vacuumizing the liquid by using a double-row pipe, repeating the steps for three times, and placing the liquid in a 120-DEG C oven for reaction for 72 hours; washing with cyclohexane/methanol mixed solution, centrifuging for 3-5 times, and vacuum drying;
(2) and (3) dispersing COF @ CNT powder into a methanol solution, adding a metal salt, performing ultrasonic homogenization, refluxing for 6 hours at 80 ℃, collecting, washing and drying to obtain the OER catalyst.
The third purpose of the invention is the application of the OER catalyst compounded by the carbon nano tube and the common organic framework in the electrolyzed water.
In one embodiment of the present invention, the application in the electrolysis of water is specifically: the OER catalyst compounded by the carbon nano tube and the covalent organic framework is adopted to modify the glassy carbon electrode to form a working electrode, and then the working electrode is applied to catalyzing oxygen precipitation reaction in electrolyzed water.
In one embodiment of the invention, the OER catalyst compounded by the carbon nanotubes and the covalent organic framework can catalyze the oxygen evolution reaction of the anode part, and can be further used for hydrogen production by water electrolysis and a zinc-air fuel battery.
The invention has the beneficial effects that:
(1) the OER catalyst adopts a solvothermal method: CNTs and COFs are subjected to a mixed solvent thermal reaction to obtain COF @ CNT, and then the COF @ CNT and a metal salt solution are refluxed to obtain a catalyst.
(2) The OER catalyst prepared by the invention can obviously improve the electron transmission of the catalyst by using CNTs as a conductive substrate, thereby improving the catalytic performance.
(3) Compared with pure COFs materials, the OER catalyst provided by the invention takes CNTs as a carrier, and the porosity of the catalyst can be remarkably improved so as to enhance catalytic mass transfer and accessibility of active sites.
(4) The OER catalyst prepared by the invention is tested in 1M KOH electrolyte and has the current density of 10mA/cm2A low overpotential of 358mV is obtained.
Drawings
FIG. 1 is a plot of polarization in 1M KOH for four different COFs loaded materials of examples 1-4.
FIG. 2 is an SEM image of COF-Co @ CNT-0.4 of example 3.
FIG. 3 is an EME image of COF-Co @ CNT-0.4 of example 3.
FIG. 4 is a small angle XRD spectrum of COF-Co and COF-Co @ CNT.
FIG. 5 is an infrared spectrum of the composite of COF-Co and CNTs.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
ElectrocatalysisDetection of oxygen evolution Activity: adding 300 microliters of isopropanol, 20 microliters of water and 10 microliters of Nafion solution (mass fraction is 5%) into 1mg of catalyst, and ultrasonically mixing uniformly to obtain a mixed solution, dripping 5 microliters of the mixed solution into a solution with the area of 0.07065cm2The OER performance of the glassy carbon electrode was tested in a 1M KOH solution.
Example 1
A preparation method of an OER catalyst compounded by carbon nanotubes and a covalent organic framework comprises the following steps:
(1) putting 3mg of carbon nano tube and 6mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin into a glass bottle, adding 2mL of mixed solution of n-butyl alcohol/o-dichlorobenzene (volume ratio is 1:1), ultrasonically mixing (ultrasonic power is 200W) for 30 minutes, adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain mixed solution;
(2) dissolving 2.4mg of terephthalaldehyde in 400 microliters of n-butanol/o-dichlorobenzene (volume ratio is 1:1) and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution in the step (1), and continuing to perform ultrasonic treatment for 20 minutes; transferring the mixed solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the mixed solution in a 120 ℃ drying oven to react for 72 hours under the condition of keeping a vacuumizing state; after the reaction is finished, washing the obtained product for 4 times by using a cyclohexane/methanol mixed solution, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ overnight to obtain COF @ CNT powder;
(3) adding COF @ CNT powder (6mg) and 10mg of cobalt acetate into a 50mL flask, adding 20mL of anhydrous methanol, and uniformly stirring (the stirring speed is 600rpm, and the stirring time is 30min) to perform reaction; a condensation reflux device is set up in the reaction process, and reflux is carried out for 6 hours under the condition of stirring at the temperature of 80 ℃; after the reaction is finished and the temperature is cooled to room temperature, taking the reaction solution, centrifugally washing the reaction solution for three times by using methanol, and drying the reaction solution in a vacuum oven at the temperature of 80 ℃ overnight; the resulting OER catalyst was named COF-Co @ CNT-2.8, 2.8 representing a mass to mass ratio of COF monomer dosed to theoretical mass of carbon nanotubes of 2.8.
The obtained OER catalyst was subjected to a performance test, and the test results are shown in fig. 1.
Example 2
A preparation method of an OER catalyst compounded by carbon nanotubes and a covalent organic framework comprises the following steps:
(1) putting 3mg of carbon nano tube and 1.5mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin into a glass bottle, adding 2mL of mixed solution of n-butyl alcohol/o-dichlorobenzene (volume ratio is 1:1), ultrasonically mixing for 30 minutes (ultrasonic power is 200W), adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain mixed solution;
(2) dissolving 0.6mg of terephthalaldehyde in 400 microliters of a mixed solution of n-butanol/o-dichlorobenzene (volume ratio is 1:1) and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution in the step (1), and continuing to perform ultrasonic treatment for 20 minutes; transferring the mixed solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the mixed solution in a 120 ℃ drying oven to react for 72 hours under the condition of keeping the vacuumizing state; after the reaction is finished, washing the obtained product for 4 times by using a cyclohexane/methanol mixed solution, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ overnight to obtain COF @ CNT powder;
(3) adding COF @ CNT powder (4mg) and 10mg of cobalt acetate into a 50mL flask, adding 20mL of anhydrous methanol, and uniformly stirring (the stirring speed is 600rpm, and the stirring time is 30min) to perform reaction; setting up a condensation reflux device in the reaction process, refluxing for 6 hours under the condition of stirring at 80 ℃, taking reaction solution, centrifugally washing the reaction solution for three times by using methanol after the reaction is finished and cooled to room temperature, and drying the reaction solution in a vacuum oven at 80 ℃ overnight; an OER catalyst was obtained, named COF-Co @ CNT-0.7, with 0.7 representing a mass to mass ratio of COF monomer dosed to theoretical mass of carbon nanotubes of 0.7.
The obtained OER catalyst was subjected to a performance test, and the test results are shown in fig. 1.
Example 3
A preparation method of an OER catalyst compounded by carbon nanotubes and a covalent organic framework comprises the following steps:
(1) putting 3.5mg of carbon nano tube and 1mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin in a glass bottle, adding 2mL of mixed solution of n-butyl alcohol/o-dichlorobenzene (volume ratio is 1:1), ultrasonically mixing for 30 minutes (ultrasonic power is 200W), adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain mixed solution;
(2) dissolving 0.4mg of terephthalaldehyde in 400 microliters of a mixed solution of n-butanol/o-dichlorobenzene (volume ratio is 1:1) and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution in the step (1), and continuing to perform ultrasonic treatment for 20 minutes; and transferring the mixed solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the mixed solution in a 120 ℃ oven for reaction for 72 hours under the condition of keeping the vacuumizing state. After the reaction is finished, washing the obtained product for 4 times by using a cyclohexane/methanol mixed solution, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ overnight to obtain COF @ CNT powder;
(3) adding COF @ CNT powder (3mg) and 10mg of cobalt acetate into a 50mL flask, adding 20mL of anhydrous methanol, and uniformly stirring (the stirring speed is 600rpm, and the stirring time is 30min) to perform reaction; setting up a condensation reflux device in the reaction process, refluxing for 6 hours under the condition of stirring at 80 ℃, taking the reaction solution, centrifugally washing the reaction solution for three times by using methanol after cooling to room temperature, and drying the reaction solution in a vacuum oven at 80 ℃ overnight; an OER catalyst was obtained, named COF-Co @ CNT-0.4, with 0.4 representing a mass to mass ratio of COF monomer dosed to theoretical mass of carbon nanotubes of 0.4.
The obtained OER catalyst was subjected to a performance test, and the test results are shown in fig. 1.
Example 4
A preparation method of an OER catalyst compounded by carbon nanotubes and a covalent organic framework comprises the following steps:
(1) putting 4mg of carbon nanotube and 0.5mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin in a glass bottle, adding 2mL of mixed solution of n-butyl alcohol/o-dichlorobenzene (volume ratio is 1:1), ultrasonically mixing for 30 minutes (ultrasonic power is 200W), adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain mixed solution;
(2) dissolving 0.2mg of terephthalaldehyde in 400 microliters of a mixed solution of n-butanol/o-dichlorobenzene (volume ratio is 1:1) and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution in the step (1), and continuing to perform ultrasonic treatment for 20 minutes; and transferring the mixed solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the mixed solution in a 120 ℃ oven for reaction for 72 hours under the condition of keeping the vacuumizing state. After the reaction is finished, washing the obtained product for 4 times by using a cyclohexane/methanol mixed solution, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ overnight to obtain COF @ CNT powder;
(3) adding COF @ CNT powder (3mg) and 10mg of cobalt acetate into a 50mL flask, adding 20mL of anhydrous methanol, and uniformly stirring (the stirring speed is 600rpm, and the stirring time is 30min) to perform reaction; setting up a condensation reflux device in the reaction process, refluxing for 6 hours under the condition of stirring at 80 ℃, taking the reaction solution, centrifugally washing the reaction solution for three times by using methanol after cooling to room temperature, and drying the reaction solution in a vacuum oven at 80 ℃ overnight; an OER catalyst was obtained, designated COF-Co @ CNT-0.175, with 0.175 representing a mass to charge COF monomer to theoretical mass to charge carbon nanotubes ratio of 0.175.
The obtained OER catalyst was subjected to a performance test, and the test results are shown in fig. 1.
FIG. 1 is a plot of the polarization of the COF-Co @ CNT-x four different COFs loaded materials in examples 1-4 in 1M KOH. At 10mA/cm2The current density is taken as a reference, and the obtained potential value-the theoretical potential value of the oxygen evolution reaction is 1.23V, thus obtaining the over potential value. And comparing the overpotential value corresponding to the material to judge the catalytic oxygen evolution performance of the material. The lower the overpotential value is, the smaller the voltage required to be applied is, the lower the energy consumption is, and the better the catalytic performance is. As shown in FIG. 1, the overpotential values for COF-Co @ CNT-2.8, COF-Co @ CNT-0.7, COF-Co @ CNT-0.4, and COF-Co @ CNT-0.175 were 425mV, 390mV, 358mV, and 395mV, respectively. Through comparison, the performance of the obtained composite catalyst is firstly reduced and then improved when the composite catalyst catalyzes OER with the increase of the input amount of the COFs monomer, wherein the COF-Co @ CNT-0.4 in example 3 is used for obtaining the best performance.
FIGS. 2 and 3 show the micro-morphology of the COF-Co @ CNT-0.4 composite material; FIG. 2 is a field scanning electron micrograph: the CNTs uniformly load the COFs layer, and no obvious local aggregation exists; FIG. 3 is a transmission electron micrograph: the CNTs crystal wall is covered with a uniform 3-5 nanometer COFs layer.
FIG. 4 is a small angle XRD spectrum of COF-Co and COF-Co @ CNT-0.4: the coordination of COF to Co ions and the complexation with CNTs do not affect the crystallinity of COFs.
FIG. 5 is an infrared spectrum of COF-Co @ CNT-0.4. As can be seen from the figure: the organic composition of the material after the reaction has taken place, where the main C ═ N and Co — N bonds support the formation of COFs and the formation of Co ions coordinated to the COFs.
Example 5 parameter optimization
The 10mg of cobalt acetate in example 3 was replaced with 3.3mg of cobalt acetate and the other conditions or parameters were identical to those of example 3 to give COF-1/3Co @ CNT-0.4. Using the same electrochemical test conditions as in examples 1-4, carbon nanotubes were found to be at 10mA/cm2The overpotential at (a) is 365 mV.
The 10mg of cobalt acetate in example 3 was replaced with 6.6mg of cobalt acetate and the other conditions or parameters were identical to those of example 3 to give COF-2/3Co @ CNT-0.4. Using the same electrochemical test conditions as in examples 1-4, carbon nanotubes were found to be at 10mA/cm2The overpotential at (a) is 360 mV.
Comparative example 1
Omitting the carbon nanotubes in example 1, obtaining COF-Co under the same conditions or parameters as in example 1, and finding that the COF-Co could not obtain 10mA/cm in the set voltage range by using the same electrochemical test conditions as in examples 1-42Indicating that the catalytic performance of COF — Co is poor.
Comparative example 2
Using the same electrochemical test conditions as in examples 1-4 using carbon nanotubes as a catalyst, carbon nanotubes were found to be at 10mA/cm2The overpotential at (A) is 484mV, which indicates that the carbon nanotubes alone have poor catalytic performance.
Comparative example 3
The metal cobalt salt (cobalt acetate) in example 1 was omitted, and the other conditions or parameters were the same as those in example 1, to obtain COFs-carbon nanotubes.
Using the same electrochemical test conditions as in examples 1-4 with the COFs-carbon nanotubes as catalysts, it was found that the COFs-carbon nanotubes could not obtain 10mA/cm within the set voltage range2Indicating catalysis of the COFs-carbon nanotubesThe chemical properties are poor.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (13)

1. The OER catalyst compounded by the carbon nano tube and the covalent organic framework is characterized in that the components of the OER catalyst comprise a molecular catalyst and a conductive carbon carrier, wherein the molecular catalyst is formed by the coordination of Covalent Organic Frameworks (COFs) and metal ions, and the conductive carbon carrier is Carbon Nano Tube (CNTs);
the mass ratio of the molecular catalyst to the conductive carbon carrier is 30:1-1: 20;
the method for preparing the OER catalyst compounded by the carbon nano tube and the covalent organic framework comprises the following steps:
(1) weighing carbon nano tube CNTs and a monomer containing polyamino COFs, dissolving the CNTs and the monomer in a mixed solvent together to form a monomer solution; then adding a catalyst, mixing uniformly, adding a solution containing the polyaldehyde COFs monomer, and mixing uniformly to obtain a mixed solution; freezing and vacuumizing the mixed solution, and then carrying out in-situ growth reaction; after the reaction is finished, washing, centrifuging and drying to obtain COF @ CNT powder;
(2) dispersing the COF @ CNT powder obtained in the step (1) in a solvent, adding a metal salt, and uniformly mixing for reaction; after the reaction is finished, collecting, washing and drying to obtain the OER catalyst compounded by the carbon nano tube and the covalent organic framework;
wherein the mass ratio of the CNTs to the monomers containing the polyamino COFs in the step (1) is 40: 1-1: 20.
2. a method for preparing the OER catalyst in which carbon nanotubes are composited with a covalent organic framework as described in claim 1, comprising the steps of:
(1) weighing carbon nano tube CNTs and a monomer containing polyamino COFs, dissolving the CNTs and the monomer in a mixed solvent together to form a monomer solution; then adding a catalyst, mixing uniformly, adding a solution containing the polyaldehyde COFs monomer, and mixing uniformly to obtain a mixed solution; freezing and vacuumizing the mixed solution, and then carrying out in-situ growth reaction; after the reaction is finished, washing, centrifuging and drying to obtain COF @ CNT powder;
(2) dispersing the COF @ CNT powder obtained in the step (1) in a solvent, adding a metal salt, and uniformly mixing for reaction; after the reaction is finished, collecting, washing and drying to obtain the OER catalyst compounded by the carbon nano tube and the covalent organic framework;
wherein the mass ratio of the CNTs to the monomers containing the polyamino COFs in the step (1) is 40: 1-1: 20.
3. the method according to claim 2, wherein the mass and volume ratio of the CNTs and the constituent monomers containing the polyamino COFs in step (1) to the mixed solvent is 2-15 mg/mL.
4. The method according to claim 2 or 3, wherein the mixed solvent in the step (1) is n-butanol and o-dichlorobenzene, and the volume ratio of n-butanol to o-dichlorobenzene is 2:1-1: 2.
5. the method according to claim 2 or 3, wherein the catalyst in step (1) is 3M acetic acid solution, and the amount of the 3M acetic acid solution is 0.05-0.4mL of acetic acid solution per mL of the mixed solvent.
6. The method according to claim 4, wherein the catalyst in step (1) is 3M acetic acid solution, and the amount of the 3M acetic acid solution is 0.05-0.4mL of acetic acid solution per mL of the mixed solvent.
7. The method of claim 4, wherein the conditions of the in-situ growth reaction of step (1) are as follows: reacting for 60-80h at 90-130 ℃.
8. The method according to any one of claims 2, 3 and 6, wherein the conditions of the in-situ growth reaction in step (1) are as follows: reacting for 60-80h at 90-130 ℃.
9. The process of claims 2, 3, 6, 7, wherein the mass to volume ratio of COF @ CNT powder to solvent in step (2) is 0.05-0.5 mg/mL.
10. The process of claim 4, wherein the mass to volume ratio of COF @ CNT powder to solvent in step (2) is from 0.05 to 0.5 mg/mL.
11. The method according to any one of claims 2, 3, 6, 7 and 10, wherein the metal salt is added in the step (2) in an amount of 0.1 to 5 times the saturation amount of the coordination sites of the COFs.
12. The method according to claim 4, wherein the metal salt is added in step (2) in an amount of 0.1 to 5 times the saturation amount of coordination sites of the COFs.
13. Use of the OER catalyst of claim 1 in combination with a common organic framework in the electrolysis of water.
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