CN114990630B - Preparation method and application of hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivative - Google Patents
Preparation method and application of hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivative Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivatization, wherein the preparation method comprises the following steps: the CoM-ZIF-67 is obtained through the reaction of cobalt salt, metal salt and dimethyl imidazole; reacting the CoM-ZIF-67 with tannic acid to obtain CoM-ZIF-67-TA; calcining and carbonizing CoM-ZIF-67-TA under a protective atmosphere to obtain a target product; the three-dimensional regular dodecahedron structure is hollow, has excellent OER and HER electrocatalytic performance, has good application in electrolyzed water, and has the advantages of very simple manufacturing method, low cost and mild reaction condition.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a preparation method and application of a hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivatization.
Background
With the continuous development of the scientific society, fossil energy is continuously consumed in the global scope, and the ecological environment problem caused by the fossil energy in the process of consumption is also more serious, so that people start to develop sustainable and renewable energy sources continuously to replace fossil fuels. Hydrogen energy is one such sustainable, renewable energy source. Electrocatalytic total water splitting is one of the effective and sustainable ways to produce hydrogen energy, a green clean energy source, which involves two half-electrode reactions: hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER), but both of these reaction kinetics are slow, especially OER is a four electron transfer process, so efficient electrocatalysts are required to reduce the additional energy loss caused by multiple electron reactions.
RuO 2 And Pt are well-known electrocatalysts with excellent oxygen evolution and hydrogen evolution reactions, but their large-scale commercial application is limited due to their high cost and scarcity. Therefore, the development of non-noble metal electrocatalysts with high efficiency and wide application range is a focus of attention in the current scientific research community.
Disclosure of Invention
The invention aims to provide a preparation method and application of a hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivative, wherein the hollow bimetallic organic framework/nitrogen-doped carbon composite material electrocatalyst has very excellent electrochemical catalytic performance, has very good catalytic activity in hydrogen evolution reaction and oxygen evolution reaction, and can further enhance the hydrogen evolution reaction and the oxygen evolution reaction.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivatization comprises the following steps:
(1) Dissolving cobalt salt and other metal salts except the cobalt salt in an alcohol solvent, adding an alcohol solution of dimethyl imidazole into the mixture under the condition of stirring, standing for growth after the mixture is uniformly mixed, and washing and drying the mixture to obtain a bimetal organic framework material CoM-ZIF-67;
(2) Dissolving a bimetal organic frame material CoM-ZIF-67 in an alcohol solvent, adding a tannic acid solution into the solution under the condition of stirring, continuously stirring for a certain time after the addition, and washing and drying to obtain a hollow bimetal organic frame material CoM-ZIF-67-TA;
(3) Calcining and carbonizing a hollow bimetal organic framework material CoM-ZIF-67-TA in an inert atmosphere to obtain the hollow bimetal MOF/nitrogen doped carbon composite material electrocatalyst based on ZIF-67 derivatization.
In the step (1), the molar ratio of cobalt salt to other metal salts except the cobalt salt to the dimethylimidazole is 1 (1-100): 1-100, preferably 1:1 to 5:5 to 40, more preferably 1:1:32.
in the step (1), the concentration of the cobalt salt in the alcohol solvent is 0.01-0.2M, preferably 0.05-0.1M; the concentration of the alcohol solution of the dimethylimidazole is 0.1-1.0M, preferably 0.2-0.5M.
In the step (1), the condition of the static growth is 10-60 ℃ for 1-24 hours, preferably 20-35 ℃ for 18-24 hours, more preferably 25 ℃ for 24 hours.
In the step (1), the cobalt salt is selected from any one or two of cobalt nitrate and cobalt chloride; the other metal salts except cobalt salts are selected from any one of nickel salts, magnesium salts and zinc salts.
The nickel salt is selected from any one or two of nickel nitrate and nickel chloride.
The magnesium salt is selected from any one or two of magnesium nitrate and magnesium chloride.
The zinc salt is selected from any one or two of zinc nitrate and zinc chloride.
The alcohol solvent is selected from any one or two of methanol and ethanol.
In the step (2), the mass ratio of the CoM-ZIF-67 to the tannic acid is 1: (0.1 to 10), preferably 1:1 to 5, more preferably 1:2.5.
in the step (2), the tannic acid solution is an aqueous solution of tannic acid, and the concentration of the tannic acid solution is 1-10 g/L, preferably 4-7 g/L; the concentration of CoM-ZIF-67 in the alcoholic solvent is 0.01 to 0.1g/mL, preferably 0.05g/mL.
In the step (2), the stirring is continued at 10℃to 60℃for 1 to 60 minutes, preferably at 20℃to 35℃for 5 to 15 minutes, more preferably at 25℃for 10 minutes.
In the step (3), the inert atmosphere is argon or nitrogen; the condition of calcination carbonization is to heat up to 300-900 ℃ for 1-8 h at a heating rate of 1-10 ℃/min, preferably to 450-580 ℃ at a heating rate of 1-5 ℃/min for 1.5-3 h, more preferably to 500 ℃ at a heating rate of 2 ℃/min for 2h.
The invention also provides a hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivative, which is prepared by the preparation method and has a hollow dodecahedron framework structure.
The invention also provides application of the hollow bimetallic MOF/nitrogen-doped carbon composite electrocatalyst based on ZIF-67 derivative as a catalyst for HER or OER reaction.
The hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivatives is prepared by firstly introducing second-phase metal into ZIF-67, then etching the second-phase metal into tannic acid solution to obtain a hollow dodecahedron frame structure, and finally carbonizing the second-phase metal in inert atmosphere. The invention takes ZIF-67 as a precursor, not only provides a framework structure in the subsequent calcination, but also provides a nitrogen source, a carbon source and a cobalt source for the material, and the addition of the second phase metal and the heterostructure of the nitrogen-doped carbon material are complementary, so that the activation energy of the full water decomposition reaction can be reduced better.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivative is simple, the morphology of the hollow dodecahedron framework structure is large, the catalyst has a specific surface area, more active sites can be provided for the catalyst to participate in HER or OER reaction, and the catalyst has excellent electrochemical catalytic activity on OER and HER.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the pale purple solid CoNi-ZIF-67 prepared in step (1) of example 1 at 10000 times;
FIG. 2 is a Transmission Electron Micrograph (TEM) at 15000 magnification of the light brown solid CoNi-ZIF-67-TA prepared in step (2) of example 1;
FIG. 3 is a Scanning Electron Micrograph (SEM) at magnification of 80000 of the cobalt-nickel hollow bimetallic organic frame/nitrogen doped carbon composite material of example 1;
FIG. 4 is a Scanning Electron Micrograph (SEM) at 20000 magnification of a cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 1;
FIG. 5 is a magnified 15000-fold Transmission Electron Micrograph (TEM) of the hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 1;
FIG. 6 is a magnified 50000 times Transmission Electron Micrograph (TEM) of the cobalt-nickel hollow bimetallic organic framework/nitrogen doped carbon composite material prepared in example 1;
FIG. 7 is an XRD pattern of the cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 1;
FIG. 8 is a Scanning Electron Micrograph (SEM) at 35000 magnification of the cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material made of example 2;
FIG. 9 is a Scanning Electron Micrograph (SEM) at 90000 Xmagnification of a cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material produced in example 2;
FIG. 10 is an SEM image of a cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material made in example 3;
FIG. 11 is a Scanning Electron Micrograph (SEM) at 30000 Xmagnification of the cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 4;
FIG. 12 is a Scanning Electron Micrograph (SEM) at a magnification of 70000 of the cobalt-magnesium hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 5;
FIG. 13 is a Transmission Electron Micrograph (TEM) of the cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material prepared in example 6;
FIG. 14 is a graph showing oxygen evolution reaction performance test of electrochemical tests of the cobalt-nickel hollow bimetallic organic frameworks/nitrogen-doped carbon composites prepared in examples 1-3 and the nitrogen-doped carbon materials prepared in comparative example 1;
FIG. 15 is a graph showing the hydrogen evolution reaction performance test of electrochemical tests of the cobalt-nickel hollow bimetallic organic frameworks/nitrogen-doped carbon composites prepared in examples 1-3 and the nitrogen-doped carbon materials prepared in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to examples and drawings.
Example 1
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.465g of cobalt nitrate hexahydrate and 0.465g of nickel nitrate hexahydrate were weighed into 20mL of methanol to form a pink solution, designated solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally centrifuging, washing and drying to obtain a light purple solid CoNi-ZIF-67, wherein an SEM image is shown in figure 1;
(2) Weighing 0.1g of CoNi-ZIF-67 prepared in the step (1), dissolving in 2mL of ethanol, and carrying out ultrasonic stirring to form a uniform mixed solution A; then 0.25g of tannic acid is weighed and evenly dispersed in 48mL of deionized water to form light brown mixed solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 10min, and finally centrifuging, washing and drying to obtain light brown solid CoNi-ZIF-67-TA, wherein an SEM image is shown in FIG. 2;
(3) Placing the prepared CoNi-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-nickel hollow bimetallic organic frame/nitrogen-doped carbon composite material.
As shown in figures 3-6, the SEM and TEM show that the cobalt-nickel hollow bimetal organic framework/nitrogen doped carbon composite material prepared by the embodiment maintains the original three-dimensional dodecahedron framework structure of ZIF-67, has uniform size and particle size distribution of 250-300nm, and has the hollow characteristic inside, and the appearance provides a large specific surface area for the material.
The XRD pattern is shown in FIG. 7.
Example 2
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.465g of cobalt nitrate hexahydrate and 0.465g of nickel nitrate hexahydrate were weighed into 20mL of methanol to form a pink solution, designated solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally centrifuging, washing and drying to obtain a light purple solid CoNi-ZIF-67;
(2) Weighing 0.1g of CoNi-ZIF-67 prepared in the step (1), dissolving in 2mL of ethanol, and carrying out ultrasonic stirring to form a uniform mixed solution A; then 0.25g of tannic acid is weighed and evenly dispersed in 48mL of deionized water to form light brown mixed solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 10min, and finally centrifuging, washing and drying to obtain light brown solid CoNi-ZIF-67-TA;
(3) Placing the prepared CoNi-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-nickel hollow bimetallic organic frame/nitrogen-doped carbon composite material.
The SEM is shown in figures 8-9, and it can be seen from the figures that the cobalt-nickel hollow bimetallic organic framework/nitrogen-doped carbon composite material with the original ZIF-67 three-dimensional dodecahedron framework structure is prepared in the embodiment, the size is uniform, the particle size is distributed at 250-300nm, but the final carbonization inside the material is incomplete due to the reduction of the calcining carbonization temperature relative to the embodiment 1, and the catalytic performance of the material is affected to a certain extent.
Example 3
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.465g of cobalt nitrate hexahydrate and 0.465g of nickel nitrate hexahydrate were weighed into 20mL of methanol to form a pink solution, designated solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally centrifuging, washing and drying to obtain a light purple solid CoNi-ZIF-67;
(2) Weighing 0.1g of CoNi-ZIF-67 prepared in the step (1), dissolving in 2mL of ethanol, and carrying out ultrasonic stirring to form a uniform mixed solution A; then 0.25g of tannic acid is weighed and evenly dispersed in 48mL of deionized water to form light brown mixed solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 10min, and finally centrifuging, washing and drying to obtain light brown solid CoNi-ZIF-67-TA;
(3) Placing the prepared CoNi-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-nickel hollow bimetallic organic frame/nitrogen-doped carbon composite material.
The SEM is shown in figure 10, and it can be seen from the figure that the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material prepared by the embodiment maintains the original three-dimensional dodecahedron framework structure of ZIF-67, has uniform size and particle size distribution of 250-300nm, and has the hollow characteristic inside, and the morphology provides a large specific surface area for the material.
Example 4
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.465g of cobalt nitrate hexahydrate and 0.465g of nickel nitrate hexahydrate were weighed into 20mL of methanol to form a pink solution, designated solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally centrifuging, washing and drying to obtain a light purple solid CoNi-ZIF-67;
(2) Weighing 0.1g of CoNi-ZIF-67 prepared in the step (1), dissolving in 2mL of ethanol, and carrying out ultrasonic stirring to form a uniform mixed solution A; then 0.25g of tannic acid is weighed and evenly dispersed in 48mL of deionized water to form light brown mixed solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 10min, and finally centrifuging, washing and drying to obtain light brown solid CoNi-ZIF-67-TA;
(3) Placing the prepared CoNi-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 600 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-nickel hollow bimetallic organic frame/nitrogen-doped carbon composite material.
As shown in the SEM image of FIG. 11, since the temperature of calcination and carbonization is raised to 600 ℃ relative to that of example 1, metal particles in the material are clustered together, and the final product cannot maintain the original ZIF-67 three-dimensional dodecahedron framework structure.
Example 5
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.620g of cobalt nitrate hexahydrate and 0.274g of magnesium nitrate hexahydrate were weighed into 20mL of methanol to form a pink solution, designated as solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally centrifuging, washing and drying to obtain a light purple solid CoMg-ZIF-67;
(2) Weighing 0.1g of CoMg-ZIF-67 prepared in the step (1), dissolving in 2mL of ethanol, and carrying out ultrasonic stirring to form a uniform mixed solution A; then 0.25g of tannic acid is weighed and evenly dispersed in 48mL of deionized water to form light brown mixed solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 10min, and finally centrifuging, washing and drying to obtain light brown solid CoMg-ZIF-67-TA;
(3) Placing the prepared CoMg-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as a protective gas, heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-magnesium hollow bimetallic organic frame/nitrogen-doped carbon composite material, wherein an SEM (scanning electron microscope) diagram is shown in figure 12.
Example 6
The preparation method of the cobalt-nickel hollow bimetal organic framework/nitrogen-doped carbon composite material comprises the following steps of:
(1) 0.621g of cobalt nitrate hexahydrate and 0.310g of nickel nitrate hexahydrate were weighed out in 20mL of methanol to form a pink solution, designated as solution A, and 4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B. Solution B was slowly added to solution A with stirring, stirring was continued for 1 hour, then allowed to stand for 24 hours, and finally dried by centrifugation to give a pale violet solid CoNi-ZIF-67.
(2) 0.2g of CoNi-ZIF-67 prepared in the step (1) is weighed and dissolved in 4mL of ethanol, ultrasonic stirring is carried out to form a uniform mixed solution A, and 0.50g of tannic acid is weighed and uniformly dispersed in 96mL of deionized water to form a light brown mixed solution B. Solution B was slowly added to solution A with stirring, stirring continued for 10min, and finally the dried single pale brown solid CoNi-ZIF-67-TA was washed by centrifugation.
(3) Placing the prepared CoNi-ZIF-67-TA in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain a black solid nitrogen-doped carbon material, namely the final product cobalt-nickel hollow bimetallic organic frame/nitrogen-doped carbon composite material.
SEM or TEM images thereof are shown in fig. 13, from which it can be seen that the simultaneous increase in the molar ratio does not affect the morphology of the final product.
Comparative example 1
The preparation method of the nitrogen-doped carbon material CoNi-ZIF-67/NC comprises the following steps:
(1) 0.465g of cobalt nitrate hexahydrate and 0.465g of nickel nitrate hexahydrate were weighed and dissolved in 20mL of methanol to form a pink solution, designated as solution A;4.200g of dimethylimidazole was dissolved in 160mL of methanol to form a clear solution B; slowly adding the solution B into the solution A under stirring, continuously stirring for 1 hour, standing and growing for 24 hours, and finally obtaining a light purple solid CoNi-ZIF-67 through centrifugal washing and drying;
(2) The method comprises the following steps of (1) carrying out treatment; placing the CoNi-ZIF-67 in a porcelain boat, placing the porcelain boat in a tube furnace, adopting argon as protective gas, heating to 600 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, and naturally cooling to obtain the black solid nitrogen-doped carbon material, namely the CoNi-ZIF-67/NC.
Application example 1
Application of hollow bimetal organic framework/nitrogen-doped carbon composite material as Oxygen Evolution Reaction (OER) catalyst
7mg of the hollow bimetallic organic frameworks prepared in examples 1-3, respectively, were each doped with carbonThe composite material and the CoNi-ZIF-67/NC prepared in comparative example 1 were milled with 2mg of acetylene black and 1mg of polyvinylidene fluoride (PVDF) powder added to agate mortar, wherein acetylene black was used as a conductive agent and PVDF was used as a binder until fine powder was obtained, and then 50mL of N-methyl-2-pyrrolidone (NMP) was added as a solvent to form a uniform mixture. Uniformly coating the obtained mixture on clean Nickel Foil (NF) with the size of 1cm multiplied by 1cm to obtain a uniform thin layer, wherein the uniform thin layer is used as a working electrode, a platinum sheet electrode is a counter electrode, an Ag/AgCl electrode is a reference electrode, and an electrolyte is potassium hydroxide solution with the concentration of 1 mol/L; at 5 mV.s by Linear Sweep Voltammetry (LSV) -1 The polarization curve is obtained at a scan rate of 90% and with an ohmic compensation. As shown in FIG. 14, the current density was 10mA cm -2 When the hollow bimetal organic frame/nitrogen doped carbon composite material prepared in the example 1 is used as a working electrode, the OER overpotential is 181mV, which indicates that the material has excellent electrochemical catalytic activity on OER.
Application example 2
Application of hollow bimetal organic framework/nitrogen-doped carbon composite material as Hydrogen Evolution Reaction (HER) catalyst
Coating the hollow bimetal organic frame/nitrogen-doped carbon composite material prepared in the examples 1-3 and the CoNi-ZIF-67/NC prepared in the comparative example 1 on nickel foil to serve as a working electrode according to the method in the application example 1, wherein a carbon rod electrode is a counter electrode, an Ag/AgCl electrode is a reference electrode, and an electrolyte is a potassium hydroxide solution of 1 mol/L; at 5 mV.s by Linear Sweep Voltammetry (LSV) -1 The polarization curve is obtained at a scan rate of 90% and with an ohmic compensation. As shown in FIG. 15, the current density was 10mA cm -2 When the hollow bimetallic organic frame/nitrogen-doped carbon composite material prepared in example 1 is used as a working electrode OER overpotential of 62mV, the material shows excellent electrochemical catalytic activity on HER, and the electrochemical catalytic activity of the hollow bimetallic organic frame/nitrogen-doped carbon composite material prepared in example 1 on HER > the electrochemical catalytic activity of the hollow bimetallic organic frame/nitrogen-doped carbon composite material prepared in example 3 on HER > the electrochemical catalytic activity of the hollow bimetallic organic frame/nitrogen-doped carbon composite material prepared in example 2 on HERThe chemical catalytic activity is greater than that of the nitrogen-doped carbon material CoNi-ZIF-67/NC prepared in comparative example 1.
The foregoing detailed description of a preparation method and application of a hollow bimetallic MOF/nitrogen doped carbon composite electrocatalyst based on ZIF-67 derivatives is illustrative and not limiting, and several examples can be listed according to the scope defined thereby, without departing from the general inventive concept, and therefore, shall fall within the scope of protection of the present invention.
Claims (10)
1. The preparation method of the hollow bimetallic MOF/nitrogen-doped carbon composite material electrocatalyst based on ZIF-67 derivatization is characterized by comprising the following steps of:
(1) Dissolving cobalt salt and other metal salts except the cobalt salt in an alcohol solvent, adding an alcohol solution of dimethyl imidazole into the mixture under the condition of stirring, standing for growth after the mixture is uniformly mixed, and washing and drying the mixture to obtain a bimetal organic framework material CoM-ZIF-67;
(2) Dissolving a bimetal organic frame material CoM-ZIF-67 in an alcohol solvent, adding a tannic acid solution into the solution under the condition of stirring, continuously stirring for a certain time after the addition, and washing and drying to obtain a hollow bimetal organic frame material CoM-ZIF-67-TA;
(3) Calcining and carbonizing a hollow bimetal organic framework material CoM-ZIF-67-TA in an inert atmosphere to obtain the hollow bimetal MOF/nitrogen doped carbon composite material electrocatalyst based on ZIF-67 derivatization.
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of cobalt salt, other metal salts than cobalt salt, and dimethylimidazole is 1 (1-100): 1-100.
3. The method according to claim 1, wherein in the step (1), the condition of the stationary growth is 10 ℃ to 60 ℃ for 1 to 24 hours.
4. A method according to any one of claims 1 to 3, wherein in step (1), the cobalt salt is selected from any one or two of cobalt nitrate and cobalt chloride; the other metal salts except cobalt salts are selected from any one of nickel salts, magnesium salts and zinc salts.
5. The method according to claim 1, wherein the alcohol solvent is one or both of methanol and ethanol.
6. The method according to claim 1, wherein in the step (2), the mass ratio of CoM-ZIF-67 to tannic acid is 1: (0.1 to 10).
7. The method according to claim 1, wherein in the step (2), the continuous stirring is performed at 10 ℃ to 60 ℃ for 1 to 60 minutes.
8. The method of claim 1, wherein in step (3), the inert atmosphere is argon or nitrogen; the conditions of calcination and carbonization are that the temperature is raised to 300-900 ℃ at a heating rate of 1-10 ℃/min, and the temperature is kept for 1-8 hours.
9. The hollow bimetallic MOF/nitrogen-doped carbon composite electrocatalyst based on ZIF-67 derivatives prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a ZIF-67 derived hollow bimetallic MOF/nitrogen doped carbon composite electrocatalyst according to claim 9 as a catalyst for HER or OER reactions.
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