CN110743603B - Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof - Google Patents

Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof Download PDF

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CN110743603B
CN110743603B CN201911146213.4A CN201911146213A CN110743603B CN 110743603 B CN110743603 B CN 110743603B CN 201911146213 A CN201911146213 A CN 201911146213A CN 110743603 B CN110743603 B CN 110743603B
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cobalt
carbon cloth
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water
iron
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CN110743603A (en
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朱桂生
姜德立
邵守言
谢吉民
许宝华
陈钢
权彪
黄春霞
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Jiangsu Sopo Engineering Technology Co ltd
JIANGSU SOPO (GROUP) CO Ltd
Jiangsu University
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JIANGSU SOPO (GROUP) CO Ltd
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Abstract

The invention discloses a cobalt-iron bimetal nitride composite electrocatalyst and a preparation method thereof. The electrocatalyst comprises the following components in percentage by mass: 20-52% of iron nitride, 44-26% of cobalt nitride and the balance of carbon cloth. The preparation method comprises the following steps: refluxing the carbon cloth with concentrated nitric acid, cleaning and drying; preparing a cobalt nitrate aqueous solution, adding the cobalt nitrate aqueous solution into a prepared 2-methylimidazole aqueous solution, stirring and mixing uniformly, then adding the treated carbon cloth into the obtained mixed solution, reacting at room temperature, cleaning and drying to obtain a ZIF-67/carbon cloth composite material, adding the ZIF-67/carbon cloth composite material into a prepared potassium ferrocyanide aqueous solution, reacting at room temperature, cleaning and drying, calcining, and cooling to room temperature to obtain the iron nitride/cobalt nitride/carbon cloth composite material. The prepared electrocatalyst can greatly reduce the overpotential and Tafel slope, has good conductivity, and can greatly improve the efficiency of preparing oxygen by decomposing water and catalyzing the composite electrocatalyst.

Description

Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of electrocatalysis, and relates to a cobalt-iron bimetallic nitride composite electrocatalyst, and a preparation method and application thereof.
Background
At present, the energy crisis and the environmental pollution seriously threaten the survival and development of human beings. With the increasing exhaustion of fossil fuels, the search for clean and sustainable energy sources has become an urgent issue. Hydrogen energy has attracted much attention because of its cleanliness, non-pollution, and high combustion value. In the development and utilization of hydrogen energy, electrochemical decomposition hydrogen production is one of the current ideal hydrogen production ways because fossil energy is not directly consumed and the process operation is simple. The water electrolysis mainly comprises two reactions of cathode electrochemical catalytic Hydrogen Evolution Reaction (HER) and anode electrochemical catalytic Oxygen Evolution Reaction (OER). Among them, OER has a slow kinetic process due to the involvement of multiple electron transfer, and requires a high overvoltage for effective driving, which has become a bottleneck that hinders the efficiency of water electrolysis. The OER electrocatalyst with better performance at present is mainly a noble metal catalyst such as Ir, Ru and the like. However, such catalysts are expensive and difficult to apply to large-scale electrolysis of water. Therefore, the development of efficient and low-cost OER electrocatalysts has become an important direction of research in this field.
In recent years, transition metal oxides and hydroxides have been widely used in the water decomposition as electrocatalysts with abundant terrestrial resources and low cost. The activity of the electrocatalyst is closely related to the surface structure and the adsorption energy of intermediates on the surface of the metal oxide. In general, the OER activity of an electrocatalyst is strongly influenced by the surface structure, and the surface state can be further changed by introducing a foreign element, resulting in a significant decrease in the overpotential of the OER, resulting in an increase in the electrocatalytic activity. Thus, binary metal oxides and hydroxides exhibit excellent electrocatalytic activity for OER due to their inherent electronic structure. However, the poor electronic conductivity and limited active sites of these binary metal oxides and hydroxides have greatly limited their large-scale application. Transition Metal Nitrides (TMNs) have better conductivity and higher chemical stability than metal oxides, which results in more efficient electron transfer during the catalytic redox process of water. In addition, the N atom may also regulate the electronic structure of the metal matrix. Metal Organic Frameworks (MOFs) have been widely used as templates to build hollow or porous structures to achieve excellent thermal properties and chemical reactivity. In addition to the direct strategy of converting MOFs into end products, MOFs can be further expanded by converting one MOF into another MOF by post-synthesis methods such as ligand exchange reactions and cation exchange reactions. However, both of these methods have technical problems including complicated heating process, time consumption, and indispensability in some cases of use of toxic organic solvents (such as methanol or dimethylformamide). Therefore, there is an urgent need to develop a gentle time and energy saving method to achieve MOF to MOF conversion.
Disclosure of Invention
The invention aims to provide a cobalt-iron bimetallic nitride composite electrocatalyst. The specific technical scheme is as follows:
a cobalt-iron bimetal nitride composite electrocatalyst comprises the following components in percentage by mass: 20-52% of iron nitride, 44-26% of cobalt nitride and the balance of carbon cloth.
Preferably, the thickness of the carbon cloth is 100-500 μm, and the density is 50-200 g/m2。
The invention also aims to provide a preparation method of the cobalt-iron bimetal nitride composite electrocatalyst. The specific technical scheme is as follows:
a preparation method of a cobalt-iron bimetal nitride composite electrocatalyst comprises the following steps:
(1) pretreatment of Carbon Cloth (CC)
Refluxing the carbon cloth with concentrated nitric acid, then sequentially ultrasonically cleaning the carbon cloth with deionized water, acetone and ethanol, and drying to obtain clean carbon cloth;
(2) preparation of Carbon Cloth (CC) -based zeolitic imidazolate frameworks (ZIF-67)
Dissolving 2-methylimidazole in water, and stirring until the solution is clear to obtain a 2-methylimidazole water solution A; dissolving cobalt nitrate in water, and stirring until the cobalt nitrate is completely dissolved to obtain a cobalt nitrate aqueous solution B; quickly adding the solution B into the solution A, and stirring until the solution B is uniformly mixed to obtain a mixed solution C; adding the clean carbon cloth obtained in the previous step into the mixed solution C, reacting (precipitating) at room temperature for 1-6 h, taking out the carbon cloth, washing with water, washing with alcohol, and drying to obtain a ZIF-67/carbon cloth composite material;
(3) Preparation of CC-based cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC)
Adding potassium ferrocyanide into water, and stirring until a clear solution is obtained, so as to obtain a potassium ferrocyanide water solution; adding the ZIF-67/carbon cloth composite material obtained in the previous step into the potassium ferrocyanide aqueous solution, reacting at room temperature (ligand exchange reaction) for 5-8 h, washing with water, washing with alcohol, and drying to obtain a precursor; introducing NH into the obtained precursor at the temperature of 300-400 DEG C3Keeping the mixed gas for 1-5 hours, and cooling to room temperature to obtain an iron nitride/cobalt nitride/carbon cloth composite material, namely the cobalt-iron bimetal nitride composite electrocatalyst;
wherein the molar ratio of cobalt nitrate to 2-methylimidazole to carbon cloth to potassium ferrocyanide is 1:8: 1-10: 0.5-2.
Preferably, the molar concentration of the 2-methylimidazole aqueous solution is 0.1-0.9 mol/L, the molar concentration of the cobalt nitrate aqueous solution is 0.01-0.09 mol/L, and the mass concentration of the potassium ferrocyanide aqueous solution is 5-20 g/L.
Preferably, the concentration of the concentrated nitric acid in the step (1) is 10-20 mol/L, the reflux temperature in the step (1) is 80-150 ℃, and the reflux time is 8-24 h.
Preferably, the drying is vacuum drying at the temperature of 30-90 ℃ for 6-24 hours.
The invention also aims to provide application of the cobalt-iron bimetal nitride composite electrocatalyst. The specific technical scheme is as follows:
the cobalt-iron bimetallic nitride composite electrocatalyst is applied to an electrocatalytic Oxygen Evolution Reaction (OER) of electrolyzed water.
The invention has the beneficial effects that:
the prepared electrocatalyst can greatly reduce the overpotential and the Tafel curve slope (Tafel slope), has good conductivity, and can greatly improve the efficiency of preparing oxygen by decomposing water and catalyzing by the composite electrocatalyst. In addition, the composite electrocatalyst synthesized by ligand exchange reaction with carbon cloth as substrate has excellent structure and appearance, and can reduce the internal resistance of electrode, raise its conducting capacity and raise the catalytic activity of the material obviously. Therefore, the cobalt-iron bimetallic nitride is synthesized by taking the carbon cloth as a substrate material, is applied to water decomposition and oxygen production, and has better application prospect.
The preparation method is synthesized by simple precipitation and calcination reaction, has simple steps, mild reaction, short reaction time, convenient operation, environment friendliness and strong repeatability; in addition, the reaction activity of the catalyst is greatly improved by applying construction interface engineering. Compared with the electrocatalysis material prepared by the prior art, the material greatly increases the specific surface area of the electrocatalysis by utilizing the special structure of the carbon cloth CC, provides more active sites, and the nano-array structure is beneficial to the release of bubbles and simultaneously avoids the reduction of the conductivity and the blockage of the reaction active sites caused by using an adhesive. The electrocatalyst material prepared by the technical scheme not only has outstanding high stability, high activity and corrosion resistance, but also has the characteristics of easy exposure of reaction sites, high electron transmission efficiency and the like, can be widely applied to the fields of water electrolysis oxygen production, alkaline medium electrolysis and the like, and is easy to realize industrial application.
Drawings
FIG. 1 is an XRD diffraction pattern of FeN/CoN/CC-15 prepared in example 1.
FIG. 2a is a SEM (scanning Electron microscope) photograph of simple ZIF-67 prepared in step (2) of example 1; FIGS. 2b and 2c are SEM photographs of the FeN/CoN/CC-15 electrocatalyst prepared in example 1; FIG. 2d is a TEM photograph of simple ZIF-67 prepared in step (2) of example 1; FIGS. 2e and 2f are TEM photographs of the FeN/CoN/CC-15 electrocatalyst prepared in example 1.
FIG. 3 is a comparison of polarization curves of the oxygen evolution reaction of the electrocatalysts prepared in examples 1-6 under the condition of 1mol/L NaOH.
FIG. 4 is a graph showing a comparison of the slopes of the Tafel curves of the oxygen evolution reaction of the electrocatalysts prepared in examples 1 to 6 under the condition of 1mol/L NaOH.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, the density is 120g/m2) Firstly using 16mol/L
Refluxing concentrated nitric acid at 120 deg.C for 12h, sequentially ultrasonic cleaning with deionized water, acetone and ethanol, and vacuum drying (60 deg.C, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, stirring to obtain a clear solution to obtain a potassium ferrocyanide aqueous solution with the concentration of 15mg/mL, adding the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 5 hours at room temperature, after the reaction is finished, washing with water, washing with alcohol, and drying in vacuum (60 ℃, 12 hours) to obtain a precursor; heating the obtained precursor at 400 deg.C at 2 deg.C/min, introducing NH3Keeping the/Ar mixed gas for 2 hours, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-15 cobalt-iron bimetallic nitride composite electrocatalyst.
Embodiment 2, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) Cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, and the density is 120g/m2) Firstly refluxing for 12h at 120 ℃ by 16mol/L concentrated nitric acid, then carrying out ultrasonic cleaning by deionized water, acetone and ethanol in sequence, and carrying out vacuum drying (60 ℃, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, and stirring until a clear solution is obtained, wherein the concentration of the deionized water is 5mg/mLAdding a potassium ferrocyanide aqueous solution into the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 5h at room temperature, washing with water and alcohol after the reaction is finished, and carrying out vacuum drying (60 ℃, 12h) to obtain a precursor; heating the obtained precursor at 400 deg.C at 2 deg.C/min, introducing NH 3Maintaining the/Ar mixed gas for 2 hours, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-5 cobalt-iron bimetal nitride composite electrocatalyst.
Embodiment 3, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, the density is 120g/m2) Firstly refluxing for 12h at 120 ℃ by 16mol/L concentrated nitric acid, then carrying out ultrasonic cleaning by deionized water, acetone and ethanol in sequence, and carrying out vacuum drying (60 ℃, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, stirring to obtain a clear solution to obtain a potassium ferrocyanide aqueous solution with the concentration of 10mg/mL, adding the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 5 hours at room temperature, after the reaction is finished, washing with water, washing with alcohol, and drying in vacuum (60 ℃, 12 hours) to obtain a precursor; heating the obtained precursor at 400 deg.C at 2 deg.C/min, introducing NH 3Keeping the/Ar mixed gas for 2 hours, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-10 cobalt-iron bimetallic nitride composite electrocatalyst.
Embodiment 4, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, the density is 120g/m2) Firstly refluxing for 12h at 120 ℃ by 16mol/L concentrated nitric acid, then carrying out ultrasonic cleaning by deionized water, acetone and ethanol in sequence, and carrying out vacuum drying (60 ℃, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, stirring to obtain a clear solution to obtain a potassium ferrocyanide aqueous solution with the concentration of 20mg/mL, adding the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 5 hours at room temperature, after the reaction is finished, washing with water, washing with alcohol, and drying in vacuum (60 ℃, 12 hours) to obtain a precursor; heating the obtained precursor at 400 deg.C at 2 deg.C/min, introducing NH 3Maintaining the/Ar mixed gas for 2 hours, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-20 cobalt-iron bimetal nitride composite electrocatalyst.
Example 5, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, and the density is 120g/m2) Firstly refluxing for 12h by 16mol/L concentrated nitric acid at the temperature of 120 ℃, then carrying out ultrasonic cleaning by deionized water, acetone and ethanol in sequence, and carrying out vacuum drying (60 ℃, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, stirring to obtain a clear solution to obtain a potassium ferrocyanide aqueous solution with the concentration of 15mg/mL, adding the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 5 hours at room temperature, after the reaction is finished, washing with water, washing with alcohol, and drying in vacuum (60 ℃, 12 hours) to obtain a precursor; heating the obtained precursor at 300 deg.C at 2 deg.C/min, introducing NH 3Keeping the/Ar mixed gas for 2 hours, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-300 cobalt-iron bimetallic nitride composite electrocatalyst.
Embodiment 6, preparation of a cobalt-iron bimetallic nitride composite electrocatalyst (FeN/CoN/CC) with Carbon Cloth (CC) as a substrate, comprising the following specific steps:
(1) cutting the cut CC (2cm is multiplied by 5cm, the thickness is 360 mu m, and the density is 120g/m2) Firstly refluxing for 12h at 120 ℃ by 16mol/L concentrated nitric acid, then carrying out ultrasonic cleaning by deionized water, acetone and ethanol in sequence, and carrying out vacuum drying (60 ℃, 12h) to obtain clean CC.
(2) 1.3136g of 2-methylimidazole is weighed, 40mL of deionized water is added, and stirring is carried out until a clear solution is obtained, so as to obtain a 2-methylimidazole water solution A; 0.5821g of cobalt nitrate is weighed, 40mL of deionized water is added and stirred until the cobalt nitrate is completely dissolved, a cobalt nitrate aqueous solution B is obtained, the solution B is rapidly added into the solution A, and the mixture is stirred until the mixture is uniformly mixed, so that a mixed solution C is obtained. Adding a cleaned carbon cloth into the mixed solution C, performing precipitation reaction for 2 hours at room temperature, taking out the carbon cloth after the reaction is finished, washing with water and alcohol, and performing vacuum drying (60 ℃, 12 hours) to obtain a ZIF-67/CC composite material;
(3) weighing potassium ferrocyanide (K)4[Fe(CN)6]) Adding 50mL of deionized water, stirring to obtain a clear solution to obtain a potassium ferrocyanide aqueous solution with the concentration of 15mg/mL, adding the ZIF-67/CC composite material obtained in the previous step, carrying out ligand exchange reaction for 8 hours at room temperature, after the reaction is finished, washing with water, washing with alcohol, and drying in vacuum (60 ℃, 12 hours) to obtain a precursor; heating the obtained precursor at 400 deg.C at 2 deg.C/min, introducing NH 3Keeping the/Ar mixed gas for 2h, calcining, and cooling to room temperature after the reaction is finished to obtain the FeN/CoN/CC-8h cobalt-iron bimetallic nitride composite electrocatalyst.
Example 7 testing
The test method comprises the following steps:
and (3) analyzing the composition morphology of the product by using an X-ray diffractometer (XRD) and a Scanning Electron Microscope (SEM). A three-electrode reaction device is adopted, a platinum wire is used as a counter electrode, a silver/silver chloride (Ag/AgCI) electrode is used as a reference electrode, and the electrochemical performance of the product is tested in 1mol/L NaOH electrolyte.
(1) Electrocatalytic activity experiment of cobalt-iron bimetallic nitride composite electrocatalyst
NaOH solution with the concentration of 1mol/L is used as electrolyte, a three-electrode reaction device is adopted, Pt is used as a counter electrode, Ag/AgCI is used as a reference electrode, the scanning speed is 5mV/s, and the performance of the cobalt-iron bimetal nitride composite electrocatalyst for electrocatalytic decomposition of water to produce oxygen in the solution is tested.
(2) EXAMPLES characterization analysis of Co-Fe bimetallic nitride composite electrocatalysts
FIG. 1 is an XRD diffraction pattern of FeN/CoN/CC-15 prepared in example 1, and it can be seen from the figure that the strong peaks in the XRD pattern of the composite material FeN/CoN/CC-15 are consistent with those of carbon cloth CC, which are diffraction peaks of carbon cloth, and the rest diffraction peaks correspond to FeN and CoN, which shows that the cobalt-iron bimetal nitride composite electrocatalyst FeN/CoN/CC is successfully prepared.
FIG. 2a is a scanning electron micrograph of pure ZIF-67 prepared in step (2) of example 1, and it can be seen from FIG. 2a that ZIF-67 is a nanosheet array; FIGS. 2b and 2c show that FeN/CoN/CC-15 prepared in example 1 is a nanosheet array; FIG. 2d is a TEM image of ZIF-67 of step (2) of example 1, with smooth nanoplatelets visible; FIG. 2e is a TEM image of the FeN/CoN/CC-15 electrocatalyst prepared in example 1, with porous nanoplatelets visible; FIG. 2f is a high resolution electron micrograph of the FeN/CoN/CC-15 electrocatalyst prepared in example 1, showing that the lattice fringes of the material are similar to those of FeN and CoN, respectively, which is the same as the result reflected by the XRD pattern.
FIG. 3 is a comparison graph of polarization curves of the cobalt-iron bimetallic nitride composite electrocatalyst prepared in examples 1 to 6 in the oxygen evolution reaction under the condition of 1mol/LNaOH, and it can be analyzed from the graph that the electrocatalytic activity of the composite material shows good catalytic activity, wherein the electrocatalytic activity of the FeN/CoN/CC-15 electrocatalyst is superior to that of other samples, and the current density is 10mA cm-2The corresponding oxygen evolution overpotential is 270 mV.
FIG. 4 is a graph comparing the slopes of Tafel curves of the FeN/CoN/CC electrocatalysts prepared in examples 1-6 in the oxygen evolution reaction under the condition of 1mol/LNaOH, and it can be seen from FIG. 4 that the FeN/CoN/CC-15 electrocatalysts have smaller Tafel slopes than other samples.

Claims (5)

1. The cobalt-iron bimetal nitride composite electrocatalyst is characterized by comprising the following components in percentage by mass: 20-52% of iron nitride, 44-26% of cobalt nitride and the balance of carbon cloth; the thickness of the carbon cloth is 100-500 μm, and the density is 50-200 g/m2(ii) a The preparation method comprises the following steps:
(1) refluxing the carbon cloth with concentrated nitric acid, then sequentially ultrasonically cleaning the carbon cloth with deionized water, acetone and ethanol, and drying to obtain clean carbon cloth;
(2) dissolving 2-methylimidazole in water, and stirring until the solution is clear to obtain a 2-methylimidazole water solution A; dissolving cobalt nitrate in water, and stirring until the cobalt nitrate is completely dissolved to obtain a cobalt nitrate aqueous solution B; quickly adding the solution B into the solution A, and stirring until the solution B is uniformly mixed to obtain a mixed solution C; adding the clean carbon cloth obtained in the previous step into the mixed solution C, reacting at room temperature for 1-6 h, taking out the carbon cloth, washing with water, washing with alcohol, and drying to obtain a ZIF-67/carbon cloth composite material;
(3) adding potassium ferrocyanide into water, and stirring until a clear solution is obtained, so as to obtain a potassium ferrocyanide water solution; adding to the aqueous potassium ferrocyanide solutionReacting the ZIF-67/carbon cloth composite material obtained in the step at room temperature for 5-8 h, washing with water, washing with alcohol, and drying to obtain a precursor; introducing NH into the obtained precursor at the temperature of 300-400 DEG C 3Keeping the mixed gas for 1-5 hours, and cooling to room temperature to obtain an iron nitride/cobalt nitride/carbon cloth composite material, namely the cobalt-iron bimetal nitride composite electrocatalyst;
wherein the molar ratio of cobalt nitrate to 2-methylimidazole to carbon cloth to potassium ferrocyanide is 1:8: 1-10: 0.5-2;
the molar concentration of the 2-methylimidazole aqueous solution is 0.1-0.9 mol/L, the molar concentration of the cobalt nitrate aqueous solution is 0.01-0.09 mol/L, and the mass concentration of the potassium ferrocyanide aqueous solution is 5-20 g/L.
2. The cobalt-iron bimetallic nitride composite electrocatalyst according to claim 1, characterized in that the concentration of the concentrated nitric acid in the step (1) is 10-20 mol/L
3. The cobalt-iron bimetal nitride composite electrocatalyst according to claim 1, wherein the reflux temperature in step (1) is 80-150 ℃, and the reflux time is 8-24 h.
4. The cobalt-iron bimetal nitride composite electrocatalyst according to claim 1, wherein the drying is vacuum drying at 30-90 ℃ for 6-24 h.
5. The cobalt-iron bimetallic nitride composite electrocatalyst according to claim 1, is applied to electrocatalytic oxygen evolution reaction of electrolyzed water.
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