CN116099566B - Preparation method of platinum-doped modified cobalt-based catalyst - Google Patents
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Abstract
The invention provides a preparation method of a platinum doped modified cobalt-based catalyst. Firstly, cobalt chloride hexahydrate and urea are used as raw materials, a layer of basic cobalt salt grows in situ on a substrate material through a hydrothermal reaction, then a layer of dopamine high polymer is wrapped on the surface of the basic cobalt salt to prevent the dopamine high polymer from falling off, the basic cobalt salt is soaked in a chloroplatinic acid solution to promote ion exchange between platinum ions and cobalt ions, so that a platinum doped basic cobalt salt precursor with the dopamine high polymer wrapped on the surface layer is obtained, and finally the platinum doped modified cobalt-based catalytic material is obtained by annealing the platinum doped basic cobalt salt precursor in a dicyandiamide atmosphere under the protection of argon.
Description
Technical Field
The invention relates to preparation of high-catalytic-performance electrocatalyst, which is applied to the field of green energy storage and conversion devices represented by fuel cells, water electrolysis devices and rechargeable metal-based batteries.
Background
Continuous consumption of fossil fuels such as petroleum, coal, etc. has prompted the development of high-efficiency energy storage and conversion technologies. Rechargeable metal-air batteries, water electrolysis devices and fuel cells are receiving attention for their inherent environmental friendliness, high energy density and safety of energy conversion. Hydrogen Evolution Reaction (HER), oxygen Evolution Reaction (OER) are two important reactions for the electrolysis of water, and Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) are considered two key processes for rechargeable metal-air batteries. These electrochemical reactions are slow in kinetics and generally require the overcoming of large overpotentials, and efforts have been made to search for electrocatalysts with high catalytic activity in order to accelerate the reaction process. At present, the widely used catalyst is mainly a noble metal-based catalyst, but the noble metal-based catalyst has scarce reserves and high cost, and is not suitable for large-scale popularization and application. The development of non-noble metal-based catalysts to reduce or replace the use of noble metal-based catalysts is an effective approach to solving the current problems.
In recent years, transition metal-nitrogen-carbon (TM-N-C) materials have been widely reported in OER and ORR, which are considered as the most promising cathode materials for rechargeable metal-air batteries. In general, the ORR electrocatalytic activity of transition metals in alkaline medium is in turn Fe > Co > Ni, while the OER electrocatalytic activity thereof is in turn Ni > Co > Fe. Clearly, the Co-N-C material is a very promising bifunctional catalyst, which also benefits from its modest free energy of adsorption-dissolution for ORR and OER intermediates. And the electronic structure of the metal cobalt (Co) is closest to that of noble metal platinum (Pt), so that the catalyst is an ideal platinum-based catalyst substitute. However, the catalytic performance of the Co-N-C catalytic material is still inferior to that of a platinum-based catalyst, if a small amount of Pt can be doped into the Co-N-C catalytic material, whether the catalyst has catalytic performance superior or not inferior to that of the platinum-based catalytic material can be ensured, and the cost of the catalyst can be effectively controlled due to the small doping amount of Pt. The method has great research significance and practical value in promoting the large-scale commercial application of the electrocatalytic material.
While carbon nanotubes (NCNTs), which are nitrogen-doped carbon (NC) base materials supporting transition metals, have large specific surface area, high conductivity, porosity, corrosion resistance, and characteristics of easy chemical modification by introducing metal sites, are considered to be ideal carriers for imparting high activity and durability to electrocatalysts. If Co@NCNTs are used as a base material and a small amount of noble metal Pt is doped to obtain the platinum doped cobalt-based catalytic material, the cobalt-based catalytic material has high catalytic potential.
Disclosure of Invention
In view of this, the present invention provides a method for obtaining a platinum doped modified cobalt-based catalyst by one-step annealing, the preparation of which comprises the following steps:
The preparation method of the platinum doped modified cobalt-based catalyst comprises the following steps:
S1, dipping a basic cobalt salt substrate material coated with a dopamine high polymer in a chloroplatinic acid solution to obtain a substrate material growing with a platinum doped basic cobalt salt precursor coated with a polydopamine high polymer on the surface layer;
s2, placing the substrate material obtained in the step S1 in a tube furnace, adding dicyandiamide, and annealing under the protection of argon to obtain the platinum doped modified cobalt-based catalyst.
Dissolving cobalt chloride and urea in deionized water, and growing a needle-shaped basic cobalt salt array on a conductive substrate by using a chemical bath deposition method to obtain a basic cobalt salt-grown substrate material;
and (3) soaking the substrate material growing with the basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface of the substrate material with deionized water, and drying to obtain the uniform dopamine high polymer coated on the surface layer of the basic cobalt salt.
The load of the basic cobalt salt on the substrate material is 0.5-2 mg/cm 2.
The concentration of the dopamine hydrochloride is 0.1-0.4 mg/L, and the soaking time of the substrate material in the dopamine hydrochloride buffer solution is 12-24 h.
The molar ratio of the platinum ions in the chloroplatinic acid solution to the cobalt ions in the basic cobalt salt (Co (OH) 2) loaded by the substrate material is 3:100-10:100.
The cobalt-platinum ion replacement temperature is 30-80 ℃ and the replacement time is 12-24 h.
The annealing temperature is 700-900 ℃ and the annealing time is 2-3 h.
Firstly, dissolving cobalt chloride hexahydrate and urea with a certain mass in deionized water, magnetically stirring to obtain a uniform solution, pouring the solution into a glass test tube, and putting the substrate into the solution to submerge the solution through the substrate, wherein the basic cobalt salt can uniformly grow on the substrate for fully contacting the substrate with the solution. And then putting the test tube into a constant temperature oven for hydrothermal reaction for a certain time, cooling, taking out, flushing the substrate material with water, and drying to obtain the basic cobalt salt growing on the substrate material in situ. This step serves to allow uniform growth of the basic cobalt salt on the substrate.
And secondly, coating the dopamine high polymer, namely dissolving dopamine hydrochloride in a weak alkaline buffer solution with the pH value of about 7.5-8.5 to prepare a dopamine hydrochloride buffer solution with a certain concentration, soaking a substrate material growing with basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface with deionized water, and drying to obtain the uniform dopamine high polymer coated on the surface layer of the basic cobalt salt. In this process, the pH of the buffer solution for dissolving dopamine hydrochloride is about 7.5-8.5, because dissolution of dopamine hydrochloride in pure water makes the solution acidic, and the acidic solution dissolves basic cobalt salts. Therefore, a weakly basic buffer must be used to solubilize and neutralize dopamine hydrochloride, and only in a neutral or weakly basic environment, the basic cobalt salt is stable. The effect of wrapping a layer of dopamine high polymer is equivalent to wrapping a layer of membrane on the outer layer of basic cobalt salt, so that the basic cobalt salt can stably grow on the base fiber without falling off. And, the high polymer may provide a nitrogen source in a subsequent annealing step to form a nitrogen-doped carbon structure.
And thirdly, doping platinum ions, namely immersing the substrate material obtained in the steps in a chloroplatinic acid solution, reacting for a certain time at a certain temperature to fully replace the platinum ions and the cobalt ions, and finally obtaining the substrate material of the platinum doped basic cobalt salt precursor with the surface layer coated with the polydopamine high polymer. Most of the platinum doped catalytic materials are doped with platinum after annealing, but the platinum is doped before annealing, and the catalytic material is obtained by one-step annealing. The preparation process of the invention is simpler and more convenient, and the platinum atoms can be distributed more uniformly in the Co/Pt Co-annealing process, so that more monoatomic platinum catalytic active sites can be formed, which is very beneficial to the catalytic performance of the catalyst.
And fourthly, precursor annealing, namely placing the Pt doped basic cobalt salt precursor, the surface layer of which is coated with the dopamine high polymer and grows on the substrate material, in the center of a tube furnace, taking a certain amount of dicyandiamide, placing the dicyandiamide in the upstream of the tube furnace, annealing for a certain time at a certain temperature under the protection of argon, and cooling and taking out the dicyandiamide to obtain the platinum doped modified cobalt-based catalytic material. In this process, the whole annealing process must be performed under the protection of argon. The high annealing temperature causes that the entering of a trace amount of air can influence the normal progress of the reaction. The annealing temperature and the annealing time are the key points of the catalyst to obtain high catalytic performance, and a large number of experiments to obtain an optimal scheme are also one of the key points of the invention.
Drawings
FIG. 1 shows ORR polarization curves of samples prepared in examples 1, 2, 3 and 4, as measured in oxygen saturated (a) alkaline, (b) neutral, (c) acid electrolyte.
Fig. 2 shows HER polarization curves measured in nitrogen saturated (a) alkaline, (b) neutral, (c) acidic electrolyte for the samples prepared in example 1, example 2, example 3 and example 4.
Fig. 3 is a graph showing the HOR polarization curves of the samples prepared in example 1, example 2, example 3 and example 4 in a hydrogen saturated alkaline electrolyte.
Fig. 4 is a HER polarization curve measured in a nitrogen saturated alkaline electrolyte for the sample prepared in example 5.
Fig. 5 is a HER polarization curve measured in a nitrogen saturated alkaline electrolyte for the sample prepared in example 6.
Fig. 6 is an XRD pattern of the samples prepared in example 1, example 3 and example 4.
Fig. 7 is an SEM image of the sample prepared in example 1.
Fig. 8 is an SEM image of the sample prepared in example 3.
Fig. 9 is an SEM image of the sample prepared in example 4.
Detailed Description
Characterization conditions:
All electrochemical tests are carried out by matching CHI760E electrochemical workstation of Shanghai Chen Hua instrument Limited company with CHI760E software. And the standard three-electrode device is assembled by taking a graphite electrode as an auxiliary electrode, a replaceable platinum electrode clamp and a test sample as working electrodes, and a mercury/mercury oxide electrode (alkaline environment), a silver/silver chloride electrode (neutral environment) or a mercury/mercury sulfite electrode (acid environment) as reference electrodes for testing.
ORR performance tests basic ORR tests of the examples of the invention were all performed in an oxygen saturated 0.1M potassium hydroxide solution, neutral ORR tests were all performed in an oxygen saturated mixed solution of dipotassium hydrogen phosphate and potassium dihydrogen phosphate (ph=7), and acidic ORR tests were all performed in an oxygen saturated 0.05M sulfuric acid solution.
HER performance tests alkaline HER tests of the examples of the invention were all performed in nitrogen saturated 1M potassium hydroxide solution, neutral HER tests were all performed in nitrogen saturated dibasic potassium phosphate and monobasic potassium phosphate mixed solution (ph=7), and acid HER tests were all performed in nitrogen saturated 0.05M sulfuric acid solution.
HOR Performance test the basic HOR test of the examples of this invention were all performed in a hydrogen saturated 0.1M potassium hydroxide solution.
Produced by Rigaku corporation of JapanXRD testing of the inventive examples by radiation UltimaIV type X-ray diffractometer TEM testing of the inventive examples was performed using a FEI Quanta 250 type scanning electron microscope manufactured by Rigaku corporation, japan.
Example 1
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 900 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
A-c in fig. 1 and table 1 show ORR catalytic performance of the example 1 samples in different electrolytes with half-wave potential (E 1/2) of 0.89V in alkaline electrolyte, E 1/2 =0.82 in neutral electrolyte, and E 1/2 =0.78V in acid electrolyte. A-c in fig. 2 and table 2 show HER catalytic performance of the example 1 samples in different electrolytes with 167mV overpotential required to achieve 10mA cm 2 current density in alkaline electrolyte, 135mV overpotential required to achieve 10mA cm 2 current density in neutral electrolyte, and 14mV overpotential required to achieve 10mA cm 2 current density in acid electrolyte. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the example 1 sample in alkaline electrolyte with a HOR half-wave potential of 18mV. The XRD and SEM images of the sample are shown in fig. 6 and 7.
Example 2
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 265uL of 1mol/L chloroplatinic acid isopropanol solution, and uniformly mixing (the mol ratio of cobalt to platinum is 100:3). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, soaking the carbon paper in the mixed solution, sealing the mixed solution, placing the carbon paper in a60 ℃ incubator for reaction for 24 hours, cooling the carbon paper, taking the carbon paper out, and washing the carbon paper with deionized water and drying the carbon paper. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 900 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
A-c in fig. 1 and table 1 show ORR catalytic performance in alkaline electrolyte for the example 2 sample with a half-wave potential (E 1/2) of 0.91V. A-c in fig. 2 and table 2 show HER catalytic performance in the alkaline electrolyte of the sample of example 2, with 167mV overpotential required to achieve 10mA cm 2 current density and 180mV overpotential required to achieve 10mA cm 2 current density in the neutral electrolyte. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the example 2 sample in alkaline electrolyte with a HOR half-wave potential of 7mV.
Example 3
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, soaking the carbon paper in the mixed solution, sealing the mixed solution, placing the carbon paper in a60 ℃ incubator for reaction for 24 hours, cooling the carbon paper, taking the carbon paper out, and washing the carbon paper with deionized water and drying the carbon paper. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 900 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
A-c in fig. 1 and table 1 show ORR catalytic performance of the example 3 samples in different electrolytes with half-wave potential (E 1/2) of 0.92V in alkaline electrolyte, E 1/2 =0.89 in neutral electrolyte and E 1/2 =0.86V in acid electrolyte. A-c in fig. 2 and table 2 show HER catalytic performance of the example 3 samples in different electrolytes with an overpotential of 131mV required to achieve a 10mA cm 2 current density in alkaline electrolyte, 126mV required to achieve a 10mA cm 2 current density in neutral electrolyte, and 1mV required to achieve a 10mA cm 2 current density in acidic electrolyte. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the sample of example 3 in alkaline electrolyte with a HOR half-wave potential of 6mV. The XRD and SEM images of the sample are shown in fig. 6 and 8. Table 4 shows the element content of the sample of example 3, from which the atomic ratio of platinum to cobalt is less than 5:100.
Example 4
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. 3mL of a 1:1 volume ratio of methanol and DMF was taken, 880uL of 1mol/L chloroplatinic acid isopropyl alcohol solution was added and mixed well (molar ratio of cobalt to platinum was 100:10). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, soaking the carbon paper in the mixed solution, sealing the mixed solution, placing the carbon paper in a60 ℃ incubator for reaction for 24 hours, cooling the carbon paper, taking the carbon paper out, and washing the carbon paper with deionized water and drying the carbon paper. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 900 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
A-c in fig. 1 and table 1 show ORR catalytic performance of the example 4 samples in different electrolytes with half-wave potential (E 1/2) of 0.92V in alkaline electrolyte, E 1/2 =0.89 in neutral electrolyte and E 1/2 =0.85V in acid electrolyte. A-c in fig. 2 and table 2 show HER catalytic performance of the example 4 samples in different electrolytes with 116mV overpotential required to achieve 10mA cm 2 current density in alkaline electrolyte, 126mV overpotential required to achieve 10mA cm 2 current density in neutral electrolyte, and 4mV overpotential required to achieve 10mA cm 2 current density in acid electrolyte. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the sample of example 4 in alkaline electrolyte with a HOR half-wave potential of 6mV. The XRD and SEM images of the sample are shown in fig. 6 and 9.
Example 5
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, soaking the carbon paper in the mixed solution, sealing the mixed solution, placing the carbon paper in a60 ℃ incubator for reaction for 24 hours, cooling the carbon paper, taking the carbon paper out, and washing the carbon paper with deionized water and drying the carbon paper. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 700 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
FIG. 4 is a plot of HER polarization measured in alkaline electrolyte for the sample of example 5, which achieves a 10mA cm 2 current density with a 66mV overpotential.
Example 6
1.428G of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking the Dongli carbon paper with the area of 10cm 2(2.5×5cm2), washing with absolute ethyl alcohol, putting the Dongli carbon paper into a mixture of water and alcohol, taking out the mixture after ultrasonic treatment for 15min, and cleaning the mixture with deionized water. The above-mentioned hydrothermal reagent and Dongli carbon paper (2.5X5 cm 2) were transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat-treated at 90℃for 2 hours. And cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of the basic cobalt salt on the carbon paper is 1mg/cm 2). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, soaking the carbon paper in the mixed solution, sealing the mixed solution, placing the carbon paper in a60 ℃ incubator for reaction for 24 hours, cooling the carbon paper, taking the carbon paper out, and washing the carbon paper with deionized water and drying the carbon paper. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃ per minute, reacting at a constant temperature for 1h, heating to 800 ℃ at 3 ℃ per minute, and reacting at a constant temperature for 2h to obtain a final sample.
FIG. 5 is a plot of HER polarization measured in alkaline electrolyte for a sample of example 6, which achieves a 10mA cm 2 current density with a 60mV overpotential.
TABLE 1 ORR catalytic performance data comparison of samples of different examples in alkaline, neutral and acidic systems
TABLE 2 comparison of HER catalytic Performance data for samples of different examples in alkaline, neutral and acidic systems
TABLE 3 comparison of HOR catalytic Performance data for samples of different examples in alkaline systems
TABLE 4 element content table for example three samples
Claims (3)
1. The preparation method of the platinum doped modified cobalt-based catalyst is characterized by comprising the following steps:
S1, dipping a basic cobalt salt substrate material coated with a dopamine polymer in a chloroplatinic acid solution to obtain a substrate material growing with a platinum doped basic cobalt salt precursor coated with a polydopamine polymer on the surface layer, wherein the molar ratio of platinum ions in the chloroplatinic acid solution to cobalt ions in basic cobalt salt Co (OH) 2 loaded by the substrate material is 5:100 or 10:100, the cobalt-platinum ion replacement temperature is 30-80 ℃, the replacement time is 12-24: 24 h, and the loading amount of basic cobalt salt on the substrate material is 0.5-2 mg/cm 2;
S2, placing the substrate material obtained in the step S1 in a tube furnace, adding dicyandiamide, and annealing under the protection of argon to obtain the platinum doped modified cobalt-based catalyst, wherein the annealing temperature is 700-900 ℃ and the annealing time is 2-3 h.
2. The preparation method of the platinum doped modified cobalt-based catalyst according to claim 1, wherein the preparation method of the basic cobalt salt base material coated with the dopamine high polymer comprises the steps of dissolving cobalt chloride and urea in deionized water, and growing a needle-shaped basic cobalt salt array on a conductive base by utilizing a chemical bath deposition method to obtain the base material with the basic cobalt salt;
and (3) soaking the substrate material growing with the basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface of the substrate material with deionized water, and drying to obtain the uniform dopamine high polymer coated on the surface layer of the basic cobalt salt.
3. The method for preparing the platinum doped modified cobalt-based catalyst according to claim 2, wherein the concentration of dopamine is 0.1-0.4 mg/L, and the soaking time of the substrate material in the dopamine hydrochloride buffer solution is 12-24 h.
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