阅读说明：本技术 一种燃料电池负极催化剂材料的制备方法 (Preparation method of fuel cell cathode catalyst material ) 是由 崔大祥 李梦飞 葛美英 张芳 于 2021-08-17 设计创作，主要内容包括：本发明公开一种燃料电池负极催化剂材料的制备方法,该材料为Fe/Co@rGO@s-C-(3)N-(4),在水热条件下,利用硫脲加热分解生成的s-C-(3)N-(4)作为前驱体,在掺杂氧化石墨烯与铁盐、钴盐,形成上面镶嵌Fe、Co的三维片网结构,不仅能够扩大催化剂的接触面积,还有利于离子与电子的运输过程。水热法制备方法简单,反应温度低,无需后续处理条件且该复合材料对氧气还原反应具有优良的催化活性和稳定性,该发明制备的Fe/Co-s-C-(3)N-(4)@rGO复合材料不仅可用于燃料电池阴极催化剂,同时还可应用于传感器和超级电容器等领域。(The invention discloses a preparation method of a fuel cell anode catalyst material, which is Fe/Co @ rGO @ s-C 3 N 4 s-C formed by thermal decomposition of thiourea under hydrothermal conditions 3 N 4 As a precursor, graphene oxide, iron salt and cobalt salt are doped to form a three-dimensional sheet-mesh structure with Fe and Co embedded on the surface, so that the contact area of the catalyst can be enlarged, and the transportation process of ions and electrons is facilitated. The hydrothermal method has the advantages of simple preparation method, low reaction temperature, no need of subsequent treatment conditions, excellent catalytic activity and stability of the composite material to oxygen reduction reaction, and Fe/Co-s-C prepared by the method 3 N 4 Not only useful as @ rGO compositeThe catalyst can be used as a cathode catalyst of a fuel cell, and can also be applied to the fields of sensors, super capacitors and the like.)

1. A preparation method of a fuel cell anode catalyst material is provided, wherein the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄Characterized in that s-C formed by thermal decomposition of thiourea is used under hydrothermal conditions₃N₄As a precursor, doping graphene oxide with iron salt and cobalt salt to form a three-dimensional sheet mesh structure with Fe and Co embedded on the surface, and the method comprises the following steps:

(1) respectively weighing 0.1-0.5 g of iron salt and cobalt salt, and placing the iron salt and the cobalt salt in a beaker, wherein the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02 g-0.1 g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 deg.C to obtain the final productFe/[email protected]@s-C₃N₄Sample catalyst.

2. The method for preparing a fuel cell anode catalyst material according to claim 1, characterized in that: rGO is reduced graphene oxide, s-C₃N₄Is sulfur doped carbon nitride.

3. The method for preparing a fuel cell anode catalyst material according to claim 1, characterized in that: in the step (2), the iron salt is at least one of ferric chloride, ferric nitrate and ferric sulfate, and the cobalt salt is at least one of cobalt chloride, cobalt nitrate and cobalt sulfate.

4. The method for preparing a fuel cell anode catalyst material according to any one of claims 1 to 3, characterized by comprising the steps of:

(1) 0.1g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

5. The method for preparing a fuel cell anode catalyst material according to any one of claims 1 to 3, characterized by comprising the steps of:

(1) 0.5g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.1g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

6. The method for preparing a fuel cell anode catalyst material according to any one of claims 1 to 3, characterized by comprising the steps of:

(1) 0.25g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

7. The method for preparing a fuel cell anode catalyst material according to any one of claims 1 to 3, characterized by comprising the steps of:

(1) 0.3g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.1g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

Technical Field

The invention relates to a preparation method of a fuel cell cathode catalyst material, in particular to a carbon-based transition metal doped s-C₃N₄A method for preparing a particle composite material.

Background

Generally, the energy conversion rate of the fuel cell can reach 40-60%, and the fuel cell has a relatively high energy conversion rate. Meanwhile, the fuel cell has no moving part, so that the fuel cell is quite quiet and does not generate noise in the operation process; furthermore, there is also little emission of atmospheric pollutants throughout the operation, for example, when hydrogen is used as a fuel, the only product is water. Therefore, the fuel cell is a high-efficiency and environment-friendly sustainable energy device. The most obstacle to large-scale commercial application of fuel cells is the cost problem caused by using noble metals such as Pt as catalysts, so research and development of non-noble metal cathode catalysts with wide raw material sources, low cost and high ORR catalytic activity to replace noble metal catalysts is the most key technology for reducing the cost of fuel cells and promoting large-scale commercial application of fuel cells.

In recent years, carbon materials have been studied because of their low cost, wide sources of raw materials, and simple synthesis processes. Carbon nitride is a novel carbon material with a unique two-dimensional structure, excellent chemical stability and tunable electronic structure. It plays a key role in the aspects of photodegradation of organic pollutants, hydrogen evolution in water, fluorescent probe detection, biological imaging and the like. Various heteroatoms are doped in the carbon nanostructure to modify the electronic structure of the carbon material, thereby changing the inert carbon into an active catalyst for ORR.

Graphene oxide is a very ideal electrocatalyst support material due to its small size, large surface area, low density, high electrical conductivity and thermal conductivity. This patent uses graphene oxide and s-C₃N₄As a carbon carrier, the method develops a new carbon-based electrocatalyst synthesis method by taking the design and preparation of an economic, efficient and stable oxygen reduction catalyst as a main research target. Due to Fe, Co and s-C₃N₄Strong coupling and synergy between @ rGO, Fe/Co @ rGO @ s-C₃N₄The composite material shows excellent catalytic activity and stability to ORR.

Disclosure of Invention

The invention aims to provide a preparation method of a fuel cell cathode catalyst material. Not only can enlarge the contact area of the catalyst, but also is beneficial to the transportation process of ions and electrons.

The purpose of the invention is realized by the following scheme: a preparation method of a fuel cell anode catalyst material is provided, wherein the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄s-C formed by thermal decomposition of thiourea under hydrothermal conditions₃N₄As a precursor, doping graphene oxide with iron salt and cobalt salt to form a three-dimensional sheet mesh structure with Fe and Co embedded on the surface, and the method comprises the following steps:

(1) respectively weighing 0.1-0.5 g of iron salt and cobalt salt, and placing the iron salt and the cobalt salt in a beaker, wherein the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02 g-0.1 g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

rGO is reduced graphene oxide, s-C₃N₄Is sulfur doped carbon nitride.

In the step (2), the iron salt is at least one of ferric chloride, ferric nitrate and ferric sulfate, and the cobalt salt is at least one of cobalt chloride, cobalt nitrate and cobalt sulfate.

By using a simpler method, s-C is doped with carbon-based transition metal₃N₄Preparation of Fe/Co-s-C from particles₃N₄The @ rGO composite material has excellent catalytic activity and stability for oxygen reduction reaction. Thus this kind ofThe composite material can be used as a high-efficiency fuel cell cathode catalyst, and can also be applied to the fields of sensors, supercapacitors and the like. The method for preparing the catalyst can be further developed and applied in the field of preparation of other materials.

The hydrothermal method has the advantages of simple preparation method, low reaction temperature, no need of subsequent treatment conditions, excellent catalytic activity and stability of the composite material to oxygen reduction reaction, and Fe/Co-s-C prepared by the method₃N₄The @ rGO composite material can be used for a fuel cell cathode catalyst, and can also be applied to the fields of sensors, supercapacitors and the like.

Drawings

FIG. 1: Fe/Co @ rGO @ s-C₃N₄TEM image of sample catalyst;

FIG. 2: Fe/Co @ rGO @ s-C₃N₄Sample CV performance curves.

Detailed Description

Example 1:

the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄s-C formed by thermal decomposition of thiourea under hydrothermal conditions₃N₄Doping graphene oxide with iron salt and cobalt salt to form a three-dimensional sheet mesh structure with Fe and Co embedded on the surface, and preparing the three-dimensional sheet mesh structure by the following steps:

(1) 0.1g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

FIG. 1 is a TEM image of the sample obtained in this example, from which it is clear that the nanoparticles and the lamellar rGO and s-C are visible₃N₄The CV performance curve of the sample measured by the three-electrode method is shown in FIG. 2, and the result shows that the sample has an obvious oxidation-reduction peak, which shows that the sample has excellent catalytic performance.

Example 2:

the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄Similar to the step of the example 1, the preparation method comprises the following steps:

(1) 0.5g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.1g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

Example 3:

the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄Similar to the step of the example 1, the preparation method comprises the following steps:

(1) 0.25g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.02g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging and cleaning the obtained product with deionized water at a speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

Example 4:

the fuel cell anode catalyst material is Fe/Co @ rGO @ s-C₃N₄Similar to the step of the example 1, the preparation method comprises the following steps:

(1) 0.3g of iron salt and cobalt salt are respectively weighed and placed in a beaker, and the molar ratio of the iron salt to the cobalt salt is 2: 1, weighing 0.1g of graphene oxide and placing the graphene oxide in the beaker;

(2) then 2g of thiourea was placed in a semi-closed porcelain boat, which was placed in a tube furnace under N₂Heating the mixture to 550 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, preserving heat for 4 hours, and then naturally cooling the mixture to obtain a powder sample;

(3) adding the powder sample into the beaker in the step (1), adding 20 ml of ethylene glycol, mixing and stirring, stirring the obtained solution in a water bath at the temperature of 80 ℃ for 10 hours, and drying at the temperature of 80 ℃ for 5 hours;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 hours at 160 ℃, and cooling to room temperature;

(5) centrifuging the obtained product with deionized water at a speed of 10000 r/min5 min, and then drying at 50 ℃ to obtain the final Fe/Co @ rGO @ s-C₃N₄Sample catalyst.

The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.