CN112002915B - Oxygen electrode bifunctional catalyst, preparation method and application - Google Patents

Oxygen electrode bifunctional catalyst, preparation method and application Download PDF

Info

Publication number
CN112002915B
CN112002915B CN202010717988.9A CN202010717988A CN112002915B CN 112002915 B CN112002915 B CN 112002915B CN 202010717988 A CN202010717988 A CN 202010717988A CN 112002915 B CN112002915 B CN 112002915B
Authority
CN
China
Prior art keywords
salt
oxygen electrode
carbon carrier
bifunctional catalyst
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010717988.9A
Other languages
Chinese (zh)
Other versions
CN112002915A (en
Inventor
王楠
文陈
冯磊
刘景军
白晶莹
崔庆新
李思振
张立功
王景润
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Satellite Manufacturing Factory Co Ltd
Original Assignee
Beijing Satellite Manufacturing Factory Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Satellite Manufacturing Factory Co Ltd filed Critical Beijing Satellite Manufacturing Factory Co Ltd
Priority to CN202010717988.9A priority Critical patent/CN112002915B/en
Publication of CN112002915A publication Critical patent/CN112002915A/en
Application granted granted Critical
Publication of CN112002915B publication Critical patent/CN112002915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to an oxygen electrode bifunctional catalyst, a preparation method and application, wherein a carbon carrier is taken as a reducing agent, and the carbon carrier and iridium salt are subjected to reduction reaction at high temperature to obtain simple substance iridium, namely, the simple substance iridium is loaded on the surface of the carbon carrier to form Ir/C; and then Ir/C is used as a carrier, ethylene glycol is used as a reducing agent, Ir/C is mixed with platinum salt, cobalt salt and tungsten salt, the mixture reacts at constant temperature in an oil bath to realize the precipitation of simple substances of platinum, cobalt and tungsten on Ir/C, and the catalyst PtCoW-Ir/C is obtained.

Description

Oxygen electrode bifunctional catalyst, preparation method and application
Technical Field
The invention relates to an oxygen electrode bifunctional catalyst, a preparation method and application, and belongs to the technical field of electrocatalysts.
Background
With the development of socio-economy, people have increasingly demanded energy. However, as the use of fossil fuels is increased, the exhaustion of fossil fuels and environmental pollution become more serious, and people are eagerly interested in the development and application of renewable energy sources. Such as wind, hydroelectric, and solar cells and fuel cells, among others. Among them, fuel cells are receiving wide attention due to their advantages of high energy density, high power density, low operating temperature, small size, etc. Fuel cells may not only act as energy storage devices, storing electrical energy in the form of hydrogen. And can also be used as a battery to convert chemical energy into electric energy. Secondary fuel cells involve the reduction of oxygen and electrolysis of water, but O2The reduction and precipitation of (A) involves a four-electron-perThe process is a very slow kinetic process. Therefore, it is required to develop a highly efficient catalyst having both oxygen reduction and oxygen evolution catalytic performances.
At present, non-noble metals are studied as oxygen electrode catalysts, such as transition metal compounds of Fe, Co, Ni and the like, and metal-N-C catalysts of Co-N-C, Fe-N-C and the like, but the performances of the catalysts are poorer than those of Pt and Ir, the stability and the like are not superior, the catalysts can only be applied to alkaline conditions, and no commercial alkaline exchange membrane exists at present. Therefore, the development of a bifunctional catalyst with an excellent noble metal-based oxygen electrode is necessary for the application of fuel cells in the fields of aerospace and the like. The best material of the OER catalyst at present is Ir or Ru and oxide IrO thereof2And RuO2However, the ORR performance is poor. The catalyst with the best ORR performance is currently Pt-based, but the OER performance of Pt is poor. The conventional oxygen electrode catalyst is currently prepared by mechanically mixing a catalyst having an OER active component and a catalyst having an ORR active component. However, this way both the OER performance of the OER active component and the ORR performance of the ORR active component are greatly reduced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an oxygen electrode bifunctional catalyst and a preparation method thereof, wherein the catalyst is a two-phase metal nanoparticle composite catalyst with PtCoW and Ir commonly loaded on a carbon carrier, has high-efficiency oxygen precipitation and oxygen reduction bifunctional catalytic performance, is simple and convenient in preparation method, can be applied to energy conversion devices such as a rechargeable fuel cell, a zinc-air battery and the like, and has excellent performance.
Another object of the present invention is to provide an application of the oxygen electrode bifunctional catalyst.
The above purpose of the invention is mainly realized by the following technical scheme:
a preparation method of an oxygen electrode bifunctional catalyst comprises the steps of firstly, taking a carbon carrier as a reducing agent, carrying out reduction reaction with iridium salt at high temperature to obtain simple substance iridium, namely, loading the simple substance iridium on the surface of the carbon carrier to form Ir/C; and then mixing Ir/C with platinum salt, cobalt salt and tungsten salt by taking Ir/C as a carrier and ethylene glycol as a reducing agent, and reacting at constant temperature in an oil bath to realize the precipitation of platinum, cobalt and tungsten on Ir/C to obtain the catalyst PtCoW-Ir/C.
In the preparation method of the oxygen electrode bifunctional catalyst, the carbon carrier is graphene, carbon black, a carbon nanotube, graphitized carbon or porous carbon; the iridium salt is iridium tetrachloride.
In the preparation method of the oxygen electrode bifunctional catalyst, the platinum salt is chloroplatinic acid, the cobalt salt is cobalt chloride, and the tungsten salt is tungsten carbonyl.
In the preparation method of the oxygen electrode bifunctional catalyst, the specific method for forming Ir/C is as follows:
(1) ultrasonically dispersing a carbon carrier in a mixed solution of ethanol and water, adding iridium salt, continuously performing ultrasonic treatment for 0.5-1.5 h, then adding dopamine, then performing magnetic stirring for 8-12 h, and drying;
(2) and (2) putting the dried article in the step (1) into a high-temperature-resistant container, raising the temperature to 700-900 ℃ at a heating rate of 5-10 ℃/min, preserving the temperature for 1-3 h, and cooling to obtain Ir/C.
In the above preparation method of the oxygen electrode bifunctional catalyst, the volume ratio of ethanol to water in the step (1) is 1: 1-3; 5-20 mg of dopamine is added into every 50mg of carbon carrier.
In the preparation method of the oxygen electrode bifunctional catalyst, the mass ratio of the iridium salt added in the step (1) to the carbon carrier is 0.8-1.5: 1; the ratio of the carbon carrier to the mixed solution is 50mg of carbon carrier per 50-100 mL of mixed solution.
In the preparation method of the oxygen electrode bifunctional catalyst, Ir/C is used as a carrier to react with platinum salt, cobalt salt and tungsten salt to obtain the catalyst PtCoW-Ir/C, and the specific method is as follows:
(1) ultrasonically dispersing Ir/C in an ethylene glycol solution, adding platinum salt, cobalt salt and tungsten salt under magnetic stirring, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to 8-10 to obtain a suspension;
(2) placing the suspension obtained in the step (3) into a hydrothermal kettle, placing the hydrothermal kettle into a flask, and carrying out heat preservation in an oil bath at the temperature of 100-150 ℃ for 1-3 hours to obtain black slurry;
(3) and (4) washing and drying the black slurry obtained in the step (3) to obtain the oxygen electrode bifunctional catalyst PtCoW-Ir/C.
In the above preparation method of the oxygen electrode bifunctional catalyst, the proportion relationship between the ethylene glycol added in the step (1) and the carbon carrier in Ir/C is as follows: 30-60 mL of ethylene glycol is added for every 50mg of carbon carrier.
In the above preparation method of the oxygen electrode bifunctional catalyst, the proportion relationship between the platinum salt, the cobalt salt, and the tungsten salt added in step (1) and the carbon carrier in Ir/C is respectively: the amount of the platinum salt, the cobalt salt and the tungsten salt is 0.05 to 0.10mmol, 0.01 to 0.10mmol and 0.001 to 0.010mmol respectively per 50mg of the carbon carrier.
An oxygen electrode bifunctional catalyst is prepared by the preparation method.
The oxygen electrode bifunctional catalyst is solid powder and is formed by uniformly loading alloy nano metal particles on the surface of a carbon carrier, wherein the alloy nano particles comprise a PtCoW and Ir two-phase structure.
In the oxygen electrode bifunctional catalyst, the mass ratio of Pt, Co, W and Ir to the carbon carrier in the alloy nanoparticles is 1-50: 1-10: 0.05-0.5: 5-40: 10-30.
The application of oxygen electrode double-function catalyst in integral fuel cell includes chargeable acid fuel cell, alkali fuel cell or metal-air cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel carbon carrier PtCoW-Ir alloy nano particle oxygen electrode bifunctional catalyst for an acidic medium and a preparation method thereof, wherein the carbon carrier is used as a reducing agent and is subjected to reduction reaction with iridium salt at high temperature to obtain simple substance iridium, namely the simple substance iridium is loaded on the surface of the carbon carrier to form Ir/C; and then taking Ir/C as a carrier and ethylene glycol as a reducing agent, mixing the Ir/C with platinum salt, cobalt salt and tungsten salt, and reacting at constant temperature in an oil bath to realize the precipitation of simple substances of platinum, cobalt and tungsten on the Ir/C to obtain the catalyst PtCoW-Ir/C. The prepared composite catalyst shows obvious two-phase structures of simple substances Ir and PtCoW and is uniformly dispersed.
(2) The method for preparing the carbon carrier loaded PtCoW and Ir nano particle composite catalyst is simple and easy to implement, strong in operability and good in repeatability; the composite catalyst can be used for catalyzing oxygen reduction and oxygen precipitation reactions in an acid environment, the electrocatalytic oxygen reduction reaction performance in the acid environment is superior to that of commercial Pt/C, and the electrocatalytic oxygen precipitation reaction performance is superior to that of commercial iridium dioxide.
(3) A large number of tests show that when the catalyst contains a small amount of OER active components such as Ir and the like, the OER performance of the catalyst is excellent, and the noble metal catalyst is supported by carbon, so that the use of noble metals can be effectively reduced, the noble metals are highly dispersed, the higher specific surface area of the exposed noble metals is increased, and the electrocatalytic performance of the catalyst is improved.
(4) According to the invention, through a large number of experiments, the raw material selection, the mass ratio, the process conditions and the like in the preparation process of the oxygen electrode bifunctional catalyst are optimized, an optimal implementation scheme is provided, and the performance of the prepared catalyst is obviously improved.
(5) The oxygen electrode bifunctional catalyst can be used for integrated fuel cells such as rechargeable acid fuel cells, alkaline fuel cells, metal air cells and the like, and has wide application range and strong practicability.
Drawings
FIG. 1 is an SEM image of Ir40/CB prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of Ir40/CB prepared in example 1 of the present invention;
FIG. 3 is an SEM image of PtCoW80-Ir80/CB prepared in example 2 of the present invention;
FIG. 4 is an XRD pattern of PtCoW80-Ir80/CB produced in example 2 of the present invention and a comparison of XRD patterns thereof after heat treatment;
FIG. 5 shows PtCoW80-Ir40/CB, PtCoW80-Ir80/CB prepared in examples 1, 2 and 3 of the present invention at 0.1M HClO4ORR performance in electrolyte is plotted versus 0.OER performance in 5M H2SO4 electrolyte is compared.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the oxygen electrode bifunctional catalyst provided by the invention is solid powder and is formed by uniformly loading alloy nano metal particles on the surface of a carbon carrier, wherein the alloy nano particles comprise PtCoW and Ir two-phase structures, namely the PtCoW and Ir two-phase structures exist at the same time. The active component with OER performance is Ir, and the ORR active component is PtCoW. The mass ratio of Pt, Co, W and Ir to the carbon carrier in the alloy nanoparticles is 1-50: 1-10: 0.05-0.5: 5-40: 10-30 respectively.
The preparation method of the oxygen electrode bifunctional catalyst comprises the following steps of firstly, taking a carbon carrier as a reducing agent, carrying out reduction reaction with iridium salt at high temperature to obtain simple substance iridium, namely, loading the simple substance iridium on the surface of the carbon carrier to form Ir/C; and then mixing Ir/C with platinum salt, cobalt salt and tungsten salt by taking Ir/C as a carrier and ethylene glycol as a reducing agent, and reacting at constant temperature in an oil bath to realize the precipitation of platinum, cobalt and tungsten on Ir/C to obtain the catalyst PtCoW-Ir/C.
The carbon carrier is graphene, carbon black, a carbon nano tube, graphitized carbon or porous carbon; the iridium salt is iridium tetrachloride.
The platinum salt is chloroplatinic acid, the cobalt salt is cobalt chloride, and the tungsten salt is tungsten carbonyl
The preparation method of the oxygen electrode bifunctional catalyst specifically comprises the following steps:
(1) ultrasonically dispersing a carbon carrier in a mixed solution of ethanol and water, adding iridium salt, continuously performing ultrasonic treatment for 0.5-1.5 h, then adding dopamine, then performing magnetic stirring for 8-12 h, and drying; the iridium salt used in this step is iridium tetrachloride. Dopamine is used as an auxiliary agent for absorbing the iridium salt on the carbon carrier, so that the Ir salt is uniformly dispersed.
In an optional embodiment of the invention, the volume ratio of the ethanol to the water is 1: 1-3; the addition amount of the dopamine is 5-20 mg of dopamine added into 50mg of carbon. The mass ratio of the added iridium salt to the carbon carrier is 0.8-1.5: 1; the ratio of the carbon carrier to the mixed solution is 50mg of carbon carrier per 50-100 mL of the solution.
(2) And (2) putting the dried article in the step (1) into a high-temperature resistant container (such as a porcelain boat), raising the temperature to 700-900 ℃ at a heating rate of 5-10 ℃/min, preserving the temperature for 1-3 h, and cooling to obtain Ir/C.
(3) Ultrasonically dispersing Ir/C in an ethylene glycol solution, adding platinum salt, cobalt salt and tungsten salt under magnetic stirring, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to 8-10 to obtain a suspension;
in an optional embodiment of the invention, 30-60 mL of ethylene glycol is required to be added every time 50mg of carbon carrier is added. The proportion relationship of the added platinum salt, cobalt salt and tungsten salt to the carbon carrier in Ir/C is respectively as follows: the amount of the platinum salt, the cobalt salt and the tungsten salt is 0.05 to 0.10mmol, 0.01 to 0.10mmol and 0.001 to 0.010mmol respectively per 50mg of the carbon carrier.
(4) Placing the suspension obtained in the step (4) into a hydrothermal kettle, placing the hydrothermal kettle into a flask, and carrying out heat preservation in an oil bath at the temperature of 100-150 ℃ for 1-3 hours to obtain black slurry;
(5) and (5) washing and drying the black slurry obtained in the step (4) to obtain the oxygen electrode bifunctional catalyst PtCoW-Ir/C.
The carbon-supported PtCoW-Ir alloy nanoparticle composite catalyst for the acidic medium is black solid powder, and the PtCoW alloy nanoparticles and the Ir particles exist in a two-phase structure form, so that a two-phase separation structure or a two-phase contact structure can be formed. In the electrocatalytic process, PtCoW promotes the ORR catalytic process, and Ir promotes the OER catalytic process.
Example 1
Preparation of PtCoW80-Ir40/CB bifunctional catalyst
(1) 50mg of Carbon Black (CB) was taken as carrier, and the reaction mixture was stirred in 20mL of water: ethanol is 1:1 for 30min by ultrasonic dispersion, and adding IrCl4The solution (0.1mmol Ir) and 10mg dopamine were sonicated for half an hour continuously until mixed well. Then magnetically stirred for 12h and subsequently dried in an oven at 70 ℃.
(2) The dried samples were ground in an agate mortar for several minutes. Then calcining for 1h in Ar atmosphere at the temperature of 900 ℃ and the heating rate of 5 ℃/min, and reducing Ir at the high temperature by using carbon. Thus, an OER catalyst with excellent performance is obtained, and is marked as Ir 40/CB.
(3) Weighing 25.7mg Ir40/CB, adding 38mL ethylene glycol, putting into an ultrasonic machine for ultrasonic homogenization, and sequentially adding 9.3mL of 0.01mM H according to the mass ratio under magnetic stirring2PtCl6Ethylene glycol solution, 0.31mL of 0.1mM CoCl2Ethylene glycol solution and 1.1mg W (CO)61.2mL of 1M NaOH solution. Then stirring for about 30min to mix them evenly. The pH was adjusted to 8 to obtain a suspension.
(4) And (4) placing the suspension obtained in the step (3) in a hydrothermal kettle, placing the hydrothermal kettle in a round-bottom flask, preserving the heat in an oil bath at the temperature of 130 ℃ for 3 hours, and cooling the suspension to room temperature in the air after the reaction is finished to obtain black slurry. Then, the mixture was washed with deionized water by suction filtration and then dried in an oven. Thus obtaining the catalyst with OER and ORR double functions, which is marked as PtCoW80-Ir40/CB
Example 2
Preparation of PtCoW80-Ir80/CB bifunctional catalyst
(1) 50mg of Carbon Black (CB) was taken as carrier, and the reaction mixture was stirred in 20mL of water: ethanol is 1:1 for 30min by ultrasonic dispersion, and adding IrCl4The solution (0.2mmol Ir) and 10mg dopamine were sonicated for half an hour continuously until mixed well. Then magnetically stirred for 12h and subsequently dried in an oven at 70 ℃.
(2) The dried samples were ground in an agate mortar for several minutes. Then calcining for 1h in Ar atmosphere at 800 ℃ and at the heating rate of 5 ℃/min, and reducing Ir at the high temperature by using carbon. Thus, an OER catalyst with excellent performance is obtained, and is marked as Ir 80/CB.
(3) Weighing 25.7mg Ir80/CB, adding 38mL ethylene glycol, putting into an ultrasonic machine for ultrasonic homogenization, and sequentially adding 9.3mL of 0.01mM H according to the mass ratio under magnetic stirring2PtCl6Ethylene glycol solution, 0.31mL of 0.1mM CoCl2Ethylene glycol solution and 1.1mg W (CO)61.2mL of 1M NaOH solution. Then stirring for about 30min to mix them evenly. The pH was adjusted to 10 to obtain a suspension.
(4) And (4) placing the suspension obtained in the step (3) in a hydrothermal kettle, placing the hydrothermal kettle in a round-bottom flask, preserving the heat in an oil bath at the temperature of 130 ℃ for 3 hours, and cooling the suspension to room temperature in the air after the reaction is finished to obtain black slurry. Then, the mixture was washed with deionized water by suction filtration and then dried in an oven. Thus obtaining the catalyst with OER and ORR double functions, which is marked as PtCoW80-Ir80/CB
Example 3
Preparation of PtCoW40-Ir80/CB bifunctional catalyst
(1) 50mg of Carbon Black (CB) was taken as carrier, and the reaction mixture was stirred in 20mL of water: ethanol is 1:1 for 30min by ultrasonic dispersion, and adding IrCl4The solution (0.2mmol Ir) and 10mg dopamine were sonicated for half an hour continuously until mixed well. Then magnetically stirred for 12h and subsequently dried in an oven at 70 ℃.
(2) The dried samples were ground in an agate mortar for several minutes. Then calcining for 2h in Ar atmosphere at 700 ℃ and at the heating rate of 10 ℃/min, and reducing Ir at the high temperature by using carbon. Thus, an OER catalyst with excellent performance is obtained, and is marked as Ir 80/CB.
(3) 51.4mg Ir80/CB is weighed, 38mL ethylene glycol is added, then the mixture is put into an ultrasonic machine for ultrasonic homogenization, and then 9.3mL of 0.01mM H is added according to the mass ratio in turn under the magnetic stirring2PtCl6Ethylene glycol solution, 0.31mL of 0.1mM CoCl2Ethylene glycol solution and 1.1mg W (CO)61.2mL of 1M NaOH solution. Then stirring for about 30min to mix them evenly. The pH was adjusted to 9 to obtain a suspension.
(4) And (3) placing the suspension obtained in the step (3) in a hydrothermal kettle, placing the hydrothermal kettle into a round-bottom flask, preserving the heat in an oil bath at 150 ℃ for 3 hours, cooling the suspension in the air to room temperature after the reaction is finished to obtain black slurry, then performing suction filtration washing by using deionized water, and then placing the black slurry into an oven for drying. Thus obtaining the catalyst with OER and ORR double functions, which is marked as PtCoW40-Ir 80/CB.
FIG. 1 shows an SEM image of Ir40/CB prepared according to example 1 of the present invention, from FIG. 1 it can be seen that the obtained Ir/C is uniformly distributed on the carbon support in steps, with larger particles of Ir nanoparticles being present locally.
As shown in FIG. 2, which is an XRD pattern of Ir40/CB prepared in example 1 of the present invention, it can be found from the XRD pattern of FIG. 2 that elemental Ir is prepared by the high temperature carbothermal reduction method.
FIG. 3 is an SEM picture of PtCoW80-Ir80/CB of example 2 of the present invention; it can be seen from FIG. 3 that the apparent PtCoW loading is more bright and evenly distributed compared to Ir/C metal.
FIG. 4 shows the XRD pattern of PtCoW80-Ir80/CB prepared in example 2 of the present invention and the comparative XRD pattern after heat treatment; as can be seen from FIG. 4, the XRD diffraction peak of PtCoW-Ir is mainly expressed as the diffraction peak of Ir simple substance, no obvious diffraction peak of Pt and its alloy appears, but after heat treatment at 750 ℃ in Ar atmosphere, the diffraction peak of Pt alloy and metal iridium simple substance appears, and the diffraction peak of Pt alloy is shifted to the right compared with simple substance platinum, which indicates that Pt is alloyed. The reason why the diffraction peak of the platinum alloy does not appear before the heat treatment may be that the grain size of the Pt alloy is too small, so that the diffraction peak is too weak and wide and is not obvious in the XRD test process.
FIG. 5 shows PtCoW80-Ir40/CB, PtCoW80-Ir80/CB prepared in examples 1, 2 and 3 of the present invention at 0.1M HClO4ORR performance in electrolyte versus OER performance in 0.5M H2SO4 electrolyte. FIG. 5 shows that PtCoW80-Ir80/C has the best OER performance and ORR performance, the ORR electrocatalytic performance is superior to that of commercial platinum carbon, and the OER electrocatalytic performance is superior to that of IrO2. In FIG. 5, ORR electrocatalytic performance is at 0.1M HClO4The scanning speed is 10 mV/s; the scanning voltage range is-0.2-0.8V; the speed of rotation is 1600 rpm. OER electrocatalytic performance is 0.5M H2SO4The scanning speed is 10mV/s, and the scanning voltage range is 0.9-1.4V. All electrochemical process potentials were relative to a saturated calomel electrode.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.

Claims (13)

1. A preparation method of an oxygen electrode bifunctional catalyst is characterized by comprising the following steps: firstly, a carbon carrier is taken as a reducing agent, and the carbon carrier and iridium salt are subjected to reduction reaction at high temperature to obtain simple substance iridium, namely, the simple substance iridium is loaded on the surface of the carbon carrier to form Ir/C; and then mixing Ir/C with platinum salt, cobalt salt and tungsten salt by taking Ir/C as a carrier and ethylene glycol as a reducing agent, and reacting at constant temperature in an oil bath to realize the precipitation of platinum, cobalt and tungsten on Ir/C to obtain the catalyst PtCoW-Ir/C.
2. The method for preparing an oxygen electrode bifunctional catalyst according to claim 1, characterized in that: the carbon carrier is graphene, carbon black, a carbon nano tube, graphitized carbon or porous carbon; the iridium salt is iridium tetrachloride.
3. The method for preparing an oxygen electrode bifunctional catalyst according to claim 1, characterized in that: the platinum salt is chloroplatinic acid, the cobalt salt is cobalt chloride, and the tungsten salt is tungsten carbonyl.
4. The method for preparing an oxygen electrode bifunctional catalyst according to any one of claims 1 to 3, characterized in that: the specific method for forming Ir/C is as follows:
(1) ultrasonically dispersing a carbon carrier in a mixed solution of ethanol and water, adding iridium salt, continuously performing ultrasonic treatment for 0.5-1.5 h, then adding dopamine, then performing magnetic stirring for 8-12 h, and drying;
(2) and (2) putting the dried article in the step (1) into a high-temperature-resistant container, raising the temperature to 700-900 ℃ at a heating rate of 5-10 ℃/min, preserving the temperature for 1-3 h, and cooling to obtain Ir/C.
5. The method for preparing an oxygen electrode bifunctional catalyst according to claim 4, characterized in that: the volume ratio of ethanol to water in the step (1) is 1: 1-3; 5-20 mg of dopamine is added into every 50mg of carbon carrier.
6. The method for preparing an oxygen electrode bifunctional catalyst according to claim 4, characterized in that: the mass ratio of the iridium salt to the carbon carrier added in the step (1) is 0.8-1.5: 1; the ratio of the carbon carrier to the mixed solution is 50mg of carbon carrier per 50-100 mL of mixed solution.
7. The method for preparing an oxygen electrode bifunctional catalyst according to any one of claims 1 to 3, characterized in that: the specific method for obtaining the catalyst PtCoW-Ir/C by taking Ir/C as a carrier and reacting with platinum salt, cobalt salt and tungsten salt is as follows:
(1) ultrasonically dispersing Ir/C in an ethylene glycol solution, adding platinum salt, cobalt salt and tungsten salt under magnetic stirring, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to 8-10 to obtain a suspension;
(2) placing the suspension obtained in the step (3) into a hydrothermal kettle, placing the hydrothermal kettle into a flask, and carrying out heat preservation in an oil bath at the temperature of 100-150 ℃ for 1-3 hours to obtain black slurry;
(3) and (4) washing and drying the black slurry obtained in the step (3) to obtain the oxygen electrode bifunctional catalyst PtCoW-Ir/C.
8. The method for preparing an oxygen electrode bifunctional catalyst according to claim 7, characterized in that: the proportion relation between the ethylene glycol added in the step (1) and the carbon carrier in Ir/C is as follows: 30-60 mL of ethylene glycol is added for every 50mg of carbon carrier.
9. The method for preparing an oxygen electrode bifunctional catalyst according to claim 7, characterized in that: the proportion relationship of the platinum salt, the cobalt salt and the tungsten salt added in the step (1) and the carbon carrier in Ir/C is respectively as follows: the amount of the platinum salt, the cobalt salt and the tungsten salt is 0.05 to 0.10mmol, 0.01 to 0.10mmol and 0.001 to 0.010mmol respectively per 50mg of the carbon carrier.
10. An oxygen electrode bifunctional catalyst, characterized by: prepared by the preparation method of any one of claims 1 to 9.
11. An oxygen electrode bifunctional catalyst, characterized by: the oxygen electrode bifunctional catalyst is solid powder and is formed by uniformly loading alloy nano metal particles on the surface of a carbon carrier, wherein the alloy nano particles comprise PtCoW and Ir two-phase structures.
12. An oxygen electrode bifunctional catalyst as claimed in claim 11, characterized in that: the mass ratio of Pt, Co, W and Ir to the carbon carrier in the alloy nanoparticles is 1-50: 1-10: 0.05-0.5: 5-40: 10-30 respectively.
13. Use of an oxygen electrode bifunctional catalyst according to any one of claims 10 to 12 in an integrated fuel cell, including a rechargeable acid fuel cell, an alkaline fuel cell or a metal air cell.
CN202010717988.9A 2020-07-23 2020-07-23 Oxygen electrode bifunctional catalyst, preparation method and application Active CN112002915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010717988.9A CN112002915B (en) 2020-07-23 2020-07-23 Oxygen electrode bifunctional catalyst, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010717988.9A CN112002915B (en) 2020-07-23 2020-07-23 Oxygen electrode bifunctional catalyst, preparation method and application

Publications (2)

Publication Number Publication Date
CN112002915A CN112002915A (en) 2020-11-27
CN112002915B true CN112002915B (en) 2021-07-13

Family

ID=73467771

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010717988.9A Active CN112002915B (en) 2020-07-23 2020-07-23 Oxygen electrode bifunctional catalyst, preparation method and application

Country Status (1)

Country Link
CN (1) CN112002915B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097509B (en) * 2021-03-22 2022-03-11 中自环保科技股份有限公司 Hydrogen fuel cell platinum-carbon catalyst and preparation method thereof
CN113398923B (en) * 2021-05-24 2023-07-25 北京化工大学 Carbon-supported IrO2@Ir heterojunction composite catalyst with strawberry-shaped structure and preparation method and application thereof
CN115161688A (en) * 2022-07-07 2022-10-11 中国科学院福建物质结构研究所 Iridium-supported cucurbit carbon composite material and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100503038C (en) * 2005-05-25 2009-06-24 南京师范大学 Complex reduction method for preparing highly alloyed Pt-based compound metal nano catalyst
CN101716530B (en) * 2009-11-25 2011-10-19 武汉理工大学 Catalyst using composite polymer as carrier
KR101575463B1 (en) * 2014-03-26 2015-12-07 현대자동차주식회사 A method for manufacturing alloy catalyst for a fuel cell
KR101774706B1 (en) * 2016-08-31 2017-09-04 현대자동차주식회사 Manufacturing method of catalyst supprot, catayst supprot theryby and catalyst for fuel cell comprising the same
CN109921045B (en) * 2017-12-12 2021-07-20 中国科学院大连化学物理研究所 Preparation and application of oxygen electrode catalyst with platinum black as carrier
CN108878902B (en) * 2018-07-06 2020-11-06 中国科学院大连化学物理研究所 Preparation and application of double-effect oxygen electrode catalyst with iridium black as carrier

Also Published As

Publication number Publication date
CN112002915A (en) 2020-11-27

Similar Documents

Publication Publication Date Title
Chen et al. Hollow and porous NiCo2O4 nanospheres for enhanced methanol oxidation reaction and oxygen reduction reaction by oxygen vacancies engineering
Wu et al. Metal-organic framework-derived, Zn-doped porous carbon polyhedra with enhanced activity as bifunctional catalysts for rechargeable zinc-air batteries
CN112002915B (en) Oxygen electrode bifunctional catalyst, preparation method and application
CN103227333B (en) Compound, the catalyst containing it, fuel cell and lithium-air battery containing it
Zhao et al. Enhancing hydrogen evolution reaction activity on cobalt oxide in alkaline electrolyte by doping inactive rare-earth metal
CN113258083B (en) Co X Bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof
WO2020167257A1 (en) Low-cost and low-platinum composite catalyst for low-temperature proton exchange membrane fuel cells
CN112221530A (en) Preparation method and application of non-noble metal single-atom dual-function electrocatalyst
CN113270597A (en) C3N4Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof
Zhang et al. Amorphous mixed Ir–Mn oxide catalysts for the oxygen evolution reaction in PEM water electrolysis for H2 production
Zhang et al. Efficiently catalyzed sea urchin-like mixed phase SmMn2O5/MnO2 for oxygen reduction reaction in zinc-air battery
Du et al. Novel Pd 13 Cu 3 S 7 nanotubes with high electrocatalytic activity towards both oxygen reduction and ethanol oxidation reactions
JP4539086B2 (en) ELECTRODE CATALYST, CATALYST CARRIER ELECTRODE, MEA FOR FUEL CELL AND FUEL CELL
US20220416260A1 (en) Hybrid catalyst suitable for use in proton exchange membrane fuel cell
CN115770621A (en) Preparation method and application of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst
Yi et al. Carbon supported Pd–Sn nanoparticle eletrocatalysts for efficient borohydride electrooxidation
Yi et al. N-Doped carbon-coated Co 2 P-supported Au nanocomposite as the anode catalyst for borohydride electrooxidation
Yi et al. N-Doped carbon-supported Au-modified NiFe alloy nanoparticle composite catalysts for BH 4− electrooxidation
CN113659151A (en) Graphene composite copper sulfide/nickel sulfide catalytic material and preparation method and application thereof
Lu et al. La0. 8Sr0. 2Mn0. 8Co0. 2O3-δ perovskite as an efficient functional electrocatalyst for oxygen reduction reactions
Chen et al. Fabrication of layered LaNi0. 6Fe0. 4O3-δ perovskite to enhance oxygen reduction catalytic performance
Pan et al. Ultrafine rhodium selenides enable efficient oxygen reduction reaction catalysis
Ma et al. Oxygen vacancy tuning of porous urchin-like nickel cobaltite for improved bifunctional electrocatalysis
Liu et al. Carbon nanotube-encapsulated Co/Co3Fe7 heterojunctions as a highly-efficient bifunctional electrocatalyst for rechargeable zinc-air batteries
Wu et al. Ultralow platinum-loading PtPdRu@ PtRuIr/C catalyst with excellent CO tolerance and high performance for the methanol oxidation reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant