CN115558959B - A bimetallic oxide catalyst and its preparation method and application - Google Patents
A bimetallic oxide catalyst and its preparation method and applicationInfo
- Publication number
- CN115558959B CN115558959B CN202211225154.1A CN202211225154A CN115558959B CN 115558959 B CN115558959 B CN 115558959B CN 202211225154 A CN202211225154 A CN 202211225154A CN 115558959 B CN115558959 B CN 115558959B
- Authority
- CN
- China
- Prior art keywords
- ceo
- carbon paper
- ceo2
- substrate
- iro
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a bimetallic oxide catalyst, a preparation method and application thereof, and relates to the technical field of electrolytic water anode materials. The bimetallic oxide catalyst provided by the invention comprises a CeO 2 substrate and an IrO 2 active component arranged on the surface of the CeO 2 substrate. The CeO 2-IrO2 bimetallic oxide catalyst designed by the invention is used as a Proton Exchange Membrane (PEM) electrolyzed water anode, and has higher catalytic activity and mass activity, good stability and lower cost compared with a pure IrO 2 catalyst.
Description
Technical Field
The invention relates to the technical field of electrolyzed water anode materials, in particular to a bimetallic oxide catalyst and a preparation method and application thereof.
Background
Hydrogen energy is attracting great attention as a clean energy source most likely to replace fossil energy, and Proton Exchange Membrane (PEM) water electrolysis devices are an efficient and environment-friendly hydrogen production mode. Where Oxygen Evolution Reactions (OER) occur on the anode side are an important catalytic process in PEM electrolyzed water, however OER typically requires a high overpotential to achieve a reaction current sufficient for practical use due to the 4 electron transfer involved. Furthermore, OER can generate a large amount of hydrogen ions to cause corrosion failure or even shedding of the anode-side catalyst in the acid electrolyte. Therefore, the development of anode catalysts with high catalytic activity and high stability has been the core of PEM electrolyzed water technology research in recent years.
At present, irO 2 catalyst has become the most widely used anode for PEM electrolyzed water under acidic electrolyte conditions. However, in practical application, the problems that (1) the catalytic activity of the pure IrO 2 is not high enough, and a certain improvement space exists, (2) the load of the pure IrO 2 on the proton exchange membrane is generally up to 2mg/cm 2, so that the cost of the electrolyzed water for producing hydrogen is too high, (3) the pure IrO 2 particles are adhered to the proton exchange membrane and are accompanied with agglomeration phenomenon, the active sites are not fully exposed, so that the quality activity of the IrO 2 is reduced, and (4) the binding force generated by the adhesion between the pure IrO 2 particles and the proton exchange membrane is weak, and the pure IrO 2 particles are easy to fall off under the action of bubbles generated in an acidic environment and oxygen evolution.
Disclosure of Invention
The invention aims to provide a bimetallic oxide catalyst, a preparation method and application thereof, and the bimetallic oxide catalyst provided by the invention has higher catalytic activity and quality activity when used as a PEM (proton exchange membrane) electrolytic water anode, good stability and lower cost.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a bimetallic oxide catalyst which comprises a CeO 2 substrate and an IrO 2 active component arranged on the surface of the CeO 2 substrate.
Preferably, the IrO 2 active component and CeO 2 substrate are connected by a heterojunction.
Preferably, the coverage rate of the IrO 2 active component on the surface of the CeO 2 substrate is 10-90%, and the mass ratio of the IrO 2 active component to the CeO 2 substrate is 0.1-10:100.
Preferably, the IrO 2 active component is granular, and the diameter of the IrO 2 active component is 10-40 nm.
Preferably, the CeO 2 substrate is in a flake shape, the area of the CeO 2 substrate is 100-1000000 nm 2, and the thickness of the CeO 2 substrate is 30-100 nm.
The invention provides a preparation method of the bimetallic oxide catalyst, which comprises the following steps:
(1) Preparing a CeO 2 sheet on the surface of the carbon paper by adopting an anodic electrodeposition method;
(2) Preparing IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 sheets by adopting an anodic electrodeposition method;
(3) And calcining the carbon paper loaded with the CeO 2 sheets and the IrO 2 particles to obtain the bimetallic oxide catalyst.
Preferably, the preparation of the CeO 2 sheet on the surface of the carbon paper by the anodic electrodeposition method in the step (1) comprises the steps of performing electrochemical oxidation by taking the carbon paper as an anode and taking an aqueous solution of trivalent cerium salt, a stabilizer and CH 3CH2 OH as an electrolyte solution, and preparing the CeO 2 sheet on the surface of the carbon paper.
Preferably, the preparation of the IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 thin sheets by adopting the anodic electrodeposition method in the step (2) comprises the steps of carrying out electrochemical oxidation by taking the carbon paper loaded with the CeO 2 thin sheets as an anode and taking an aqueous solution of trivalent iridium salt and a stabilizer as an electrolyte solution, and preparing the IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 thin sheets.
Preferably, the calcining temperature in the step (3) is 500-800 ℃, and the calcining time is more than 2 hours.
The invention provides an application of the bimetallic oxide catalyst in the technical scheme or the bimetallic oxide catalyst prepared by the preparation method in the technical scheme in an electrolytic water anode.
The invention provides a bimetallic oxide catalyst which comprises a CeO 2 substrate and an IrO 2 active component arranged on the surface of the CeO 2 substrate. According to the invention, ceO 2 is introduced into IrO 2 to construct CeO 2-IrO2 bimetallic oxide, so that the use amount of noble metal Ir can be reduced, and the inherent electronic structure of the active site of IrO 2 can be optimized. Compared with the pure IrO 2 catalyst, the CeO 2-IrO2 bimetallic oxide catalyst provided by the invention has lower cost and higher catalytic activity on OER. In addition, the CeO 2-IrO2 bimetallic oxide designed by the invention can form a heterojunction, which is beneficial to anchor the IrO 2 active component on the surface of the CeO 2 substrate and promote the discrete and uniform distribution of the IrO 2 active component. Compared with the pure IrO 2 catalyst, the CeO 2-IrO2 bimetallic oxide catalyst provided by the invention has improved stability and quality activity.
Compared with the preparation methods of common noble metal oxide catalysts such as Adam fusion method, thermal decomposition method and hydrothermal method, the preparation method of the bimetallic oxide catalyst provided by the invention can simply and controllably prepare the CeO 2-IrO2 bimetallic oxide catalyst with heterojunction by adopting the anode electrodeposition method.
In the invention, when the CeO 2-IrO2 bimetallic oxide catalyst is used as a PEM electrolyzed water anode, compared with a commercial pure IrO 2 catalyst, the overpotential required for reaching 10 mA.cm -2 is reduced by 20-120 mV, the quality activity is improved by 1-7 mA.mu.g Ir -1, the stability performance is enhanced by at least 2 times, and meanwhile, the dosage of noble metal Ir is reduced by more than 20%.
Drawings
FIG. 1 is an SEM image of carbon paper of example 1 at 500nm scale (the inset is an SEM image at 50nm scale);
FIG. 2 is an SEM image of a carbon paper carrying CeO 2 flakes prepared in example 1 of the present invention at 500nm scale (the inset is an SEM image at 50nm scale);
Fig. 3 is an SEM image of carbon paper loaded with CeO 2 flakes and IrO 2 particles prepared in example 1 of the present invention at 500nm scale (the inset is an SEM image at 50nm scale).
Detailed Description
The invention provides a bimetallic oxide catalyst which comprises a CeO 2 substrate and an IrO 2 active component arranged on the surface of the CeO 2 substrate.
The bimetallic oxide catalyst provided by the invention comprises a CeO 2 substrate. In the invention, the CeO 2 substrate is preferably in a flake shape, the area of the CeO 2 substrate is preferably 100-1000000 nm 2, more preferably 250000-400000 nm 2, and the thickness of the CeO 2 substrate is preferably 30-100 nm, more preferably 30-60 nm.
The bimetallic oxide catalyst provided by the invention comprises an IrO 2 active component arranged on the surface of the CeO 2 substrate. In the present invention, the IrO 2 active component and CeO 2 substrate are preferably connected by a heterojunction. In the invention, the IrO 2 active component is preferably granular, and the diameter of the IrO 2 active component is preferably 10-40 nm, more preferably 20-30 nm.
In the invention, the coverage rate of the IrO 2 active component on the surface of the CeO 2 substrate is preferably 10-90%, more preferably 40-80%, further preferably 60%, and the mass ratio of the IrO 2 active component to the CeO 2 substrate is preferably 0.1-10:100, more preferably 0.5-8:100, further preferably 3:100.
The invention provides a preparation method of the bimetallic oxide catalyst, which comprises the following steps:
(1) Preparing a CeO 2 sheet on the surface of the carbon paper by adopting an anodic electrodeposition method;
(2) Preparing IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 sheets by adopting an anodic electrodeposition method;
(3) And calcining the carbon paper loaded with the CeO 2 sheets and the IrO 2 particles to obtain the bimetallic oxide catalyst.
The CeO 2 slice is prepared on the surface of the carbon paper by adopting an anodic electrodeposition method. The present invention preferably further comprises pretreating the carbon paper prior to preparing the CeO 2 flakes. In the present invention, the pretreatment preferably includes acetone washing, ethanol washing, acid washing, water washing, and drying in this order. In the present invention, the acetone washing is preferably performed using an acetone solution having a purity of 99wt% or more, and the ethanol washing is preferably performed using an ethanol solution having a purity of 99wt% or more. In the present invention, the hydrogen ion concentration of the pickling solution is preferably 0.01 to 1mol/L, more preferably 0.1mol/L, and the pickling solution is preferably an aqueous HCl solution. In the invention, the acetone washing, the ethanol washing and the acid washing are preferably ultrasonic washing, and the time of each ultrasonic washing is independently preferably more than 20min, more preferably 30min. In the present invention, the water washing is preferably deionized water washing. The invention is preferably water-washed to neutrality. According to the invention, acetone washing, ethanol washing, acid washing and water washing are sequentially performed, so that the impurities on the surface of the carbon paper are completely removed.
In the invention, the preparation of the CeO 2 sheet on the surface of the carbon paper by adopting the anodic electrodeposition method preferably comprises the steps of carrying out electrochemical oxidation by taking the carbon paper as an anode and taking an aqueous solution of trivalent cerium salt, a stabilizer and CH 3CH2 OH as an electrolyte solution, and preparing the CeO 2 sheet on the surface of the carbon paper. In the present invention, the trivalent cerium salt preferably includes Ce (NO 3)3 or CeCl 3, more preferably Ce (NO 3)3. In the present invention, the stabilizer preferably includes acetic acid or acetate, the acetate preferably includes CH 3COONH4 or CH 3 COONa, more preferably CH 3COONH4. In the present invention, NH 4 + in CH 3COONH4 may refine CeO 2 thin film crystal grains.
In the invention, CH 3CH2 OH acts as an additive in the electrolyte solution, so that the compactness of the CeO 2 film can be improved.
In the invention, the concentration of the trivalent cerium salt in the electrolyte solution is preferably 0.01-0.1 mol/L, more preferably 0.05mol/L, the concentration of the stabilizer is preferably 0.01-1 mol/L, more preferably 0.1mol/L, and the volume percentage of CH 3CH2 OH in the electrolyte solution is preferably 10-40%, more preferably 10-30%. In the electrochemical oxidation according to the present invention, it is preferable to keep the temperature and pH of the electrolyte solution constant. In the invention, the temperature of the electrolyte solution is preferably 30-70 ℃, more preferably 50-60 ℃, and the pH value of the electrolyte solution is preferably 5-7, more preferably 6.2. In the invention, the potential of the electrochemical oxidation is preferably 0.8-1.6V, more preferably 1.2-1.4V, and the time of the electrochemical oxidation is preferably 10-60 min, more preferably 30-40 min. In the electrochemical oxidation according to the invention, the cathode is preferably graphite or platinum sheet.
After the carbon paper loaded with the CeO 2 thin sheet is obtained, the invention adopts an anodic electrodeposition method to prepare IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 thin sheet.
In the invention, the preparation of IrO 2 particles on the surface of the carbon paper loaded with CeO 2 sheets by adopting an anodic electrodeposition method preferably comprises the steps of carrying out electrochemical oxidation by taking the carbon paper loaded with CeO 2 sheets as an anode and taking an aqueous solution of trivalent iridium salt and a stabilizer as an electrolyte solution, and preparing the IrO 2 particles on the surface of the carbon paper loaded with CeO 2 sheets. In the present invention, the trivalent iridium salt preferably includes IrCl 3 or iridium sulfite, more preferably IrCl 3. In the present invention, the stabilizer preferably comprises acetic acid or an acetate salt, and the acetate salt preferably comprises CH 3COONH4 or CH 3 COONa, more preferably CH 3COONH4.
In the invention, the concentration of trivalent iridium salt in the electrolyte solution is preferably 0.001-0.1 mol/L, more preferably 0.004mol/L, and the concentration of the stabilizer is preferably 0.01-0.1 mol/L, more preferably 0.02mol/L. In the electrochemical oxidation according to the present invention, it is preferable to keep the pH of the electrolyte solution constant at normal temperature. In the present invention, the pH of the electrolyte solution is preferably 9 to 12, more preferably 10.2 to 11. In the invention, the potential of the electrochemical oxidation is preferably 0.6-1.0V, more preferably 0.8V, and the time of the electrochemical oxidation is preferably 5-30 min, more preferably 15-20 min. In the electrochemical oxidation according to the invention, the cathode is preferably graphite or platinum sheet.
After the carbon paper loaded with the CeO 2 thin sheet and the IrO 2 particles is obtained, the carbon paper loaded with the CeO 2 thin sheet and the IrO 2 particles is calcined to obtain the bimetallic oxide catalyst. In the present invention, the calcination is preferably performed in a high temperature furnace. In the invention, the calcination temperature is preferably 500-800 ℃, more preferably 600-700 ℃, and the calcination time is preferably more than 2 hours, more preferably 4 hours. The invention calcines the carbon paper loaded with CeO 2 flake and IrO 2 particle at high temperature, ensuring complete decarbonization.
The invention provides application of the bimetallic oxide catalyst in the technical scheme or the bimetallic oxide catalyst prepared by the preparation method in the technical scheme in an electrolyzed water anode, and is preferably applied to a Proton Exchange Membrane (PEM) electrolyzed water anode.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The pretreatment of the carbon paper comprises the steps of sequentially placing the carbon paper in an acetone solution with the purity of 99.9wt%, an ethanol solution with the purity of 99.9wt% and an HCl solution with the hydrogen ion concentration of 0.1mol/L for 30min for ultrasonic cleaning, and finally washing with deionized water and fully drying to obtain the pretreated carbon paper, and storing the pretreated carbon paper in the acetone solution with the purity of 99.9wt% for later use.
Preparing a CeO 2 slice, namely preparing an aqueous solution containing 0.05mol/L Ce (NO 3)3、0.1mol/L CH3COONH4 and 10% (volume percentage) CH 3CH2 OH) in an electrolytic cell as an electrolyte solution, adopting pretreated carbon paper as an anode, adopting a platinum sheet as a cathode, keeping the temperature of the electrolyte solution at 50℃, pH value of 6.2, and carrying out electrochemical oxidation for 30min at 1.2V potential to prepare the CeO 2 slice on the surface of the carbon paper.
Preparing IrO 2 particles, namely preparing an aqueous solution containing 0.004mol/L IrCl 3、0.02mol/L CH3COONH4 as an electrolyte solution in an electrolytic cell, adopting carbon paper loaded with CeO 2 sheets as an anode, adopting a platinum sheet as a cathode, keeping the pH value of the electrolyte solution at 10.2 at normal temperature, carrying out electrochemical oxidation at 0.8V potential for 15min, and preparing the IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 sheets.
Calcining at high temperature, namely placing the carbon paper loaded with CeO 2 sheets and IrO 2 particles into a furnace, and calcining for 4 hours at 600 ℃ to obtain the bimetallic oxide catalyst.
In the bimetallic oxide catalyst prepared in the embodiment, heterojunction is formed between a CeO 2 substrate and an IrO 2 active component, the coverage rate of the IrO 2 active component on the surface of the CeO 2 substrate is 60%, the mass ratio of the IrO 2 active component to the CeO 2 substrate is 3:100, the IrO 2 active component is granular, the diameter of the granule is 20-30 nm, the CeO 2 substrate is lamellar, the area of the lamellar is 250000nm 2, and the thickness of the lamellar is 30nm.
When the bimetallic oxide catalyst prepared by the embodiment is used as a PEM electrolyzed water anode, compared with a commercial pure IrO 2 catalyst (overpotential: 350mV, mass activity: 0.6mA.mu.g Ir -1, stability: 40h, noble metal Ir dosage: 2mg/cm 2), the overpotential required when the catalyst reaches the current density of 10mA.cm -2 is reduced by 130mV, the mass activity of the catalyst at 300mV overpotential is improved by 6.4mA.mu.g Ir -1, the service life of the catalyst at the current density of 10mA.cm -2 is 200h, namely the stability is enhanced by 5 times, the dosage of the noble metal Ir added is 0.8mg/cm 2, the dosage of the noble metal Ir is obviously reduced, and the cost is reduced.
The SEM image of the carbon paper adopted in this embodiment is shown in fig. 1, and the microscopic morphology of the carbon paper can be observed to be in a vermicular staggered structure when the carbon paper is enlarged from the 500nm scale to the 50nm scale.
The SEM image of the carbon paper loaded with the CeO 2 flakes prepared in this example is shown in fig. 2, and it can be seen that CeO 2 is in a flake morphology and uniformly distributed on the carbon paper, and the carbon paper loaded with the CeO 2 flakes is enlarged from a 500nm scale to a 50nm scale, so that good crystallinity of CeO 2 can be observed.
The SEM image of the carbon paper loaded with CeO 2 flakes and IrO 2 particles prepared in this example is shown in fig. 3, where at 500nm scale, some discrete flakes can be observed, and at 50nm scale, some very fine particles can be observed to be also distributed on the flakes. As can be seen by comparing fig. 2, the flakes correspond to CeO 2 and the particles correspond to IrO 2.
Example 2
The pretreatment of the carbon paper comprises the steps of sequentially placing the carbon paper in an acetone solution with the purity of 99.9wt%, an ethanol solution with the purity of 99.9wt% and an HCl solution with the hydrogen ion concentration of 0.1mol/L for 30min for ultrasonic cleaning, and finally washing with deionized water and fully drying to obtain the pretreated carbon paper, and storing the pretreated carbon paper in the acetone solution with the purity of 99.9wt% for later use.
Preparing a CeO 2 slice, namely preparing an aqueous solution containing 0.05mol/L Ce (NO 3)3、0.1mol/L CH3COONH4 and 10% (volume percentage) CH 3CH2 OH) in an electrolytic cell as an electrolyte solution, adopting pretreated carbon paper as an anode, adopting a platinum sheet as a cathode, keeping the temperature of the electrolyte solution at 50℃, pH value of 6.2, and carrying out electrochemical oxidation at 1.4V potential for 60min to prepare the CeO 2 slice on the surface of the carbon paper.
Preparing IrO 2 particles, namely preparing an aqueous solution containing 0.004mol/L IrCl 3、0.02mol/L CH3COONH4 as an electrolyte solution in an electrolytic cell, adopting carbon paper loaded with CeO 2 sheets as an anode, adopting a platinum sheet as a cathode, keeping the pH value of the electrolyte solution at 10.2 at normal temperature, carrying out electrochemical oxidation at 0.8V potential for 15min, and preparing the IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 sheets.
Calcining at high temperature, namely placing the carbon paper loaded with CeO 2 sheets and IrO 2 particles into a furnace, and calcining for 4 hours at 600 ℃ to obtain the bimetallic oxide catalyst.
In the bimetallic oxide catalyst prepared in the embodiment, heterojunction is formed between a CeO 2 substrate and an IrO 2 active component, the coverage rate of the IrO 2 active component on the surface of the CeO 2 substrate is 40%, the mass ratio of the IrO 2 active component to the CeO 2 substrate is 0.5:100, the IrO 2 active component is granular, the diameter of the granular is 20-30 nm, the CeO 2 substrate is flake, the flake area is 400000nm 2, and the flake thickness is 60nm.
When the bimetallic oxide catalyst prepared by the embodiment is used as a PEM electrolyzed water anode, compared with a commercial pure IrO 2 catalyst (overpotential: 350mV, mass activity: 0.6mA.mu.g Ir -1, stability: 40h, noble metal Ir dosage: 2mg/cm 2), the overpotential required when the catalyst reaches the current density of 10mA.cm -2 is reduced by 100mV, the mass activity of the catalyst at 300mV overpotential is improved by 1.8mA.mu.g Ir -1, the service life of the catalyst at the current density of 10mA.cm -2 is 120h, namely the stability is enhanced by 3 times, the dosage of the noble metal Ir added is 0.8mg/cm 2, the dosage of the noble metal Ir is obviously reduced, and the cost is reduced.
Example 3
The pretreatment of the carbon paper comprises the steps of sequentially placing the carbon paper in an acetone solution with the purity of 99.9wt%, an ethanol solution with the purity of 99.9wt% and an HCl solution with the hydrogen ion concentration of 0.1mol/L for 30min for ultrasonic cleaning, and finally washing with deionized water and fully drying to obtain the pretreated carbon paper, and storing the pretreated carbon paper in the acetone solution with the purity of 99.9wt% for later use.
Preparing a CeO 2 slice, namely preparing an aqueous solution containing 0.05mol/L Ce (NO 3)3、0.1mol/L CH3COONH4 and 10% (volume percentage) CH 3CH2 OH) in an electrolytic cell as an electrolyte solution, adopting pretreated carbon paper as an anode, adopting a platinum sheet as a cathode, keeping the temperature of the electrolyte solution at 50℃, pH value of 6.2, and carrying out electrochemical oxidation for 30min at 1.2V potential to prepare the CeO 2 slice on the surface of the carbon paper.
Preparing IrO 2 particles, namely preparing an aqueous solution containing 0.004mol/L IrCl 3、0.02mol/L CH3COONH4 as an electrolyte solution in an electrolytic cell, adopting carbon paper loaded with CeO 2 sheets as an anode and platinum sheets as a cathode, maintaining the pH value of the electrolyte solution at 10.2 at normal temperature, carrying out electrochemical oxidation at 0.8V potential for 30min, and preparing the IrO 2 particles on the surface of the carbon paper loaded with the CeO 2 sheets.
Calcining at high temperature, namely placing the carbon paper loaded with CeO 2 sheets and IrO 2 particles into a furnace, and calcining for 4 hours at 600 ℃ to obtain the bimetallic oxide catalyst.
In the bimetallic oxide catalyst prepared in the embodiment, heterojunction is formed between a CeO 2 substrate and an IrO 2 active component, the coverage rate of the IrO 2 active component on the surface of the CeO 2 substrate is 80%, the mass ratio of the IrO 2 active component to the CeO 2 substrate is 8:100, the IrO 2 active component is granular, the diameter of the granule is 30-40 nm, the CeO 2 substrate is lamellar, the area of the lamellar is 250000nm 2, and the thickness of the lamellar is 30nm.
When the bimetallic oxide catalyst prepared by the embodiment is used as a PEM electrolyzed water anode, compared with a commercial pure IrO 2 catalyst (overpotential: 350mV, mass activity: 0.6mA.mu.g Ir -1, stability: 40h, noble metal Ir dosage: 2mg/cm 2), the overpotential required when the catalyst reaches the current density of 10mA.cm -2 is reduced by 130mV, the mass activity of the catalyst at 300mV overpotential is improved by 3.0mA.mu.g Ir -1, the service life of the catalyst at the current density of 10mA.cm -2 is 60h, namely the stability is enhanced by 1.5 times, the dosage of the noble metal Ir added is 1.6mg/cm 2, the dosage of the noble metal Ir is reduced, and the cost is reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211225154.1A CN115558959B (en) | 2022-10-09 | 2022-10-09 | A bimetallic oxide catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211225154.1A CN115558959B (en) | 2022-10-09 | 2022-10-09 | A bimetallic oxide catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115558959A CN115558959A (en) | 2023-01-03 |
| CN115558959B true CN115558959B (en) | 2025-08-08 |
Family
ID=84744813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211225154.1A Active CN115558959B (en) | 2022-10-09 | 2022-10-09 | A bimetallic oxide catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115558959B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2543256C (en) * | 2003-10-29 | 2010-06-29 | Umicore Ag & Co Kg | Precious metal oxide catalyst for water electrolysis |
| CN1908237B (en) * | 2006-07-20 | 2011-06-01 | 福州大学 | High-cerium-content iridium-coated titanium anode with high oxygen evolution activity |
| CN113046784B (en) * | 2021-03-17 | 2022-06-14 | 宁波材料所杭州湾研究院 | Oxygen-rich defect IrO2-TiO2 solid solution material, its preparation method and application |
| CN114540871B (en) * | 2022-02-20 | 2024-04-05 | 浙江大学 | Preparation method of amorphous iridium-manganese binary catalyst for PEM water electrolysis anode |
| CN114561662A (en) * | 2022-03-21 | 2022-05-31 | 天津大学 | A kind of PEM electrolysis water catalyst, its preparation method and use |
-
2022
- 2022-10-09 CN CN202211225154.1A patent/CN115558959B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| "Isotopic Oxygen Exchange Study to Unravel Noble Metal Oxide/Support Interactions: The Case of RuO2 and IrO2 Nanoparticles Supported on CeO2, TiO2 and YSZ;Yasmine M. Hajar et al.;ChemCatChem;20200306;第2548–2555页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115558959A (en) | 2023-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111790415B (en) | A kind of B-P co-doped double transition metal catalyst and its preparation method and application | |
| CN107177862A (en) | One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene | |
| CN109364963A (en) | A kind of ruthenium-phosphorus co-modified nickel composite catalyst and preparation method thereof | |
| CN103887522A (en) | Preparation method of activated carbon air cathode of manganese dioxide modified microbial fuel cell | |
| CN117604551A (en) | Method for preparing oxygen evolution electrode, oxygen evolution electrode and electrolytic cell | |
| CN117721488A (en) | A high-entropy alloy catalyst for hydrogen production by alkaline electrolysis of water and its preparation method | |
| CN115491715B (en) | A cerium-based cobalt oxide electrocatalyst with an interface structure and a preparation method thereof | |
| CN115558959B (en) | A bimetallic oxide catalyst and its preparation method and application | |
| CN101306364A (en) | A kind of preparation method of direct methanol fuel cell anode catalyst | |
| CN113249743A (en) | Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof | |
| CN117737784B (en) | Precious metal catalyst and its preparation method and application | |
| CN108411349B (en) | A kind of preparation method of graphene-doped porous RuO2 anode | |
| CN115369443B (en) | Preparation method and application of nanosheet Bi-Bi2O3 electrocatalyst | |
| CN117867562A (en) | A water electrolysis anode catalyst using cerium oxide as a carrier and a preparation method thereof | |
| CN113774425B (en) | Preparation method and application of a Ru-modified FeCo@NF electrocatalyst | |
| CN118422268A (en) | Manganese dioxide-supported high-density iridium monoatomic material and preparation method and application thereof | |
| CN116590733A (en) | High-performance oxygen evolution electrode and preparation method thereof | |
| CN116463673A (en) | Anode catalytic layer of water electrolysis hydrogen production membrane electrode, membrane electrode and application | |
| CN116463671A (en) | Pt-NiP/Co (OH) for electrocatalytic hydrogen production 2 Preparation method of composite material | |
| CN119859816B (en) | A trimetallic site synergistically regulated alkaline water electrolysis electrode, its preparation method and application | |
| CN118825292B (en) | Ru embedded TiO2Preparation method of hydrogen hydroxide precipitation electrocatalyst with lattice rich in heterojunction interface | |
| CN117026288B (en) | SPE water electrolysis anode catalyst layer with uniform network structure, preparation method and membrane electrode | |
| CN116103693B (en) | Hydrogen evolution electrode, preparation method thereof and application thereof in hydrogen production by water electrolysis | |
| CN110665509A (en) | Preparation method and application of FeNi3 phase electrocatalyst powder with dendritic morphology | |
| US20250305154A1 (en) | Electrodes for electrochemical water splitting |
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 |