CN116262975A - Preparation and application of a supported nanometer ruthenium dioxide catalyst - Google Patents
Preparation and application of a supported nanometer ruthenium dioxide catalyst Download PDFInfo
- Publication number
- CN116262975A CN116262975A CN202111545800.8A CN202111545800A CN116262975A CN 116262975 A CN116262975 A CN 116262975A CN 202111545800 A CN202111545800 A CN 202111545800A CN 116262975 A CN116262975 A CN 116262975A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- reaction
- ruo
- sulfite
- reaction system
- 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.)
- Pending
Links
Images
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
- 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
-
- 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
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)
- Catalysts (AREA)
Abstract
The invention discloses a supported RuO 2 The preparation method and application of the nano catalyst are as follows: step one, adding an aqueous solution containing sulfite ions into an Ru precursor aqueous solution to carry out complexation reaction to obtain [ Ru (SO) 3 ) 3 ] 3‑ A complex; step two, adding an alkaline aqueous solution into the reaction system of the step one to adjust the pH value, so that the complex is separated out in a precipitation form; step three, washing the precipitate and then mixing with H 2 O 2 Carrying out a reaction to obtain ruthenium oxide colloid dispersion; and step four, adding a carrier into the colloid dispersion liquid for soaking, centrifuging, washing and drying to obtain the supported ruthenium dioxide nano catalyst. The preparation method provided by the invention avoids adsorption poisoning of chloride ions on the surface of the catalyst, and simultaneously, H 2 O 2 The oxidant replaces air to raise temperature for oxidation, the reaction temperature is low, and the method can avoidRuO 2 The agglomeration grows up, which is helpful for improving the activity of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method and application of a ruthenium dioxide nano catalyst.
Background
Compared with other oxides, the ruthenium dioxide has good conductivity, ru has more chemical valence states, the ruthenium dioxide material has small internal stress and stable structure in the conversion process of different valence states, and has wide application prospect in the fields of chlor-alkali, chlorate production, electrocatalysis, super capacitor and the like. Numerous research surfaces, ruO 2 Catalytic performance of (C) and RuO 2 (110) RuO with nanoscale related to Ru atoms with unsaturated coordination on the face 2 Has better reactivity and high utilization efficiency, thus the supported RuO 2 The research and development of the nano catalyst have important significance.
The preparation of supported ruthenium dioxide nano catalyst usually adopts a method of sodium hydroxide sedimentation reoxidation, for example, chinese patent CN1522176A discloses a method for preparing alumina supported ruthenium and a method for oxidizing alcohol, and the applicant uses sodium hydroxide and RuCl 3 The reaction is carried out to obtain Ru (OH) 3 Alumina intermediate state, and then oxidized in air to obtain RuO 2 Alumina. Also, alkaline substances such as NaOH or NaHCO are used 3 For RuCl 3 Precipitating, then gelling, and then oxidizing with hydrogen peroxide or chlorine gas solution, or oxidizing by heat treatment to prepare nanometer RuO 2 . It has also been proposed to prepare nanoscale RuO by chemical vapor deposition using organoruthenium as a precursor 2 And is used for high performance supercapacitor materials and gas sensors, etc. (J Electrochem Soc, 2005). Liu et al propose the preparation of RuO by magnetron sputtering 2 (Small, 2005), US20130059078A1 discloses a RuO 2 Is prepared through depositing an organic metal atom to obtain seed layer, and RuO 4 Steam is used as a precursor, and RuO is utilized 4 Reacts with seed layers to form RuO 2 A nano-film. The RuO is prepared by decomposing and gasifying metallic ruthenium by a direct oxidation method and reacting the metallic ruthenium with oxygen in industry 2 However, the method has low preparation efficiency, difficult separation, uncontrollable granularity and high requirement on instruments in the whole process, and adopts a calcination method to directly calcine rutheniumThe obtained ruthenium dioxide powder has large granularity and grain shape difference and poor uniformity, is only suitable for manufacturing high-resistance materials, and has limited application range.
To sum up, currently supported nano RuO 2 The catalyst still faces the complex preparation process and RuO 2 The nano particles are larger, the agglomeration of the particles is serious, the nano particles are difficult to uniformly disperse on the carrier, the acting force with the carrier is weak, and the like. With development and utilization of ruthenium resources, ruO 2 Because of the outstanding electrochemical performance and catalytic performance of the nano RuO catalyst, people are increasingly focused in the new energy field, how to prepare the high-performance supported nano RuO 2 A catalyst such that RuO 2 The catalyst is highly and evenly dispersed on the surface of the carrier, has smaller particle size, has less impurity content on the surface of the catalyst and high reaction activity, is an important research content about Ru utilization at home and abroad at present, and is also one of important technologies for Ru resource development and utilization.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a supported RuO 2 The preparation method of the nano catalyst is different from the prior method for preparing RuO by directly adopting RuCl3 to precipitate with alkali solution and then oxidize 2 According to the traditional method, chloride ions in RuCl3 are replaced based on a ligand replacement method, so that adsorption poisoning of the chloride ions on the surface of the catalyst is avoided, and the activity of the catalyst is high; next, the invention uses liquid H 2 O 2 The oxidant is used for replacing air to raise the temperature for oxidization, the reaction temperature is lower, and RuO can be avoided 2 Agglomeration and growth; thirdly, the invention has simple steps for synthesizing the water system, and can solve the existing supported RuO 2 The preparation process of the nano catalyst is complex, the conditions are harsh, and the mass preparation is difficult.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
supported RuO 2 The preparation method of the nano catalyst comprises the following steps:
step one, adding an aqueous solution containing sulfite ions into an Ru precursor aqueous solution to carry out complexation reaction to obtain [ Ru (SO) 3 ) 3 ] 3- A complex;
step two, adding an alkaline aqueous solution into the reaction system of the step one to adjust the pH value, so that the complex is separated out in a precipitation form;
step three, washing the precipitate and then mixing with H 2 O 2 Carrying out a reaction to obtain ruthenium oxide colloid dispersion;
step four, adding a carrier into the colloid dispersion liquid for soaking, centrifuging, washing and drying after soaking to obtain the supported RuO 2 A nano catalyst.
Preferably, the preparation method specifically comprises the following steps:
step 1, adding a water-soluble Ru precursor into deionized water, and performing ultrasonic treatment until the Ru precursor is completely dissolved to prepare an Ru precursor aqueous solution;
step 3, slowly adding the alkaline aqueous solution into the reaction system in the step 2, stirring at the same time, and adjusting the pH of the reaction system to 8-11, wherein the reaction system gradually changes from light green to dark green;
step 4, maintaining the pH value of the reaction system unchanged, continuously dropwise adding the aqueous solution containing sulfite ions into the dark green solution in the step 3 under the stirring condition, wherein blue-green precipitates are generated in the reaction system, stopping dropwise adding after the blue-green precipitates are not separated out, and continuously reacting for 1-2 hours after the dropwise adding is finished so as to ensure that the precipitates are complete;
step 5, washing, filtering and drying the blue-green precipitate generated in the step 4 by using a large amount of deionized water to obtain blue-green ruthenium sulfite powder;
step 6, dissolving blue-green ruthenium sulfite powder in a dilute acid aqueous solution under the stirring condition, adding a carrier material, and dropwise adding H into a reaction system after ultrasonic dispersion 2 O 2 The aqueous solution is heated to react for 2 to 3 hours, then cooled, and the acidic aqueous solution is continuously added to promote RuO 2 Sedimentation on the surface of the support;
step 7, centrifugally separating the reaction liquid in the step 6, washing the reaction liquid with a large amount of deionized water, and drying the reaction liquid after solid-liquid separation to obtain the supported RuO 2 A nano catalyst.
Preferably, the Ru precursor in the step 1 is one or more of ruthenic acid chloride, ruthenium trichloride, potassium ruthenate chloride, sodium ruthenate chloride and ammonium ruthenate chloride, and the Ru concentration in the Ru precursor aqueous solution is 5-50g/[.
Preferably, the slow dropping speed in the step 2 is 1-3mL/min, the stirring rotating speed is 200-1000r/min, the sulfite aqueous solution is one or more of sulfite, sodium bisulfate, potassium sulfite and potassium bisulfate aqueous solution, and the concentration of the sulfite in the aqueous solution is 50-100g/L; when the solution turns to light green, the pH of the reaction system is 4-5, and the molar ratio of sulfite to Ru ions in the reaction system is 5:1-20:1.
Preferably, the dropping speed of the alkaline aqueous solution in the step 3 is 5-10mL/min, the stirring speed is 200-1000r/min, and the alkaline aqueous solution adopts one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide or aqueous ammonia.
Preferably, the pH of the reaction system in the step 4 is 7.5-10, the stirring speed is 200-1000rpm, and the reaction temperature is 0-60 ℃.
Preferably, the dilute acid solution in the step 6 is one or more of dilute sulfuric acid, dilute hydrochloric acid and acetic acid aqueous solution, the concentration is 0.05-0.2mol/L, the pH of the reaction system is 2-5, and the pH in the step 6 is H 2 O 2 The molar ratio of the addition amount to the ruthenium sulfite is 1:1-5:1; the reaction temperature is 60-90 ℃; the carrier comprises one or more of active carbon, conductive carbon, mesoporous carbon, carbon aerosol, aluminum oxide, silicon dioxide, zirconium dioxide and cerium dioxide.
Preferably, the solid-liquid separation in the step 7 is centrifugation or filtration; the drying temperature is 30-60 ℃.
RuO in the catalyst prepared by the method 2 The particle size of the nano particles is 1-5 nanometers.
The invention also discloses the supported RuO prepared by the method 2 The nano catalyst can be used for electrolytic water oxygen evolution reaction.
The reason that the water-soluble Ru precursor is adopted in the step 1 is that the water-soluble Ru precursor is easy to prepare and low in price, and the water phase synthesis is beneficial to subsequent batch amplification, so that the environmental pollution is small, and the preparation cost is low;
The purpose of adopting the slow dropwise adding of sulfite in the step 2 is to control the adding amount of sulfite, because the sulfite has a certain reducibility, the Ru precursor is easy to directly reduce and generate due to the excessively fast dropwise adding, and [ Ru (SO) 3 ) 3 ] 3- A complex;
the slow addition of the alkaline aqueous solution in step 3 is to adjust the pH of the reaction system to weakly alkaline because [ Ru (SO) 3 ) 3 ] 3- The complex exists in the form of ions in strong acid and strong alkaline solutions, and can be separated out from the solution in the form of green precipitation only when the pH is weak alkaline;
continuously adding a sulfite solution in the step 4 ensures that precipitation is complete, and ensures that 100% of Ru species in the solution are separated out from the solution and are completely converted into ruthenium sulfite;
in the step 5, a large amount of deionized water is adopted for washing so as to ensure the effective removal of impurity ions;
in step 6, H is adopted 2 O 2 Is an oxidizing agent due to H 2 O 2 After the reaction, the product is water, so that pollution to a reaction system is avoided; and liquid H 2 O 2 The oxidant is used for replacing air to raise the temperature for oxidization, the reaction temperature is lower, and RuO can be avoided 2 The agglomeration grows up, and dilute acid aqueous solution is added after the reaction to destroy RuO 2 Colloid stability, and subsequent solid-liquid separation to obtain supported RuO 2 A nano-catalyst;
the drying temperature in the step 7 is maintained at 30-60 ℃ to avoid RuO caused by high-temperature drying 2 Agglomeration phenomenon of nanoparticles.
From the above description, it can be seen that the present invention has the following advantages:
1. unlike the prior art in which RuCl is directly adopted 3 Precipitating with alkali solution and oxidizing to prepare RuO 2 The present invention relates to a ligand-displacement method for RuCl 3 The medium chloride ions are replaced, so that adsorption poisoning of the chloride ions on the surface of the catalyst is avoided, and the activity of the catalyst is high;
2. the invention uses liquid H 2 O 2 The oxidant is used for replacing air to raise the temperature for oxidization, the reaction temperature is lower, and RuO can be avoided 2 Agglomeration and growth;
3. the invention can prepare RuO with small size and good dispersivity in aqueous solution without adding protective agent 2 The nano catalyst has the advantages of simple operation, mild reaction condition, environmental protection, low production cost and easy amplified synthesis.
Drawings
FIG. 1 is a RuO prepared in comparative example 1 of the present invention 2 TEM pictures of catalyst.
FIG. 2 is a RuO prepared in comparative example 1 of the present invention 2 XRD spectrum of catalyst/C.
FIG. 3 is a RuO prepared in example 1 of the present invention 2 TEM pictures of catalyst.
FIG. 4 is a RuO prepared in example 1 of the present invention 2 XRD spectrum of catalyst/C.
Detailed Description
The invention is described in detail below with reference to examples. Unless otherwise specified, the raw materials used in the following examples and comparative examples were all commercially available conventional raw materials.
Comparative example 1
Activated carbon supported RuO 2 Preparation of C nanocatalyst
1 g RuCl was added at room temperature 3 And 1.5 g XC-72R carbon black are dissolved in 10mL deionized water in an ultrasonic dispersion way, 50g/L sodium hydroxide aqueous solution is added dropwise, the dropping speed is 2 mL/min, the dropwise addition is stopped when the pH value of the reaction system rises to 13, ru (OH) is arranged at the bottom of the container after the reaction is continued for five days after the reaction is continued 3 precipitating/XC-72R, centrifuging, and drying to obtain Ru (OH) 3 The solid powder of XC-72R is heat treated for 1 hour at 300 ℃ in air atmosphere to obtain RuO 2 The XRD and TEM characterization shows that the ruthenium oxide particles in the prepared catalyst have large size and serious agglomeration, and partial ruthenium oxide is decomposed into reduced metal Ru in the heat treatment of air.
The electrochemical activity of the obtained catalyst is evaluated by adopting a rotary disk electrode, and the specific steps are as follows: accurately weigh 5mg of RuO 2 And (3) mixing the catalyst/C with 20 microliters of Nafion (5 wt%) solution and 5 milliliters of ethanol, performing ultrasonic treatment to obtain uniformly dispersed catalyst slurry, transferring 10 microliters of catalyst slurry to coat on a GC rotating disc electrode with the area of 0.19625 square centimeters, and drying to obtain the working electrode. The activity of the catalyst on the oxygen evolution reaction of electrolyzed water was evaluated in a 0.1M sulfuric acid aqueous solution with nitrogen gas, by scanning from 0 to 1.2 volts at a scan rate of 10mV/s at room temperature, recording 10mA/cm 2 The oxygen evolution reaction corresponding to the electrolysis current has overpotential, and the lower the overpotential is, the indication of RuO 2 The oxygen evolution reaction activity of/C is high. RuO obtained in comparative example 1 2 XC-72R at 10mA/cm 2 The corresponding oxygen evolution reaction overpotential was 400mV.
Example 1
Step 1, 1 g RuCl at room temperature 3 Ultrasonic dispersing and dissolving in 75mL deionized water to prepare RuCl 3 The concentration of the aqueous solution is 5gRu/L according to Ru;
step 3, adjusting the pH of the reaction system to be 12 by using a sodium carbonate aqueous solution, stopping dripping, and gradually changing the reaction system from light green to dark green;
step 4, maintaining the pH value of the reaction system unchanged by using a sodium carbonate aqueous solution, continuously dropwise adding a sulfite aqueous solution into the dark green solution in the step 3 under the stirring condition, generating blue-green precipitate in the reaction system, and continuously stirring and reacting for 1 hour under the room temperature condition to ensure that the precipitate is complete;
and 5, separating the white precipitate from the supernatant by adopting a centrifugal machine, and washing the blue-green precipitate by adopting a large amount of deionized water until no chloride ions exist in the precipitate.
Step 6, dissolving the washed blue-green precipitate with 0.2mol/L dilute sulfuric acid solution to obtain light blue transparent liquid, adding 1.48g of Xc-72R carbon black, and adding excessive H after ultrasonic dispersion 2 O 2 Aqueous solution (30 wt% H) 2 O 2 Aqueous solution, wherein H 2 O 2 The molar ratio of Ru to Ru is 2:1), the reaction temperature of the reaction system is controlled to be 80 ℃, a condensing tube is required to be installed during the heating process and the reaction to prevent excessive volatilization loss of moisture, the concentration of reactants in the reaction system is kept unchanged, the reaction is carried out for 3 hours, 20 milliliters of sulfuric acid solution with the concentration of 0.5 mol/L is added into the reaction system after the temperature is reduced, and the reaction system is kept stand for 1 hour;
and 7, centrifugally separating the reaction solution in the step 6, washing with a large amount of deionized water, putting the obtained solid after centrifugation in a vacuum oven, drying at 40 ℃ for 4 hours, and taking out to obtain the ruthenium oxide nano catalyst.
FIG. 2 shows the prepared RuO 2 XRD spectrum of XC-72R nano catalyst, from the extent of broadening of corresponding XRD diffraction peak, the prepared RuO 2 The XC-72R nano catalyst particles are smaller, and the average grain size of the ruthenium oxide particles is about 1.0nm as calculated by using the Shelle formula.
Adopts and connectsComparative example 1 the same apparatus and Activity evaluation method test the RuO prepared in example 1 2 Catalytic Activity of the XC-72R catalyst. As a result, it was found that under the same test conditions, ruO prepared in example 1 2 XC-72R corresponds to 10mA/cm 2 The overpotential of the oxygen evolution reaction under the current density is 250mV, which is 150mV lower than that of the catalyst prepared by the comparative example, and the oxygen evolution reaction activity is high.
Example 2
The specific experimental procedure of this example is similar to that of example 1, except that KB-300J conductive carbon black is used as the carbon support and 50g of Ru precursor is used Ru Potassium chlororuthenate/L, a sulfite precursor solution is 50g/L potassium sulfite aqueous solution, wherein the dropping speed of sulfite into Ru precursor is 5ml/min, when the solution turns from reddish brown to light green, the mole ratio of the sulfite solution to Ru precursor in a reaction system is 10:1, the pH value is about 4, the stirring speed of 1000rpm is kept, the dropping is stopped when the pH value of the reaction system is regulated to be 10 by using sodium hydroxide aqueous solution, and the solution turns into dark green and has a small amount of blue-green precipitate; continuously dropwise adding a potassium sulfite aqueous solution into the reaction system until precipitation is not increased any more; the subsequent steps are the same as in example 1. RuO prepared in this example 2 The loading of the catalyst/KB-300J was 30wt%, in which RuO 2 The mass ratio of the catalyst to KB-300J is 3:7.
The obtained RuO is treated 2 The oxygen evolution reaction activity of the KB-300J catalyst was evaluated by using a rotating disk electrode, and the specific procedure was as in example 1. As a result, it was found that 10mA/cm 2 RuO prepared in example 2 at oxygen evolution current density 2 The oxygen evolution reaction overpotential corresponding to the ratio of KB-300J is 243mV, compared with RuO prepared in comparative example 2 A decrease in/XC-72R was 157mV.
Example 3
The experimental procedure of this example is similar to that of example 1, except that the carbon support is a carbon nanotube and the Ru precursor is 40g Ru Ruthenium acetate/L, sulfite precursor solution 80g/L potassium sulfite aqueous solution, wherein the dropping speed of sulfite into Ru precursor is 4ml/min, when the solution turns from reddish brown to light green, the reaction systemThe mol ratio of the sulfite solution to the Ru precursor is 20:1, the pH is about 5 at the moment, the stirring speed of 800rpm is kept, the dropwise addition is stopped when the pH of the reaction system is regulated to be 10.5 by using sodium hydroxide aqueous solution, and the color of the solution is changed into dark green and a small amount of blue-green precipitate is separated out; continuously dropwise adding a potassium sulfite aqueous solution into the reaction system until precipitation is not increased any more; the subsequent steps are the same as in example 1. RuO prepared in this example 2 The loading of the carbon nanotube catalyst was 40wt%, where RuO 2 The mass ratio of the catalyst to KB-300J is 4:6.
The obtained RuO is treated 2 The carbon nanotube catalyst was evaluated for oxygen evolution reactivity by using a rotating disk electrode, and the procedure was the same as in example 1. As a result, it was found that 10mA/cm 2 RuO prepared in example 3 at oxygen evolution current density 2 The overpotential of oxygen evolution reaction corresponding to/KB-300J is 213mV, compared with RuO prepared in comparative example 2 The decrease in XC-72R was 187mV.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111545800.8A CN116262975A (en) | 2021-12-15 | 2021-12-15 | Preparation and application of a supported nanometer ruthenium dioxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111545800.8A CN116262975A (en) | 2021-12-15 | 2021-12-15 | Preparation and application of a supported nanometer ruthenium dioxide catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116262975A true CN116262975A (en) | 2023-06-16 |
Family
ID=86722768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111545800.8A Pending CN116262975A (en) | 2021-12-15 | 2021-12-15 | Preparation and application of a supported nanometer ruthenium dioxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116262975A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000254502A (en) * | 1998-03-05 | 2000-09-19 | Sumitomo Chem Co Ltd | Method for producing supported ruthenium oxide catalyst |
| CN1326816A (en) * | 2001-05-18 | 2001-12-19 | 清华大学 | Method for preparing CO poisoning resisting platinum-ruthenium electro-catalyst |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| CN1795293A (en) * | 2003-05-27 | 2006-06-28 | 德·诺拉电极股份公司 | Catalyst for oxygen reduction |
-
2021
- 2021-12-15 CN CN202111545800.8A patent/CN116262975A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000254502A (en) * | 1998-03-05 | 2000-09-19 | Sumitomo Chem Co Ltd | Method for producing supported ruthenium oxide catalyst |
| CN1326816A (en) * | 2001-05-18 | 2001-12-19 | 清华大学 | Method for preparing CO poisoning resisting platinum-ruthenium electro-catalyst |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| CN1795293A (en) * | 2003-05-27 | 2006-06-28 | 德·诺拉电极股份公司 | Catalyst for oxygen reduction |
Non-Patent Citations (1)
| Title |
|---|
| A. K. SHUKLA ET AL: ""A 5 W liquid-feed solid-polymer-electrolyte direct methanol fuel cell stack with stainless steel"", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》, vol. 29, 1 August 1998 (1998-08-01), pages 129 - 132, XP000859176, DOI: 10.1023/A:1003460106154 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103153870B (en) | Preparation method and use of manganese dioxide nano-rod | |
| CN110556548B (en) | A cauliflower-like structure carbon material with oxygen reduction active nitrogen-sulfur co-doping, oxygen reduction electrode and preparation method, and fuel cell | |
| WO2021068570A1 (en) | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof | |
| CN112756000A (en) | Method for preparing sulfide semiconductor/metal nano-particles by using sulfur vacancy defects and application thereof | |
| CN103263920B (en) | A kind of TiO2 loaded highly dispersed metal catalyst and preparation method thereof | |
| CN107522227A (en) | A kind of method that ultrasonic method prepares the bismoclite flat crystal with oxygen defect | |
| CN115465904B (en) | Process for preparing nano iridium dioxide by strong dispersion | |
| CN114808020B (en) | Long-life supported oxygen evolution reaction electrocatalyst, preparation method and application | |
| CN102389837A (en) | Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof | |
| CN110813300A (en) | A kind of nano-carbon material supporting cobalt-zinc bimetal and its preparation method and application in catalytic oxidation of magnesium sulfite | |
| JP5740658B2 (en) | Gold hydroxo anion complex solution and method for producing gold nanoparticle carrier | |
| CN112086648A (en) | Method for synthesizing AuPd @ C material for oxygen reduction reaction electrocatalysis | |
| CN108273502A (en) | One kind preparing C3H6O3 catalyst and preparation method thereof by glycerine | |
| CN115558954A (en) | Oxygen-doped carbon nanosheet-supported palladium monatomic catalyst and preparation method and application thereof | |
| CN108855131A (en) | A kind of preparation and application of silver-nickel bimetal doping titanium dioxide nano composite material | |
| WO2021104087A1 (en) | Metal oxide nanoparticles, and preparation method therefor and application thereof | |
| CN112993278A (en) | Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof | |
| CN109731583A (en) | A two-step method for preparing Zn0.2Cd0.8S/rGO composites | |
| WO2023221315A1 (en) | Metal-doped ruthenium oxide nano material, preparation method therefor, and use thereof | |
| CN106745180A (en) | A kind of cupric oxide electrode material of porous nanometer structure, preparation method and applications | |
| CN115637456B (en) | A core-shell structure Cu2O@(Co,Cu)(OH)2 nanocube electrocatalyst and its preparation and application | |
| CN119101946A (en) | Ruthenium oxide catalyst with high oxygen vacancy, preparation method, hydrogen production material and electrode thereof | |
| CN116262975A (en) | Preparation and application of a supported nanometer ruthenium dioxide catalyst | |
| CN114452990A (en) | Preparation method and composite catalyst of transition metal carbide | |
| CN115212900B (en) | A bismuth iodide and high bismuth iodide heterojunction photocatalytic material and its preparation method and application |
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 |