CN107195911A - The preparation method of ruthenium-oxide bacteria cellulose composite load palladium base fuel-cell catalyst - Google Patents

The preparation method of ruthenium-oxide bacteria cellulose composite load palladium base fuel-cell catalyst Download PDF

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CN107195911A
CN107195911A CN201710458227.4A CN201710458227A CN107195911A CN 107195911 A CN107195911 A CN 107195911A CN 201710458227 A CN201710458227 A CN 201710458227A CN 107195911 A CN107195911 A CN 107195911A
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bacteria cellulose
ruthenium
oxide
cell catalyst
base fuel
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温翠莲
吴军茹
洪云
张腾
萨百晟
魏颖
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Fuzhou University
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    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of preparation method of ruthenium-oxide bacteria cellulose composite load palladium base fuel-cell catalyst, belong to fuel cell catalyst technical field of material.Preparing raw material composition is RuCl3·3H2O, bacteria cellulose, chlorine palladium acid and reducing agent.By RuCl3·3H2The bacteria cellulose fully dispersed stirring soluble in water of O and pre-treatment, drying and calcination obtain ruthenium-oxide bacteria cellulose complex carrier, are subsequently added in chlorine palladium acid solution and are sufficiently stirred for, pass through liquid phase reduction supported palladium nano-catalyst particles.Complex carrier significantly improves the dispersiveness of palladium particle, so as to improve catalytic activity and stability of the catalyst to alcohols.Preparing raw material of the present invention is simple and easy to get, process stabilizing, with industrialization prospect.

Description

The preparation of ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst Method
Technical field
The invention belongs to fuel cell catalyst technical field of material, and in particular to a kind of ruthenium-oxide-bacteria cellulose The preparation method of composite load palladium base fuel-cell catalyst.
Background technology
Direct alcohol fuel cell is one kind in Proton Exchange Membrane Fuel Cells in fact, and it is with proton exchange membrane technology Based on（Centered on PEM, the distribution of electrodes of catalyst is scribbled in both sides）It is proton by fuel instead of alcohols The hydrogen in film battery is exchanged, its energy density is higher in theory, and fuel source is extensive, it is not necessary to obtained by reforming technique Hydrogen-rich combustion gas as fuel, fuel state is liquid, is conducive to transporting and stores, and existing fuel system can be direct Supply.Because with above-mentioned advantage, people increasingly pay attention to direct alcohol fuel cell research and development.
The fuel of fuel cell mainly includes methanol, ethanol, formic acid etc., the most frequently used in current anode of fuel cell to urge It is platinum base alloy to change material, but platinum scarcity of resources, expensive, and the shortcomings of easy generation anthracemia, limitation The application of platinum catalyst.Palladium and platinum are same family's elements, and they have similar characteristic, are all face-centered cubic crystal structures, and The size of atom is close.Palladium is in more than 50 times that the reserves of the earth are platinum, and the market price of palladium is about 1/3rd of platinum, because one Adsorption strength of the carbonoxide intermediate product on palladium electrode is less than its adsorption strength on platinum electrode, so the oxidation on palladium Carbon poisoning does not have on platinum so strongly, and therefore, palladium catalyst, which is that instead of platinum, turns into one kind of fuel battery anode catalysis material Preferably selection.In recent years, researcher is prepared for the palladium-based catalyst of various active component high degree of dispersion with a variety of methods.Pd Base catalyst is not only cheaper than Pt, resource reserve enrich, but its still have the shortcomings that it is serious, such as Pd as during catalyst During electro-catalysis, because the intermediate product CO that fuel incomplete oxidation is produced makes catalyst poisoning, so as to reduce catalytic activity.
Transition metal oxide has stronger chemical stability and electrochemical stability, organic small in formic acid, methanol etc. Among the oxidizing process of molecule, the resistance to overturning of catalyst material can be lifted, the loss of electrochemical surface area is reduced.Receive Rice ruthenium-oxide（RuO2）Passed with excellent catalytic activity, good heat endurance and chemical stability and electronics, Lacking oxygen Pass ability.Bacteria cellulose（Bacterial Cellulose, BC）, also referred to as micro organism cellulose；Chemical formula is (C6H10O)n, it is a kind of straight-chain polysaccharide biomass as formed by β-D-Glucose monomer with β-Isosorbide-5-Nitrae glycosidic bond connection.Due to gathering around There are ultra-fine three-dimensional net structure, substantial amounts of nanoscale pore-size distribution, very big specific surface area and abundant surface hydroxyl base Group, meets the requirement of fuel-cell catalyst carrier.
The content of the invention
The problem of for catalyst CO poisonings and activity reduction, the invention provides a kind of ruthenium-oxide-bacteria cellulose is multiple Close the preparation method of supported palladium base fuel battery catalyst.Pass through the synergy of ruthenium-oxide bacteria cellulose complex carrier, energy Dispersiveness and particle diameter of the palladium nano-catalyst particles in carrier surface are enough significantly improved, and then improves its catalytic performance.
The present invention is implemented by following technical solution：
A kind of preparation method of ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst, specifically includes following step Suddenly：
（1）Block bacteria cellulose film is added in sodium hydroxide solution, the water bath processing under 358 K.Water bath processing is finished Afterwards, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then bacteria cellulose film is put into NaOH/urea/H2O In mixed solution（It is cooled to -12 DEG C in advance）, strong stirring to block bacteria cellulose all dissolves, that is, obtains transparent bacterium fine The plain solution of dimension；
（2）By RuCl3·3H2O and step（1）After processing bacteria cellulose mixing ultrasound 0.5 ~ 5 hour it is fully dispersed, then Continue magnetic agitation 0.5 ~ 8 hour, then 2 mol/L HCl solution be added dropwise to make pH value in neutrality, finally by centrifuge washing It is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 300 ~ 500 DEG C, guarantor are warming up in protective gas atmosphere Temperature 0.5 ~ 8 hour, obtains ruthenium-oxide-bacteria cellulose complex carrier；
（4）Ruthenium-oxide-bacteria cellulose complex carrier is then added into ultrasonic agitation 0.5 ~ 6 hour in chlorine palladium acid solution；
（5）Dissolve reduce agent in after water, be slowly added dropwise step（4）In the solution of gained, magnetic agitation 1 ~ 10 is small at room temperature When, centrifuge washing is dried to obtain ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst.
Step（1）Described in sodium hydroxide solution mass percent concentration be 0.3 ~ 2.5%, water-curing treatment duration is 0.5-5 hours, NaOH/urea/H2NaOH, urea and H in O mixed solutions2O mass percent is 7:12:81.
Step（2）Described in RuCl3·3H2The mass ratio of O and bacteria cellulose is 1:5~5:1.
Step（2）Described in magnetic agitation carried out under room temperature or 90 DEG C of oil baths.
Step（3）Described in protective gas be nitrogen, argon gas and hydrogen in one or more.
Step（4）The mol ratio of ruthenium and palladium element in middle complex carrier and chlorine palladium acid solution is 1:3~3:1.
Step（4）Described in chlorine palladium acid solution concentration be 10 ~ 50 mmol/L；Step（5）Described in reductant solution be 0.1~0.5 mol/L NaBH4Solution, step（4）The mixed liquor of gained and the volume ratio 1 of reductant solution:1.
The solvent of centrifuge washing in the step is absolute ethyl alcohol or water.
The remarkable advantage of the present invention is：
Complex carrier is obtained with ruthenium-oxide and bacteria cellulose material, point of the palladium nano-catalyst particles on carrier is significantly improved Dissipate property, in combination with liquid phase reduction obtain size uniform palladium nano-particles, to the Aalcohols fuels such as ethanol and methanol have compared with High catalytic activity.Raw material of the present invention is simple and easy to get, stable preparation process, with industrialization prospect.
Brief description of the drawings
Fig. 1 is the TEM shapes of the ruthenium-oxide-bacteria cellulose composite load catalyst prepared under the conditions of the embodiment of the present invention 1 Looks；
Fig. 2 is the TEM patterns of the single bacteria cellulose supported catalyst prepared under the conditions of the embodiment of the present invention 1.
Embodiment
The present invention provides a kind of preparation method of ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst, To make the purpose of the present invention, technical scheme and effect clearer, clear and definite, with reference to specific embodiment, this is expanded on further Invention.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that Read after the content of the invention lectured, those skilled in the art can make various changes or modifications to the present invention, these etc. Valency form equally falls within the application appended claims limited range.
Embodiment 1：
（1）Block bacteria cellulose film is added and boiled in the sodium hydroxide solution of mass percent concentration 0.3%, under 358 K Water bath processing 5 hours.After water bath processing is finished, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then by bacterium It is 7 that cellulose membrane, which is put into mass percent,:12:81 NaOH/urea/H2In O mixed solutions（It is cooled to -12 DEG C in advance）, strongly stir Mix to block bacteria cellulose and all dissolve, that is, obtain transparent bacterial cellulose solution；
（2）By RuCl3·3H2O and step（1）Bacteria cellulose in mass ratio 1 after processing:5 mixing ultrasounds 0.5 hour are fully Scattered, continuing thereafter with magnetic agitation 8 hours, then 2 mol/L HCl solution is added dropwise makes pH value in neutrality, finally by second Alcohol centrifuge washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 300 DEG C, insulation 8 are warming up in protective gas atmosphere Hour, obtain ruthenium-oxide-bacteria cellulose complex carrier；
（4）It is then 1 according to the mol ratio of ruthenium and palladium element:Ruthenium-oxide-bacteria cellulose complex carrier is added 10 mmol/ by 3 Ultrasonic agitation 0.5 hour in L chlorine palladium acid solutions；
（5）By reducing agent NaBH4It is dissolved in after water and obtains solution concentration for 0.1 mol/L, is by volume 1:1 is slowly added dropwise Step（4）The solution of gained, magnetic agitation 1 hour, washes centrifugal drying and obtains ruthenium-oxide-bacteria cellulose Compound Negative at room temperature Carry palladium base fuel-cell catalyst.
Gained catalyst is 18 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）'s Attenuation rate is only 11%.
Fig. 1 is the TEM patterns of ruthenium-oxide-bacteria cellulose composite load palladium-based catalyst prepared by the embodiment of the present invention 1, Fig. 2 is the single bacteria cellulose for preparing under the conditions of the embodiment of the present invention 1（There is no ruthenium-oxide in carrier）Load palladium base catalysis The TEM patterns of agent.Two kinds of carrier loaded palladium-based catalysts are can be seen that from Fig. 1 and Fig. 2 can preferably to disperse, simultaneously The grain shape of catalyst all comparison rules.Comparison diagram 1 and Fig. 2 are understood, carrier is used as compared to single bacteria cellulose Catalyst, it is scattered more preferable by the particle of ruthenium-oxide and the compound palladium-based catalyst as carrier of bacteria cellulose, almost do not have Agglomeration, while the granularity of palladium is smaller, the nm of average grain diameter about 3.1, and single bacteria cellulose is used as the catalysis of carrier Agent, palladium particle has part reunion, while average grain diameter is about 6.7 nm.Illustrate, pass through the compound of ruthenium-oxide and bacteria cellulose Effect, can further improve the dispersiveness and particle diameter of palladium base fuel-cell catalyst, be conducive to the catalysis for improving catalyst to live Property.
Embodiment 2：
（1）Block bacteria cellulose film is added in the sodium hydroxide solution of mass percent concentration 1.0%, the water-bath under 358 K Processing 4 hours.After water bath processing is finished, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then by bacterial fibers It is 7 that plain film, which is put into mass percent,:12:81 NaOH/urea/H2In O mixed solutions（It is cooled to -12 DEG C in advance）, strong stirring is extremely Block bacteria cellulose all dissolves, that is, obtains transparent bacterial cellulose solution；
（2）By RuCl3·3H2O and step（1）Bacteria cellulose in mass ratio 5 after processing:1 mixing ultrasound is fully divided for 1 hour Dissipate, continue thereafter with magnetic agitation 6 hours, then be added dropwise 2 mol/L HCl solution make pH value in neutrality, finally by go from Sub- water centrifuge washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 350 DEG C, insulation 6 are warming up in protective gas atmosphere Hour, obtain ruthenium-oxide-bacteria cellulose complex carrier；
（4）It is then 3 according to the mol ratio of ruthenium and palladium element:Ruthenium-oxide-bacteria cellulose complex carrier is added 20 mmol/ by 1 Ultrasonic agitation 2 hours in L chlorine palladium acid solutions；
（5）By reducing agent NaBH4It is dissolved in after water and obtains solution concentration for 0.2 mol/L, is by volume 1:1 is slowly added dropwise Step（4）The solution of gained, magnetic agitation 2 hours, wash centrifugal drying and obtain ruthenium-oxide-bacteria cellulose Compound Negative at room temperature Carry palladium base fuel-cell catalyst.
Gained catalyst is 16 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）'s Attenuation rate is only 12%.
Embodiment 3：
（1）Block bacteria cellulose film is added in the sodium hydroxide solution of mass percent concentration 2.5%, the water-bath under 358 K Processing 2 hours.After water bath processing is finished, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then by bacterial fibers It is 7 that plain film, which is put into mass percent,:12:81 NaOH/urea/H2In O mixed solutions（It is cooled to -12 DEG C in advance）, strong stirring is extremely Block bacteria cellulose all dissolves, that is, obtains transparent bacterial cellulose solution；
（2）By RuCl3·3H2O and step（1）Bacteria cellulose in mass ratio 2 after processing:3 mixing ultrasounds are fully divided for 3 hours Dissipate, continue thereafter with magnetic agitation 4 hours, then be added dropwise 2 mol/L HCl solution make pH value in neutrality, finally by go from Sub- water centrifuge washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 400 DEG C, insulation 6 are warming up in protective gas atmosphere Hour, obtain ruthenium-oxide-bacteria cellulose complex carrier；
（4）It is then 1 according to the mol ratio of ruthenium and palladium element:Ruthenium-oxide-bacteria cellulose complex carrier is added 30 mmol/ by 1 Ultrasonic agitation 3 hours in L chlorine palladium acid solutions；
（5）By reducing agent NaBH4It is dissolved in after water and obtains solution concentration for 0.3 mol/L, is by volume 1:1 is slowly added dropwise Step（4）The solution of gained, magnetic agitation 4 hours at room temperature, it is multiple that ethanol cleaning centrifugal drying obtains ruthenium-oxide-bacteria cellulose Close supported palladium base fuel battery catalyst.
Gained catalyst is 15 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）'s Attenuation rate is only 12%.
Embodiment 4：
（1）Block bacteria cellulose film is added in the sodium hydroxide solution of mass percent concentration 1.5%, the water-bath under 358 K Processing 1 hour.After water bath processing is finished, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then by bacterial fibers It is 7 that plain film, which is put into mass percent,:12:81 NaOH/urea/H2In O mixed solutions（It is cooled to -12 DEG C in advance）, strong stirring is extremely Block bacteria cellulose all dissolves, that is, obtains transparent bacterial cellulose solution；
（2）By RuCl3·3H2O and step（1）Bacteria cellulose in mass ratio 3 after processing:2 mixing ultrasounds are fully divided for 4 hours Dissipate, continue thereafter with magnetic agitation 2 hours, then be added dropwise 2 mol/L HCl solution make pH value in neutrality, finally by ethanol Centrifuge washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 350 DEG C, insulation 6 are warming up in protective gas atmosphere Hour, obtain ruthenium-oxide-bacteria cellulose complex carrier；
（4）It is then 1 according to the mol ratio of ruthenium and palladium element:Ruthenium-oxide-bacteria cellulose complex carrier is added 40 mmol/ by 1 Ultrasonic agitation 4 hours in L chlorine palladium acid solutions；
（5）By reducing agent NaBH4It is dissolved in after water and obtains solution concentration for 0.4 mol/L, is by volume 1:1 is slowly added dropwise Step（4）The solution of gained, magnetic agitation 8 hours at room temperature, it is multiple that ethanol cleaning centrifugal drying obtains ruthenium-oxide-bacteria cellulose Close supported palladium base fuel battery catalyst.
Gained catalyst is 19 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）'s Attenuation rate is only 9%.
Embodiment 5：
（1）Block bacteria cellulose film is added in the sodium hydroxide solution of mass percent concentration 2.0%, the water-bath under 358 K Processing 0.5 hour.After water bath processing is finished, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality.Then it is bacterium is fine It is 7 that the plain film of dimension, which is put into mass percent,:12:81 NaOH/urea/H2In O mixed solutions（It is cooled to -12 DEG C in advance）, strong stirring All dissolved to block bacteria cellulose, that is, obtain transparent bacterial cellulose solution；
（2）By RuCl3·3H2O and step（1）Bacteria cellulose in mass ratio 4 after processing:1 mixing ultrasound is fully divided for 5 hours Dissipate, continue thereafter with magnetic agitation 0.5 hour, then be added dropwise 2 mol/L HCl solution make pH value in neutrality, finally by second Alcohol centrifuge washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 500 DEG C, insulation are warming up in protective gas atmosphere 0.5 hour, obtain ruthenium-oxide-bacteria cellulose complex carrier；
（4）It is then 1 according to the mol ratio of ruthenium and palladium element:Ruthenium-oxide-bacteria cellulose complex carrier is added 50 mmol/ by 1 Ultrasonic agitation 6 hours in L chlorine palladium acid solutions；
（5）By reducing agent NaBH4It is dissolved in after water and obtains solution concentration for 0.5 mol/L, is by volume 1:1 is slowly added dropwise Step（4）The solution of gained, magnetic agitation 10 hours at room temperature, ethanol cleaning centrifugal drying obtains ruthenium-oxide-bacteria cellulose Composite load palladium base fuel-cell catalyst.
Gained catalyst is 18 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）'s Attenuation rate is only 11%.
It the foregoing is only the better embodiment of the present invention, all equivalent changes done according to scope of the present invention patent With modification, it should all belong to the covering scope of the present invention.

Claims (8)

1. a kind of preparation method of ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst, it is characterised in that：Tool Body comprises the following steps：
（1）Block bacteria cellulose film is added in sodium hydroxide solution, the water bath processing under 358 K, water bath processing is finished Afterwards, rinsed repeatedly with a large amount of deionized waters, until pH value is in neutrality, then bacteria cellulose film is put into and pre- is cooled to -12 DEG C NaOH/urea/H2In O mixed solutions, strong stirring to block bacteria cellulose all dissolves, that is, obtains transparent bacterial fibers Plain solution；
（2）By RuCl33H2O and step（1）After processing bacterial cellulose solution mixing ultrasound 0.5 ~ 5 hour it is fully dispersed, Continue thereafter with magnetic agitation 0.5 ~ 8 hour, then be added dropwise 2 mol/L HCl solution make pH value in neutrality, finally by centrifugation Washing is freeze-dried to obtain solid powder；
（3）By step（2）Obtained solid powder is positioned over tube furnace, and 300 ~ 500 DEG C, guarantor are warming up in protective gas atmosphere Temperature 0.5 ~ 8 hour, obtains ruthenium-oxide-bacteria cellulose complex carrier；
（4）Ruthenium-oxide-bacteria cellulose complex carrier is then added into ultrasonic agitation 0.5 ~ 6 hour in chlorine palladium acid solution；
（5）Dissolve reduce agent in after water, be slowly added dropwise step（4）In the solution of gained, magnetic agitation 1 ~ 10 is small at room temperature When, centrifuge washing is dried to obtain ruthenium-oxide-bacteria cellulose composite load palladium base fuel-cell catalyst.
2. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（1）Described in the mass percent concentration of sodium hydroxide solution be 0.3 ~ 2.5%, at water-bath The reason time is 0.5-5 hours, NaOH/urea/H2NaOH, urea and H in O mixed solutions2O mass percent is 7:12:81.
3. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（2）Described in RuCl3·3H2The mass ratio of O and bacteria cellulose is 1:5~5:1.
4. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（2）Described in magnetic agitation carried out under room temperature or 90 DEG C of oil baths.
5. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（3）Described in protective gas be nitrogen, argon gas and hydrogen in one or more.
6. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（4）The mol ratio of ruthenium and palladium element in middle complex carrier and chlorine palladium acid solution is 1:3~3: 1。
7. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：Step（4）Described in chlorine palladium acid solution concentration be 10 ~ 50 mmol/L；Step（5）Described in also Former agent solution is 0.1 ~ 0.5 mol/L NaBH4Solution, adds step（4）The mixed liquor of gained and the volume ratio of reductant solution 1:1。
8. a kind of system of ruthenium-oxide according to claim 1-bacteria cellulose composite load palladium base fuel-cell catalyst Preparation Method, it is characterised in that：The solvent of centrifuge washing in the step is absolute ethyl alcohol or water.
CN201710458227.4A 2017-06-16 2017-06-16 The preparation method of ruthenium-oxide bacteria cellulose composite load palladium base fuel-cell catalyst Withdrawn CN107195911A (en)

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CN113278990A (en) * 2021-05-25 2021-08-20 中北大学 Ruthenium quantum dot-loaded carbon fiber hydrogen evolution catalyst and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
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Publication number Priority date Publication date Assignee Title
CN113278990A (en) * 2021-05-25 2021-08-20 中北大学 Ruthenium quantum dot-loaded carbon fiber hydrogen evolution catalyst and preparation method and application thereof
CN113278990B (en) * 2021-05-25 2023-08-22 中北大学 Ruthenium quantum dot loaded carbon fiber hydrogen evolution catalyst and preparation method and application thereof

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