CN107369839B - preparation method of ruthenium oxide-diatomite composite supported fuel cell catalyst - Google Patents
preparation method of ruthenium oxide-diatomite composite supported fuel cell catalyst Download PDFInfo
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
the invention discloses a preparation method of a ruthenium oxide-diatomite composite load fuel cell catalyst, belonging to the technical field of preparation of fuel cell catalytic materials. The composition of the preparation raw material is RuCl3·3H2O, diatomite, chloropalladate and a reducing agent. Adding RuCl3·3H2dissolving O and pretreated diatomite in water, fully dispersing and stirring, drying and calcining to obtain the ruthenium oxide-diatomite composite carrier, then adding the ruthenium oxide-diatomite composite carrier into a chloropalladate solution, fully stirring, and loading palladium nano catalyst particles by a liquid phase reduction method. The composite carrier obviously improves the dispersibility of palladium particles, thereby improving the catalytic activity and stability of the catalyst to alcohols. The preparation method has the advantages of simple and easily obtained raw materials, stable process and industrial prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of fuel cell catalytic materials, and particularly relates to a preparation method of a ruthenium oxide-diatomite composite supported fuel cell catalyst.
background
the fuel cell is an electrochemical reaction device which directly converts chemical energy of fuel into electric energy, has the advantages of high power generation efficiency, high energy density, good environmental characteristics and the like, and is an advanced green energy technology. The fuel of the fuel cell mainly comprises methanol, ethanol, formic acid and the like, and the most commonly used catalytic material in the anode of the fuel cell is platinum-based alloy at present, but the platinum resource is scarce, the price is high, carbon monoxide poisoning and other defects are easily generated, and the application of the platinum catalyst is limited. Palladium and platinum are elements of the same group, have similar characteristics, are all in a face-centered cubic crystal structure, and have similar atomic sizes. The storage capacity of palladium on earth is more than 50 times of that of platinum, while the market price of palladium is about one third of that of platinum, because the adsorption strength of the carbon monoxide intermediate product on the palladium electrode is less than that on the platinum electrode, the carbon monoxide poisoning on palladium is not as strong as that on platinum, and therefore, the palladium catalyst is a better choice for replacing platinum as the catalytic material of the anode of the fuel cell.
In recent years, researchers have used various methods to prepare palladium-based catalysts in which various active components are highly dispersed. Although the palladium-based catalyst is cheaper than platinum and has abundant resource reserves, the palladium-based catalyst still has serious defects, such as that when the palladium is used as the catalyst, in the electrocatalysis process, the catalyst is poisoned by intermediate product CO generated by incomplete oxidation of fuel, so that the catalytic activity is reduced.
the transition metal oxide has stronger chemical stability and electrochemical stability, and can improve the overall stability of the catalyst material and reduce the loss of electrochemical active area in the oxidation process of organic micromolecules such as formic acid, methanol and the like. The nano ruthenium oxide has excellent catalytic activity, good thermal stability and chemical stability and electron and oxygen vacancy transfer capacity, and has complex interaction with noble metals, and the interaction has important influence on the catalytic performance of the composite catalyst.
The natural diatomite belongs to a new material in silicon materials, and has the advantages of wide distribution, large natural reserve, uniform distribution of silicon hydroxyl on the surface of the diatomite, regular mesopores on the surface, more uniform particle size distribution of a palladium catalyst loaded on the surface of the diatomite, mainly nano-scale size and proper particle size. The method of carrying out chemical loading on the surface of the natural diatomite ensures that the loaded palladium catalyst is firmer, and the loading capacity is easier to regulate, so that the catalytic efficiency and the reutilization capability of the novel heterogeneous catalyst are greatly improved and ensured.
Disclosure of Invention
the invention aims to solve the problems of CO poisoning and activity reduction of a catalyst in the prior art, and provides a preparation method of a ruthenium oxide-diatomite composite supported fuel cell catalyst. The dispersibility and the particle size of the palladium nano catalyst particles on the surface of the carrier can be obviously improved through the synergistic effect of the ruthenium oxide-diatomite composite carrier, so that the catalytic performance of the palladium nano catalyst particles is improved.
In order to realize the purpose, the invention is implemented by the following technical scheme:
A preparation method of a ruthenium oxide-diatomite composite supported fuel cell catalyst specifically comprises the following steps:
(1) Dissolving diatomite and a surfactant in an ethanol solvent, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) Adding RuCl3·3H2dissolving the modified diatomite obtained in the step (1) in water, fully dispersing by ultrasonic for 0.5 ~ 5 hours, then magnetically stirring for 0.5 ~ 8 hours, and then washing and drying by centrifugation to obtain solid powder;
(3) placing the solid powder obtained in the step (2) in a tube furnace, heating to 300 ~ 500 ℃ in a protective gas atmosphere, and keeping the temperature for 0.5 ~ 8 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) Then adding the ruthenium oxide-diatomite composite carrier into a chloropalladate solution, and ultrasonically stirring for 0.5 ~ 6 hours;
(5) And (3) dissolving a reducing agent in water, slowly and dropwise adding the solution obtained in the step (4), magnetically stirring for 1 ~ 10 hours at room temperature, centrifuging, washing and drying to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
In the step (1), the surfactant is one or more of CTAB, CTAC, P123 and F127, and the diatomite and the surfactant are mixed according to the molar ratio of 1:1 ~ 10: 1.
RuCl described in step (2)3·3H2The mass ratio of the O to the modified diatomite is 1:5 ~ 5:1
The magnetic stirring described in step (2) is carried out in an oil bath at room temperature or at 90 ℃.
and (3) the protective gas in the step (3) is one or more of nitrogen, argon and hydrogen.
In the raw material in the step (4), the molar ratio of the ruthenium to the palladium element is 1:3 ~ 3: 3.
the concentration of the chloropalladate solution in the step (4) is 10 ~ 50 mmol/L.
In the step (5), the reducing agent is NaBH4The concentration after dissolving in water is 0.1 ~ 0.5.5 mol/L, NaBH4The volume ratio of the solution to the solution obtained in the step (4) is 1: 1.
And (3) the solvent for centrifugal washing in the step (2) and the step (5) is absolute ethyl alcohol or water.
The invention has the following remarkable advantages:
The composite carrier is obtained by ruthenium oxide and diatomite materials, the dispersibility of palladium nano catalyst particles on the carrier is obviously improved, and the palladium nano particles with uniform size are obtained by combining a liquid phase reduction method, so that the composite carrier has higher catalytic activity on alcohol fuels such as ethanol, methanol and the like. The invention has the advantages of simple and easily obtained raw materials, stable preparation process and industrial prospect.
Drawings
FIG. 1 shows the TEM morphology of a ruthenium oxide-diatomite composite supported palladium-based catalyst prepared in example 1 of the present invention;
Fig. 2 is a TEM morphology of a diatomite-supported palladium-based catalyst prepared in a comparative example.
Detailed Description
the invention provides a preparation method of a ruthenium oxide-diatomite composite supported fuel cell catalyst, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further explained below by combining with specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
comparative example:
(1) dissolving diatomite and a surfactant CTAB in an ethanol solvent according to a molar ratio of 1:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) placing the modified diatomite powder obtained in the step (1) into a tube furnace, heating to 300 ℃ in a protective gas atmosphere, and keeping the temperature for 8 hours to obtain a diatomite carrier;
(3) Then adding the diatomite carrier into 10 mmol/L chloropalladate solution according to the mass ratio of the diatomite carrier to the chloropalladate being 3:5, and ultrasonically stirring for 0.5 hour;
(4) adding a reducing agent NaBH4and (3) dissolving the solution in water to obtain a solution with the concentration of 0.1 mol/L, slowly dropwise adding the solution obtained in the step (3) according to the volume ratio of 1:1, magnetically stirring the solution at room temperature for 1 hour, washing the solution with water, and centrifugally drying the solution to obtain the diatomite-loaded palladium-based fuel cell catalyst.
Example 1:
(1) dissolving diatomite and a surfactant CTAB in an ethanol solvent according to a molar ratio of 1:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) adding RuCl3·3H2Dissolving the O and the modified diatomite obtained in the step (1) in water according to the mass ratio of 1:5, performing ultrasonic treatment for 0.5 hour to fully disperse the O and the modified diatomite, then placing the mixture at room temperature, continuing to perform magnetic stirring for 8 hours, and then washing the mixture with water, centrifuging and drying the mixture to obtain solid powder;
(3) placing the solid powder obtained in the step (2) in a tubular furnace, heating to 300 ℃ in a protective gas atmosphere, and keeping the temperature for 8 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) then adding the ruthenium oxide-diatomite composite carrier into 10 mmol/L chloropalladate solution according to the molar ratio of ruthenium to palladium element of 1:3, and ultrasonically stirring for 0.5 hour;
(5) adding a reducing agent NaBH4Dissolving in water to obtain solution with concentration of 0.1 mol/L, slowly dropwise adding the solution obtained in step (4) according to volume ratio of 1:1, and magnetically stirring at room temperatureWashing with water, centrifuging and drying for 1 hour to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
The specific activity of the obtained catalyst on ethanol catalysis is 16 mA cm-2The decay rate of continuous operation for 12 hours (65 ℃, 0.65V) was only 12%.
Example 2:
(1) Dissolving diatomite and a surfactant CTAC in an ethanol solvent according to a molar ratio of 3:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) Adding RuCl3·3H2Dissolving the O and the modified diatomite obtained in the step (1) in water according to the mass ratio of 5:1, performing ultrasonic treatment for 1 hour to fully disperse the O and the modified diatomite, then placing the mixture at room temperature, continuing to perform magnetic stirring for 6 hours, and then washing the mixture with water, centrifuging and drying the mixture to obtain solid powder;
(3) Placing the solid powder obtained in the step (2) in a tubular furnace, heating to 350 ℃ in a protective gas atmosphere, and keeping the temperature for 6 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) Then adding the ruthenium oxide-diatomite composite carrier into 20 mmol/L chloropalladate solution according to the molar ratio of ruthenium to palladium element of 3:1, and ultrasonically stirring for 2 hours;
(5) Adding a reducing agent NaBH4And (3) dissolving the solution in water to obtain a solution with the concentration of 0.2 mol/L, slowly dropwise adding the solution obtained in the step (4) according to the volume ratio of 1:1, magnetically stirring the solution at room temperature for 2 hours, washing the solution, and centrifugally drying the solution to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
The specific activity of the obtained catalyst on ethanol catalysis is 15 mA cm-2The decay rate of continuous operation for 12 hours (65 ℃, 0.65V) was only 12%.
example 3:
(1) Dissolving diatomite and a surfactant P123 in an ethanol solvent according to a molar ratio of 5:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) Adding RuCl3·3H2dissolving the O and the modified diatomite obtained in the step (1) in water according to the mass ratio of 2:3, and performing ultrasonic treatment on the mixture for 3 hoursfully dispersing, then placing at room temperature, continuing to magnetically stir for 4 hours, washing with water, centrifuging and drying to obtain solid powder;
(3) Placing the solid powder obtained in the step (2) in a tubular furnace, heating to 400 ℃ in a protective gas atmosphere, and preserving heat for 6 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) then adding the ruthenium oxide-diatomite composite carrier into 30 mmol/L chloropalladate solution according to the molar ratio of ruthenium to palladium element of 1:1, and ultrasonically stirring for 3 hours;
(5) Adding a reducing agent NaBH4And (3) dissolving the solution in water to obtain a solution with the concentration of 0.3 mol/L, slowly dropwise adding the solution obtained in the step (4) according to the volume ratio of 1:1, magnetically stirring for 4 hours at room temperature, washing with ethanol, centrifuging and drying to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
the specific activity of the obtained catalyst on ethanol catalysis is 18 mA cm-2The decay rate of continuous operation for 12 hours (65 ℃, 0.65V) was only 11%.
Example 4:
(1) dissolving diatomite and a surfactant F127 in an ethanol solvent according to a molar ratio of 7:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) adding RuCl3·3H2Dissolving the O and the modified diatomite obtained in the step (1) in water according to the mass ratio of 3:2, performing ultrasonic treatment for 4 hours to fully disperse the O and the modified diatomite, then placing the mixture at room temperature, continuing to perform magnetic stirring for 2 hours, and then washing the mixture with water, centrifuging and drying the mixture to obtain solid powder;
(3) Placing the solid powder obtained in the step (2) in a tubular furnace, heating to 450 ℃ in a protective gas atmosphere, and preserving heat for 2 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) then adding the ruthenium oxide-diatomite composite carrier into 40 mmol/L chloropalladate solution according to the molar ratio of ruthenium to palladium element of 1:1, and ultrasonically stirring for 4 hours;
(5) adding a reducing agent NaBH4dissolving in water to obtain a solution with the concentration of 0.4 mol/L, slowly dropwise adding the solution obtained in the step (4) according to the volume ratio of 1:1,Magnetically stirring for 8 hours at room temperature, washing with ethanol, centrifuging and drying to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
the specific activity of the obtained catalyst on ethanol catalysis is 17 mA cm-2the decay rate of continuous operation for 12 hours (65 ℃, 0.65V) was only 11%.
example 5:
(1) dissolving diatomite and a surfactant CTAB in an ethanol solvent according to a molar ratio of 10:1, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) adding RuCl3·3H2Dissolving the O and the modified diatomite obtained in the step (1) in water according to the mass ratio of 4:1, performing ultrasonic treatment for 5 hours to fully disperse the O and the modified diatomite, then placing the mixture at room temperature, continuing to perform magnetic stirring for 0.5 hour, and then washing the mixture with water, centrifuging and drying the mixture to obtain solid powder;
(3) placing the solid powder obtained in the step (2) in a tubular furnace, heating to 500 ℃ in a protective gas atmosphere, and keeping the temperature for 0.5 hour to obtain a ruthenium oxide-diatomite composite carrier;
(4) Then adding the ruthenium oxide-diatomite composite carrier into 50 mmol/L chloropalladate solution according to the molar ratio of ruthenium to palladium element of 1:1, and ultrasonically stirring for 6 hours;
(5) Adding a reducing agent NaBH4And (3) dissolving the solution in water to obtain a solution with the concentration of 0.5 mol/L, slowly dropwise adding the solution obtained in the step (4) according to the volume ratio of 1:1, magnetically stirring the solution at room temperature for 10 hours, washing the solution with ethanol, and centrifugally drying the solution to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst.
the specific activity of the obtained catalyst on ethanol catalysis is 16 mA cm-2The decay rate of continuous operation for 12 hours (65 ℃, 0.65V) was only 11%.
Fig. 1 is a TEM morphology of a ruthenium oxide-diatomite composite supported palladium-based catalyst prepared in example 1 of the present invention, and fig. 2 is a TEM morphology of a diatomite supported palladium-based catalyst prepared in a comparative example. As can be seen from fig. 1 and 2, both supported palladium-based catalysts are well dispersed, and the particle shapes of the catalysts are relatively regular. Comparing fig. 1 and 2, it can be seen that the palladium-based catalyst supported by the complex combination of ruthenium oxide and modified diatomite has better particle dispersion and almost no agglomeration phenomenon, while the palladium has a smaller particle size, and an average particle size of about 4 nm, compared to the catalyst supported by single modified diatomite (i.e., no ruthenium oxide in the carrier), whereas the palladium particles partially agglomerate, while the average particle size is about 5.6 nm. It is demonstrated that the dispersibility and particle size of the palladium-based catalyst can be further improved by the composite action of ruthenium oxide and modified diatomite, which is beneficial to improving the catalytic activity of the catalyst.
Claims (7)
1. A preparation method of a ruthenium oxide-diatomite composite load fuel cell catalyst is characterized by comprising the following steps: in particular to
(1) dissolving diatomite and a surfactant in an ethanol solvent, performing ultrasonic treatment for 1 hour to uniformly disperse the diatomite and the surfactant, and performing centrifugal drying to obtain modified diatomite powder;
(2) Adding RuCl3·3H2Dissolving the modified diatomite powder obtained in the step (1) in water, fully dispersing by ultrasonic for 0.5 ~ 5 hours, then magnetically stirring for 0.5 ~ 8 hours, and then washing and drying by centrifugation to obtain solid powder;
(3) Placing the solid powder obtained in the step (2) in a tube furnace, heating to 300 ~ 500 ℃ in a protective gas atmosphere, and keeping the temperature for 0.5 ~ 8 hours to obtain a ruthenium oxide-diatomite composite carrier;
(4) then adding the ruthenium oxide-diatomite composite carrier into a chloropalladate solution, and ultrasonically stirring for 0.5 ~ 6 hours;
(5) Dissolving a reducing agent in water, slowly and dropwise adding the solution obtained in the step (4), magnetically stirring for 1 ~ 10 hours at room temperature, centrifuging, washing and drying to obtain the ruthenium oxide-diatomite composite supported palladium-based fuel cell catalyst;
In the step (1), the surfactant is one or more of CTAB, CTAC, P123 and F127, and the diatomite and the surfactant are mixed according to the molar ratio of 1:1 ~ 10: 1;
RuCl described in step (2)3·3H2The mass ratio of O to the modified diatomite powder is1:5~5:1。
2. The method for preparing a ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein: the magnetic stirring described in step (2) is carried out in an oil bath at room temperature or at 90 ℃.
3. The method for preparing a ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein: and (3) the protective gas in the step (3) is one or more of nitrogen, argon and hydrogen.
4. The method for preparing a ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein the molar ratio of the ruthenium to the palladium element in the step (4) is 1:3 ~ 3: 1.
5. the method for preparing the ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein the concentration of the chloropalladate solution in the step (4) is 10 ~ 50 mmol/L.
6. The method for preparing a ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein: in the step (5), the reducing agent is NaBH4The concentration after dissolving in water is 0.1 ~ 0.5.5 mol/L, NaBH4The volume ratio of the solution to the solution obtained in the step (4) is 1: 1.
7. the method for preparing a ruthenium oxide-diatomite composite supported fuel cell catalyst according to claim 1, wherein: and (3) the solvent for centrifugal washing in the step (2) and the step (5) is absolute ethyl alcohol or water.
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