CN108499562B - Carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning and preparation method thereof - Google Patents
Carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 208000001408 Carbon monoxide poisoning Diseases 0.000 title claims abstract description 11
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 16
- NVGDLDWVAKLSCC-UHFFFAOYSA-N [W](=O)(=O)=O.[Pt] Chemical compound [W](=O)(=O)=O.[Pt] NVGDLDWVAKLSCC-UHFFFAOYSA-N 0.000 abstract description 15
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- 238000005516 engineering process Methods 0.000 abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
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- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012905 visible particle Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B01J35/33—
Abstract
The invention belongs to the technical field of nano catalyst preparation, and particularly relates to a carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning and a preparation method thereof. According to the preparation method provided by the invention, the platinum salt, the carbon carrier and the tungsten trioxide are fully mixed, the carbon-supported platinum-tungsten trioxide catalyst material is prepared on the basis of the disclosed microwave-assisted method, and the tungsten trioxide is reduced to a low valence state by a reduction sintering technology, so that the carbon-supported platinum-tungsten dioxide electrocatalyst is prepared, the oxidation potential of carbon monoxide on the catalyst is greatly reduced, and the carbon monoxide resistance of the catalyst is improved. The particle size distribution of platinum in the carbon-supported platinum-tungsten dioxide electrocatalyst provided by the invention is about 4 nanometers, and the carbon-supported platinum-tungsten dioxide electrocatalyst has better utilization efficiency. Compared with the oxidation current of the platinum-carbon catalyst under 0.7V vs. Ag/AgCl, the carbon-supported platinum-tungsten dioxide electrocatalyst has more excellent carbon monoxide oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of nano catalyst preparation, and particularly relates to a carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning and a preparation method thereof.
Background
Platinum-based electrocatalysts are commonly used electrocatalytic materials and are in high demand for use in fuel cells. Conventionally, a platinum-carbon catalyst has been prepared using a dip reduction method, which is suitable for mass production of platinum-carbon catalysts, but has a disadvantage in that the particle size of the product is large. The chinese patent publication CN1775362A discloses that the platinum/carbon nano-catalyst is prepared by using microwave-assisted technology, and the prepared catalyst has a smaller particle size and higher catalytic performance.
For organic small molecule fuels such as methanol, the simple use of platinum catalysts tends to cause strong adsorption of carbon monoxide intermediates, thereby causing a catalyst poisoning phenomenon. In order to solve the problem, a bi-component platinum-based electrocatalyst is often used, for example, chinese patent No. cn01118132.x discloses a platinum-ruthenium catalyst with Ru as a carbon monoxide resistant component, which can effectively catalyze the oxidation of carbon monoxide and reduce the catalyst poisoning phenomenon. There is also a document to provide a method for preparing platinum-tungsten trioxide and its application in methanol oxidation, but tungsten trioxide used in the method is the highest valence state of transition metal tungsten, and its co-catalysis has room for improvement as reducible transition metal oxide (A.K. Shukla; M.K. Ravikumar; et. al, Journal of Applied Electrochemistry 1995,25(6), 528-.
Disclosure of Invention
The invention aims to provide a carbon-supported platinum-tungsten dioxide electrocatalyst for resisting carbon monoxide poisoning and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning, which comprises the following steps:
the method comprises the following steps: grinding a carbon carrier and tungsten trioxide, and dispersing the ground carbon carrier and tungsten trioxide in ethylene glycol to obtain a first suspension;
step two: adding a chloroplatinic acid solution and a pH regulating solution into the first suspension to obtain a second suspension;
step three: placing the second suspension liquid in a microwave reactor for microwave reaction to obtain a third suspension liquid;
step four: filtering, cleaning and drying the third suspension to obtain solid powder;
step five: and sintering the solid powder in a reducing atmosphere to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
In the above technical scheme, the carbon carrier is conductive carbon powder.
In the technical scheme, the mass ratio of the platinum content in the chloroplatinic acid solution to the carbon carrier is (100-200): (300-400).
In the technical scheme, the mass ratio of the platinum content to the tungsten trioxide in the chloroplatinic acid solution is (100-200): (20-100).
In the above technical scheme, the mass ratio of the platinum content in the chloroplatinic acid solution to the carbon carrier is 100:400, wherein the mass ratio of the platinum content to the tungsten trioxide in the chloroplatinic acid solution is 200: 100, wherein the mass ratio of the ethylene glycol to the carbon carrier is 1000: 10.
in the above technical solution, the pH value of the second suspension is adjusted to 10 by the pH adjusting liquid.
In the technical scheme, in the step five, the solid powder is reduced by using the mixed gas of hydrogen and inert gas, and the volume percentage of the hydrogen is 5-20%.
In the above technical scheme, the temperature for reduction in the fifth step is 400-.
In the technical scheme, the reduction temperature in the fifth step is 500 ℃, and the reduction time is 1 hour.
The invention also provides the carbon-supported platinum-tungsten dioxide electrocatalyst prepared by the preparation method.
The invention has the beneficial effects that:
the preparation method of the carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning, provided by the invention, is characterized in that a platinum salt, a carbon carrier and tungsten trioxide are fully mixed, and then the carbon-supported platinum-tungsten trioxide catalyst material is prepared on the basis of a disclosed microwave-assisted method. And reducing the tungsten trioxide to a low valence state by a reduction sintering technology to prepare the carbon-supported platinum-tungsten dioxide electrocatalyst, so that the oxidation potential of carbon monoxide on the catalyst is greatly reduced, and the carbon monoxide resistance of the catalyst is improved.
The catalyst is characterized by a transmission electron microscope, and the obtained result shows that the particle size of platinum is distributed about 4 nanometers, so that the catalyst has better utilization efficiency. The oxidation effect of the catalyst on carbon monoxide is analyzed by a rotating disc electrode, and the result is that the catalyst has oxidation current generation on carbon monoxide under 0.1V vs. Ag/AgCl, and has more excellent carbon monoxide oxidation resistance compared with the oxidation current of a platinum carbon catalyst under 0.7V vs. Ag/AgCl.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a transmission electron micrograph of the carbon-supported platinum-tungsten dioxide electrocatalyst prepared in example 1 according to the present invention on a 20nm scale.
Figure 2 is an X-ray diffraction pattern of a carbon supported platinum-tungsten dioxide electrocatalyst prepared in example 1 according to the present invention.
Fig. 3 is a plot of cyclic voltammetry scans for the recovery of the carbon supported platinum-tungsten dioxide electrocatalyst prepared in example 1 of the present invention after poisoning with carbon monoxide in a hydrogen saturated solution.
Fig. 4 is a plot of cyclic voltammetry scans for the recovery of performance of the carbon-supported platinum electrocatalyst prepared in comparative example 1 in a hydrogen-saturated solution after poisoning with carbon monoxide.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a preparation method of a carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning, which comprises the steps of firstly, grinding a carbon carrier and tungsten trioxide, and dispersing the carbon carrier and the tungsten trioxide into ethylene glycol to obtain a first suspension; then adding a chloroplatinic acid solution and a pH regulating solution into the first suspension to obtain a second suspension; the platinum salt was reduced by a microwave method using a publicly known technique to obtain a third suspension, i.e., platinum-tungsten trioxide on carbon. After being filtered and washed, the carbon-supported platinum-tungsten dioxide electrocatalyst is prepared by reduction sintering under proper conditions.
The preparation method of the carbon-supported platinum-tungsten dioxide electrocatalyst capable of resisting carbon monoxide poisoning specifically comprises the following steps:
the method comprises the following steps: grinding a carbon carrier and tungsten trioxide, and dispersing the ground carbon carrier and tungsten trioxide in ethylene glycol to obtain a first suspension;
step two: adding a chloroplatinic acid solution and a pH regulating solution into the first suspension to obtain a second suspension;
step three: placing the second suspension liquid in a microwave reactor for microwave reaction to obtain a third suspension liquid;
step four: filtering, cleaning and drying the third suspension to obtain solid powder;
step five: and sintering the solid powder in a reducing atmosphere to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
According to the invention, firstly, a carbon carrier and tungsten trioxide are ground and then dispersed in a mixed solvent of ethylene glycol and a dispersing agent to obtain a first suspension; the dispersing method is not particularly limited, and preferably an ultrasonic dispersing method is adopted, the ultrasonic dispersing time is preferably 1 to 3 hours, more preferably 1.5 to 2 hours, and the carbon carrier is a carbon carrier known to those skilled in the art, and is not particularly limited, and is preferably conductive carbon powder.
According to the invention, after a first suspension liquid is obtained, adding a chloroplatinic acid solution and a pH regulating solution into the first suspension liquid, and stirring at room temperature for 1-2 hours to obtain a second suspension liquid; the mass ratio of the platinum content to the carbon carrier in the chloroplatinic acid solution is preferably (100-200): (300-400), more preferably 100: 400. The mass ratio of the ethylene glycol to the carbon carrier is preferably (5000-10000): (2-10), more preferably 1000: 10. the mass ratio of the platinum content to the tungsten trioxide in the chloroplatinic acid solution is preferably (100-200): (20-100), more preferably 200: 100.
according to the invention, the second suspension is placed in a microwave reactor, and microwave reaction is carried out for a period of time to obtain a third suspension. Wherein, the ethylene glycol is used as a reducing agent, can reduce chloroplatinic acid into nano platinum and is dispersed on the surfaces of the carbon carrier and the tungsten trioxide. The microwave time is preferably 30 to 80 seconds, more preferably 50 seconds. The microwave power used is preferably 500-.
According to the present invention, after stirring, the obtained third suspension is subjected to suction filtration, washed and dried to obtain a carbon-supported platinum-tungsten trioxide complex. According to the invention, deionized water with the resistivity of 17-19M omega-cm is preferably used for carrying out suction filtration and washing on the reaction product until no chloride ions and no organic solvent exist. According to the invention, sodium borohydride solution is added into the first filtrate obtained by washing, and no black precipitate appears, which indicates that no chloroplatinic acid residue exists in the reaction product. And adding a silver nitrate solution into the final filtrate obtained by washing, wherein no precipitate appears, and the existence of chloride ions in the reaction product is indicated. The washed reaction product is subjected to a drying treatment well known to those skilled in the art to obtain a carbon supported platinum-tungsten trioxide catalyst.
According to the present invention, a carbon-supported platinum-tungsten trioxide catalyst is placed in a reducing atmosphere furnace and subjected to a sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, the volume percentage of the hydrogen is 5-20%, and the preferred condition is 5%. The preferred sintering temperature is 400-600 ℃. Further preferably, the sintering temperature is 500 ℃. The reaction time is preferably 0.5 to 3 hours, and more preferably 1 hour. And grinding the sintered solid to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
The invention also provides the carbon-supported platinum-tungsten dioxide electrocatalyst prepared by the preparation method.
The carbon-supported platinum-tungsten dioxide electrocatalyst against carbon monoxide poisoning and the preparation method thereof according to the present invention will be described in detail with reference to the following specific examples. The raw materials used in the following examples are all conventional chemicals available on the market.
Example 1
Chloroplatinic acid was dissolved in ethylene glycol to prepare a chloroplatinic acid solution containing 0.01g/mL of platinum.
1g of sodium hydroxide was dissolved in 100mL of ethylene glycol, and the mixture was stirred for 1 hour to prepare a pH-adjusted solution.
Tungsten trioxide nanopowder (2.5 mg) produced by the national reagent and activated carbon (20 mg) produced by Cabot corporation, Vulcan XC-72, trade name, were ground for 1 hour, 20mL of ethylene glycol was added thereto, and ultrasonic dispersion was carried out for 2 hours to obtain a first suspension. And after the first suspension is uniformly dispersed, adding 0.5mL of chloroplatinic acid solution and 1mL of pH regulating solution into the first suspension, regulating the pH of the solution to 10, and stirring for 2 hours to obtain a second suspension. And placing the second suspension in a microwave reactor, and carrying out microwave reaction for 80 seconds under the power of 800W to obtain a third suspension. And (3) carrying out suction filtration and washing on the third suspension by using deionized water with the resistivity of 18.2M omega-cm, filtering to obtain a first filtrate, adding 0.01g/mL of aqueous solution of sodium borohydride into the first filtrate, and clarifying the filtrate without precipitation. And after washing and filtering for many times, adding silver chloride with the mass concentration of 0.01g/mL into the final filtrate, and clarifying the filtrate without precipitation. And drying the filtrate at 80 ℃ in vacuum to obtain the carbon-supported platinum-tungsten trioxide catalyst.
And placing the carbon-supported platinum-tungsten trioxide catalyst in a reducing atmosphere furnace for sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, the volume percentage content of the hydrogen is 5 percent, the sintering temperature is 500 ℃, and after 1 hour of reaction, the sintered solid is ground to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
Ultrasonically dispersing the carbon-supported platinum-tungsten dioxide electrocatalyst in ethanol to obtain a suspension; after the suspension is coated on a copper mesh and dried, scanning is carried out on the copper mesh by an electron microscope, and as a result, referring to fig. 1, fig. 1 is a transmission electron microscope photo of the carbon-supported platinum-tungsten dioxide electrocatalyst prepared in example 1 under a 20nm ruler, the visible particle size is about 3-5nm, and the Pt nano particles are uniformly dispersed on the carbon carrier and have no aggregation phenomenon. XRD characterization of the carbon supported platinum-tungsten dioxide electrocatalyst was performed, and the results are shown in fig. 2, demonstrating the crystal structures of platinum and tungsten dioxide.
Adding 5mg of the carbon-supported platinum-tungsten dioxide electrocatalyst into 1mL of absolute ethyl alcohol and a 5% Nafion solution produced by 50 mu L of Aldrich and having a mass concentration, and performing ultrasonic dispersion for 30 minutes to obtain a solution; dripping 10 mu L of the solution on a glassy carbon electrode, and airing at room temperature to obtain a thin film electrode; in a three-electrode system with a silver-silver chloride electrode as a reference electrode and a platinum sheet as a counter electrode, carbon monoxide is firstly introduced into a solution at 0.02V for 10 minutes to poison a catalyst, then pure hydrogen is introduced into the solution to carry out cyclic voltammetry scanning test, and the scanning speed is 50 mV/s. Results referring to fig. 3, fig. 3 is a plot of cyclic voltammetry scans for the recovery capacity of a carbon supported platinum-tungsten dioxide electrocatalyst in a sulfuric acid solution. Generating positive current under 0.1-0.15V/s.Ag/AgCl, and recovering catalytic ability under 0.4-0.5V/s.Ag/AgCl.
Example 2
Chloroplatinic acid was dissolved in ethylene glycol to prepare a chloroplatinic acid solution containing 0.01g/mL of platinum.
1g of sodium hydroxide was dissolved in 100mL of ethylene glycol, and the mixture was stirred for 1 hour to prepare a pH-adjusted solution.
Tungsten trioxide nanopowder (5 mg) produced by a national reagent and activated carbon (20 mg) produced by Cabot corporation, Vulcan XC-72, trade name, were ground for 1 hour, 20mL of ethylene glycol was added thereto, and ultrasonic dispersion was carried out for 2 hours to obtain a first suspension. And after the first suspension is uniformly dispersed, adding 0.5mL of chloroplatinic acid solution and 1mL of pH regulating solution into the first suspension, regulating the pH of the solution to 10, and stirring for 2 hours to obtain a second suspension. And placing the second suspension in a microwave reactor, and carrying out microwave reaction for 80 seconds under the power of 800W to obtain a third suspension. And (3) carrying out suction filtration and washing on the third suspension by using deionized water with the resistivity of 18.2M omega-cm, filtering to obtain a first filtrate, adding 0.01g/mL of aqueous solution of sodium borohydride into the first filtrate, and clarifying the filtrate without precipitation. And after washing and filtering for many times, adding silver chloride with the mass concentration of 0.01g/mL into the final filtrate, and clarifying the filtrate without precipitation. Drying the filtrate at 80 ℃ in vacuum to obtain the carbon-supported platinum-tungsten trioxide catalyst.
And placing the carbon-supported platinum-tungsten trioxide catalyst in a reducing atmosphere furnace for sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, and the hydrogen content is 10 percent. The sintering temperature is 400 ℃, and after 0.5 hour of reaction, the sintered solid is ground to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
The carbon-supported platinum-tungsten dioxide electrocatalyst is ultrasonically dispersed in ethanol, and the particle size is observed to be within the range of 3-5nm by the electron microscope scanning method as in example 1, and the carbon-supported platinum-tungsten dioxide electrocatalyst is uniformly distributed without aggregation.
The electrochemical test method was the same as in example 1, and the cyclic voltammetry scan curve for the recovery capability of the carbon-supported platinum-tungsten dioxide electrocatalyst in the sulfuric acid solution was obtained. Generating positive current under 0.15-0.2V/s.Ag/AgCl and restoring catalytic ability under 0.45-0.55V/s.Ag/AgCl.
Example 3
Chloroplatinic acid was dissolved in ethylene glycol to prepare a chloroplatinic acid solution containing 0.01g/mL of platinum.
1g of sodium hydroxide was dissolved in 100mL of ethylene glycol, and the mixture was stirred for 1 hour to prepare a pH-adjusted solution.
Tungsten trioxide nanopowder (2 mg) produced by a national reagent and 30mg of activated carbon (Vulcan XC-72) produced by Cabot corporation, USA, were ground for 1 hour, 20mL of ethylene glycol was added thereto, and ultrasonic dispersion was carried out for 2 hours to obtain a first suspension. And after the first suspension is uniformly dispersed, adding 1.0mL of chloroplatinic acid solution and 1mL of pH regulating solution into the first suspension, regulating the pH of the solution to 10, and stirring for 2 hours to obtain a second suspension. And placing the second suspension in a microwave reactor, and carrying out microwave reaction for 80 seconds under the power of 800W to obtain a third suspension. And (3) carrying out suction filtration and washing on the third suspension by using deionized water with the resistivity of 18.2M omega-cm, filtering to obtain a first filtrate, adding 0.01g/mL of aqueous solution of sodium borohydride into the first filtrate, and clarifying the filtrate without precipitation. After multiple times of washing and filtration, 0.01g/mL of silver chloride is added into the final filtrate, and the filtrate is clear and has no precipitate. And drying the filtrate at 80 ℃ in vacuum to obtain the carbon-supported platinum-tungsten trioxide catalyst.
And placing the carbon-supported platinum-tungsten trioxide catalyst in a reducing atmosphere furnace for sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, and the hydrogen content is 20 percent. The sintering temperature is 600 ℃, and after 3 hours of reaction, the sintered solid is ground to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
The carbon-supported platinum-tungsten dioxide electrocatalyst is ultrasonically dispersed in ethanol, and the particle size is observed to be within the range of 3-5nm by the electron microscope scanning method as in example 1, and the carbon-supported platinum-tungsten dioxide electrocatalyst is uniformly distributed without aggregation.
The electrochemical test method was the same as in example 1, and the cyclic voltammetry scan curve for the recovery capability of the carbon-supported platinum-tungsten dioxide electrocatalyst in the sulfuric acid solution was obtained. Generating positive current under 0.15-0.2V/s.Ag/AgCl and restoring catalytic ability under 0.55-0.6V/s.Ag/AgCl.
Example 4
Chloroplatinic acid was dissolved in ethylene glycol to prepare a chloroplatinic acid solution containing 0.01g/mL of platinum.
1g of sodium hydroxide was dissolved in 100mL of ethylene glycol, and the mixture was stirred for 1 hour to prepare a pH-adjusted solution.
Tungsten trioxide nanopowder (5 mg) produced by a national reagent and 30mg of activated carbon (Vulcan XC-72) produced by Cabot corporation, USA, were ground for 1 hour, 20mL of ethylene glycol was added thereto, and ultrasonic dispersion was carried out for 2 hours to obtain a first suspension. And after the first suspension is uniformly dispersed, adding 2.0mL of chloroplatinic acid solution and 1mL of pH regulating solution into the first suspension, regulating the pH of the solution to 10, and stirring for 2 hours to obtain a second suspension. And placing the second suspension in a microwave reactor, and carrying out microwave reaction for 80 seconds under the power of 800W to obtain a third suspension. And (3) carrying out suction filtration and washing on the third suspension by using deionized water with the resistivity of 18.2M omega-cm, filtering to obtain a first filtrate, adding 0.01g/mL of aqueous solution of sodium borohydride into the first filtrate, and clarifying the filtrate without precipitation. And after washing and filtering for many times, adding silver chloride with the mass concentration of 0.01g/mL into the final filtrate, and clarifying the filtrate without precipitation. And drying the filtrate at 80 ℃ in vacuum to obtain the carbon-supported platinum-tungsten trioxide catalyst.
And placing the carbon-supported platinum-tungsten trioxide catalyst in a reducing atmosphere furnace for sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, and the hydrogen content is 5 percent. The sintering temperature is 500 ℃, and after 1 hour of reaction, the sintered solid is ground to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
The carbon-supported platinum-tungsten dioxide electrocatalyst is ultrasonically dispersed in ethanol, and the particle size is observed to be within the range of 3-5nm by the electron microscope scanning method as in example 1, and the carbon-supported platinum-tungsten dioxide electrocatalyst is uniformly distributed without aggregation.
The electrochemical test method was the same as in example 1, and the cyclic voltammetry scan curve for the recovery capability of the carbon-supported platinum-tungsten dioxide electrocatalyst in the sulfuric acid solution was obtained. Generating positive current under 0.1-0.15V/s.Ag/AgCl, and recovering catalytic ability under 0.45-0.5V/s.Ag/AgCl.
Comparative example 1
For comparison, a carbon-supported platinum catalyst, which does not contain tungsten trioxide, was prepared using a microwave method.
Chloroplatinic acid was dissolved in ethylene glycol to prepare a chloroplatinic acid solution containing 0.01g/mL of platinum.
1g of sodium hydroxide was dissolved in 100mL of ethylene glycol, and the solution was stirred for 1 hour to prepare a pH-adjusted solution.
20mg of activated carbon, manufactured by Cabot (Cabot) USA, and having a trade name of Vulcan XC-72, was ground for 1 hour, 20mL of ethylene glycol was added thereto, and ultrasonic dispersion was carried out for 2 hours to obtain a first suspension. And after the first suspension is uniformly dispersed, adding 0.4mL of chloroplatinic acid solution and 1mL of pH regulating solution into the first suspension, regulating the pH of the solution to 10, and stirring for 2 hours to obtain a second suspension. And placing the second suspension in a microwave reactor, and carrying out microwave reaction for 80 seconds under the power of 800W to obtain a third suspension. And (3) carrying out suction filtration and washing on the third suspension by using deionized water with the resistivity of 18.2M omega-cm, filtering to obtain a first filtrate, adding 0.01g/mL of aqueous solution of sodium borohydride into the first filtrate, and clarifying the filtrate without precipitation. And after washing and filtering for many times, adding silver chloride with the mass concentration of 0.01g/mL into the final filtrate, and clarifying the filtrate without precipitation. And drying the filtrate in vacuum at 80 ℃ to obtain the carbon-supported platinum catalyst.
As a process comparison, the carbon-supported platinum catalyst is placed in a reducing atmosphere furnace for sintering treatment. The sintering atmosphere is a mixed gas of hydrogen and inert gas, and the hydrogen content is 5 percent. The sintering temperature is 500 ℃, and after 1 hour of reaction, the sintered solid is ground to obtain the treated carbon-supported platinum electrocatalyst.
The carbon-supported platinum-tungsten dioxide electrocatalyst is ultrasonically dispersed in ethanol, and the particle size is observed to be within the range of 3-5nm by the electron microscope scanning method as in example 1, and the carbon-supported platinum-tungsten dioxide electrocatalyst is uniformly distributed without aggregation.
The electrochemical test method was the same as in example 1, and the cyclic voltammetry scan curve for the recovery capability of the carbon-supported platinum-tungsten dioxide electrocatalyst in the sulfuric acid solution was obtained. As shown in FIG. 4, a positive current was generated at 0.6-0.7V vs. Ag/AgCl, and the catalytic ability was recovered at 0.7-0.8V s. Ag/AgCl.
The comparative results show that the platinum-tungsten dioxide reduction-sintered catalyst is capable of oxidizing carbon monoxide at a lower potential. The carbon-supported platinum-tungsten dioxide electrocatalyst produced by the invention has good carbon monoxide resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon-supported platinum-tungsten dioxide electrocatalyst for resisting carbon monoxide poisoning is characterized by comprising the following steps:
the method comprises the following steps: grinding a carbon carrier and tungsten trioxide, and dispersing the ground carbon carrier and tungsten trioxide in ethylene glycol to obtain a first suspension;
step two: adding a chloroplatinic acid solution and a pH regulating solution into the first suspension to obtain a second suspension;
step three: placing the second suspension liquid in a microwave reactor for microwave reaction to obtain a third suspension liquid;
step four: filtering, cleaning and drying the third suspension to obtain solid powder;
step five: and sintering the solid powder in a reducing atmosphere to obtain the carbon-supported platinum-tungsten dioxide electrocatalyst.
2. The method of claim 1, wherein the carbon support is a conductive carbon powder.
3. The production method according to claim 1, wherein the mass ratio of the platinum content to the carbon support in the chloroplatinic acid solution is (100 to 200): (300-400).
4. The production method according to claim 1, wherein the mass ratio of the platinum content to the tungsten trioxide in the chloroplatinic acid solution is (100 to 200): (20-100).
5. The production method according to claim 1, wherein the mass ratio of the platinum content to the carbon support in the chloroplatinic acid solution is 100:400, wherein the mass ratio of the platinum content to the tungsten trioxide in the chloroplatinic acid solution is 200: 100, wherein the mass ratio of the ethylene glycol to the carbon carrier is 1000: 10.
6. the method according to claim 1, wherein the pH adjusting liquid adjusts the pH of the second suspension to 10.
7. The method of claim 1, wherein the solid powder is reduced in the fifth step by using a mixed gas of hydrogen and an inert gas, and the volume percentage of hydrogen is 5-20%.
8. The method as claimed in claim 1, wherein the temperature of the reduction in step five is 400-600 ℃ and the time of the reduction is 0.5-3 hours.
9. The method according to claim 1, wherein the temperature of the reduction in the fifth step is 500 ℃ and the time of the reduction is 1 hour.
10. A carbon-supported platinum-tungsten dioxide electrocatalyst prepared according to the preparation method of any one of claims 1 to 9.
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