CN113862716A - Nano tin oxide supported platinum alloy catalyst and preparation method and application thereof - Google Patents
Nano tin oxide supported platinum alloy catalyst and preparation method and application thereof Download PDFInfo
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- CN113862716A CN113862716A CN202111214938.XA CN202111214938A CN113862716A CN 113862716 A CN113862716 A CN 113862716A CN 202111214938 A CN202111214938 A CN 202111214938A CN 113862716 A CN113862716 A CN 113862716A
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Abstract
The invention discloses a nano tin oxide supported platinum alloy catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: the tin source solution is stirred in an ice-water bath under the condition of ammonia water to precipitate tin ions, deionized water and ammonia water are added into the precipitate, suspension formed by ultrasonic is subjected to hydrothermal reaction to obtain tin oxide, and the tin oxide is calcined with non-noble metal salt and platinum salt and then is placed in a plasma reaction furnace to be activated in plasma atmosphere to obtain the nano tin oxide supported platinum alloy catalyst. The preparation process of the tin oxide supported platinum alloy catalyst prepared by the invention is simple and low in cost, and the tin oxide supported by the platinum alloy exposes a special crystal face, so that the special crystal face of the tin oxide and the platinum alloy nanoparticles generate a synergistic effect, the reaction catalytic activity and stability of preparing ozone by electrolyzing water are obviously improved, and the current efficiency of preparing ozone by electrolyzing water is greatly improved.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a nano tin oxide supported platinum alloy catalyst, and a preparation method and application thereof.
Background
Ozone has strong oxidizing power, and can be used for deodorizing, decolorizing, sterilizing, and degrading microorganisms. In the aspect of sterilization and disinfection, compared with the traditional chlorine-containing disinfectant, the ozone is reduced into oxygen in the disinfection process, and no secondary pollution exists, so that the ozone is more and more concerned, and the ozone is widely applied to the fields of water treatment, medical care, agriculture, food processing and fresh keeping and the like.
The current methods for preparing ozone mainly comprise: corona discharge, ultraviolet irradiation, electrolysis, and the like. The corona discharge method has large production equipment and high cost, and a certain amount of Nitrogen Oxides (NO) can be remained in the ozone mixture due to high-voltage ionizationx) Carcinogenic substances. The ultraviolet irradiation method has the disadvantages of low yield, complicated structure and difficult wavelength control. Compared to the first two methods, the electrolytic method has the following advantages: the method takes water as a raw material, has mild operation conditions, high concentration of generated ozone, small equipment investment and good application prospect. In the process of preparing ozone by an electrolytic method, ozone and oxygen are generated at the anode, hydrogen is generated at the cathode, and the selection of anode materials with high overpotential can effectively inhibit the generation of oxygen and improve the current efficiency of generating ozone.
At present, the anode materials for preparing ozone by electrolyzing water are mainly lead dioxide and platinum. Lead dioxide has good conductivity, but poor stability, short service life and certain toxicity; the platinum has high oxygen evolution overpotential and good stability, and a platinum oxide film is formed on the surface of the platinum electrode in the ozone precipitation process, has good conductivity, has high oxygen overpotential, is beneficial to generating ozone, but is not beneficial to large-scale production and application due to high price. On the premise of ensuring the performance of preparing ozone, the production cost can be reduced by reducing the platinum loading capacity, so that the low-platinum loading catalyst has important research significance.
The tin dioxide is used as a catalyst carrier and is widely applied to the fields of lithium ion batteries, supercapacitors, ozone preparation by an electrolytic method and the like. However, tin dioxide has poor conductivity, and the conductivity is generally improved by doping nickel and antimony, but antimony element is a toxic element, and excessive use of tin oxide does not meet the requirement of green environment, and tin trioxide and tin tetraoxide, which are tin oxide, have high oxygen evolution overpotential and have conductivity far superior to that of tin dioxide, so that mixed valence tin oxide is directly used as a catalyst carrier, so that the electrocatalytic reaction efficiency can be improved, and the environmental pollution can be avoided, thereby having research value.
At present, the preparation of the mixed valence tin oxide catalyst loaded with platinum alloy and the related research for preparing ozone by electrolyzing water have not been reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a nano tin oxide supported platinum alloy catalyst, a preparation method and application thereof.
The invention discloses a preparation method of a nano tin oxide supported platinum alloy catalyst, which is characterized by comprising the following steps of:
1) adding a tin source and deionized water into a reactor, and stirring until the tin source is completely dissolved to obtain a solution;
2) adding ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring the solution to precipitate tin ions, carrying out centrifugal separation, and washing the obtained precipitate with deionized water for 2 to 8 times;
3) transferring the precipitate obtained in the step 2) into a beaker, adding deionized water and ammonia water, performing ultrasonic treatment for 15-30 minutes to form a suspension, transferring the suspension into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a hydrothermal kettle, performing hydrothermal reaction at 100-200 ℃ for 3-24 hours, naturally cooling to room temperature, performing suction filtration, washing for 2-8 times with absolute ethyl alcohol and deionized water respectively, and performing freeze drying for 6-24 hours to obtain tin oxide serving as a carrier material;
4) fully mixing the tin oxide carrier material obtained in the step 3), non-noble metal salt and platinum salt, grinding the mixture into uniform powder, placing the powder into a porcelain boat, and roasting the powder for 3 to 24 hours at 800 ℃ in a tubular furnace under the nitrogen atmosphere to obtain a tin oxide supported platinum alloy catalyst;
5) placing the tin oxide supported platinum alloy catalyst obtained in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 50-250W, the reaction temperature is 30-250 ℃, introducing high-purity gas under the vacuum-pumping condition and forming a plasma atmosphere, the vacuum degree is 30-150Pa, and activating the tin oxide supported platinum alloy catalyst for 0.5-3 hours under the plasma atmosphere to obtain the nano tin oxide supported platinum alloy catalyst.
Further, the invention also defines that the tin source in the step 1) is tin (IV) salt or tin (II) salt, the tin (IV) salt comprises tin chloride or tin bromide, and the tin (II) salt comprises stannous sulfate, stannous chloride or stannous bromide.
Further, the invention also defines that the molar ratio of the tin (IV) to the tin (II) in the tin oxide in the step 1) is 1:1 or 1:2, and the tin oxide is tin sesquioxide or tin tetraoxide.
Further, the invention also limits the concentration of the ammonia water in the step 3) to be 20-30%, and the volume ratio of the deionized water, the absolute ethyl alcohol and the ammonia water to be 1:1: 1-5.
Further, the invention also limits that the platinum salt in the step 4) is chloroplatinic acid, platinum acetylacetonate or potassium tetrachloroplatinate, the loading amount of platinum in tin oxide is 5-20%, and the mass ratio of platinum to non-noble metal is 1: 0.8-1.2.
Further, the invention also defines that the non-noble metal in the non-noble metal salt in the step 4) is at least one metal element of cobalt and nickel, preferably cobalt acetylacetonate, cobalt acetate, nickel acetate or nickel acetylacetonate.
Further, the invention also limits the plasma voltage in the step 5) to be 150-; the reaction temperature is 150-200 ℃; the high purity gas is hydrogen, argon or nitrogen with a purity of > 99%.
Further, the preparation method of the nano tin oxide supported platinum alloy catalyst specifically comprises the following steps:
1) adding a tin source into a 50mL beaker, adding 10-20mL deionized water, and stirring for 5-60 minutes to completely dissolve the tin source;
2) adding 100-800 mu L ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring for 5-30 minutes to precipitate tin ions, and washing the precipitate for 2-8 times by using 20-50mL deionized water;
3) transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL deionized water, 3mL absolute ethyl alcohol and 3-15mL ammonia water, carrying out ultrasonic treatment for 15-30 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, carrying out hydrothermal reaction at 100-200 ℃ for 3-24 hours, naturally cooling to room temperature, carrying out suction filtration, washing with 20-50mL absolute ethyl alcohol and 20-50mL deionized water for 2-8 times respectively, and carrying out freeze drying for 6-24 hours to obtain a tin oxide carrier material, wherein in the step, 3-15mL ammonia water is added, and due to Sn, the Sn is added4+And Sn2+Is easily hydrolyzed, and excessive alkali can inhibit the hydrolysis, which provides an opportunity for dynamically controlling the shape of the tin oxide nanocrystals;
4) fully mixing and grinding 100-500mg of tin oxide carrier material obtained in the step 3), 10-100mg of non-noble metal salt and 10-100mg of platinum salt into uniform powder, placing the powder in a porcelain boat, and roasting the powder for 3-24 hours at 800 ℃ in a tubular furnace under the nitrogen atmosphere to obtain the tin oxide supported platinum alloy catalyst;
5) placing the tin oxide supported platinum alloy catalyst obtained in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 50-250W, the reaction temperature is 30-250 ℃, introducing high-purity gas under the vacuum-pumping condition and forming a plasma atmosphere, the vacuum degree is 30-150Pa, and the tin oxide supported platinum alloy catalyst is activated for 0.5-3 hours under the plasma atmosphere, so that the nano tin oxide supported platinum alloy catalyst can be obtained.
Still further, the present invention also defines the nano tin oxide-supported platinum alloy catalyst prepared by the method defined by the present invention, which consists of different types of tin oxides and platinum-non-noble metal alloys supported on different types of tin oxides.
Furthermore, the invention also defines the application of the prepared nano tin oxide supported platinum alloy catalyst in the reaction of preparing ozone by electrocatalytic decomposition of water, and the application process comprises the following steps: the constant current instrument is used for controlling voltage and current, an H-type electrolytic cell is used for reaction, water and gas are kept to be smooth between two electrode chambers, saturated potassium sulfate aqueous solution is used as electrolyte, the tin oxide supported platinum alloy catalyst is coated on carbon cloth to be used as a working electrode in an anode chamber, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction current is controlled to be 500mA, the cell voltage is controlled to be 1-10V, and the ozone is prepared by electrocatalysis to obtain an ozone product.
By adopting the technology, compared with the prior art, the invention has the beneficial effects that:
1) the tin oxide supported platinum alloy catalyst takes tin (IV) salt and tin (II) salt as raw materials, and after a carrier is obtained through simple hydrothermal and freeze drying, the platinum cobalt or platinum nickel alloy is supported through roasting, and the preparation method is simple, low in cost and easy to regulate and control;
2) the tin oxide supported platinum alloy catalyst disclosed by the invention exposes special crystal faces {110} and {111}, so that the special crystal faces of the tin oxide and platinum alloy nanoparticles generate a synergistic effect, the reaction catalytic activity and stability of preparing ozone by electrolyzing water are obviously improved, basic application research is provided for the materials in the field of electrocatalysis, and the tin oxide supported platinum alloy catalyst has a wide application prospect.
Drawings
FIG. 1 is a schematic Transmission Electron Microscope (TEM) of a platinum-nickel alloy catalyst supported on tin trioxide prepared in example 1 at 10 nm;
FIG. 2 is a scanning electron microscope of a platinum-nickel alloy catalyst supported on tin trioxide prepared in example 1 at 3 μm;
FIG. 3 is a schematic transmission electron microscope at 10nm of a platinum-nickel alloy catalyst supported on tri-tin tetroxide prepared in example 2;
FIG. 4 is a scanning electron microscope depiction of the platinum nickel alloy on tin tetraoxide catalyst prepared in example 2 at 3 μm;
FIG. 5 is a graph comparing data of real-time detection of ozone concentration when the tin oxide-supported platinum alloy catalysts prepared in examples 1 to 4 were used for preparing ozone by electrocatalysis.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: platinum-nickel alloy catalyst PtNi/Sn loaded by tin sesquioxide2O3The preparation method comprises the following steps:
1) adding 350.6mg of stannic chloride pentahydrate, 225.6mg of stannous chloride dihydrate and 17mL of deionized water into a 50mL beaker, and stirring for 3 minutes to completely dissolve the materials to obtain a solution;
2) adding 700 mu L of ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring for 20 minutes to precipitate tin ions, and washing the precipitate obtained by centrifugal separation for 3 times by using deionized water;
3) transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL deionized water, 3mL absolute ethyl alcohol and 10mL ammonia water, performing ultrasonic treatment for 15 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, putting the lining into a hydrothermal kettle, performing hydrothermal treatment at 200 ℃ for 12 hours, naturally cooling to room temperature, performing suction filtration, washing with 30mL absolute ethyl alcohol and 30mL deionized water for 3 times respectively, and freeze-drying the sample at about-10 ℃ for 10 hours in a vacuum environment;
4) mixing 160mg of the solid product obtained in the step 3) with 16mg of platinum acetylacetonate and 34mg of nickel acetylacetonate, grinding the mixture into powder, and roasting the powder in a ceramic boat in a tubular furnace at the temperature of 250 ℃ for 5 hours under the nitrogen atmosphere to obtain a tin sesquioxide loaded platinum nickel alloy catalyst;
5) and (3) placing the product obtained in the step 4) in a plasma reaction furnace, introducing nitrogen under the conditions of plasma voltage of 150W and reaction temperature of 150 ℃ and vacuumizing to form a plasma atmosphere, wherein the vacuum degree is 150Pa, and activating the tin trioxide supported platinum-nickel alloy catalyst for 2 hours under the plasma atmosphere to obtain the activated tin trioxide supported platinum-nickel alloy catalyst.
Transmission electron microscope schematic view at 10nm and scanning electron microscope at 3 μm of the platinum-nickel alloy catalyst supported by tin sesquioxide obtained in example 1The schematic diagrams of the micromirror are shown in fig. 1 and fig. 2, respectively, the tin trioxide supported platinum-nickel alloy catalyst particle is a slender dodecahedron structure, the dodecahedron structure can expose the special crystal faces {110} and {111} of the tin trioxide, the combination of the two crystal faces and the platinum-non-noble metal alloy is more stable, compared with the tin trioxide without the special crystal faces, the tin trioxide with the special crystal faces {110} and {111} and the platinum-noble metal alloy have special electron transfer effect, and the PtNi/Sn catalyst particle has the special electron transfer effect between the tin trioxide with the special crystal faces {110} and the platinum-noble metal alloy2O3Under the action of the catalyst, the electrolytic water reaction is easier to carry out.
The tin sesquioxide supported platinum nickel alloy catalyst of example 1 was used in the electrolytic water preparation ozone reaction:
weighing 8mg of prepared tin sesquioxide-loaded platinum-nickel alloy catalyst particles, mixing with 900 mu L of ethanol and 100 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), performing ultrasonic treatment for 20 minutes, and completely dispersing the catalyst in a mixed solution of the ethanol and the Nafion solution to obtain uniform catalyst slurry. Cutting the carbon cloth into the size of about 2cm multiplied by 2cm, uniformly dripping all dispersed catalyst slurry on the carbon cloth, and drying to be used as a working electrode (namely coating the tin sesquioxide load platinum nickel alloy catalyst on the carbon cloth as the working electrode).
The voltage and current are controlled by a constant current instrument, and an H-shaped electrolytic bath is adopted for reaction. In the anode chamber, a tin oxide supported platinum alloy catalyst is coated on carbon cloth to be used as a working electrode; in the cathode chamber, a platinum sheet is used as a counter electrode, and the electrolyte is saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic cell is connected with an ozone detector to detect the generation condition of ozone in real time. When the electro-catalysis is used for preparing ozone, the current is controlled to be 200mA, the cell voltage is controlled to be 3-9V, and the reaction time is 2 hours. A real-time plot of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeded is shown in figure 5. As can be seen from FIG. 5, the ozone concentration gradually increased as the reaction proceeded, and when the reaction time reached approximately 2 hours, the ozone concentration reached 3376 ppb.
In order to verify the catalytic stability of the platinum-nickel alloy catalyst particles supported by tin sesquioxide prepared in example 1, the anode chamber working electrode after the above reaction for 1 time was left for 24 hours, and an experiment for repeated electrocatalytic ozone preparation reaction was performed (the anode chamber working electrode was left for one day after each use and then used again). In the 1 st experiment of the anode chamber working electrode recycling reaction, the ozone concentration after the reaction time reaches 2 hours can reach 3370 ppb. In the 2 nd experiment of the anode chamber working electrode recycling reaction, the ozone concentration after the reaction reaches 2 hours can reach 3420 ppb. In the 3 rd experiment of the anode chamber working electrode recycling reaction, the ozone concentration after the reaction reaches 2 hours can reach 3415 ppb. It can be seen that the electrocatalytic effect is not substantially reduced during the recycling of the working electrode in the anode chamber, which indicates that the stannous oxide supported platinum-nickel alloy catalyst particles prepared in example 1 have better stability.
Example 2: tri-tin tetroxide supported platinum-nickel alloy catalyst PtNi/Sn3O4The preparation method comprises the following steps:
1) adding 175mg of stannic chloride pentahydrate and 225.6mg of stannous chloride dihydrate into a 50mL beaker, adding 18mL of deionized water, and stirring for 10 minutes to completely dissolve the materials;
2) adding 600 mu L of ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring for 10 minutes to precipitate tin ions, and washing the precipitate for 4 times by deionized water;
3) transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL deionized water, 3mL absolute ethyl alcohol and 9mL ammonia water, performing ultrasonic treatment for 20 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, putting the lining into a hydrothermal kettle, performing hydrothermal treatment at 180 ℃ for 9 hours, naturally cooling to room temperature, performing suction filtration, washing with 30mL absolute ethyl alcohol and 30mL deionized water for 3 times respectively, and freeze-drying the sample at about-10 ℃ for 8 hours in a vacuum environment;
4) mixing 100mg of the solid product obtained in the step 3), 14mg of chloroplatinic acid and 15mg of nickel acetate, grinding the mixture into powder, and roasting the powder in a ceramic boat in a tubular furnace at 600 ℃ for 9 hours in a nitrogen atmosphere to obtain a stannic oxide supported platinum-nickel alloy catalyst;
5) and (3) placing the product obtained in the step 4) in a plasma reaction furnace, wherein the plasma voltage is 200W, the reaction temperature is 200 ℃, nitrogen is introduced under the vacuum pumping condition to form a plasma atmosphere, the vacuum degree is 100Pa, and the tri-tin tetroxide supported platinum-nickel alloy catalyst is activated for 3 hours under the plasma atmosphere to obtain the activated tri-tin tetroxide supported platinum-nickel alloy catalyst.
A schematic diagram of a transmission electron microscope and a schematic diagram of a scanning electron microscope under 10nm and 3 μm of the platinum-nickel alloy supported on tin tetroxide obtained in example 2 are respectively shown in fig. 3 and 4, where the platinum-nickel alloy supported on tin tetroxide catalyst particle has a slender dodecahedron structure, the dodecahedron structure can expose the specific crystal planes {110} and {111} of the tin tetroxide, the two crystal planes are more stably combined with the platinum-non-noble metal alloy, and compared with the tin tetroxide without the specific crystal plane, the tin tetroxide with the specific crystal planes {110} and {111} and the platinum-noble metal alloy have a specific electron transfer effect, and the PtNi/Sn has a specific electron transfer effect between the PtNi/Sn3O4Under the action of the catalyst, the electrolytic water reaction is easier to carry out.
The tri-tin tetroxide supported platinum-nickel alloy catalyst of example 2 is used for the reaction of preparing ozone by electrolyzing water:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 2 of the same quality, and the remaining operating conditions were the same as those in the experimental process for preparing ozone by electrolyzing water of example 1, and the change of the concentration of ozone generated by the catalytic reaction of electrolyzed water with the reaction time was shown in FIG. 5.
Example 3: platinum-cobalt alloy catalyst PtCo/Sn loaded by dibutyltin trioxide2O3The preparation method comprises the following steps:
1) adding 438mg of tin bromide and 214mg of stannous sulfate into a 50mL beaker, adding 17mL of deionized water, and stirring for 10 minutes to completely dissolve the tin bromide and the stannous sulfate;
2) adding 650 mu L of ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring for 5 minutes to precipitate tin ions, and washing the precipitate for 4 times by deionized water;
3) transferring the precipitate obtained in the step 2) into a 50mL beaker, carrying out ultrasonic treatment for 25 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, putting the lining into a hydrothermal kettle, carrying out hydrothermal treatment at 100 ℃ for 12 hours, naturally cooling to room temperature, carrying out suction filtration, washing with 30mL absolute ethyl alcohol and 30mL deionized water for 3 times respectively, and carrying out freeze drying on the sample at-10 ℃ in a vacuum environment for 12 hours;
4) mixing and grinding 250mg of the solid product obtained in the step 3), 34mg of chloroplatinic acid and 53mg of cobalt acetylacetonate into powder, and roasting the powder in a ceramic boat in a tubular furnace at the temperature of 500 ℃ for 8 hours under the nitrogen atmosphere to obtain a tin sesquioxide loaded platinum cobalt alloy catalyst;
5) and (3) placing the product obtained in the step 4) in a plasma reaction furnace, wherein the plasma voltage is 50W, the reaction temperature is 50 ℃, nitrogen is introduced under the vacuum-pumping condition, a plasma atmosphere is formed, the vacuum degree is 150Pa, and the tin trioxide supported platinum-cobalt alloy catalyst is activated for 2.5 hours under the plasma atmosphere, so that the activated tin trioxide supported platinum-cobalt alloy catalyst can be obtained.
The tin sesquioxide supported platinum cobalt alloy catalyst of example 3 was used in the electrolytic water preparation ozone reaction:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 3 of the same quality, and the remaining operating conditions were the same as those in the experimental process for preparing ozone by electrolyzing water of example 1, and the change of the concentration of ozone generated by the catalytic reaction of electrolyzed water with the reaction time was shown in FIG. 5.
Example 4: tri-tin tetroxide supported platinum-cobalt alloy catalyst PtCo/Sn3O4The preparation method comprises the following steps:
1) adding 219mg of tin bromide and 278mg of stannous bromide into a 50mL beaker, adding 17mL of deionized water, and stirring for 5 minutes to completely dissolve the tin bromide and the stannous bromide;
2) adding 500 mu L of ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring for 30 minutes to precipitate tin ions, and washing the precipitate for 4 times by deionized water;
3) transferring the precipitate obtained in the step 2) into a 50mL beaker, performing ultrasonic treatment for 30 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, putting the lining into a hydrothermal kettle, performing hydrothermal treatment for 3 hours at 150 ℃, naturally cooling to room temperature, performing suction filtration, washing for 3 times by using 30mL absolute ethyl alcohol and 30mL deionized water respectively, and freeze-drying the sample at-10 ℃ for 16 hours in a vacuum environment;
4) mixing and grinding 200mg of the solid product obtained in the step 3), 25mg of platinum acetylacetonate and 40mg of cobalt acetate into powder, and roasting the powder in a ceramic boat in a tubular furnace at the temperature of 200 ℃ for 5 hours under the nitrogen atmosphere to obtain the stannic oxide supported platinum-cobalt alloy catalyst.
5) And (3) placing the product obtained in the step 4) in a plasma reaction furnace, wherein the plasma voltage is 250W, the reaction temperature is 250 ℃, nitrogen is introduced under the vacuum-pumping condition, a plasma atmosphere is formed, the vacuum degree is 50Pa, and the tri-tin tetroxide supported platinum-cobalt alloy catalyst is activated for 1.5 hours under the plasma atmosphere, so that the activated tri-tin tetroxide supported platinum-cobalt alloy catalyst can be obtained.
The tri-tin tetroxide supported platinum-cobalt alloy catalyst of example 4 was used in the electrolysis of water to produce ozone reaction:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 4 of the same quality, and the remaining operating conditions were the same as those in the experimental process for preparing ozone by electrolyzing water of example 1, and the change of the concentration of ozone generated by the catalytic reaction of electrolyzed water with the reaction time was shown in FIG. 5.
Comparative example 5: commercial lead dioxide catalysts were prepared and used for the electrocatalytic ozone production reaction:
weighing 8mg of commercial lead dioxide catalyst (purchased from an Allantin reagent net), mixing with 900. mu.L of ethanol and 100. mu.L of Nafion solution (the mass concentration of the Nafion solution is 5%), performing ultrasonic treatment for 0.5 hour, and completely dispersing the catalyst in a mixed solution of the ethanol and the Nafion solution to obtain uniform catalyst slurry. The carbon cloth is cut to a size of about 2cm × 2cm, the dispersed catalyst slurry is completely and uniformly dripped on the carbon cloth, and the carbon cloth is dried to be used as a working electrode (namely, the material of the Pt/C catalyst coated on the carbon cloth is used as the working electrode).
The voltage and current are controlled by a constant current instrument, and an H-shaped electrolytic bath is adopted for reaction. In the anode chamber, a material of Pt/C catalyst coated on carbon cloth is used as a working electrode; in the cathode chamber, a platinum sheet is used as a counter electrode, and the electrolyte is saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic cell is connected with an ozone detector to detect the generation condition of ozone in real time. When the electro-catalysis is used for preparing ozone, the current is controlled to be 200mA, the cell voltage is controlled to be 3-9V, and the reaction time is 2 hours. A real-time plot of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeded is shown in figure 5. As can be seen from FIG. 5, the ozone concentration gradually increased as the reaction proceeded, and the ozone concentration was about 1408ppb when the reaction time was about 2 hours.
Claims (10)
1. A preparation method of a nano tin oxide supported platinum alloy catalyst is characterized by comprising the following steps:
1) adding a tin source and deionized water into a reactor, and stirring until the tin source is completely dissolved to obtain a solution;
2) adding ammonia water into the solution obtained in the step 1), placing the solution in an ice water bath, stirring the solution to precipitate tin ions, carrying out centrifugal separation, and washing the obtained precipitate with deionized water for 2 to 8 times;
3) transferring the precipitate obtained in the step 2) into a beaker, adding deionized water and ammonia water, performing ultrasonic treatment for 15-30 minutes to form a suspension, transferring the suspension into a polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining into a hydrothermal kettle, performing hydrothermal reaction at 100-200 ℃ for 3-24 hours, naturally cooling to room temperature, performing suction filtration, washing for 2-8 times with absolute ethyl alcohol and deionized water respectively, and performing freeze drying for 6-24 hours to obtain tin oxide serving as a carrier material;
4) fully mixing the tin oxide, the non-noble metal salt and the platinum salt obtained in the step 3), grinding the mixture into uniform powder, placing the powder into a porcelain boat, and roasting the powder for 3 to 24 hours at the temperature of 800 ℃ in a tubular furnace under the nitrogen atmosphere to obtain a tin oxide supported platinum alloy catalyst;
5) placing the tin oxide supported platinum alloy catalyst obtained in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 50-250W, the reaction temperature is 30-250 ℃, introducing high-purity gas under the vacuum-pumping condition and forming a plasma atmosphere, the vacuum degree is 30-150Pa, and activating the tin oxide supported platinum alloy catalyst for 0.5-3 hours under the plasma atmosphere to obtain the nano tin oxide supported platinum alloy catalyst.
2. The preparation method of the nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the tin source in the step 1) is tin (IV) salt or tin (II) salt, the tin (IV) salt comprises tin chloride or tin bromide, and the tin (II) salt comprises stannous sulfate, stannous chloride or stannous bromide.
3. The preparation method of the nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the molar ratio of tin (IV) to tin (II) in the tin oxide in the step 1) is 1:1 or 1:2, and the tin oxide is tin sesquioxide or tin tetraoxide.
4. The preparation method of the nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the concentration of the ammonia water in the step 3) is 20-30%, and the volume ratio of the deionized water to the absolute ethyl alcohol to the ammonia water is 1:1: 1-5.
5. The preparation method of the nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the platinum salt in the step 4) is chloroplatinic acid, platinum acetylacetonate or potassium tetrachloroplatinate, the loading amount of platinum in the tin oxide is 5% -20%, and the mass ratio of platinum to non-noble metal is 1: 0.8-1.2.
6. The method for preparing a nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the non-noble metal in the non-noble metal salt in step 4) is at least one metal element selected from cobalt and nickel, preferably cobalt acetylacetonate, cobalt acetate, nickel acetate or nickel acetylacetonate.
7. The method for preparing a nano tin oxide supported platinum alloy catalyst as claimed in claim 1, wherein the plasma voltage in step 5) is 150-200W; the reaction temperature is 150-200 ℃; the high purity gas is hydrogen, argon or nitrogen with a purity of > 99%.
8. A nano tin oxide-supported platinum alloy catalyst prepared according to the method of any one of claims 1 to 7.
9. The use of the nano tin oxide-supported platinum alloy catalyst according to claim 8 in a reaction for producing ozone by electrocatalytic decomposition of water.
10. Use according to claim 9, characterized in that it comprises the following steps: the constant current instrument is used for controlling voltage and current, an H-type electrolytic cell is used for reaction, water and gas are kept to be smooth between two electrode chambers, saturated potassium sulfate aqueous solution is used as electrolyte, the tin oxide supported platinum alloy catalyst is coated on carbon cloth to be used as a working electrode in an anode chamber, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction current is controlled to be 500mA, the cell voltage is controlled to be 1-10V, and the ozone is prepared by electrocatalysis to obtain an ozone product.
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