CN113862716B - Nanometer tin oxide loaded platinum alloy catalyst and preparation method and application thereof - Google Patents

Nanometer tin oxide loaded platinum alloy catalyst and preparation method and application thereof Download PDF

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CN113862716B
CN113862716B CN202111214938.XA CN202111214938A CN113862716B CN 113862716 B CN113862716 B CN 113862716B CN 202111214938 A CN202111214938 A CN 202111214938A CN 113862716 B CN113862716 B CN 113862716B
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tin oxide
tin
alloy catalyst
platinum alloy
reaction
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CN113862716A (en
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钟兴
汪潇洒
王建国
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/089—Alloys
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a nano tin oxide loaded 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, the tin oxide, non-noble metal salt and platinum salt are roasted, and then the tin oxide is placed in a plasma reaction furnace to be activated in a plasma atmosphere to obtain the nano tin oxide supported platinum alloy catalyst. The tin oxide loaded platinum alloy catalyst prepared by the invention has simple preparation process and low cost, and the tin oxide loaded by the platinum alloy exposes a special crystal face, so that the special crystal face of the tin oxide and platinum alloy nano particles generate a synergistic effect, the catalytic activity and stability of the reaction for preparing ozone by electrolyzing water are obviously improved, and the ozone current efficiency of preparing the ozone by electrolyzing water is greatly improved.

Description

Nanometer tin oxide loaded platinum alloy catalyst and preparation method and application thereof
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 extremely strong oxidizing ability and can be used for deodorizing, decoloring, sterilizing and degrading microorganisms. In the aspect of sterilization and disinfection, compared with the traditional chlorine-containing disinfectant, ozone is reduced to oxygen in the disinfection process, and no secondary pollution is caused, so that the ozone is more and more concerned, and has wide application in the fields of water treatment, medical care, agriculture, food processing, fresh keeping and the like.
The current preparation method for ozone mainly comprises the following steps: corona discharge method, ultraviolet irradiation method, electrolytic method, etc. 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-pressure ionization x ) Carcinogens. The ultraviolet irradiation method has the advantages of low yield, complex structure and difficult wavelength control. Compared with the former two methods, the electrolytic method has the following advantages: the method takes water as raw material, has mild operation condition, high concentration of generated ozone, small equipment investment and good application prospect. In the process of preparing ozone by an electrolytic method, yangOzone and oxygen are generated extremely, hydrogen is generated by the cathode, and the anode material with high overpotential is selected to effectively inhibit the generation of oxygen and improve the current efficiency of ozone generation.
At present, anode materials for preparing ozone by water electrolysis 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 layer of platinum oxide film is formed on the surface of a platinum electrode in the ozone precipitation process, and the platinum oxide film has good conductivity, and the oxygen overpotential is very high, thereby being beneficial to ozone generation, but being unfavorable for 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 loading of platinum, so that the catalyst with low platinum loading has important research significance.
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, the conductivity is generally improved by a nickel and antimony doping mode, but antimony element is a toxic element, and excessively used tin oxide is not in accordance with the requirements of green environment, and tin oxide is tin oxide, namely ditin oxide and tin oxide, has high oxygen evolution overpotential and far better conductivity than tin dioxide, so that the mixed valence tin oxide is directly used as a catalyst carrier, on one hand, the electrocatalytic reaction efficiency can be improved, and on the other hand, the environmental pollution can be avoided, and the research value is very high.
At present, the related research of loading platinum alloy on a mixed valence tin oxide catalyst and preparing ozone by electrolyzing water is not reported yet.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a nano tin oxide loaded platinum alloy catalyst, and 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:
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 to precipitate tin ions, centrifugally separating, and washing the obtained precipitate with deionized water for 2-8 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 placing the polytetrafluoroethylene lining into a hydrothermal kettle, performing hydrothermal reaction for 3-24 hours at 100-200 ℃, naturally cooling to room temperature, performing suction filtration, respectively washing for 2-8 times by using absolute ethyl alcohol and deionized water, and performing freeze drying for 6-24 hours to obtain tin oxide serving as a carrier material;
4) Fully mixing and grinding the tin oxide carrier material, the non-noble metal salt and the platinum salt obtained in the step 3) into uniform powder, placing the powder into a porcelain boat, and roasting for 3-24 hours at 200-800 ℃ in a nitrogen atmosphere in a tube furnace 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 ℃, high-purity gas is introduced under the condition of vacuumizing, a plasma atmosphere is formed, 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 is obtained.
Further, the invention also defines that the tin source in step 1) is a tin (iv) salt or a tin (ii) salt, the tin (iv) salt comprising tin chloride or tin bromide, and the tin (ii) salt comprising stannous sulfate, stannous chloride or stannous bromide.
Further, the invention also defines that the mole 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 stannous trioxide or stannous tetraoxide.
Further, the invention also defines that the concentration of the ammonia water in the step 3) is 20-30%, and the volume ratio of deionized water, absolute ethyl alcohol and ammonia water is 1:1:1-5.
Furthermore, the invention also defines that the platinum salt in the step 4) is chloroplatinic acid, platinum acetylacetonate or potassium tetrachloroplatinate, the loading 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 present invention also defines that the non-noble metal in the non-noble metal salt in 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 defines that the plasma voltage in the step 5) is 150-200W; the reaction temperature is 150-200 ℃; the high purity gas is hydrogen, argon or nitrogen with purity of > 99%.
Further, the preparation method of the nano tin oxide supported platinum alloy catalyst provided by the invention specifically comprises the following steps:
1) Adding a tin source into a 50mL beaker, adding 10-20mL of deionized water, and stirring for 5-60 minutes to completely dissolve the tin source;
2) Adding 100-800 mu L of ammonia water into the solution obtained in the step 1), placing the solution into an ice-water bath, stirring for 5-30 minutes to precipitate tin ions, and washing the precipitate with 20-50mL of deionized water for 2-8 times;
3) Transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL of deionized water, 3mL of absolute ethyl alcohol and 3-15mL of ammonia water, performing ultrasonic treatment for 15-30 minutes to form a suspension, transferring the suspension into a 25mL of polytetrafluoroethylene lining, performing hydrothermal reaction for 3-24 hours at 100-200 ℃ and then naturally cooling to room temperature, performing suction filtration, washing with 20-50mL of absolute ethyl alcohol and 20-50mL of deionized water for 2-8 times respectively, and freeze-drying for 6-24 hours to obtain a tin oxide carrier material, wherein 3-15mL of ammonia water is added in the step, and because of Sn 4+ And Sn (Sn) 2+ Readily hydrolyzes, and excess base can inhibit hydrolysis, which provides an opportunity for dynamic control of tin oxide nanocrystal shape;
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 into a porcelain boat, and roasting for 3-24 hours at 200-800 ℃ in a nitrogen atmosphere in a tubular furnace 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 condition of vacuumizing to form a plasma atmosphere, 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.
Furthermore, the invention also defines a nano tin oxide supported platinum alloy catalyst prepared by the method defined by the invention, and the nano tin oxide supported platinum alloy catalyst consists of different types of tin oxides and platinum-non-noble metal alloys supported on the 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 meter is used for controlling voltage and current, an H-shaped electrolytic tank is used for carrying out reaction, water and gas are kept smooth between two electrode chambers, a 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 100-500mA, the tank voltage is controlled to be 1-10V, and an ozone reaction is carried out to prepare an ozone product.
By adopting the technology, compared with the prior art, the invention has the beneficial effects that:
1) The tin oxide loaded platinum alloy catalyst takes tin (IV) salt and tin (II) salt as raw materials, and realizes the loading of platinum cobalt or platinum nickel alloy through roasting after a carrier is obtained through simple hydrothermal and freeze-drying, 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 has the advantages that the special crystal faces {110} and {111} are exposed, so that a synergistic effect is generated between the special crystal face of the tin oxide and platinum alloy nano particles, the catalytic activity and stability of the reaction for preparing ozone by electrolyzing water are obviously improved, and the basic application research is provided for the material in the field of electrocatalysis, so that the tin oxide supported platinum alloy catalyst has a wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a transmission electron microscope at 10nm of a platinum nickel alloy catalyst supported on stannous trioxide prepared in example 1;
FIG. 2 is a schematic diagram of a scanning electron microscope at 3 μm of a platinum nickel alloy catalyst supported on stannous trioxide prepared in example 1;
FIG. 3 is a schematic diagram of a transmission electron microscope at 10nm of the three-tin-tetraoxide-supported platinum-nickel alloy catalyst prepared in example 2;
FIG. 4 is a schematic diagram of a scanning electron microscope at 3 μm of a platinum nickel alloy catalyst supported on three tin tetroxide prepared in example 2;
fig. 5 is a graph showing comparison of real-time detection data of the concentration of ozone generated when the tin oxide-supported platinum alloy catalysts prepared in examples 1 to 4 were used for preparing ozone by electrocatalytic reaction.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: tin oxide loaded platinum nickel alloy catalyst PtNi/Sn 2 O 3 The preparation method of (2) comprises the following steps:
1) 350.6mg of stannic chloride pentahydrate, 225.6mg of stannous chloride dihydrate and 17mL of deionized water are added into a 50mL beaker, and the mixture is stirred for 3 minutes to be fully dissolved 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, centrifuging to obtain precipitate, and washing the precipitate with deionized water for 3 times;
3) Transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL of deionized water, 3mL of absolute ethyl alcohol and 10mL of ammonia water, performing ultrasonic treatment for 15 minutes to form a suspension, transferring the suspension into a 25mL of polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, performing hydrothermal treatment at 200 ℃ for 12 hours, naturally cooling to room temperature, performing suction filtration, washing 3 times with 30mL of absolute ethyl alcohol and 30mL of deionized water respectively, and freeze-drying a sample in a vacuum environment at about-10 ℃ for 10 hours;
4) Mixing 160mg of the solid product obtained in the step 3), 16mg of platinum acetylacetonate and 34mg of nickel acetylacetonate, grinding into powder, and placing the powder in a porcelain boat to be roasted for 5 hours at 250 ℃ in a nitrogen atmosphere in a tube furnace to obtain the tin oxide loaded 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 150W, the reaction temperature is 150 ℃, nitrogen is introduced under the condition of vacuumizing, a plasma atmosphere is formed, the vacuum degree is 150Pa, and the tin oxide supported platinum nickel alloy catalyst is activated for 2 hours under the plasma atmosphere, so that the activated tin oxide supported platinum nickel alloy catalyst is obtained.
The transmission electron microscope diagram at 10nm and the scanning electron microscope diagram at 3 μm of the obtained tin oxide-supported platinum-nickel alloy catalyst of example 1 are shown in FIG. 1 and FIG. 2, respectively, the tin oxide-supported platinum-nickel alloy catalyst particles have an elongated dodecahedral structure, which can expose the specific crystal planes {110} and {111} of the tin oxide, the combination of the two crystal planes with the platinum-non-noble metal alloy is more stable, and the tin oxide-noble metal alloy has a specific electron transfer effect between the tin oxide having the specific crystal planes {110} and {111} and the platinum-noble metal alloy, compared with the tin oxide having no specific crystal plane, the platinum-noble metal alloy has a specific electron transfer effect between PtNi/Sn 2 O 3 Under the action of the catalyst, the electrolytic water reaction is easier to carry out.
The stannous oxide supported platinum nickel alloy catalyst of example 1 was used for the electrolytic water preparation ozone reaction:
8mg of the prepared tin oxide-supported platinum nickel alloy catalyst particles were weighed, mixed with 900. Mu.L of ethanol and 100. Mu.L of Nafion solution (the mass concentration of the Nafion solution is 5%), sonicated for 20 minutes, and the catalyst was completely dispersed in the mixed solution of ethanol and Nafion solution to obtain a uniform catalyst slurry. Cutting carbon cloth to a size of about 2cm multiplied by 2cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain a working electrode (namely, coating a stannous oxide supported platinum nickel alloy catalyst on the carbon cloth to serve as the working electrode).
The constant current instrument controls the voltage and the current, and the H-shaped electrolytic tank 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 a saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic tank is connected with an ozone detector, and the ozone generation condition is detected in real time. When the electrocatalytic reaction is carried out to prepare ozone, the current is controlled at 200mA, the cell voltage is controlled between 3 and 9V, and the reaction time is 2 hours. The graph of the real-time detection of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeds is shown in FIG. 5. As is clear from FIG. 5, as the reaction proceeds, the ozone concentration gradually increases, and as the reaction time reaches approximately 2 hours, the ozone concentration can reach 3376ppb.
To verify the catalytic stability of the stannous oxide supported platinum nickel alloy catalyst particles prepared in example 1, the anode chamber working electrode after 1 reaction was left for 24 hours, and repeated electrocatalytic preparation ozone reaction experiments were performed (one day after each use of the anode chamber working electrode, and then the next use was performed). In experiment 1, the ozone concentration after the reaction reaches 2 hours can reach 3370ppb. In experiment 2 of the anode chamber working electrode recycling reaction, the ozone concentration after the reaction reaches 2 hours can reach 3420ppb. In experiment 3 of the anode chamber working electrode recycling reaction, the ozone concentration after the reaction reaches 2 hours can reach 3415ppb. It can be seen that the electrocatalytic effect is not reduced basically in the recycling process of the working electrode of the anode chamber, which indicates that the stannous trioxide supported platinum nickel alloy catalyst particles prepared in the embodiment 1 have better stability.
Example 2: ptNi/Sn catalyst of platinum nickel alloy loaded with three tin tetraoxide 3 O 4 The preparation method of (2) comprises the following steps:
1) In a 50mL beaker, add 175mg of tin tetrachloride pentahydrate, 225.6mg of stannous chloride dihydrate, add 18mL deionized water, and stir for 10 minutes to dissolve all;
2) Adding 600 mu L of ammonia water into the solution obtained in the step 1), placing the solution into an ice-water bath, stirring for 10 minutes, precipitating tin ions, and washing the precipitate with deionized water for 4 times;
3) Transferring the precipitate obtained in the step 2) into a 50mL beaker, adding 3mL of deionized water, 3mL of absolute ethyl alcohol and 9mL of ammonia water, performing ultrasonic treatment for 20 minutes to form a suspension, transferring the suspension into a 25mL of polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, performing hydrothermal treatment at 180 ℃ for 9 hours, naturally cooling to room temperature, performing suction filtration, washing 3 times with 30mL of absolute ethyl alcohol and 30mL of deionized water respectively, and freeze-drying a sample in a vacuum environment at about-10 ℃ for 8 hours;
4) Mixing 100mg of the solid product obtained in the step 3), 14mg of chloroplatinic acid and 15mg of nickel acetate, grinding into powder, and placing the powder into a porcelain boat to be roasted for 9 hours at 600 ℃ in a nitrogen atmosphere in a tube furnace to obtain the three-tin-tetraoxide-loaded 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 condition of vacuumizing, a plasma atmosphere is formed, the vacuum degree is 100Pa, and the activated three-tin-tetraoxide-supported platinum-nickel alloy catalyst is activated for 3 hours under the plasma atmosphere, so that the activated three-tin-tetraoxide-supported platinum-nickel alloy catalyst can be obtained.
The transmission electron microscope schematic diagram at 10nm and the scanning electron microscope schematic diagram at 3 μm of the three-tin-oxide-supported platinum-nickel alloy catalyst obtained in example 2 are shown in fig. 3 and 4 respectively, the three-tin-oxide-supported platinum-nickel alloy catalyst particles have an elongated dodecahedron structure, the dodecahedron structure can expose the special crystal faces {110} and {111} of the tri-tin tetroxide, the combination of the two crystal faces and the platinum-non-noble metal alloy is more stable, and compared with the tri-tin tetroxide without the special crystal faces, the tri-tin tetroxide with the special crystal faces {110} and {111} and the platinum-noble metal alloy have special electron transfer effect, and the combination of the two crystal faces and the platinum-non-noble metal alloy is PtNi/Sn 3 O 4 Under the action of the catalyst, the electrolytic water reaction is easier to carry out.
The three tin oxide supported platinum nickel alloy catalyst of example 2 was used for the electrolytic water preparation ozone reaction:
in the process of preparing the electrode anode by using the catalyst prepared in the example 1, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 2 with the same quality, and the rest of operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, and the change relation of the concentration of the ozone generated by the electrolyzed water catalytic reaction with the reaction time is shown in figure 5.
Example 3: tin oxide loaded platinum cobalt alloy catalyst PtCo/Sn 2 O 3 The preparation method of (2) 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 materials;
2) Adding 650 mu L of ammonia water into the solution obtained in the step 1), placing the solution into an ice-water bath, stirring for 5 minutes, precipitating tin ions, and washing the precipitate with deionized water for 4 times;
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, placing 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 3 times with 30mL of absolute ethyl alcohol and 30mL of deionized water respectively, and freeze-drying the sample at about-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 placing the powder in a porcelain boat to be roasted for 8 hours at 500 ℃ in a nitrogen atmosphere in a tube furnace to obtain the tin oxide 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 condition of vacuumizing, a plasma atmosphere is formed, the vacuum degree is 150Pa, and the tin oxide supported platinum cobalt alloy catalyst is activated for 2.5 hours under the plasma atmosphere, so that the activated tin oxide supported platinum cobalt alloy catalyst can be obtained.
The tin oxide supported platinum cobalt alloy catalyst of example 3 was used for the reaction of water electrolysis to prepare ozone:
in the process of preparing the electrode anode by using the catalyst prepared in the example 1, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 3 with the same quality, and the rest of operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, and the change relation of the concentration of the ozone generated by the electrolyzed water catalytic reaction with the reaction time is shown in figure 5.
Example 4: tritin tetraoxide loaded platinum cobalt alloy catalyst PtCo/Sn 3 O 4 The preparation method of (2) comprises the following steps:
1) 219mg of tin bromide, 278mg of stannous bromide and 17mL of deionized water are added into a 50mL beaker, and the mixture is stirred for 5 minutes to be completely dissolved;
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, precipitating tin ions, and washing the precipitate with deionized water for 4 times;
3) Transferring the precipitate obtained in the step 2) into a 50mL beaker, carrying out ultrasonic treatment for 30 minutes to form a suspension, transferring the suspension into a 25mL polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, carrying out hydrothermal treatment at 150 ℃ for 3 hours, naturally cooling to room temperature, carrying out suction filtration, washing 3 times with 30mL of absolute ethyl alcohol and 30mL of deionized water respectively, and freeze-drying the sample at about-10 ℃ in a vacuum environment for 16 hours;
4) 200mg of the solid product obtained in the step 3), 25mg of platinum acetylacetonate and 40mg of cobalt acetate are mixed and ground into powder, and the powder is placed in a porcelain boat and is roasted for 5 hours at 200 ℃ in a nitrogen atmosphere in a tube furnace, so that the three-tin-tetraoxide supported platinum-cobalt alloy catalyst can be obtained.
5) Placing the product obtained in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 250W, the reaction temperature is 250 ℃, nitrogen is introduced under the condition of vacuumizing, a plasma atmosphere is formed, the vacuum degree is 50Pa, and the activated three-tin-oxide-supported platinum-cobalt alloy catalyst is activated for 1.5 hours under the plasma atmosphere, so that the activated three-tin-oxide-supported platinum-cobalt alloy catalyst can be obtained.
The three tin oxide supported platinum cobalt alloy catalyst of example 4 was used for the water electrolysis to produce ozone:
in the process of preparing the electrode anode by using the catalyst prepared in the example 1, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 4 with the same quality, and the rest of the operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, and the change relation of the concentration of the ozone generated by the electrolyzed water catalytic reaction with the reaction time is shown in figure 5.
Comparative example 5: preparation of commercial lead dioxide catalyst and use in electrocatalytic ozone production reactions:
8mg of commercial lead dioxide catalyst (available from Aba Ding Shiji mesh) was weighed, mixed with 900. Mu.L of ethanol and 100. Mu.L of Nafion solution (Nafion solution mass concentration: 5%) and sonicated for 0.5 hours to completely disperse the catalyst in the mixture of ethanol and Nafion solution to give a uniform catalyst slurry. Cutting carbon cloth to a size of about 2cm multiplied by 2cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain a working electrode (namely, a material of Pt/C catalyst coated on the carbon cloth is used as the working electrode).
The constant current instrument controls the voltage and the current, and the H-shaped electrolytic tank 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 a saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic tank is connected with an ozone detector, and the ozone generation condition is detected in real time. When the electrocatalytic reaction is carried out to prepare ozone, the current is controlled at 200mA, the cell voltage is controlled between 3 and 9V, and the reaction time is 2 hours. The graph of the real-time detection of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeds is shown in FIG. 5. As can be seen from fig. 5, the ozone concentration gradually increased as the reaction proceeded, and the ozone concentration was about 1408ppb as the reaction time was shortened to approximately 2 hours.

Claims (10)

1. The preparation method of the nano tin oxide supported platinum alloy catalyst 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, wherein the tin source is tin (IV) salt and tin (II) salt;
2) Adding ammonia water into the solution obtained in the step 1), placing the solution in an ice-water bath, stirring to precipitate tin ions, centrifugally separating, and washing the obtained precipitate with deionized water for 2-8 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 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, respectively washing for 2-8 times by using absolute ethyl alcohol and deionized water, and performing freeze drying for 6-24 hours to obtain tin oxide, wherein the tin oxide is stannous oxide or stannous oxide, and the tin oxide is of a dodecahedral structure;
4) Fully mixing and grinding the tin oxide, the non-noble metal salt and the platinum salt obtained in the step 3) into uniform powder, placing the powder into a porcelain boat, and roasting for 3-24 hours at 200-800 ℃ in a nitrogen atmosphere in a tube furnace to obtain a tin oxide supported platinum alloy catalyst, wherein the non-noble metal in the non-noble metal salt is at least one metal element of cobalt and nickel, the loading amount of platinum in the tin oxide is 5-20%, and the mass ratio of platinum to the non-noble metal is 1:0.8-1.2;
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 condition of vacuumizing to form a plasma atmosphere, 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, wherein the high-purity gas is hydrogen, argon or nitrogen.
2. The method for preparing the nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the tin (iv) salt in the step 1) comprises tin chloride or tin bromide, and the tin (ii) salt comprises stannous sulfate, stannous chloride or stannous bromide.
3. The method for preparing a 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 step 3) is 1:1 or 1:2.
4. The method for preparing a nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the concentration of ammonia water in the step 3) is 20-30%, and the volume ratio of deionized water, absolute ethyl alcohol and ammonia water is 1:1:1-5.
5. The method for preparing a 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.
6. The method for preparing a nano tin oxide supported platinum alloy catalyst according to claim 1, wherein the non-noble metal salt in the step 4) is cobalt acetylacetonate, cobalt acetate, nickel acetate or nickel acetylacetonate.
7. The method for preparing a nano tin oxide supported platinum alloy catalyst according to 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 purity of > 99%.
8. A nano tin oxide supported platinum alloy catalyst prepared according to the method of any one of claims 1-7.
9. Use of the nano tin oxide supported platinum alloy catalyst according to claim 8 in an electrocatalytic decomposition reaction for water to ozone.
10. Use according to claim 9, characterized by comprising the steps of: the constant current meter is used for controlling voltage and current, an H-shaped electrolytic tank is used for carrying out reaction, water and gas are kept smooth between two electrode chambers, a 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 100-500mA, the tank voltage is controlled to be 1-10V, and an ozone product is obtained by carrying out electrocatalytic preparation ozone reaction.
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