CN115874216A - Platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and preparation method thereof - Google Patents
Platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and smelting platinum, nickel, copper and phosphorus in proportion to obtain a platinum-based amorphous alloy sheet; vacuum hot pressing to embed nano barium titanate particles into the surface of the platinum-based amorphous alloy sheet; then soaking the substrate in an acid solution to dissolve barium titanate particles to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure; then carrying out electrodeposition, wherein the electrolyte is a mixed solution of ruthenium chloride and potassium chloride, and obtaining a platinum-based amorphous alloy porous substrate with the surface loaded with nano-scale ruthenium; then carrying out heat treatment to obtain a finished product; the platinum-based amorphous alloy porous catalyst comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate; the catalyst has high catalytic efficiency, long-term stability, simple preparation method and low cost, improves the reaction efficiency of chlorine evolution reaction, increases the generation amount of chlorine, and is suitable for batch production.
Description
Technical Field
The invention relates to the technical field of catalysts for water disinfection, in particular to a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and a preparation method thereof.
Background
The water disinfection technology plays an important role in reducing the occurrence and death of infectious diseases caused by pathogenic microorganisms as the greatest public health achievement in the 20 th century. Chlorine disinfection is the most widely used disinfection method in the world due to low cost, good disinfection effect and convenient use. The drinking water sanitary standard of China specifies: the content of free residual chlorine in the centralized water supply and delivery water is not less than 0.3 mg/L, and the content of water at the tail end of a pipe network is not less than 0.05 mg/L. Besides being used for tap water treatment, the chlorine can also carry out effective advanced treatment on the municipal sewage. The social demand of chlorine as an important disinfectant is also gradually rising. The chlorine preparation comes from the chlor-alkali industry, which belongs to the traditional extensive development mode and has the following problems: high investment cost, low chlorine generating efficiency, large consumption, aggravated production cost and caused a plurality of economic and environmental problems. Therefore, it is urgently needed to develop a new efficient and stable catalyst, which is applied to chlorine evolution reaction, improves the performance and stability of electrode chlorine evolution, improves the efficiency of chlorine evolution reaction, improves the efficiency of chlorine generation, reduces the production cost, and provides new important material storage and method selection for drinking water and wastewater treatment and preparation of public place disinfectants.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and a preparation method thereof aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the platinum-based amorphous alloy porous catalyst for chlorine evolution reaction comprises the following steps:
s1, mixing platinum, nickel, copper and phosphorus in proportion, smelting, performing suction casting, and cutting to obtain a platinum-based amorphous alloy sheet;
s2, placing nano barium titanate particles on the platinum-based amorphous alloy sheet, and carrying out hot pressing in a vacuum environment to embed the nano barium titanate particles into the surface of the platinum-based amorphous alloy sheet to obtain the platinum-based amorphous alloy sheet with barium titanate particles on the surface layer;
s3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in an acid solution, and dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure;
s4, carrying out electrodeposition on the platinum-based amorphous alloy substrate with the nanoscale porous structure, wherein the electrolyte of the electrodeposition is a ruthenium chloride-potassium chloride mixed solution, so as to obtain the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface;
and S5, carrying out heat treatment on the platinum-based amorphous alloy porous substrate loaded with the nano-scale ruthenium on the surface to obtain the platinum-based amorphous alloy porous catalyst loaded with the nano-scale ruthenium oxide on the surface.
Further, in the step S1, the mass ratio of platinum, nickel, copper and phosphorus is 36 57.5 Cu 14.7 Ni 5.3 P 22.5 。
Further, in the step S1, obtaining a platinum-based amorphous alloy bar after suction casting, and cutting the platinum-based amorphous alloy bar into platinum-based amorphous alloy wafers, wherein the thickness of the platinum-based amorphous alloy wafers is 750-800um, and the diameter of the platinum-based amorphous alloy wafers is 2-5mm.
Further, in the step S2, the particle size of the nano-sized barium titanate particles is 30-200nm, the hot pressing temperature is 190-205 ℃, the vacuum degree is 5-10Pa, and the hot pressing pressure is 15-20kN.
Further, in step S3, the acidic solution is a hydrochloric acid solution of 4-8mol/L, and the reaction soaking time is 10-12h.
Further, in step S4, the electro-deposition electrode system is a three-electrode system, the working electrode is a platinum-based amorphous alloy substrate with a nano-scale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, the electro-deposition voltage is-0.356V and the electro-deposition time is 500-800S relative to the standard hydrogen electrode.
Further, in step S4, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.1 to 0.5mmol/L, and the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.05 to 0.15 mol/L.
Further, in step S5, the heat treatment temperature is 420-450 ℃ and the heat treatment time is 150-180min.
Further, the particle size of the surface-supported ruthenium oxide is 140-400nm.
The invention also provides a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction, which is obtained by adopting the preparation method and comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The pore diameter of the porous structure of the platinum-based amorphous alloy substrate is 30-200nm, and the particle size of the nano ruthenium oxide is 140-400nm.
The invention has the beneficial effects that: the preparation method of the platinum-based amorphous alloy porous catalyst for chlorine evolution reaction comprises the steps of firstly preparing a platinum-based amorphous alloy, then embedding nano barium titanate particles into the platinum-based amorphous alloy in a hot pressing mode, dissolving the barium titanate particles through a corresponding acid solution to form a nano porous structure on the surface of the platinum-based amorphous alloy, carrying out electrodeposition and heat treatment on an amorphous alloy substrate with the nano porous structure to load nano ruthenium oxide on the surface of the amorphous alloy substrate, and forming the platinum-based amorphous alloy porous catalyst with the nano ruthenium oxide loaded on the surface; according to the platinum-based amorphous alloy porous catalyst, the platinum-based amorphous alloy is used as a substrate, and has thermoplasticity which is not possessed by common metal materials, so that a nano porous surface is easy to form, and the stability is high; the porous structure on the platinum-based amorphous alloy substrate can greatly improve the specific surface area, and more active sites are realized to improve the chlorine evolution reaction efficiency; meanwhile, the ruthenium oxide is in a nanometer level, has high catalytic efficiency, stable performance and overlong stability, can be stably used for more than 200 hours, improves the reaction efficiency of chlorine evolution reaction, and increases the generation amount of chlorine; the platinum-based amorphous alloy porous catalyst has the advantages of simple process requirement, strong repeatability and low cost, and is suitable for large-scale production.
Drawings
The invention will be further described with reference to the following drawings and examples, in which:
fig. 1 is an SEM image of a platinum-based amorphous alloy substrate having a nano-scale porous structure of example 1 of the present invention;
FIG. 2 is an SEM image of a platinum-based amorphous alloy porous substrate supporting nano-scale ruthenium on the surface of the substrate in example 1 of the present invention;
fig. 3 is an XRD pattern of the platinum-based amorphous alloy porous substrate of example 1 of the present invention on which nanoscale ruthenium is supported on the surface;
FIG. 4 is an EDS diagram of a platinum-based amorphous alloy porous catalyst with a nano-sized ruthenium oxide supported on the surface thereof according to example 1 of the present invention, wherein the first is an electron microscope diagram, the second is an oxygen element distribution diagram, and the third is a ruthenium element distribution diagram;
FIG. 5 is a graph of the efficiency-voltage tendency of the platinum-based amorphous alloy porous catalyst of example 3 of the present invention in a 3 mol/L NaCl solution for 900S;
FIG. 6 shows the results of the reaction of the platinum-based amorphous alloy porous catalyst of example 3 of the present invention in a 3 mol/L NaCl solution and 3 mol/L NaNO solution 3 Medium linear sweep voltammogram;
FIG. 7 is a graph of efficiency-voltage-time in a 3 mol/L NaCl solution for the platinum-based amorphous alloy porous catalyst of example 3 of the present invention;
FIG. 8 is a graph of efficiency versus voltage versus time for a commercial ruthenium oxide catalyst of the comparative example in a 3 mol/L NaCl solution.
Detailed Description
For a more clear understanding of the technical features, objects, and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
The invention provides a preparation method of a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction, which comprises the following steps:
s1, mixing platinum, nickel, copper and phosphorus in proportion, smelting, performing suction casting, and cutting to obtain a platinum-based amorphous alloy sheet.
Further, the mass ratio of platinum, nickel, copper and phosphorus is preferably 36 57.5 Cu 14.7 Ni 5.3 P 22.5 The alloy of the component can form amorphous alloy, so that the amorphous alloy has thermoplasticity which is not possessed by common metal, the surface of the amorphous alloy is easy to form nano-porous due to good thermoplasticity, and meanwhile, the amorphous alloy is strong in stability and suitable for being used as a substrate of a porous catalyst.
Further, the platinum-based amorphous alloy with the rod-shaped structure is obtained after suction casting, the rod-shaped structure is easy to produce, a plurality of platinum-based amorphous alloy wafers can be formed by cutting the platinum-based amorphous alloy rod according to the selection of the whole length and the preset thickness of the platinum-based amorphous alloy rod, and 600-2000-mesh abrasive paper can be used for grinding and polishing after cutting. The thickness of the platinum-based amorphous alloy wafer includes, but is not limited to, 750-800um; the diameter is 2-5mm, the diameter is too large to be produced easily, and a high cooling rate needs to be achieved, and the diameter of the platinum-based amorphous alloy wafer is preferably 2-5mm, and more preferably 5mm.
The preparation method of the platinum-based amorphous alloy sheet comprises the following steps: placing platinum, nickel and copper in a copper cavity of a WK series vacuum arc furnace according to a mass ratio of 36:1, starting a mechanical pump, pumping the interior of the arc furnace to 5Pa or below, starting a molecular pump on the premise of low vacuum, and pumping high vacuum to 3 × 10 -3 And Pa, opening an argon valve, introducing a proper amount of argon, pressing an arc striking switch, striking an arc striking electric arc gun, and igniting a titanium ingot by using 120A current to suck oxygen so as to ensure that no oxygen exists in the furnace. And aligning the current to the copper cavity, adjusting the arc current to 70-120A, extinguishing the arc gun after the raw materials are completely melted, turning over by using a spoon, striking the arc gun again, repeating the subsequent steps, and repeating the melting for three to five times to uniformly fuse the raw materials together. The smelting mother alloy containing platinum, nickel and copper and phosphorus with corresponding mass are loaded into a test tube (the mass ratio of platinum, nickel, copper and phosphorus is 36. And (3) performing electromagnetic induction melting on the sealed test tube by using a vacuum rapid quenching spray casting machine, stepping a pedal to adjust the current to 20A until the sample is completely melted, and uniformly mixing P (phosphorus) and the master alloy. And replacing a new test tube, adding a mother alloy of boron trioxide and induction smelting mixed P (phosphorus), carrying out induction smelting purification by using a vacuum rapid quenching spray casting machine, and finally carrying out suction casting on the mother alloy which is melted with phosphorus and purified in a copper cavity of a vacuum arc furnace to obtain the platinum-based amorphous alloy bar. The diameter, length, etc. of the platinum-based amorphous alloy bar may be determined according to the forming die, such as the diameter of 5mm, etc.
S2, placing the platinum-based amorphous alloy sheet in a mold, placing the nano barium titanate particles above the platinum-based amorphous alloy sheet, and carrying out hot pressing in a vacuum, high-temperature and argon cooling environment to embed the nano barium titanate particles into the surface of the platinum-based amorphous alloy sheet, so as to obtain the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer.
Further, the particle size of the nano-sized barium titanate particles is 30-200nm, preferably the particle size of the nano-sized barium titanate particles is 30nm; barium titanate has a nano-scale size, does not agglomerate, is easily removed by reaction in an acidic solution, and is a very suitable particle material for forming a porous structure, so that pores formed on the platinum-based amorphous alloy sheet are 30-200nm in diameter. The hot pressing temperature is 190-205 ℃, the hot pressing heat preservation is 15-30 seconds, the vacuum degree is 5-10Pa, protective gas argon is introduced after vacuum, and the hot pressing pressure is 15-20kN. When the temperature is about 190 ℃, the platinum-based amorphous alloy sheet can be gradually softened, the nano barium titanate particles are embedded into the surface of the platinum-based amorphous alloy sheet under the action of pressure, and the nano barium titanate particles are dissolved to form a nano porous structure in situ.
In a die cavity of the die, preferably uniformly placing nano barium titanate particles above the platinum-based amorphous alloy sheet, wherein the usage amount of the nano barium titanate particles is arranged corresponding to the surface of the platinum-based amorphous alloy sheet so as to fully cover the surface of the platinum-based amorphous alloy sheet; for example, a platinum-based amorphous alloy wafer with the diameter of 5mm is selected, and the nano barium titanate particles can be ensured to completely cover the platinum-based amorphous alloy wafer.
And S3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in an acidic solution, and completely dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain the platinum-based amorphous alloy substrate with the nano-scale porous structure.
Further, the acid solution is 4-8mol/L hydrochloric acid solution, and the reaction soaking time is 10-12h, so that the nano barium titanate particles are fully dissolved; preferably 6mol/L hydrochloric acid solution, and the effect of dissolving barium titanate particles is better. The barium titanate particles are soaked in the hydrochloric acid solution to react with the hydrochloric acid solution and do not react with the platinum-based amorphous alloy sheet.
The prepared platinum-based amorphous alloy substrate with the nanoscale porous structure comprises a platinum-based amorphous alloy sheet and a porous structure formed on the platinum-based amorphous alloy sheet; the porous structure is formed by pressing nano barium titanate particles into the surface of the platinum-based amorphous alloy after the platinum-based amorphous alloy is softened by heating and removing the nano barium titanate particles.
And S4, placing the platinum-based amorphous alloy substrate with the nanoscale porous structure in a three-electrode system for electrodeposition, wherein in the three-electrode system, the working electrode is the platinum-based amorphous alloy substrate with the nanoscale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, and the electrolyte is a ruthenium chloride-potassium chloride mixed solution, so that the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface is obtained.
Specifically, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.1-0.5mmol/L, the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.05-0.15 mol/L, the voltage of electrodeposition is-0.356V (VS SHE, specifically, the voltage relative to a standard hydrogen electrode) when electrodeposition is carried out, and the electrodeposition time is 500-800s, so that ruthenium in the electrolyte is uniformly deposited on the platinum-based amorphous alloy substrate, and further the platinum-based amorphous alloy porous substrate with the nano-scale ruthenium loaded on the surface is obtained.
And S5, carrying out heat treatment on the platinum-based amorphous alloy porous substrate loaded with the nanoscale ruthenium on the surface, so that the nanoscale ruthenium is oxidized at high temperature to form ruthenium oxide, and finally obtaining the platinum-based amorphous alloy porous catalyst loaded with the nanoscale ruthenium on the surface. Specifically, the platinum-based amorphous alloy porous substrate with the surface loaded with the nanoscale ruthenium can be placed into an annealing furnace for heat treatment, and the sample tube provided with the platinum-based amorphous alloy porous substrate with the surface loaded with the nanoscale ruthenium is subjected to sealing treatment by a sealing plug; the heat treatment temperature is 420-450 ℃, the heat treatment time is 150-180min, so that the nano ruthenium is fully oxidized to form ruthenium oxide, and the particle size of the formed ruthenium oxide is 140-400nm.
The invention also provides a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction, which is obtained by adopting the preparation method and comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The pore diameter of the porous structure of the platinum-based amorphous alloy substrate is 30-200nm, and the particle size of the nano ruthenium oxide is 140-400nm.
The invention provides a preparation method of a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction, which comprises the steps of firstly preparing a platinum-based amorphous alloy, then embedding nano barium titanate particles into the platinum-based amorphous alloy in a hot pressing mode, dissolving the barium titanate particles through a corresponding acid solution to form a nano porous structure on the surface of the platinum-based amorphous alloy, carrying out electrodeposition and heat treatment on an amorphous alloy substrate sample with the nano porous structure to load nano ruthenium oxide on the surface of the amorphous alloy substrate sample, and forming the platinum-based amorphous alloy porous catalyst with the nano ruthenium oxide loaded on the surface; according to the platinum-based amorphous alloy porous catalyst, a platinum-based amorphous alloy is selected as a substrate, the platinum-based amorphous alloy has thermoplasticity which is not possessed by common metal materials, a nano porous surface is easy to form, and meanwhile, the stability is strong; the porous structure on the platinum-based amorphous alloy substrate can greatly improve the specific surface area, and more active sites are realized to improve the chlorine evolution reaction efficiency; meanwhile, the electrodeposited ruthenium oxide is in a nano level, the catalytic efficiency is high, the performance is stable, the reaction efficiency of chlorine evolution reaction is improved, and the generation amount of chlorine is increased; the platinum-based amorphous alloy porous catalyst has the advantages of simple process requirement, strong repeatability and low cost, and is suitable for large-scale production.
Example 1
A platinum-based amorphous alloy porous catalyst for chlorine evolution reaction comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The pore diameter of the porous structure of the platinum-based amorphous alloy substrate is about 30nm, and the particle size of the nano ruthenium oxide is about 140nm.
The preparation method comprises the following steps:
s1, placing platinum, nickel and copper in a copper cavity of a WK series vacuum arc furnace according to a mass ratio of 36:1, starting a mechanical pump, pumping the interior of the arc furnace to 5Pa or below, starting a molecular pump on the premise of low vacuum, and pumping high vacuum to 3 x 10 -3 And Pa, opening an argon valve, introducing a proper amount of argon, pressing down an arc starting switch, starting an arc gun, and igniting a titanium ingot by using 120A current to inhale oxygen so as to ensure that no oxygen exists in the furnace. And aligning the current to the copper cavity, adjusting the arc current to 70A, extinguishing the arc gun after the raw materials are completely melted, turning over by using a spoon, striking the arc gun again, repeating the subsequent steps, and repeating the melting for three to five times to uniformly fuse the raw materials together. The method comprises the following steps of (1)And sealing the test tube by using a compound fertilizer Kang Pa at the flow rate of 200L/H due to a water fuel oxyhydrogen machine when the pressure is lower than 5 Pa. And (3) carrying out electromagnetic induction melting on the sealed test tube by using a vacuum rapid quenching injection molding machine, regulating the current by stepping a pedal by 20A until the sample is completely melted, and uniformly mixing P (phosphorus) and the master alloy. Replacing new test tube, adding mother alloy of boron trioxide and induction smelting mixed P (phosphorus), induction smelting and purifying by using vacuum rapid quenching spray casting machine, and finally suction casting the mother alloy melted with phosphorus and purified in copper cavity of vacuum arc furnace to obtain platinum-based amorphous alloy bar (with Pt as component) 57.5 Cu 14.7 Ni 5.3 P 22.5 ) And cutting into a platinum-based amorphous alloy wafer with the thickness of 750 um and the diameter of 2 mm.
S2, placing the platinum-based amorphous alloy wafer into a mold, placing nanoscale barium titanate particles (with the particle size of about 30 nm) above the platinum-based amorphous alloy wafer, carrying out hot pressing in a vacuum, high-temperature and argon cooling environment, keeping the temperature for 30 seconds, embedding the nanoscale barium titanate particles into the surface of the platinum-based amorphous alloy wafer, wherein the hot pressing temperature is 190 ℃, the vacuum degree is 5Pa, and the hot pressing pressure is 15kN, so as to obtain the platinum-based amorphous alloy wafer with the barium titanate particles on the surface layer.
S3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in 4mol/L hydrochloric acid solution 5 for 12h, dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure, wherein the component of the platinum-based amorphous alloy substrate with the nano-scale porous structure is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The structure of the nano-scale porous platinum-based amorphous alloy substrate is the same as that of a platinum-based amorphous alloy sheet with barium titanate particles on the surface layer, and the nano-scale porous platinum-based amorphous alloy substrate comprises a platinum-based amorphous alloy substrate and a porous structure formed on the platinum-based amorphous alloy substrate. An SEM image of the platinum-based amorphous alloy substrate having the nano-scale porous structure is shown in fig. 1, and it can be seen from the SEM image that the nano-porous structure existing on the surface of the platinum-based amorphous alloy increases the specific surface area thereof, thereby increasing the active area of the reaction.
And S4, placing the platinum-based amorphous alloy substrate with the nanoscale porous structure in a three-electrode system for electrodeposition, wherein in the three-electrode system, the working electrode is the platinum-based amorphous alloy substrate with the nanoscale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, the electrolyte is a ruthenium chloride-potassium chloride mixed solution, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.1mmol/L, the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.05mol/L, the electrodeposition voltage is-0.356V (relative to the voltage of a standard hydrogen electrode), and the electrodeposition time is 500S, so that the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface is obtained. An SEM image of the platinum-based amorphous alloy porous substrate having the nano-sized ruthenium supported on the surface thereof is shown in fig. 2, and it can be seen that the nano-sized ruthenium has been successfully deposited on the surface of the platinum-based amorphous alloy substrate having the nano-sized porous structure. The XRD pattern of the platinum-based amorphous alloy porous substrate with the nano-scale ruthenium supported on the surface thereof is shown in fig. 3, and as can be seen from fig. 3, the X-ray diffraction pattern after electrodeposition is compared with the diffraction peak of standard Ru (ruthenium) in the database, and it is also confirmed that the metallic ruthenium is successfully deposited on the surface of the platinum-based amorphous alloy substrate with the nano-scale porous structure.
And S5, placing the platinum-based amorphous alloy porous substrate with the surface loaded with the nano-scale ruthenium into an annealing furnace for heat treatment, sealing by using a sealing plug, and sealing, wherein the heat treatment temperature is 420 ℃, and the heat treatment time is 180min, so that the platinum-based amorphous alloy porous catalyst with the surface loaded with the nano-scale ruthenium oxide is obtained. The EDS of the platinum-based amorphous alloy porous catalyst with the surface loaded with nanoscale ruthenium oxide is shown in fig. 4, where the first is an electron micrograph, the second is an oxygen distribution diagram, and the third is a ruthenium distribution diagram, and it can be seen from the diagrams that the distributions of ruthenium and oxygen are substantially coincident, demonstrating that nanoscale metal ruthenium has been successfully oxidized to nanoscale ruthenium oxide.
Example 2
A platinum-based amorphous alloy porous catalyst for chlorine evolution reaction comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The pore diameter of the porous structure of the platinum-based amorphous alloy substrate is 100nm, and the particles of the nano ruthenium oxideThe diameter is 250nm.
The preparation method comprises the following steps:
s1, placing platinum, nickel and copper in a copper cavity of a WK series vacuum arc furnace according to a mass ratio of 36:1, starting a mechanical pump, pumping the interior of the arc furnace to 5Pa or below, starting a molecular pump on the premise of low vacuum, and pumping high vacuum to 3 x 10 -3 And Pa, opening an argon valve, introducing a proper amount of argon, pressing an arc striking switch, striking an arc striking electric arc gun, and igniting a titanium ingot by using 120A current to suck oxygen so as to ensure that no oxygen exists in the furnace. And aligning the current to the copper cavity, adjusting the arc current to 100A, extinguishing the arc gun after the raw materials are completely melted, turning over by using a spoon, striking the arc gun again, repeating the subsequent steps, and repeating the melting for three to five times to uniformly fuse the raw materials together. The smelted master alloy containing platinum, nickel and copper and phosphorus with corresponding mass are loaded into a test tube (the mass ratio of platinum, nickel, copper and phosphorus is 36. And (3) carrying out electromagnetic induction melting on the sealed test tube by using a vacuum rapid quenching injection molding machine, regulating the current by stepping a pedal by 20A until the sample is completely melted, and uniformly mixing P (phosphorus) and the master alloy. Replacing new test tube, adding mother alloy of boron trioxide and induction smelting mixed P (phosphorus), induction smelting and purifying by using vacuum rapid quenching spray casting machine, and finally suction casting the mother alloy melted with phosphorus and purified in copper cavity of vacuum arc furnace to obtain platinum-based amorphous alloy bar (with Pt as component) 57.5 Cu 14.7 Ni 5.3 P 22.5 ) And cutting into a platinum-based amorphous alloy wafer with the thickness of 780 um and the diameter of 3 mm.
S2, placing the platinum-based amorphous alloy wafer into a mold, placing nano barium titanate particles (with the particle size of about 110 nm) above the platinum-based amorphous alloy wafer, and carrying out hot pressing in a vacuum environment, wherein the hot pressing temperature is 195 ℃, the vacuum degree is 7Pa, and the hot pressing pressure is 18kN, so that the platinum-based amorphous alloy wafer with the barium titanate particles on the surface layer is obtained.
S3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in 6mol/L hydrochloric acid solution for 11h, and completely dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure;
s4, placing the platinum-based amorphous alloy substrate with the nanoscale porous structure into a three-electrode system for electrodeposition, wherein in the three-electrode system, the working electrode is the platinum-based amorphous alloy substrate with the nanoscale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, the electrolyte is a ruthenium chloride-potassium chloride mixed solution, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.3mmol/L, the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.1mol/L, the electrodeposition voltage is-0.356V (relative to the voltage of a standard hydrogen electrode), and the electrodeposition time is 600S, so that the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface is obtained;
and S5, carrying out heat treatment on the platinum-based amorphous alloy porous substrate loaded with the nano-scale ruthenium on the surface, wherein the heat treatment temperature is 430 ℃, and the heat treatment time is 175min, so as to obtain the platinum-based amorphous alloy porous catalyst loaded with the nano-scale ruthenium oxide on the surface.
Example 3
A platinum-based amorphous alloy porous catalyst for chlorine evolution reaction comprises a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The aperture of the porous structure of the platinum-based amorphous alloy substrate is 200nm, and the particle size of the nanoscale ruthenium oxide is 380nm.
The preparation method comprises the following steps:
s1, placing platinum, nickel and copper in a copper cavity of a WK series vacuum arc furnace according to a mass ratio of 36:1, starting a mechanical pump, pumping the interior of the arc furnace to 5Pa or below, starting a molecular pump on the premise of low vacuum, and pumping high vacuum to 3 multiplied by 10 -3 And Pa, opening an argon valve, introducing a proper amount of argon, pressing down an arc starting switch, starting an arc gun, and igniting a titanium ingot by using 120A current to inhale oxygen so as to ensure that no oxygen exists in the furnace. Aligning the current to the copper cavity, adjusting the arc current to 100A, and extinguishing the arc when the raw materials are completely meltedAnd (3) turning over the arc gun by using a spoon, striking the arc gun again, repeating the subsequent steps, and melting for three to five times to uniformly fuse the raw materials. The smelted master alloy containing platinum, nickel and copper and phosphorus with corresponding mass are loaded into a test tube (the mass ratio of platinum, nickel, copper and phosphorus is 36. And (3) performing electromagnetic induction melting on the sealed test tube by using a vacuum rapid quenching spray casting machine, stepping a pedal to adjust the current to 20A until the sample is completely melted, and uniformly mixing P (phosphorus) and the master alloy. Replacing new test tube, adding mother alloy of boron trioxide and induction smelting mixed P (phosphorus), induction smelting and purifying by using vacuum rapid quenching spray casting machine, and finally suction casting the mother alloy melted with phosphorus and purified in copper cavity of vacuum arc furnace to obtain platinum-based amorphous alloy bar (with Pt as component) 57.5 Cu 14.7 Ni 5.3 P 22.5 ) And cutting into pieces of 5mm diameter platinum-based amorphous alloy with a thickness of 800 um.
S2, placing the platinum-based amorphous alloy wafer into a mold, placing nano barium titanate particles (the particle size is about 200 nm) above the platinum-based amorphous alloy wafer, and carrying out hot pressing in a vacuum environment, wherein the hot pressing temperature is 205 ℃, the vacuum degree is 10Pa, and the hot pressing pressure is 20kN, so that the platinum-based amorphous alloy wafer with the barium titanate particles on the surface layer is obtained.
S3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in 8mol/L hydrochloric acid solution for 10h, and completely dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure;
s4, placing the platinum-based amorphous alloy substrate with the nanoscale porous structure in a three-electrode system for electrodeposition, wherein in the three-electrode system, the working electrode is the platinum-based amorphous alloy substrate with the nanoscale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, the electrolyte is a ruthenium chloride-potassium chloride mixed solution, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.5mmol/L, the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixed solution is 0.15mol/L, the electrodeposition voltage is-0.356V (relative to the voltage of a standard hydrogen electrode), and the electrodeposition time is 800S, so that the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface is obtained;
and S5, carrying out heat treatment on the platinum-based amorphous alloy porous substrate loaded with the nano-scale ruthenium on the surface, wherein the heat treatment temperature is 450 ℃, and the heat treatment time is 150min, so as to obtain the platinum-based amorphous alloy porous catalyst loaded with the nano-scale ruthenium oxide on the surface.
Comparative example
The catalyst of the comparative example is commercial common ruthenium oxide, and the catalytic effect of the chlorine evolution reaction is detected by using the common ruthenium oxide catalyst. The specific operation is as follows:
drop coating of RuO 2 (ruthenium oxide) electrode: the prepared dripping slurry comprises the following raw materials: the concentration of each raw material in the slurry is 5mg/mL of ruthenium oxide, 700 uL/mL of ultrapure water, 280uL/mL of absolute ethyl alcohol and 20uL/mL of 5% Nafion aqueous solution (perfluorosulfonate polymer). And (3) treating the slurry in ultrasonic cleaning for 30 minutes before dripping to uniformly disperse the slurry, then dripping 30uL of the slurry on a glassy carbon electrode with the diameter of 5mm for three times, and airing to obtain the required dripping electrode. The performance of chlorine evolution reaction of a dripping electrode is tested by using a three-electrode system of the Chenghua CHI660 electrochemical workstation, the dripping electrode is a working electrode, a platinum sheet electrode is a counter electrode, a silver/silver chloride electrode is a reference electrode, an electrolyte is 3 mol/L sodium chloride solution, a timed current method is used for efficiency test, a voltage-efficiency-time diagram is shown in figure 8, and the curve in the diagram shows that the current density is 30 mA cm -2 Its catalytic efficiency for chlorine evolution reaction is only 44.8%.
The catalytic effect of chlorine evolution reaction is detected on the platinum-based amorphous alloy porous catalyst with the surface loaded with the nano-scale ruthenium oxide in the embodiment 3 of the invention. The operation is as follows: taking a piece of platinum-based amorphous alloy porous catalyst sample with the diameter of 5mm and the surface loaded with nano-scale ruthenium oxide, and adhering the catalyst sample to a straight line by using silver adhesiveOn a glassy carbon electrode with the diameter of 5mm, a working electrode with a platinum-based amorphous alloy porous catalyst with nano ruthenium oxide loaded on the surface is formed after the silver colloid is solidified. A standard three-electrode system is used, a silver-silver chloride electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, a glassy carbon electrode with a platinum-based amorphous alloy porous catalyst loaded with nanoscale ruthenium oxide on the surface is used as a working electrode, 3 mol/L sodium chloride solution is used as electrolyte, and the test is carried out by using a Chenhua CHI660 electrochemical workstation. Wherein the calculation formula of the concentration of the theoretical chlorine gas generation amount is as follows:
q in the formula is the amount of charge generated; l is the volume of the electrolyte; f is the faraday constant and the actual chlorine generation concentration is tested using a hash chlorine test apparatus.
As shown in fig. 5, for a voltage-efficiency diagram of the chlorine evolution reaction, the efficiency test time corresponding to each voltage is 150 s, and it can be known from the diagram that as the voltage rises, the generation efficiency of chlorine gas shows a rising trend, which indicates that the platinum-based amorphous alloy porous catalyst with the surface loaded with the nano-scale ruthenium oxide has a better catalytic effect on the chlorine evolution reaction, and as the voltage rises, the efficiency of chlorine gas generation also increases, and it can be understood that the porous structure on the platinum-based amorphous alloy can greatly increase the specific surface area, and realize more active sites to increase the efficiency of the chlorine evolution reaction; meanwhile, the electro-deposition ruthenium oxide is in a nano level, the catalytic efficiency is high, the performance is stable, the reaction efficiency of chlorine evolution reaction is improved, and the generation amount of chlorine is increased.
The platinum-based amorphous alloy porous catalyst with the surface loaded with the nano-scale ruthenium oxide in example 3 of the invention is subjected to linear potential scanning (linear scanning voltammetry, LSV) in 3 mol/L sodium chloride solution and 3 mol/L sodium nitrate solution respectively, the LSV curve is shown in FIG. 6, only nitrate radical exists in sodium nitrate, so that the generation of oxygen evolution reaction is replaced by the LSV curve, and as can be seen from the curve in FIG. 6, the generation potential of the chlorine evolution reaction is far earlier than that of the oxygen evolution reaction, and the current density is 10mA/cm 2 When the voltage is 1.4-1.6V, the overpotential is only 97 mV, and the chlorine evolution reaction is far more than the oxygen evolution reaction, further explaining the inventionThe catalyst has excellent catalytic effect, and chlorine evolution reaction can be carried out at extremely low voltage, so that energy can be saved. Meanwhile, as shown in fig. 7, which is a voltage-efficiency-time diagram of the chlorine evolution reaction, it can be known from curves in the diagram that the catalytic efficiency of the platinum-based amorphous alloy porous catalyst can be stably maintained at about 65% in the catalytic chlorine evolution reaction process of 200 hours, the catalytic efficiency is high and the long-term effect is achieved; when the current density is 30 mA/cm 2 In the process, the voltage-time diagram shows that the voltage is not obviously improved or fluctuated within 200 hours, so that the platinum-based amorphous alloy nano-porous catalyst prepared by the method is high in efficiency and has overlong stability in the application of catalyzing chlorine evolution.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields will be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction is characterized by comprising the following steps:
s1, mixing platinum, nickel, copper and phosphorus in proportion, smelting, performing suction casting, and cutting to obtain a platinum-based amorphous alloy sheet;
s2, placing nano barium titanate particles on the platinum-based amorphous alloy sheet, and carrying out hot pressing in a vacuum environment to embed the nano barium titanate particles into the surface of the platinum-based amorphous alloy sheet to obtain the platinum-based amorphous alloy sheet with barium titanate particles on the surface layer;
s3, soaking the platinum-based amorphous alloy sheet with the barium titanate particles on the surface layer in an acid solution, and dissolving the barium titanate particles embedded in the platinum-based amorphous alloy sheet to obtain a platinum-based amorphous alloy substrate with a nano-scale porous structure;
s4, carrying out electrodeposition on the platinum-based amorphous alloy substrate with the nanoscale porous structure, wherein the electrolyte of the electrodeposition is a ruthenium chloride-potassium chloride mixed solution, so as to obtain the platinum-based amorphous alloy porous substrate with the nanoscale ruthenium loaded on the surface;
and S5, carrying out heat treatment on the platinum-based amorphous alloy porous substrate loaded with the nano-scale ruthenium on the surface to obtain the platinum-based amorphous alloy porous catalyst loaded with the nano-scale ruthenium oxide on the surface.
2. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein in the step S1, the mass ratio of platinum, nickel, copper and phosphorus is 36 57.5 Cu 14.7 Ni 5.3 P 22.5 。
3. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 2, wherein in the step S1, a platinum-based amorphous alloy rod is obtained after suction casting and cut into platinum-based amorphous alloy discs, and the platinum-based amorphous alloy discs have a thickness of 750-800um and a diameter of 2-5mm.
4. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein in the step S2, the particle size of the nano-sized barium titanate particles is 30-200nm, the hot pressing temperature is 190-205 ℃, the vacuum degree is 5-10Pa, and the hot pressing pressure is 15-20kN.
5. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein in step S3, the acidic solution is a hydrochloric acid solution of 4-8mol/L, and the reaction soaking time is 10-12h.
6. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein in step S4, the electrodeposition electrode system is a three-electrode system, the working electrode is a platinum-based amorphous alloy substrate with a nano-scale porous structure, the counter electrode is a platinum sheet, the reference electrode is a silver chloride electrode, the electrodeposition voltage is-0.356V relative to a standard hydrogen electrode, and the electrodeposition time is 500-800S.
7. The method of claim 1, wherein in step S4, the concentration of ruthenium chloride in the ruthenium chloride-potassium chloride mixture is 0.1 to 0.5mmol/L, and the concentration of potassium chloride in the ruthenium chloride-potassium chloride mixture is 0.05 to 0.15 mol/L.
8. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein in step S5, the heat treatment temperature is 420 to 450 ℃ and the heat treatment time is 150 to 180min.
9. The method for preparing a platinum-based amorphous alloy porous catalyst for chlorine evolution reaction according to claim 1, wherein the particle size of the ruthenium oxide supported on the surface is 140-400nm.
10. A platinum-based amorphous alloy porous catalyst for chlorine evolution reaction, which is obtained by the preparation method of any one of claims 1 to 9, and is characterized by comprising a platinum-based amorphous alloy substrate with a nano-scale porous structure and nano-scale ruthenium oxide loaded on the surface of the platinum-based amorphous alloy substrate, wherein the platinum-based amorphous alloy substrate is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 The pore diameter of the porous structure of the platinum-based amorphous alloy substrate is 30-200nm, and the particle size of the nano ruthenium oxide is 140-400nm.
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