CN109161926B - Iridium-based solid solution perovskite catalyst SrTi (Ir) O3And application thereof in electrocatalytic water cracking oxygen production - Google Patents

Iridium-based solid solution perovskite catalyst SrTi (Ir) O3And application thereof in electrocatalytic water cracking oxygen production Download PDF

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CN109161926B
CN109161926B CN201811193533.0A CN201811193533A CN109161926B CN 109161926 B CN109161926 B CN 109161926B CN 201811193533 A CN201811193533 A CN 201811193533A CN 109161926 B CN109161926 B CN 109161926B
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邹晓新
梁宵
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Hefei Conservation Of Momentum Green Energy Co ltd
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Abstract

Iridium-based solid solution perovskite catalyst SrTi (Ir) O3And the application thereof in the production of oxygen by electrocatalysis water cracking, belonging to the field of inorganic functional materials. Uniformly mixing a strontium source, an organic polybasic acid, a titanium source, an iridium source, an organic polyhydric alcohol and water in different proportions in a water bath, heating to evaporate water, fully calcining, and finally carrying out acid treatment to obtain solid solution perovskite catalysts SrTi (Ir) O with different iridium contents3. Using classical perovskite SrTiO3Induced SrIrO3Synthesized in the presence of increased SrIrO3The specific surface area is increased, and the dosage of the iridium noble metal in the system is reduced to a greater extent. Meanwhile, the titanium at the B site can weaken the oxygen adsorption energy of iridium at the active sites of the rest B sites, and the p-band center of oxygen can be closer to the Fermi level, so that the performance of the catalyst for electrocatalysis of acidic water oxidation is improved finally. Wherein the electrocatalytic acidic water oxidation activity is best SrTi (Ir) O3(Ir-29 percent) and the current density can reach 10mA/cm only by an overpotential of 248mV2。

Description

Iridium-based solid solution perovskite catalyst SrTi (Ir) O3And application thereof in electrocatalytic water cracking oxygen production
Technical Field
The invention belongs to the field of inorganic functional materials, and particularly relates to an iridium-based solid solution perovskite catalyst and application thereof in electrocatalytic water cracking oxygen production.
Background
After the twenty-first century, environmental pollution and energy crisis become two major problems facing all mankind, so that the development of energy storage modes and the research of conversion processes become the key points for developing clean and renewable energy. The oxygen generation reaction (OER) is an important half-reaction in the water splitting reaction, but its slow reaction kinetics greatly hinders its widespread use. This problem is particularly pronounced in acidic water splitting systems, which typically require a large overpotential to achieve the desired current density, and which also results in a severe loss of overall efficiency of water splitting. At the same time, under the oxidation conditions in an acidic medium, most compounds having oxygen-generating activity cannot exist stably. At present, the acid electricity generally accepted by peopleThe most common catalytic oxygen-generating catalysts are noble metal oxides, e.g. IrO2，RuO2However, the development and utilization of noble metal oxides are greatly limited by their scarce resources and high cost, which also prompts people to continuously search for acid water oxidation catalytic materials capable of reducing the cost.
The perovskite-type composite oxide has been actively studied in various fields in recent years, and the rapid development thereof in the field of catalysis has been attracting much attention. The perovskite type composite oxide is usually formed by ABO3It is shown that the a ion is usually an alkali metal or alkaline earth metal having a large radius, and coordinates with 12 oxygen atoms, thereby greatly stabilizing the perovskite structure. The B ion is generally a transition metal with a small radius, coordinated with 6 oxygens to form BO6Octahedron. During the catalytic process, the B site assumes the main catalytic role. In recent years, perovskite catalysts are superior in research direction of electrocatalytic water cracking due to the variability and stability. For example, in acidic water oxidation catalysis, IrOx/SrIrO3(Science 2016 volume 353, 1011 pages) has high intrinsic activity. However, perovskite SrIrO3Is not SrIrO3The most stable crystal phase, the dielectric stability of which brings great challenges to its synthesis, often needs to adopt the methods of high-temperature high-pressure synthesis and template extension growth to synthesize perovskite SrIrO3Pure phase. Meanwhile, SrIrO3The amount of medium Ir used may be further reduced. In response to the above problems, we thought to utilize the classic perovskite SrTiO3Induced perovskite SrIrO3The catalyst grows to be formed under normal pressure (101.325kPa) and at lower temperature (600 ℃), thereby greatly improving the structural stability and further reducing the content of noble metal in the catalyst. In the process of testing the catalytic activity of the perovskite, the formed iridium-based solid solution perovskite is found to have extremely high activity and stability in the aspect of catalyzing the oxidation of acidic water, so that the win-win effect of cost and activity is realized, and the perovskite has a wide development prospect.
Disclosure of Invention
The invention aims to research and develop a high-activity acidic water oxidation catalyst, synthesizes a series of iridium-based solid solution perovskite catalysts with different iridium contents, and has appearanceIs an adhesive nano-sheet with the diameter of 30-70 nm and the thickness of 5-15 nm, has ultrahigh acidic water oxidation catalytic activity and can be used for preparing a nano-sheet with the current density of 10mA/cm2Stably catalyzing for more than 50h under the condition of (1); due to perovskite SrIrO3In a metastable state, the conventional synthesis method is high-temperature high-pressure synthesis or template extension growth, and in the invention, the classical perovskite SrTiO is utilized3Induced perovskite SrIrO3Growing to realize the synthesis of SrIrO-containing at normal pressure (101.325kPa) and at low temperature (600-800℃)3Solid solution perovskite of (a); simultaneously adding a titanium source and an iridium source, and realizing the synthesis of a series of iridium-based solid solution perovskite SrTi (Ir) O with different proportions by regulating and controlling the input amount of reactant raw materials of the titanium source and the iridium source3And the proportion of each element in the perovskite can be accurately controlled.
The iridium-based solid solution perovskite catalyst provided by the invention is prepared by mixing a strontium source, a titanium source, an iridium source, organic polyol, organic polyacid and water in water bath at different proportions, heating and evaporating to dryness, then calcining and evaporating to dryness reactants, finally soaking the calcined product in 0.5-2 mol/L acid for 3-10 h, and fully washing and drying to obtain a corresponding compound.
In order to synthesize solid solution perovskites with different iridium contents, the types and the input amount of different reactant raw materials are regulated and controlled, and the method comprises the following specific steps:
(1) preparation of mixed solution: weighing naMolar strontium source, nbMolar organic polybasic acid, ncMolar titanium source, ndMolar iridium source, inorganic raw material naMolar strontium source, ndMolar source of iridium and ncDissolving a molar titanium source in distilled water to obtain a water phase; organic raw material nbDissolving a molar organic polybasic acid in organic polyol to obtain an organic phase; mixing the water phase and the organic phase, and then placing the mixture in a water bath (60-90 ℃) to heat and stir for more than 3 hours, so that the mixture is uniformly mixed to obtain a transparent mixed solution;
(2) drying and calcining: placing the mixed solution obtained in the step (1) in an environment of 100-200 ℃ to evaporate water, cooling to room temperature, directly heating and raising the temperature in a gradient manner, calcining at the temperature of 600-800 ℃ for 6-26 h, and naturally cooling to room temperature to obtain a powdery product;
(3) acid treatment and drying: and (3) soaking the powdery product obtained in the step (2) in 0.5-2 mol/L acid, standing for 5-10 h, then fully washing with distilled water and ethanol, centrifuging, and drying at 80-120 ℃ to finally obtain the iridium-based solid solution perovskite catalyst.
The strontium source in the above method is a strontium-containing compound soluble in water or organic polyol, and further includes strontium nitrate, strontium chloride, strontium hydroxide, strontium carbonate, and the like, but is not limited thereto.
The titanium source in the above method is a titanium-containing compound soluble in water or an organic polyol, and further includes tetrabutyl titanate, titanium trichloride, titanium tetrachloride, and the like, but is not limited thereto.
The iridium source in the above method is an iridium-containing compound soluble in water or an organic polyol, and further potassium hexachloroiridium (IV), potassium hexachloroiridium (III), iridium chloride, chloroiridic acid, and the like, but is not limited thereto.
The organic polyol solvent used in the above method is ethylene glycol, glycerol, etc., but is not limited thereto.
The organic polybasic acid in the above method is a polycarboxylic acid compound soluble in water or an organic polyhydric alcohol, and further includes citric acid, tartaric acid, oxalic acid, and the like, but is not limited thereto.
In the above process, nb:(nc+nd)＝2～20:1，na:(nc+nd) The iridium-based solid solution perovskite can be synthesized by adjusting the input amount of each reactant appropriately to 2-14: 1.
In the above process, ncAnd ndAccording to the molar ratio of titanium to iridium in the product to be obtained, in general nc:ndAnd (3) the feeding ratio is 0.5-4: 1, namely the actual ratio of titanium to iridium in the obtained product.
In the above method, the acid used in the acid treatment process is a common inorganic acid in a laboratory, and further includes hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and the like, but is not limited thereto.
In the above method, the solvent of the aqueous phase solution is distilled water, and the amount of the solvent is generally 5mL or more, and the inorganic salt can be sufficiently dissolved.
In the method, in the step (2), the temperature is directly raised to 600-800 ℃ at the speed of 0.5-3 ℃/min; the gradient temperature rise is carried out by raising the temperature to 180-220 ℃ at the speed of 0.5-3 ℃/min for 5-7 h, raising the temperature to 280-320 ℃ for 5-7 h, raising the temperature to 480-520 ℃ for 2-4 h and raising the temperature to 580-620 ℃ for 5-7 h.
Advantageous effects
1. The synthesis operation is simple, the synthesis environment is mild, the ratio of titanium to iridium in the synthesized product can be accurately regulated, the repeatability is good, and the mass production can be realized.
2. The obtained iridium-based solid solution perovskite has a nano-scale size, the size of a product is far smaller than that of a film body material or a block material in the conventional synthetic method, and the specific surface area of the material is greatly increased.
3. The obtained iridium-based solid solution perovskite reduces the using amount of iridium noble metal in the system to a greater extent, wherein the molar percentage of iridium in the catalyst with the highest effective acidic water oxidation activity accounts for only 29 percent of the total amount of the catalyst.
4. In the perovskite structure, the titanium existing at the B site can weaken the oxygen adsorption energy of iridium at the active sites of the rest B sites, thereby being beneficial to oxygen desorption in a catalytic mechanism and promoting the dynamics of oxygen generation reaction, thereby improving the activity of the catalyst.
5. In the obtained strontium iridate-containing solid solution perovskite, the existence of titanium can promote the p-band center of oxygen on the basis of strontium iridate to be closer to a Fermi level, so that the performance of the catalyst is improved.
6. Thanks to the stable framework of the classic perovskite strontium titanate, the stability of the strontium iridate-containing solid solution perovskite is remarkably improved, and the catalytic material can stably exist in an acidic environment or under the oxidation condition of acidic water and can continuously catalyze for more than 50 hours.
Drawings
FIG. 1: iridium-based solid solution perovskite SrTi (Ir) O in example 13(molar fraction)Several Ir-19%) of the X-ray diffraction (XRD) spectrum (panel a); iridium-based solid solution perovskite SrTi (Ir) O3(molar fraction Ir-29%) X-ray diffraction (XRD) pattern (panel B); iridium-based solid solution perovskite SrTi (Ir) O3(mole fraction Ir-42%) X-ray diffraction (XRD) pattern (panel C); iridium-based solid solution perovskite SrTi (Ir) O3(molar fraction Ir-51%) of the X-ray diffraction (XRD) pattern (Panel D).
FIG. 2: iridium-based solid solution perovskite SrTi (Ir) O in example 13(Ir-19%) Transmission Electron Microscopy (TEM) picture (FIG. A); iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) Transmission Electron Microscopy (TEM) picture (FIG. B); iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) Transmission Electron Microscopy (TEM) picture (fig. C); iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) Transmission Electron Microscopy (TEM) picture (FIG. D).
FIG. 3: iridium-based solid solution perovskite SrTi (Ir) O with different iridium contents (Ir-19%, Ir-29%, Ir-42%, Ir-51%) obtained in example 13At 0.21mg/cm2The supported amount of (A) was dropped on a glassy carbon electrode at 0.1M HClO4The electrocatalytic cracking water in the electrolyte generates oxygen performance, namely an oxygen generation polarization curve.
FIG. 4: iridium-based solid solution perovskite SrTi (Ir) O with different iridium contents (Ir-19%, Ir-29%, Ir-42%, Ir-51%) obtained in example 13At 0.21mg/cm2The supported amount of (A) was dropped on a glassy carbon electrode at 0.1M HClO4Electrocatalytic stability curve in electrolyte, i.e. the curve of potential variation with time.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the following examples. It will be apparent to those skilled in the art that variations or modifications of the present invention can be made without departing from the spirit and scope of the invention, and these variations or modifications are also within the scope of the invention.
Example 1
Iridium-based solid solution perovskite catalyst SrTi (Ir) O3(Ir-19%) preparation
420mg (1.985mmol) of strontium nitrate, 280mg (1.332mmol) citric acid and 80mg (0.166 mmol) potassium hexachloroiridate (IV) are placed in 10mL distilled water and stirred well to give a dark brown transparent solution called solution a; 225mg (0.664mmol) of tetrabutyltitanate are transferred into 4mL of ethylene glycol and stirred well until a clear, colorless and transparent solution appears, referred to as solution b. The solution a is slowly transferred into the solution b and placed in a water bath at 70 ℃ to be heated and stirred for 3 hours, and the solution is brownish red and transparent. Subsequently, the solution was left at 120 ℃ for 12h to ensure that the water was evaporated to dryness. In this example, na:nb:(nc+nd)＝2.4：1.6：1；nc：nd4: 1. The evaporated solid sample is heated for 6h, 6h, 3h and 6h at 200 ℃, 300 ℃, 500 ℃ and 600 ℃ respectively at a heating rate of 1.7 ℃/min. After natural cooling to room temperature, the product was ground well to give a brownish black powder. Soaking the catalyst for 6 hours by using 1mol/L hydrochloric acid, cleaning the catalyst by using distilled water and ethanol in sequence, centrifuging the solution, transferring the solution to an oven at 80 ℃, drying the dried product, and collecting sample powder, namely the iridium-based solid solution perovskite catalyst SrTi (Ir) O3(Ir-19%) and the mass of the product was 0.4 g.
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) preparation
420mg (1.985mmol) of strontium nitrate, 280mg (1.332mmol) of citric acid and 80mg (0.166 mmol) of potassium hexachloroiridium (IV) are placed in 10mL of distilled water and stirred well to give a dark brown transparent solution called solution a; 113mg (0.332mmol) of tetrabutyltitanate are transferred into 4mL of ethylene glycol and stirred well until a clear, colorless and transparent solution appears, referred to as solution b. The solution a is slowly transferred into the solution b and placed in a water bath at 70 ℃ to be heated and stirred for 3 hours, and the solution is brownish red and transparent. Subsequently, the solution was left at 120 ℃ for 12h to ensure that the water was evaporated to dryness. In this example, na:nb:(nc+nd)＝4：2.7：1；nc：nd2: 1. The evaporated solid sample is heated for 6h, 6h, 3h and 6h at 200 ℃, 300 ℃, 500 ℃ and 600 ℃ respectively at a heating rate of 1.7 ℃/min. After natural cooling to room temperature, the product was ground well to give a brownish black powder. Soaking in 1mol/L hydrochloric acid for 6 hr, washing with distilled water and ethanol, and separatingTransferring the heart to an oven at 80 ℃ for drying, and collecting sample powder to obtain the iridium-based solid solution perovskite catalyst SrTi (Ir) O3(Ir-29%) and the product mass was 0.3 g.
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) preparation
420mg (1.985mmol) of strontium nitrate, 280mg (1.332mmol) of citric acid and 80mg (0.166 mmol) of potassium hexachloroiridium (IV) are placed in 10mL of distilled water and stirred well to give a dark brown transparent solution called solution a; 57mg (0.116mmol) of tetrabutyltitanate are transferred into 4mL of ethylene glycol and stirred well until a clear, colorless and transparent solution is obtained, which is referred to as solution b. The solution a is slowly transferred into the solution b and placed in a water bath at 70 ℃ to be heated and stirred for 3 hours, and the solution is brownish red and transparent. Subsequently, the solution was left at 120 ℃ for 12h to ensure that the water was evaporated to dryness. In this example, na:nb:(nc+nd)＝6：4：1；nc：nd1: 1. The evaporated solid sample is heated for 6h, 6h, 3h and 6h at 200 ℃, 300 ℃, 500 ℃ and 600 ℃ respectively at a heating rate of 1.7 ℃/min. After natural cooling to room temperature, the product was ground well to give a brownish black powder. Soaking the catalyst for 6 hours by using 1mol/L hydrochloric acid, cleaning the catalyst by using distilled water and ethanol in sequence, centrifuging the solution, transferring the solution to an oven at 80 ℃, drying the dried product, and collecting sample powder, namely the iridium-based solid solution perovskite catalyst SrTi (Ir) O3(Ir-42%) and the product mass was 0.2 g.
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) preparation
420mg (1.985mmol) of strontium nitrate, 280mg (1.332mmol) of citric acid and 80mg (0.166 mmol) of potassium hexachloroiridium (IV) are placed in 10mL of distilled water and stirred well to give a dark brown transparent solution called solution a; 29mg (0.058mmol) of tetrabutyltitanate are transferred into 4mL of ethylene glycol and stirred well until a clear, colorless and transparent solution is obtained, which is referred to as solution b. The solution a is slowly transferred into the solution b and placed in a water bath at 70 ℃ to be heated and stirred for 3 hours, and the solution is brownish red and transparent. Subsequently, the solution was left at 120 ℃ for 12h to ensure that the water was evaporated to dryness. In this example, na:nb:(nc+nd)＝9：6：1；nc：nd1: 2. The evaporated solid sample is heated for 6h, 6h, 3h and 6h at 200 ℃, 300 ℃, 500 ℃ and 600 ℃ respectively at a heating rate of 1.7 ℃/min. After natural cooling to room temperature, the product was ground well to give a brownish black powder. Soaking the catalyst for 6 hours by using 1mol/L hydrochloric acid, cleaning the catalyst by using distilled water and ethanol in sequence, centrifuging the solution, transferring the solution to an oven at 80 ℃, drying the dried product, and collecting sample powder, namely the iridium-based solid solution perovskite catalyst SrTi (Ir) O3(Ir-51%) and the mass of the product was 0.1 g.
Carrying out electrocatalytic water cracking Oxygen Evolution (OER) property test on the material prepared by the method in a standard three-electrode electrolytic cell; the product of the invention is mixed in 10-50% naphthol isopropanol solution, the solution is dropped on a glassy carbon electrode as a working electrode in an electrolytic cell, and the loading amount of a catalyst on the working electrode is ensured to be 0.21mg/cm2(ii) a The reference electrode is a saturated calomel electrode, the counter electrode is a platinum wire, and the electrolyte is 0.1M HClO4. It should be noted that all potentials obtained by taking saturated calomel as a reference electrode in an electrocatalysis test are converted into reversible hydrogen electrode potentials in a property diagram, and an external power supply is a main battery of an electrochemical working station.
Some structural and performance studies were performed on the materials prepared by the above methods. FIG. 1A shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) X-ray diffraction (XRD) pattern; FIG. 1B shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) X-ray diffraction (XRD) pattern; FIG. 1C shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) X-ray diffraction (XRD) pattern; FIG. 1D shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) X-ray diffraction (XRD) pattern. It can be seen that the iridium-based solid solution perovskite SrTi (Ir) O with different iridium contents3All have classic perovskite diffraction peaks and are perovskite solid solution pure phases. At the same time, it can be observed that as the iridium content increases, the XRD diffraction peak shifts to a low angle direction, indicating that an increase in iridium content causes lattice expansion.
FIG. 2A shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) Transmission Electron Microscopy (TEM) pictures; FIG. 2BTo obtain iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) Transmission Electron Microscopy (TEM) pictures; FIG. 2C shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) Transmission Electron Microscopy (TEM) pictures; FIG. 2D shows the obtained iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) Transmission Electron Microscopy (TEM) pictures. Solid solution perovskites with different iridium contents can be observed to have basically consistent appearances, namely the adhered nanosheets with the diameter of 30-70 nm.
FIG. 3 shows the product of the present invention as an acidic water oxidation catalyst in 0.1M HClO4Water splitting Oxygen Evolution (OER) polarization curve in solution. FIG. 3A shows SrTi (Ir) O3(Ir-19%) and the water oxidation current density can reach 10mA/cm when the overpotential is 300mV2(ii) a FIG. 3B shows SrTi (Ir) O3(Ir-29%) and the OER polarization curve has the water oxidation current density reaching 10mA/cm when the overpotential is 247mV2(ii) a FIG. 3C shows SrTi (Ir) O3(Ir-42%) and the water oxidation current density can reach 10mA/cm when the overpotential is 268mV2(ii) a FIG. 3D shows SrTi (Ir) O3(Ir-51%) and the OER polarization curve has the water oxidation current density reaching 10mA/cm when the overpotential is 273mV2. As can be seen, the above four ratios of the iridium-based solid solution perovskite SrTi (Ir) O3The catalyst has good catalytic activity for oxidizing acidic water, wherein the solid solution perovskite catalytic property with the Ir content of 29 percent is optimal.
FIG. 4 shows the product of the present invention as an acidic water oxidation catalyst in 0.1M HClO4Electrocatalytic stability curve in solution (v-t), i.e. the curve of the potential variation with time. FIG. 4A shows SrTi (Ir) O3(Ir-19%) the current density in water oxidation was 10mA/cm2A v-t curve of time; FIG. 4B shows SrTi (Ir) O3(Ir-29%) the current density in water oxidation was 10mA/cm2A v-t curve of time; FIG. 4C shows SrTi (Ir) O3(Ir-42%) at a current density of 10mA/cm in water oxidation2A v-t curve of time; FIG. 4D shows SrTi (Ir) O3(Ir-51%) current density in water oxidation of 10mA/cm2V-t curve of time. As can be seen, the above four ratios of the iridium-based solid solution perovskite SrTi (Ir) O3The electrocatalytic stability of the catalyst is maintained in the 50h catalysis processThe stability is better, and the solid solution perovskite catalytic property with the Ir content of 29 percent is optimal.
Example 2
Same as example 1 except that an iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) reduction of 420mg (1.985mmol) of strontium nitrate to 350mg (1.654mmol) in the preparation ofa：nb：(nc+nd) 2: 1.6: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-19％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) 420mg (1.985mmol) of strontium nitrate was reduced to 210mg (0.993mmol) in the preparation, when na：nb：(nc+nd) 2: 2.7: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-29％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) the amount of 420mg (1.985mmol) of strontium nitrate was reduced to 140mg (0.661mmol) in the preparation of na：nb：(nc+nd) 2: 4:1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-42％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) the amount of 420mg (1.985mmol) of strontium nitrate was reduced to 93mg (0.441mmol) in the preparation of na：nb：(nc+nd) 2: 6: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-51％)。
Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) the current density can reach 10mA/cm at the overpotential of 300mV2；SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 247mV2；SrTi(Ir)O3(Ir-42%) the current density can reach 10mA/cm at an overpotential of 268mV2； SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at an overpotential of 273mV2。
Example 3
Same as example 1 except that an iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) increase in preparation 420mg (1.985mmol) of strontium nitrate to 3500mg (16.540mmol) when na：nb：(nc+nd) 20: 1.6: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-19％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) preparation 420mg (1.985mmol) of strontium nitrate was increased to 2100mg (9.925mmol) when na：nb：(nc+nd) 20: 2.7: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-29％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) the amount of 420mg (1.985mmol) of strontium nitrate in the preparation was increased to 1400mg (6.620mmol), when na：nb：(nc+nd) 20: 4:1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-42％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) the amount of 420mg (1.985mmol) of strontium nitrate was increased to 933mg (4.410mmol) in the preparation, when na：nb：(nc+nd) 20: 6: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-51％)。
Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) the current density can reach 10mA/cm at the overpotential of 300mV2；SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 247mV2；SrTi(Ir)O3(Ir-42%) the current density can reach 10mA/cm at an overpotential of 268mV2； SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at an overpotential of 273mV2。
Example 4
Same as example 1 except that an iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) 280mg (1.332mmol) of citric acid were reduced to 350mg of (A)1.655mmol) of the reaction solution, in which case na：nb：(nc+nd) 2.4: 2: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-19％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) 280mg (1.332mmol) of citric acid were reduced to 207mg (0.987mmol) in the preparation of this, when na：nb：(nc+nd) 4: 2: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-29％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) the amount of 280mg (1.332mmol) strontium citrate was reduced to 140mg (0.666mmol) in the preparation of na：nb：(nc+nd) 6: 2: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-42％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) the amount of 280mg (1.332mmol) strontium citrate in the preparation was reduced to 93mg (0.444mmol) when na：nb：(nc+nd) 9: 2: 1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-51％)。
Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) the current density can reach 10mA/cm at the overpotential of 300mV2；SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 247mV2；SrTi(Ir)O3(Ir-42%) the current density can reach 10mA/cm at an overpotential of 268mV2； SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at an overpotential of 273mV2。
Example 5
Same as example 1 except that an iridium-based solid solution perovskite SrTi (Ir) O3(Ir-19%) 280mg (1.332mmol) of citric acid were increased in the preparation to 2450mg (11.66mmol) when na：nb：(nc+nd) 2.4: 14:1, the amounts and conditions of the other reactants are unchanged, and the product obtained isSrTi(Ir)O3(Ir-19％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-29%) increase 280mg (1.332mmol) of citric acid to 1452mg (6.907mmol) in the preparation, when na：nb：(nc+nd) 4: 14:1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-29％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-42%) the amount of 280mg (1.332mmol) strontium citrate was increased to 980mg (4.662mmol) in the preparation of na：nb：(nc+nd) 6: 14:1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-42％)。
Iridium-based solid solution perovskite SrTi (Ir) O3(Ir-51%) the amount of 280mg (1.332mmol) of strontium citrate was increased to 653mg (3.108mmol) in the preparation of na：nb：(nc+nd) 9: 14:1, the amounts and conditions of the other reactants are unchanged, and SrTi (Ir) O is obtained3(Ir-51％)。
Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) the current density can reach 10mA/cm at the overpotential of 300mV2；SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 247mV2；SrTi(Ir)O3(Ir-42%) the current density can reach 10mA/cm at an overpotential of 268mV2； SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at an overpotential of 273mV2。
Example 6
The same procedure as in example 1 was repeated except that the calcination was changed from the gradient temperature to the direct temperature. Directly heating to 600 ℃ from room temperature, calcining for 6h, and keeping the heating rate unchanged at 2 ℃/min. Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) the current density can reach 10mA/cm at the overpotential of 300mV2； SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 247mV2； SrTi(Ir)O3(Ir-42%) at overpotentialAt 268mV, the current density can reach 10mA/cm2； SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at an overpotential of 273mV2。
Example 7
Same as example 1 except that the acid catalyst electrolyte was 0.1M HClO4Solution was changed to 0.5M H2SO4And (3) solution. Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) when the over potential is 350mV, the current density can reach 10mA/cm2；SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 270mV2；SrTi(Ir)O3(Ir-42%) when the over potential is 260mV, the current density can reach 10mA/cm2；SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at the overpotential of 249mV2。
Example 8
Same as example 1, except that the supporting amount of the catalytic sample was increased to 0.42mg/cm2. Electrocatalytic performance of the obtained samples: SrTi (Ir) O3(Ir-19%) when the over potential is 350mV, the current density can reach 10mA/cm2； SrTi(Ir)O3(Ir-29%) the current density can reach 10mA/cm at the overpotential of 270mV2； SrTi(Ir)O3(Ir-42%) when the over potential is 260mV, the current density can reach 10mA/cm2；SrTi(Ir)O3(Ir-51%) the current density can reach 10mA/cm at the overpotential of 249mV2。

Claims (6)

1. Iridium-based solid solution perovskite catalyst SrTi (Ir) O3The method is characterized in that: which is prepared by the following steps of,
(1) preparation of mixed solution: weighing naMolar strontium source, nbMolar organic polybasic acid, ncMolar titanium source, ndDissolving a molar iridium source, a strontium source, a titanium source and an iridium source in distilled water to obtain a water phase; dissolving organic polybasic acid in organic polyalcohol to obtain an organic phase; mixing the water phase and the organic phase, placing the mixture in a water bath at the temperature of 60-90 ℃, heating and stirring for more than 3 hours, and uniformly mixing to obtain a mixtureA clear mixed solution; n isb:(nc+nd)＝2～20:1，na:(nc+nd)＝2～14:1，nc:nd＝0.5～4:1；
(2) Drying and calcining: placing the mixed solution obtained in the step (1) in an environment of 100-200 ℃ to evaporate water, cooling to room temperature, directly heating to 600-800 ℃ to calcine for 6-26 h, or cooling to room temperature and then carrying out gradient heating, wherein the gradient heating is carried out by heating to 180-220 ℃ at the speed of 0.5-3 ℃/min for 5-7 h, heating to 280-320 ℃ for 5-7 h, heating to 480-520 ℃ for 2-4 h and heating to 580-620 ℃ for 5-7 h;
(3) acid treatment and drying: soaking the powdery product obtained in the step (2) in 0.5-2 mol/L acid, standing for 5-10 h, then fully washing with distilled water and ethanol, centrifuging, and drying at 80-120 ℃ to finally obtain the iridium-based solid solution perovskite catalyst SrTi (Ir) O3。
2. An iridium-based solid solution perovskite catalyst SrTi (Ir) O as claimed in claim 13The method is characterized in that: the strontium source in the step (1) is strontium nitrate, strontium chloride, strontium hydroxide or strontium carbonate, the titanium source is tetrabutyl titanate, titanium trichloride or titanium tetrachloride, and the iridium source is potassium hexachloroiridium (IV), potassium hexachloroiridium (III), iridium chloride or chloroiridic acid.
3. An iridium-based solid solution perovskite catalyst SrTi (Ir) O as claimed in claim 13The method is characterized in that: the organic polyhydric alcohol solvent in the step (1) is ethylene glycol or glycerol, and the organic polybasic acid is citric acid, tartaric acid or oxalic acid.
4. An iridium-based solid solution perovskite catalyst SrTi (Ir) O as claimed in claim 13The method is characterized in that: in the step (2), the temperature is directly increased to 600-800 ℃ at the speed of 0.5-3 ℃/min; the gradient heating is performed by heating to 180-220 deg.C for 5-7 h at a rate of 0.5-3 deg.C/min, heating to 280-320 deg.C for 5-7 h, and heating to 480-520 deg.C for 2-EHeating for 4 hours and heating to 580-620 ℃ for 5-7 hours.
5. An iridium-based solid solution perovskite catalyst SrTi (Ir) O as claimed in claim 13The method is characterized in that: the acid in the step (3) is hydrochloric acid, sulfuric acid, nitric acid or perchloric acid.
6. An iridium-based solid solution perovskite catalyst SrTi (Ir) O as claimed in any one of claims 1 to 53The application in the production of oxygen by electrocatalytic water cracking.
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