CN110055555B - Oxygen evolution reaction catalyst and preparation method and application thereof - Google Patents
Oxygen evolution reaction catalyst and preparation method and application thereof Download PDFInfo
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- CN110055555B CN110055555B CN201810373870.1A CN201810373870A CN110055555B CN 110055555 B CN110055555 B CN 110055555B CN 201810373870 A CN201810373870 A CN 201810373870A CN 110055555 B CN110055555 B CN 110055555B
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Abstract
The invention provides an oxygen evolution reaction catalyst and a preparation method and application thereof. The oxygen evolution reaction catalyst is Y2‑xMxRu2O7Wherein M is Pr or Zn, and 0<x<2. The preparation method comprises preparing mixed solution of Y salt, M salt and Ru salt, adding metal ion complex into the mixed solution, and performing ligand reaction to prepare Y2Ru2O7Precursor, to said Y2Ru2O7And calcining the precursor and the like. The oxygen evolution reaction catalyst has low content of noble metal, high conductivity, high oxygen evolution catalytic activity and stable catalytic performance. And the preparation method has the advantages of easily controlled process conditions, good repeatability and high production efficiency. The oxygen evolution reaction catalyst can be applied to the preparation of oxygen evolution reaction electrodes, electrochemical devices and methods for generating hydrogen and oxygen from water, so that the efficiency of generating hydrogen and oxygen from water is improved, and the economic cost is reduced.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalysis, and particularly relates to an oxygen evolution reaction catalyst, and a preparation method and application thereof.
Background
The hydrogen is used as an important secondary energy source and has wide application prospect in future energy patterns of human society. The hydrogen is a clean and efficient energy carrier, the electricity-to-gas technology of the fuel cell is taken as a core node, intermittent renewable energy sources such as wind energy, solar energy and the like are used for generating electricity to prepare the hydrogen, and the large-scale clean energy conversion and storage requirements which are urgently needed can be met.
The Power to gas technology (often abbreviated as P2G or PtG) is a technology for converting electric Power into gas fuel, and is a new large-scale industrial hydrogen production technology by electrolyzing water, which is tightly combined with clean energy, especially intermittent renewable energy Power generation, which is emerging in recent years. The key of the electric gas conversion technology is to decompose water into oxygen and hydrogen by means of electrolysis of electricity. Hydrogen gas can be used as a means of storing energy, so this use is also referred to as hydrogen storage energy. Taking a wind power hydrogen production and energy storage technology as an example, the core idea is that when wind power is sufficient but the wind power cannot be on the net and the wind needs to be abandoned, the wind power is utilized to electrolyze water into hydrogen and oxygen, and the hydrogen is used as an energy carrier to be stored; when electric energy is needed, the stored hydrogen is converted into electric energy through different modes (an internal combustion engine, a fuel cell or other modes) and is transmitted to the Internet. Compared with the traditional alkaline water electrolysis hydrogen production technology, the Proton Exchange Membrane (PEM) water electrolysis has the advantages of high efficiency, high dynamic response speed, large current density working range, modular design, large or small scale and the like, and is more suitable for the energy storage technology of a smart power grid.
The Oxygen Evolution Reaction (OER) plays a key role in the water splitting process to produce hydrogen. Although the performance of electrolyzed water is improved by the efforts of researchers, the oxygen evolution reaction electrocatalyst still has problems of slow reaction kinetics and low stability in an acidic environment. Most catalytically active oxides are unstable under severe acidic conditions. Ruthenium (Ru) and iridium (Ir) oxides are the best two OER catalysts in acidic media. Ruthenium oxide has a high activity, but its long-term stability is not good, and iridium oxide is mostly used as a commercial OER catalyst currently in the mainstream. However, ruthenium and iridium are both precious metals and are expensive, and the use of ruthenium and iridium in large quantities is not beneficial to reducing the cost of the water electrolysis hydrogen production technology. In order to accelerate the industrial development of PEM water electrolysis hydrogen production, the reduction of the content of noble metal in the membrane electrode is particularly important. At present, the biggest challenge in the research of oxygen evolution reaction electrocatalysts is to find an electrocatalytic material which has high electrocatalytic activity and is not corroded under the acidity and high oxygen evolution potential.
In order to reduce the content of noble metals so as to realize the economic cost of the oxygen evolution reaction electrocatalyst, at present, the electrocatalyst with the content of noble metals reduced is also tried to be reduced, but in practical application, the problem that the conductivity of the oxygen evolution reaction electrocatalyst is relatively low along with the reduction of the content of noble metals, which is not beneficial to the electron transfer process in the catalytic reaction process, so that the catalytic activity is not high is found.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an oxygen evolution reaction catalyst, a preparation method and an application thereof, so as to solve the technical problems that the existing oxygen evolution reaction catalyst is high in cost and unsatisfactory in stability due to the adoption of noble metal, or the existing first noble metal content is low in conductivity.
In order to achieve the above object, according to one aspect of the present invention, there is provided an oxygen evolution reaction catalyst. The oxygen evolution reaction catalyst is Y2-xMxRu2O7Wherein M is Pr or Zn, and 0<x<2。
In another aspect of the invention, a method for preparing an oxygen evolution reaction catalyst is provided. The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
according to Y2-xMxRu2O7Neutralizing Y, M and Ru element molar ratio, dissolving Y salt, M salt and Ru salt, and preparing a mixed solution; wherein M is Pr or Zn, and 0<x<2；
Adding a metal ion complex into the mixed solution to perform ligand reaction, and then removing the solvent in the mixed solution to obtain a solid mixture;
and carrying out pulverization treatment on the solid mixture, and then calcining the solid mixture in an oxygen-containing atmosphere.
In yet another aspect of the present invention, an oxygen evolution reaction electrode is provided. The oxygen evolution reaction electrode comprises the oxygen evolution reaction catalyst or the oxygen evolution reaction catalyst prepared by the preparation method.
In yet another aspect of the present invention, there is provided an electrochemical device comprising an anode and a cathode, the anode being an oxygen evolution reaction electrode of the present invention.
In yet another aspect of the invention, a method of generating hydrogen and oxygen from water is provided. The method comprises the following steps:
providing water in contact with said anode comprised in the electrochemical device of the invention;
energizing the electrochemical device to convert at least a portion of the water to hydrogen and oxygen at the cathode and anode, respectively.
The oxygen evolution reaction catalyst adopts Y2-xMxRu2O7As the electrocatalyst, Y with M-doped pyrochlore structure is adopted2Ru2O7On one hand, the oxygen evolution reaction catalyst has good conductivity, effectively improves the catalytic activity and has high stability in an acid environment; on the other hand, the content of Y is effectively reduced, the content of noble metal is effectively reduced, and the economic cost is reduced.
According to the preparation method of the oxygen evolution reaction catalyst, Y, M and Ru-containing ion solution is adopted to prepare a precursor of the oxygen evolution reaction catalyst by a sol-gel method, and then calcination treatment is directly carried out. Therefore, the preparation method ensures that the oxygen evolution reaction catalyst obtained by calcination has low precious metal content, high conductivity and oxygen evolution catalytic activity, and can ensure stable catalytic performance of the oxygen evolution reaction catalyst. In addition, the preparation method has the advantages of easily controlled process conditions, good repeatability and high production efficiency, and effectively reduces the production cost.
The oxygen evolution reaction electrode and the electrochemical device have high oxygen evolution rate and low cost because the oxygen evolution reaction catalyst or the oxygen evolution reaction catalyst prepared by the preparation method contains.
The method for generating hydrogen and oxygen from water has high efficiency of generating hydrogen and oxygen from water and low economic cost because of adopting the electrochemical device.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is Y provided in example 11, which is provided in example 111.8Pr0.2Ru2O7And Y prepared in comparative example 112Ru2O7X-ray powder diffraction pattern of (a);
FIG. 2 is Y provided in example 111.8Pr0.2Ru2O7Y provided in comparative example 112Ru2O7Catalyst and commercial IrO as provided in comparative example 122A polarization graph of (a);
FIG. 3 is Y provided in example 121.85Zn0.15Ru2O7Y provided in comparative example 112Ru2O7Catalyst and commercial IrO as provided in comparative example 122A polarization graph of (a);
FIG. 4 is Y provided in example 111.8Pr0.2Ru2O7Y provided in comparative example 112Ru2O7Catalyst and commercial IrO as provided in comparative example 122Stability test chart of (1).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide an oxygen evolution reaction catalyst. The oxygen evolution reaction catalyst is Y2- xMxRu2O7Wherein M is Pr or Zn, and 0<x<2. Thus, the oxygen evolution reaction catalyst is represented by Y having a pyrochlore structure2Ru2O7On the basis, Pr or Zn is adopted for doping, so that Y is effectively improved2Ru2O7Is the conductivity of said Y2-xMxRu2O7The catalyst has excellent conductivity, improves the electron transfer process in the catalytic reaction process, thereby improving the catalytic performance of the oxygen evolution reaction catalyst, and has high stability in an acidic environment, so that the usage amount of the oxygen evolution reaction catalyst is greatly reduced under the condition of equivalent performance, and the cost of hydrogen production by water electrolysis is reduced; on the other hand, because of the existence of the M element, the content of the yttrium contained in the element is obviously reduced and is far lower than that of IrO according to the relationship of the type and the content of the element contained in the element2(86% wt) and RuO2The content of the noble metal in (76 wt%) effectively reduces the content of the noble metal and the economic cost.
In one embodiment, controlling said Y2-xMxRu2O7The particle size of (A) is 100nm-800 nm. The particle size is controlled to further improve the oxygen evolution catalytic activity.
In another aspect, the embodiment of the present invention further provides a preparation method of the oxygen evolution reaction catalyst described above. The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
s01: according to Y2-xMxRu2O7Neutralizing Y, M and Ru element molar ratio, dissolving Y salt, M salt and Ru salt, and preparing a mixed solution;
s02: adding a metal ion complex into the mixed solution for a complex reaction, and then removing the solvent in the mixed solution to obtain a solid mixture;
s03: and carrying out pulverization treatment on the solid mixture, and then calcining the solid mixture in an oxygen-containing atmosphere.
Wherein, in the step S01, Y2-xMxRu2O7As indicated above for Y2-xMxRu2O7Accordingly, the molar ratio of Y, M to Ru element is as described above, in particular, if M is Pr or Zn, 0<x<2. The dissolution of the Y, M and Ru salts may be in a solvent capable of dissolving the salts, such as but not limited to water. The Y salt, the M salt and the Ru salt can be prepared into salt solutions respectively and then mixed according to the proportion, or the Y salt, the M salt and the Ru salt can be directly dissolved in the same solventAnd directly preparing a mixed solution. In the prepared mixed solution, Y, M and Ru ions were uniformly dispersed. In one embodiment, the Y salt optionally includes Y (NO)3)3∙6H2O, anhydrous YCl3、YCl3∙6H2At least one of O and Ru salt can be selected from RuCl3、(NH4)2RuCl6、K2RuCl5(H2O). As for the M salt, since the M may be Pr or Zn, the M salt may be a Pr salt or a Zn salt. When the M salt is Pr salt, the Pr salt is Pr (NO)3)3、PrCl3At least one of; when the M salt is Zn salt, the Zn salt is at least one of zinc nitrate hexahydrate, zinc citrate, anhydrous zinc acetate and dihydrate zinc acetate. The Y salt, the M salt and the Ru salt have good solubility, so that stable solution can be conveniently prepared; in addition, the salt impurities are few, so that the finally prepared oxygen evolution reaction catalyst has high purity, and the catalytic activity and stability of the oxygen evolution reaction catalyst are effectively improved. In addition, the first and second substrates are,
in a specific embodiment, the concentration of the Y salt in the mixed solution is 0.001-0.1 mol L-1The concentration of the Ru salt is 0.001-0.1 mol L-1The concentration of the Pr salt is 0.001-0.1 mol L-1The concentration of the Zn salt is 0.001-0.1 mol L-1。
In the step S02, a metal ion complex, which is effective to form a ligand with the metal ion Y, M and the Ru ion, is added to the mixed solution. Thus, the metal ion complex should be added in an amount sufficient relative to the amount of Y, M and Ru ions to achieve adequate ligand formation with the Y, M and Ru ions. In one embodiment, the metal ion complex is added to the mixed solution in such an amount that the molar ratio of the metal ion complex to the total amount of Y, M and Ru metal ions in the mixed solution is (1-10): 1. in a specific embodiment, the metal ion complex is at least one of citric acid and ethylene diamine tetraacetic acid. The metal ion complexes selected have excellent ion complexation, form stable ligands with Y, M and Ru metal ions, and do not carry impurity elements in subsequent calcination.
And after the metal ion complex is added for ligand reaction, adjusting the pH value of the mixed solution containing the ligand to be alkaline so as to increase the stability of the ligand and form stable sol. In one embodiment, the pH value of the mixed solution containing the ligand is adjusted to 8.5-9. The agent for adjusting the pH of the mixed solution may be, but is not limited to, ammonia water, and preferably ammonia water, so as to avoid mixing impurity ions that are difficult to volatilize during sintering into the mixed solution. The solvent in the mixed solution can be removed by direct vacuum drying, or by heating such as water bath to volatilize the solvent and remove the solvent to obtain a solid mixture.
Of course, the mixed solution containing the ligand may be subjected to a standing aging treatment directly to precipitate the ligand, and then subjected to solid-liquid separation to remove the solvent to obtain a solid mixture.
The solid mixture obtained by removing the solvent from the mixed solution, i.e. Y2-xMxRu2O7And (3) precursor. Preferably, after the solvent removal and drying treatment, the method further comprises the step of drying the solid in vacuum at 120 ℃, for example, drying for 6-24 hours is sufficient, and the solvent is sufficiently removed.
In the step S03, the solid mixture obtained in the step S02 is subjected to pulverization treatment, so that the particle size of the calcined product can be effectively controlled; on the other hand, the solid mixture can be fully calcined. The method of subjecting the solid mixture to pulverization treatment may be, but not limited to, grinding or the like.
Calcining the solid mixture subjected to pulverization treatment in an oxygen-containing atmosphere to generate Y in the solid mixture at high temperature2-xMxRu2O7. In one embodiment, the calcination treatment is performed at 800-1200 ℃ for 6-20 hours. In a specific embodiment, when M is Pr, the calcination treatment is carried out at 800-1200 ℃ for 6-20 h; when M is Zn, the calcining treatment is carried out at 1100-1200 ℃ for 6-20 h. By passingThe temperature and time of calcination are optimized so that the calcined product is sufficiently sintered and Y is formed2-xMxRu2O7。
Therefore, the oxygen evolution reaction catalyst prepared by the preparation method of the oxygen evolution reaction catalyst has low content of noble metal, still has high oxygen evolution catalytic activity, can ensure stable catalytic performance of the oxygen evolution reaction catalyst, contains M doping element and endows Y with2-xMxRu2O7Excellent conductivity. In addition, the preparation method has the advantages of easily controlled process conditions, good repeatability and high production efficiency, and effectively reduces the production cost. In addition, the oxygen evolution reaction catalyst Y prepared by the preparation method of the oxygen evolution reaction catalyst is detected2-xMxRu2O7The particle size of (B) is 100-800 nm.
In another aspect, embodiments of the present invention further provide an oxygen evolution reaction electrode on the basis of the oxygen evolution reaction catalyst and the preparation method thereof. The oxygen evolution reaction electrode comprises an oxygen evolution reaction catalyst as described above. Therefore, the oxygen evolution reaction catalyst has low content of noble metal, high conductivity, high oxygen evolution catalytic activity, high stability in an acid environment, easily controlled process conditions and good repeatability. Therefore, the oxygen evolution reaction electrode has low economic cost and high oxygen evolution rate.
Further, the embodiment of the invention also provides an electrochemical device. The electrochemical device includes necessary components such as an anode and a cathode. Wherein, the anode is an oxygen evolution reaction electrode of the embodiment of the invention. The electrochemical device electrolyzes water to produce hydrogen with low cost and high efficiency because the oxygen evolution reaction electrode has low economic cost and high oxygen evolution rate. In a particular embodiment, the electrochemical device may be a Proton Exchange Membrane (PEM) water electrolysis device.
In yet another aspect, embodiments of the present invention provide a method of generating hydrogen and oxygen from water, based on the oxygen evolution reaction electrode and the electrochemical device described above. The method comprises the following steps:
s04: providing water in contact with an anode contained in an electrochemical device;
s05: energizing the electrochemical device to convert at least a portion of the water to hydrogen gas and oxygen gas at a cathode and an anode of the electrochemical device, respectively.
Here, the electrochemical device in step S04 is the electrochemical device according to the embodiment of the present invention, and therefore, the anode included therein is the oxygen evolution reaction electrode according to the embodiment of the present invention. Thus, the anode of the electrochemical device contains the oxygen evolution reaction catalyst described above. Thus, the method for generating hydrogen and oxygen from water has high efficiency of generating hydrogen and oxygen from water and low economic cost due to the adoption of the electrochemical device of the embodiment of the invention.
Several specific examples are now provided to further illustrate the invention.
1. Oxygen evolution reaction catalyst and method for preparing the same
Example 11
This example provides an oxygen evolution reaction catalyst and a method for preparing the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure1.8Pr0.2Ru2O7。
The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
s11, mixing Y (NO)3)3∙6H2Dissolving O in deionized water to obtain a first solution with the concentration of 0.045mol L-1。
S12, adding Pr (NO)3)3∙6H2Dissolving O in deionized water to obtain a second solution with the concentration of 0.005mol L-1；
S13 RuCl3Adding the second solution of S12 to obtain a third solution, RuCl3Has a concentration of 0.05mol L-1Stirring for 10 minutes;
s14, dissolving citric acid in the third solution of S13, stirring for 30 minutes, wherein the concentration of the citric acid is 0.20mol L-1；
S15, heating the solvent S14 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s16, grinding the dried powder obtained in the step S15 for 20 minutes, putting the ground powder into a crucible, and calcining the ground powder in air for 10 hours at the temperature of 1000 ℃.
Example 12
This example provides an oxygen evolution reaction catalyst and a method for preparing the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure1.85Zn0.15Ru2O7。
The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
s11, mixing Y (NO)3)3∙6H2Dissolving O in deionized water to obtain a first solution with the concentration of 0.04625mol L-1。
S12, adding Zn (NO)3)3∙6H2Dissolving O in deionized water to obtain a second solution with the concentration of 0.00375mol L-1；
S13 RuCl3Adding the second solution of S12 to obtain a third solution, RuCl3Has a concentration of 0.05mol L-1Stirring for 10 minutes;
s14, dissolving citric acid in the third solution of S13, stirring for 30 minutes, wherein the concentration of the citric acid is 0.30mol L-1；
S15, heating the solvent S14 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s16, grinding the dried powder obtained in the step S15 for 20 minutes, putting the ground powder into a crucible, and calcining the ground powder in air for 10 hours at the temperature of 1000 ℃.
Example 13
This example provides an oxygen evolution reaction catalyst and a method for preparing the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure1.8Pr0.2Ru2O7。
The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
s11, mixing YCl3Dissolving in deionized water to obtain a first solution with a concentration of 0.045mol L-1。
S12, mixing PrCl3Dissolve in toIonized water to obtain a second solution with the concentration of 0.005mol L-1；
S13, (NH)4)2RuCl6Adding the second solution of S12 to obtain a third solution, (NH)4)2RuCl6Has a concentration of 0.05mol L-1Stirring for 10 minutes;
s14, dissolving citric acid in the third solution of S13, stirring for 30 minutes, wherein the concentration of the ethylene diamine tetraacetic acid is 0.20mol L-1；
S15, heating the solvent S14 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s16, grinding the dried powder obtained in the step S15 for 20 minutes, putting the ground powder into a crucible, and calcining the ground powder in air for 10 hours at the temperature of 1000 ℃.
Example 14
This example provides an oxygen evolution reaction catalyst and a method for preparing the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure1.85Zn0.15Ru2O7。
S11, mixing Y (NO)3)3∙6H2Dissolving O in deionized water to obtain a first solution with the concentration of 0.04625mol L-1。
S12, dissolving zinc acetate in deionized water to obtain a second solution with the concentration of 0.00375mol L-1；
S13, mixing K2RuCl5(H2O) adding the second solution of S12 to obtain a third solution, K2RuCl5(H2O) concentration of 0.05mol L-1Stirring for 10 minutes;
s14, dissolving citric acid in the third solution of S13, stirring for 30 minutes, wherein the concentration of the citric acid is 0.30mol L-1；
S15, heating the solvent S14 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s16, grinding the dried powder obtained in the step S15 for 20 minutes, putting the ground powder into a crucible, and calcining the ground powder in air for 8 hours at the calcining temperature of 1200 ℃.
Example 15
This example provides an oxygen evolution reaction catalyst and a method for preparing the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure0.8Pr1.2Ru2O7。
The preparation method of the oxygen evolution reaction catalyst comprises the following steps:
s11, mixing Y (NO)3)3∙6H2Dissolving O in deionized water to obtain a first solution with the concentration of 0.005mol L-1。
S12, adding Pr (NO)3)3∙6H2Dissolving O in deionized water to obtain a second solution with the concentration of 0.0075mol L-1；
S13 RuCl3Adding the second solution of S12 to obtain a third solution, RuCl3Has a concentration of 0.05mol L-1Stirring for 10 minutes;
s14, dissolving citric acid in the third solution of S13, stirring for 30 minutes, wherein the concentration of the citric acid is 0.20mol L-1；
S15, heating the solvent S14 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s16, grinding the dried powder obtained in the step S15 for 20 minutes, putting the ground powder into a crucible, and calcining the ground powder in air for 10 hours at the temperature of 1000 ℃.
Comparative example 11
The present comparative example provides an oxygen evolution reaction catalyst and a method of making the same. The oxygen evolution reaction catalyst is Y with pyrochlore structure2Ru2O7。
Said Y is2Ru2O7The preparation method comprises the following steps:
s11, mixing Y (NO)3)3∙6H2Dissolving O in deionized water to obtain a first solution with the concentration of 0.005mol L-1；
S12 RuCl3Adding the solution described in S11 to obtain a second solution, RuCl3Has a concentration of 0.005mol L-1Stirring for 10 minutes;
s13, dissolving citric acid in the solutionStirring the second solution of S12 for 30 minutes, wherein the concentration of citric acid is 0.022mol L-1；
S14, heating the solvent S13 in a water bath at 80 ℃, evaporating the solvent to dryness, and putting the obtained product into a vacuum drying oven to dry for 10 hours at 120 ℃;
s15, grinding the dried powder obtained in the step S14 for 20 minutes, putting the ground powder into a crucible, and calcining the powder in air for 12 hours at the temperature of 1000 ℃.
Comparative example 12
Existing commercial IrO2A catalyst.
2. Oxygen evolution reaction electrode and electrochemical device embodiment
Example 21
The oxygen evolution reaction catalyst Y provided in example 11 was taken1.8Pr0.2Ru2O7Taking acetylene black 1mg as a catalyst, dissolving the acetylene black in 0.7mL of isopropanol and 0.3mL of deionized water solution, carrying out ultrasonic treatment for 10min, measuring 30uL of 5wt% Nafion solution by using a liquid transfer gun, and continuing to carry out ice bath dispersion for 1 h. Coating 8uL on a glassy carbon electrode with the diameter of 5mm, and naturally drying. A standard hydrogen electrode is used as a reference electrode, a platinum net is used as a counter electrode to form a three-electrode electrochemical system, and the electrochemical system is at 0.5M H2SO4And (4) in the solution, carrying out electrochemical performance test under the condition of introducing nitrogen.
Example 22
The oxygen evolution reaction catalyst Y provided in example 13 was taken1.85Zn0.15Ru2O7Taking acetylene black 1mg as a catalyst, dissolving the acetylene black in 0.7mL of isopropanol and 0.3mL of deionized water solution, carrying out ultrasonic treatment for 10min, measuring 30uL of 5wt% Nafion solution by using a liquid transfer gun, and continuing to carry out ice bath dispersion for 1 h. Coating 8uL on a glassy carbon electrode with the diameter of 5mm, and naturally drying. A standard hydrogen electrode is used as a reference electrode, a platinum net is used as a counter electrode to form a three-electrode electrochemical system, and the electrochemical system is at 0.5M H2SO4And (4) in the solution, carrying out electrochemical performance test under the condition of introducing nitrogen.
Comparative example 21
Taking Y in comparative example 112Ru2O7Dissolving acetylene black 1mg in 0.7mL isopropanol and 0.3mL deionized water solution for 10min, and treating with liquid-transfering gun30uL of 5wt% Nafion solution was measured and dispersed for 1h in ice bath. Coating 8uL on a glassy carbon electrode with the diameter of 5mm, and naturally drying. A standard hydrogen electrode is used as a reference electrode, a platinum net is used as a counter electrode to form a three-electrode electrochemical system, and the electrochemical system is at 0.5M H2SO4And (4) in the solution, carrying out electrochemical performance test under the condition of introducing nitrogen.
Comparative example 22
Commercial IrO as comparative example 122Taking acetylene black 1mg as a catalyst, dissolving the acetylene black in 0.7mL of isopropanol and 0.3mL of deionized water solution, carrying out ultrasonic treatment for 10min, measuring 30uL of 5wt% Nafion solution by using a liquid transfer gun, and continuing to carry out ice bath dispersion for 1 h. Coating 8uL on a glassy carbon electrode with the diameter of 5mm, and naturally drying. A standard hydrogen electrode is used as a reference electrode, a platinum net is used as a counter electrode to form a three-electrode electrochemical system, and the electrochemical system is at 0.5M H2SO4And (4) in the solution, carrying out electrochemical performance test under the condition of introducing nitrogen. This was used as a comparative sample.
3. Testing of correlation Performance
Y provided in example 111.8Pr0.2Ru2O7And Y prepared in comparative example 112Ru2O7The catalyst was subjected to X-ray powder diffraction, wherein the diffraction curves of the products of this example 11 and comparative example 11 are shown in fig. 1. As can be seen from FIG. 1, the product catalyst has the same characteristic peak, actually Y1.8Pr0.2Ru2O7、Y2Ru2O7And has high purity. Y provided in example 121.85Zn0.15Ru2O7The doped catalyst provided by other examples is also subjected to X-ray analysis, and the doped catalyst provided by each example has corresponding characteristic peaks, and is proved to be the catalyst of the corresponding molecular formula and have high purity.
Y prepared in example 111.8Pr0.2Ru2O7Catalyst, Y provided in example 121.85Zn0.15Ru2O7Y provided in comparative example 112Ru2O7And commercial IrO as provided in comparative example 122Oxygen evolution catalystRespectively carrying out polarization test and stability test, wherein the scanning frequency of the polarization test is 10mV s-1(ii) a The cyclic volt-ampere scanning frequency of the stability test is 2000 times, the scanning voltage range is 1.35V-1.6V, and the scanning speed is 100mV s-1。
Tested, Y provided in example 111.8Pr0.2Ru2O7Y of comparative example2Ru2O7Catalyst and commercial IrO2FIG. 2 shows the polarization curve of Y at the same applied potential as shown in FIG. 21.8Pr0.2Ru2O7The current density of the alloy is obviously superior to that of Y2Ru2O7And IrO2And Y is2Ru2O7The current density of the alloy is obviously superior to that of IrO2. Description of Y1.8Pr0.2Ru2O7Electrochemical performance ratio Y2Ru2O7、IrO2Excellent but Y2Ru2O7The electrochemical performance is better than that of IrO2。
Example 12Y1.85Zn0.15Ru2O7Y of comparative example2Ru2O7Catalyst and commercial IrO2FIG. 3 shows the polarization curve of Y at the same applied potential as shown in FIG. 31.85Zn0.15Ru2O7The current density of the alloy is obviously superior to that of Y2Ru2O7And IrO2And Y is2Ru2O7The current density of the alloy is obviously superior to that of IrO2. Description of Y1.85Zn0.15Ru2O7Electrochemical performance ratio Y2Ru2O7、IrO2Excellent but Y2Ru2O7The electrochemical performance is better than that of IrO2。
Example 11 provides Y1.8Pr0.2Ru2O7Y of comparative example2Ru2O7Catalyst and commercial IrO2The stability of (A) is shown in FIG. 4. from FIG. 4, it can be seen that under 2000 cyclic voltammetric scans (electricity)Pressing a scanning range: 1.1-1.6V, scanning rate: 100mV/s), Y1.8Pr0.2Ru2O7Has stability obviously superior to Y2Ru2O7、IrO2And Y is2Ru2O7The stability of the compound is obviously superior to that of IrO2. Description of Y1.8Pr0.2Ru2O7Stability ratio Y2Ru2O7、IrO2Excellent but Y2Ru2O7Has better stability than IrO2。
Other examples each of the catalysts provided in the examples was tested for polarization and stability in accordance with the method of testing polarization and stability of the catalyst of example 11, and each of the catalysts provided in the examples was similar to the characteristics presented in fig. 2 to 4, respectively.
Therefore, the oxygen evolution reaction catalyst provided by the embodiment of the invention has the advantages of high conductivity, high catalytic activity, good stability, high purity and good repeatability of the preparation method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. An oxygen evolution reaction anode characterized in that: the oxygen evolution reaction anode comprises an oxygen evolution reaction catalyst which is Y2-xMxRu2O7Wherein M is Zn and x = 0.15; the preparation method of the oxygen evolution reaction catalyst comprises the following steps:
according to Y2-xMxRu2O7Neutralizing Y, M and Ru element molar ratio, dissolving Y salt, M salt and Ru salt, and preparing a mixed solution;
adding a metal ion complex into the mixed solution to perform ligand reaction, and then removing the solvent in the mixed solution to obtain a solid mixture;
carrying out pulverization treatment on the solid mixture and then calcining the solid mixture in an oxygen-containing atmosphere;
the metal ion complex is citric acid;
the Y salt is Y (NO)3)3、∙6H2O, the Ru salt is RuCl3The M salt is zinc nitrate hexahydrate;
the concentration of the Y salt is 0.04625mol L-1The concentration of the Ru salt is 0.05mol L-1The concentration of the M salt is 0.00375mol L-1；
The concentration of the citric acid is 0.30mol L-1；
The calcination treatment is carried out at 1000 ℃ for 10 hours.
2. The oxygen evolution reaction anode according to claim 1, characterized in that: said Y is2-xMxRu2O7The particle size of (A) is 100nm-800 nm.
3. An electrochemical device comprising an anode and a cathode, wherein: the anode is the oxygen evolution reaction anode of claim 1 or 2.
4. A method of generating hydrogen and oxygen from water, the method comprising the steps of:
providing water in contact with said anode comprised in the electrochemical device of claim 3;
energizing the electrochemical device to convert at least a portion of the water to hydrogen and oxygen at the cathode and anode, respectively.
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| Title |
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| "Evidence of a correlation between magnetic and structural transitions in Y2-xZnxRu2O7 pyrochlore compounds";Giulia Berti等;《RSC Adv.》;20151118;第5卷;第100809页 * |
| "High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media";Jaemin Kim等;《J.Am.Chem.Soc.》;20170627;第139卷;第12077页 * |
| "Novel Y2-xPrxRu2O7 (x=0-2) Pyrochlore Oxides Prepared Using a Soft Chemistry Route and their Electrical Properties";Chiara Abate等;《J.Am.Ceram.Soc.》;20100701;第93卷(第7期);第1972页 * |
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