CN109289843B - Sea urchin-shaped rutile type titanium dioxide supported ruthenium oxide oxygen precipitation catalyst, and preparation method and application thereof - Google Patents
Sea urchin-shaped rutile type titanium dioxide supported ruthenium oxide oxygen precipitation catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a sea urchin-shaped RuO2/r‑TiO2A method of preparing an oxygen evolution catalyst comprising: adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2(ii) a Rutile TiO with oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension; mixing the first suspension with ruthenium salt solution, stirring, washing, drying and calcining to obtain sea urchin-shaped RuO2/r‑TiO2. The invention adopts the treated r-TiO2As carrier, it is prepared into sea urchin-shaped RuO by wet chemical method through high-temperature reduction with certain oxygen defect2/r‑TiO2A catalyst; wherein RuO2Is in the form of particles, passing through r-TiO with oxygen defects2Inducing to generate thorn-shaped structure, and combining the two to generate sea urchin-shaped structure. The catalyst prepared by the method has good electrochemical performance.
Description
Technical Field
The invention relates to the technical field of electrolyzed water, in particular to sea urchin-shaped RuO2/r-TiO2An oxygen evolution catalyst, a method for its preparation and use.
Background
Hydrogen energy is used as clean energy with the most development prospect at present, and only pollution-free water is generated in the process of converting the hydrogen energy into electric energy, so that the development of the hydrogen energy is a key ring for promoting the scale use of the clean energy. A Proton Exchange Membrane (PEM) water electrolysis device is a device which electrochemically decomposes water to produce hydrogen and oxygen.
The Hydrogen Evolution Reaction (HER) is the main use of the electrolytic water reaction, however the anodic oxygen Evolution reaction involves a 4-electron process resulting in slower kinetic rates and higher overpotentials [ YANG T, DU M, ZHU H, ethyl. ionization of Pt Nanoparticles in Carbon Nanoparticles: Bifunctional catalyst for Hydrogen Evolution and Electrochemical Sensor [ J ]. Electrochimica Acta,2015,167(48-54) ]. The slow kinetic process of the OER electrocatalyst in the acidic medium is mainly due to the fact that the oxygen intermediate species process of electron transfer to the catalyst surface is slow, the proton (electron) conduction rate can be improved in the acidic medium, side reactions are reduced, and the OER reaction is more favorably carried out [ SARDAR K, PETRUCCO E, HILEY C I, et al. In acidic solutions, the OER electrocatalysts available are limited because most catalysts are unstable under acidic electrolysis conditions.
Currently used in OER catalytic reactions is IrO2And RuO2IrO in these two substances2Has higher stability, RuO2Has better catalytic activity [ NONG H N, OH H S, REIER T, et alxcore-shellparticles as efficient,cost-effective,and stable catalysts forelectrochemicalwater splitting[J].Angewandte Chemie,2015,54(10):2975-2989.]。RuO2Instability mainly forms more unstable RuO4Therefore, it is very necessary to develop a catalyst having a good catalytic activity and a high stability.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a sea urchin-shaped RuO2/r-TiO2Method for preparing oxygen evolution catalyst, sea urchin-shaped RuO prepared by the invention2/r-TiO2The oxygen evolution catalyst has high catalytic activity and good stability.
The invention provides a sea urchin-shaped RuO2/r-TiO2A method of preparing an oxygen evolution catalyst comprising:
A) adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2；
B) The rutile type TiO with the oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension;
C) mixing and stirring the first suspension and a ruthenium salt solution, washing, drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst.
Preferably, the calcining temperature in the step A) is 700-1200 ℃; the calcination time is 1-10 h.
Preferably, the inert gas in the step A) is one or more of nitrogen, helium, neon and argon; the volume percentage of the hydrogen and the inert gas is 5 to 20 percent.
Preferably, the reducing agent in the step B) is sodium borohydride; the dispersion of step B) is ultrasonic dispersion; the ultrasonic power is 80-100W; the ultrasonic time is 15-60 min.
Preferably, the ruthenium salt is a ruthenium halide; the molar ratio of the ruthenium salt to the reducing agent is 1: (5-40); the rutile type TiO having oxygen deficiency2The molar ratio of ruthenium salt to ruthenium salt is 1: (0.25-2).
Preferably, the drying temperature in the step C) is 50-80 ℃; the drying time is 6-24 h.
Preferably, the calcination of step C) is performed in a quartz boat; the calcination temperature is 300-400 ℃; the calcination time is 0.5-3 h.
The invention provides a sea urchin-shaped RuO2/r-TiO2The oxygen evolution catalyst is prepared by the preparation method of any one of the technical schemes.
The invention provides sea urchin-shaped RuO prepared by the preparation method of any one of the technical schemes2/r-TiO2Application of oxygen evolution catalyst in anodic oxygen evolution of electrolyzed water.
The invention provides a method for electrolyzing water, which comprises the step of preparing sea urchin-shaped RuO by the preparation method of any one of the technical schemes2/r-TiO2Oxygen evolution catalyst.
Compared with the prior art, the invention provides a sea urchin-shaped RuO2/r-TiO2A method of preparing an oxygen evolution catalyst comprising: A) adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2(ii) a B) The rutile type TiO with the oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension; C) mixing and stirring the first suspension and a ruthenium salt solution, washing, drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst. The invention adopts the treated r-TiO2As carrier, it is prepared into sea urchin-shaped RuO by wet chemical method through high-temperature reduction with certain oxygen defect2/r-TiO2A catalyst; wherein, RuO2Is itself in the form of particles, passing through r-TiO with oxygen defects2Inducing to generate thorn-shaped structure, and combining the two to generate sea urchin-shaped structure. Wherein r-TiO2And also can inhibit Ru from being oxidized into a high valence state, thereby improving the stability of the Ru-based catalyst. Experimental results show that the catalyst prepared by the method has good electrochemical performance, the treatment method is simple and convenient to operate, the preparation period is short, and the electrochemical performance is obviously improved. In addition, the method provided by the invention is simple to operate, mild in condition, simple in operation steps and easy for large-scale production.
Drawings
FIG. 1 shows a-TiO prepared in example 1 of the present invention2And r-TiO2XRD pattern of (a);
FIG. 2 shows RuO prepared in example 1 of the present invention2,RuO2/a-TiO2,RuO2/r-TiO2XRD pattern of (a);
FIG. 3 shows RuO prepared in example 1 of the present invention2/a-TiO2SEM picture of (1);
FIG. 4 shows RuO prepared in example 2 of the present invention2/r-TiO2SEM picture of (1);
FIG. 5 shows RuO according to embodiment 4 of the present invention2,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2The LSV graph of (a);
FIG. 6 shows RuO according to embodiment 4 of the present invention2,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2A chronopotentiometric map of (a);
FIG. 7 shows RuO prepared in comparative example 1 of the present invention2/r0-TiO2SEM image of (d).
Detailed Description
The invention provides a sea urchin-shaped RuO2/r-TiO2The oxygen evolution catalyst, the preparation method and the application thereof can be realized by appropriately modifying the process parameters by the technical personnel in the field by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a sea urchin-shaped RuO2/r-TiO2A method of preparing an oxygen evolution catalyst comprising:
A) adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2；
B) The rutile type TiO with the oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension;
C) mixing and stirring the first suspension and a ruthenium salt solution, washing, drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst.
The invention providesSea urchin-like RuO for supply2/r-TiO2The preparation method of the oxygen evolution catalyst comprises the steps of firstly, preparing anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2。
The invention uses anatase type TiO2Is marked as a-TiO2Rutile type TiO2Is noted as r-TiO2。
The invention is directed to the anatase TiO2Without limitation, commercially available, well known to those skilled in the art; is to take commercial anatase type TiO2As Ti source, there was no other treatment.
The inert gas is preferably one or more of nitrogen, helium, neon and argon; more preferably one or more of nitrogen, helium and argon; argon is most preferred.
The volume percentage of the hydrogen to the inert gas is preferably 5 to 20 percent; more preferably 8% to 18%; most preferably 10% to 16%.
The calcination temperature is preferably 700-1200 ℃; more preferably 800-1100 ℃; most preferably 1000 ℃; the calcination time is preferably 1-10 h; more preferably 2-9 h; most preferably 3-8 h.
The invention adopts the treated r-TiO2As a carrier, reducing rutile TiO with certain oxygen defect at high temperature2。
The rutile type TiO with the oxygen defect2And mixing the dispersed solution with a reducing agent to obtain a first suspension.
Specifically, first, rutile type TiO with oxygen defect2Dispersing in solvent to obtain suspension.
The dispersion is ultrasonic dispersion; the ultrasonic dispersion temperature is room temperature. 20-35 ℃ as is well known to those skilled in the art; preferably 20 to 28 ℃. The ultrasonic power is 80-100W; the ultrasonic time is 15-60 min. The present invention is not limited to the specific operation of the ultrasound, and is well known to those skilled in the art.
The solvent is preferably deionized water.
Mixing the suspension with a reducing agent preferably comprises adding a reducing agent to the suspension to obtain a first suspension. The mixing is preferably stirring mixing, and the present invention is not limited to the specific operation and parameters of the stirring, and the stirring may be performed by those skilled in the art.
The reducing agent is preferably sodium borohydride; the present invention is not limited in its source, and may be commercially available.
And after the first suspension is obtained, mixing and stirring the first suspension and the ruthenium salt solution to obtain a first precipitate.
The ruthenium salt of the present invention is preferably a ruthenium halide; can be ruthenium fluoride, ruthenium chloride, ruthenium bromide and ruthenium iodide; preferably RuCl3。
The molar ratio of ruthenium salt to reducing agent according to the invention is preferably 1: (5-40); more preferably 1: (10-30); most preferably 1: (15-25); most preferably 1: 20.
The rutile type TiO with oxygen defect of the invention2The molar ratio to ruthenium salt is preferably 1: (0.25-2); more preferably 1: (0.5 to 1.5); most preferably 1: 1.
the first precipitate is formed during the stirring process, and the present invention is not limited to the specific operation and parameters of the stirring process, and the stirring process is well known to those skilled in the art.
Washing and drying the first precipitate to obtain a second precipitate; the invention does not limit the specific mode of the washing, and the skilled person is familiar with the washing; after washing, preferably performing suction filtration or centrifugation; and then dried to obtain a second precipitate.
The drying temperature is preferably 50-80 ℃; more preferably 50 ℃ to 70 ℃; most preferably from 50 ℃ to 60 ℃. The drying time is preferably 6-24 h; more preferably 6 to 12 hours; most preferably 6 to 8 hours. The drying according to the invention is preferably carried out in a thermostated drying cabinet.
Drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst. Specifically, the second precipitate is calcined to obtain a third precipitate, namely sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst.
The calcination of the invention is preferably carried out in a quartz boat; the calcination is preferably carried out in an air atmosphere.
The calcination temperature is preferably 300-400 ℃; more preferably 350-400 ℃; the calcination time is preferably 0.5-3 h; more preferably 1-2 h.
The invention provides a sea urchin-shaped RuO2/r-TiO2A method of preparing an oxygen evolution catalyst comprising: A) adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2(ii) a B) The rutile type TiO with the oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension; C) mixing and stirring the first suspension and a ruthenium salt solution, washing, drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst. The invention adopts the treated r-TiO2As carrier, it is prepared into sea urchin-shaped RuO by wet chemical method through high-temperature reduction with certain oxygen defect2/r-TiO2A catalyst; wherein, RuO2Is itself in the form of particles, passing through r-TiO with oxygen defects2Inducing to generate thorn-shaped structure, and combining the two to generate sea urchin-shaped structure. Wherein r-TiO2And also can inhibit Ru from being oxidized into a high valence state, thereby improving the stability of the Ru-based catalyst. Experimental results show that the catalyst prepared by the method has good electrochemical performance, the treatment method is simple and convenient to operate, the preparation period is short, and the electrochemical performance is obviously improved. In addition, the method provided by the invention is simple to operate, mild in condition, simple in operation steps and easy for large-scale production.
The sea urchin shape of the invention is particularly a sea urchin shape well known to those skilled in the art; in particular r-TiO with oxygen defects2As a substrate, growing a thorn-like structure RuO on the surface2(ii) a The whole body is in the shape of sea urchin as shown in the attached drawing of the invention.
The invention provides a sea urchin-shaped RuO2/r-TiO2The oxygen evolution catalyst is prepared by the preparation method of any one of the technical schemes.
The preparation method of the invention has been clearly described above, and is not repeated herein.
The invention provides sea urchin-shaped RuO prepared by the preparation method of any one of the technical schemes2/r-TiO2Application of oxygen evolution catalyst in anodic oxygen evolution of electrolyzed water.
The catalyst prepared by the preparation method provided by the invention can be used for oxygen precipitation of the anode of the electrolyzed water.
The invention provides a method for electrolyzing water, which comprises the step of preparing sea urchin-shaped RuO by the preparation method of any one of the technical schemes2/r-TiO2Oxygen evolution catalyst.
The catalyst provided by the invention is particularly applied to electrolyzed water under acidic conditions. The parameters of the rest of the conditions for the electrolysis of water are not limited in the present invention and are well known to those skilled in the art.
The specific application method is the same as the application method of the anode catalyst for electrolyzing water in the prior art, and the usage amount is added according to the actual requirement.
The invention also provides RuO2/r-TiO2The physical characterization and catalytic activity detection method of the oxygen evolution catalyst comprises the following steps: putting the prepared catalyst into a reaction vessel, continuously introducing nitrogen into the reaction vessel for 15min to exhaust the air in the reaction vessel, then adding the prepared sulfuric acid solution into the reaction vessel,
the catalyst prepared by the method has excellent activity of oxygen precipitation in an acid system, and the stability is obviously improved, so that the catalyst with the sea urchin-shaped structure provides an effective way for anode water electrolysis.
To further illustrate the present invention, the following examples are given to illustrate a sea urchin-like RuO of the present invention2/r-TiO2Oxygen evolution catalysts, methods of making and using the same are described in detail.
Example 1
At room temperature (25 ℃), adding anatase type TiO2At H2In the atmosphere of/Ar (wherein the hydrogen accounts for 10 percent) at 1000 DEG CCalcining for 2h to obtain treated TiO2The crystal form is converted into rutile TiO with oxygen defect2(ii) a 0.2mmol of r-TiO is weighed2Uniformly dispersing the mixture in deionized water for 20min at 80W to obtain a suspension; adding 4mmol NaBH to the first suspension4Obtaining a first suspension; 0.2mmol of RuCl is taken3Adding the solution into the first suspension, and generating a first precipitate in the stirring process; washing the first precipitate, and drying in a constant-temperature drying oven at 50 ℃ for 6h to obtain a second precipitate; taking out the second precipitate, calcining in quartz boat at 400 deg.C for 1 hr to obtain sea urchin-shaped RuO2/r-TiO2。
TiO before and after treatment of example 12XRD characterization was performed, and the results are shown in FIG. 1, FIG. 1 is a-TiO prepared in example 1 of the present invention2And r-TiO2XRD pattern of (a); as can be seen from FIG. 1, anatase TiO2The crystal form is converted into rutile TiO after treatment2. RuO for example 12,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2XRD characterization was performed, and the results are shown in FIG. 2, FIG. 2 is RuO prepared in example 1 of the present invention2,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2XRD pattern of (a); as can be seen in FIG. 1, RuO2,RuO2/a-TiO2,RuO2/r0-TiO2In which Ru is completely oxidized, and RuO2/r-TiO2Elemental Ru is present. RuO for example 12/a-TiO2,RuO2/r-TiO2SEM characterization is carried out, the results are shown in FIGS. 3 and 4, wherein FIG. 3 shows RuO prepared in example 1 of the present invention2/a-TiO2SEM picture of (1); FIG. 4 shows RuO prepared in example 1 of the present invention2/r-TiO2SEM picture of (1); as can be seen from FIGS. 3 and 4, RuO2/a-TiO2RuO for dispersing uniform particles2/r-TiO2Is of sea urchin structure.
Example 2
At room temperature (25 ℃), adding anatase type TiO2At H2In an/Ar atmosphere (wherein hydrogen is present)20 percent) and calcined at 800 ℃ for 4 hours to obtain treated TiO2The crystal form is converted into rutile TiO with oxygen defect2(ii) a 0.2mmol of r-TiO is weighed2Uniformly dispersing the mixture in deionized water for 20min at 80W to obtain a suspension; adding 5mmol NaBH to the suspension4Obtaining a first suspension; 0.2mmol of RuCl is taken3Adding the solution into the first suspension, and generating a first precipitate in the stirring process; washing the first precipitate, and drying in a constant-temperature drying oven at 60 ℃ for 7h to obtain a second precipitate; taking out the second precipitate, calcining in quartz boat at 350 deg.C for 1.5 hr to obtain sea urchin-shaped RuO2/r-TiO2。
RuO prepared in example 22/r-TiO2SEM characterization was performed, and the structure of sea urchin was determined as shown in FIG. 4.
Example 3
At room temperature (25 ℃), adding anatase type TiO2At H2Calcining at 1100 ℃ for 3h in an Ar atmosphere (wherein the hydrogen accounts for 15%) to obtain the treated TiO2The crystal form is converted into rutile TiO with oxygen defect2(ii) a 0.3mmol of r-TiO is weighed2Uniformly dispersing the mixture in deionized water for 30min at 100W to obtain a suspension; adding 5mmol NaBH to the suspension4Obtaining a first suspension; 0.2mmol of RuCl is taken3Adding the solution into the first suspension, and generating a first precipitate in the stirring process; washing the first precipitate, and drying in a constant-temperature drying oven at 70 ℃ for 8h to obtain a second precipitate; taking out the second precipitate, putting the second precipitate into a quartz boat, and calcining the second precipitate in the air at 350 ℃ for 2 hours to obtain sea urchin-shaped RuO2/r-TiO2。
RuO prepared in example 32/r-TiO2And performing SEM characterization to determine the structure of the sea urchin.
Comparative example 1
0.2mmol of commercial rutile form r is weighed0-TiO2Uniformly dispersing the mixture in deionized water for 20min at 80W to obtain a suspension; adding 4mmol NaBH to the first suspension4Obtaining a first suspension; 0.2mmol of RuCl is taken3Adding the solution into the first suspension, and generating a first precipitate in the stirring process; washing the first precipitate at 50 deg.CDrying in a constant-temperature drying oven for 6h to obtain a second precipitate; taking out the second precipitate, calcining the second precipitate in a quartz boat for 1 hour at the temperature of 400 ℃ in the air to obtain RuO2/r0-TiO2。
The results are shown in FIG. 7, and FIG. 7 shows RuO prepared in comparative example 1 of the present invention2/r0-TiO2SEM image of (d). RuO can be seen from the figure2/r0-TiO2Is a granular structure with uniform dispersion.
Example 4
Sea urchin-like RuO prepared in inventive example 1 and comparative example 12/r-TiO2And (5) carrying out performance measurement.
EG was used for electrochemical measurements at room temperature&E273 electrochemical workstation. Phi4A glassy carbon electrode as a working electrode and saturated calomel Hg/Hg2Cl2As a reference electrode and a platinum sheet as a counter electrode. All potentials were relative to a Saturated Calomel Electrode (SCE) if not expressly noted. The ink dropped on the working electrode was formulated as follows: 3mg of sea urchin-like RuO prepared in example 1 of the present invention2/r-TiO2The catalyst and 15 mul (5%) Nafion were added to 300 mul ethanol, mixed evenly by ultrasound for 30min, 5 mul ink was transferred and dropped on a clean glassy carbon electrode. Electrochemical test is carried out at 30min N20.5MH of2SO4First, a Cyclic Voltammetry (CV) test was performed to activate the electrodes at a sweep rate of 50mVs-1Sweep 5 cycles, voltage range 0.05V-1.25V (vs SCE). The activated electrode was subjected to a Linear Sweep Voltammetry (LSV) test at a sweep rate of 5mVs-1The voltage range is 0.85V-1.45V (vsSCE).
Results referring to FIG. 5, FIG. 5 shows RuO according to example 4 of the present invention2,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2LSV diagram of (1), as can be seen from FIG. 5, RuO prepared in example 12/r-TiO2Has a mass specific activity of 0.239A g-1(η mV 300mV), far higher than that of homemade RuO2(0.164A g-1) RuO of comparative example 12/r0-TiO2(0.196A g-1) Comparison of Mass specific Activity, RuO2/r-TiO2Obviously superior to RuO2/r0-TiO2. The sample is subjected to a chronopotentiometric test with a current density of 10mAcm -21 × 2cm for working electrode2The duration of the test of the glassy carbon plate is 6 hours, and the result is shown in FIG. 6, and FIG. 6 shows RuO of example 4 of the present invention2,RuO2/a-TiO2,RuO2/r0-TiO2,RuO2/r-TiO2A chronopotentiometric map of (a); as can be seen from FIG. 6, RuO of example 12Deactivated during the test, RuO2/r-TiO2The stability is superior to RuO2/r0-TiO2And RuO2/a-TiO2And the efficiency is hardly lost, and the stability is obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Sea urchin-shaped RuO2/r-TiO2A method of preparing an oxygen evolution catalyst comprising:
A) adding anatase type TiO2Calcining in the mixed atmosphere of hydrogen and inert gas to obtain rutile TiO with oxygen defect2；
B) The rutile type TiO with the oxygen defect2Mixing the dispersed solution with a reducing agent to obtain a first suspension;
C) mixing and stirring the first suspension and a ruthenium salt solution, washing, drying and calcining to obtain sea urchin-shaped RuO2/r-TiO2Oxygen evolution catalyst.
2. The preparation method according to claim 1, wherein the calcination temperature in step A) is 700-1200 ℃; the calcination time is 1-10 h.
3. The method according to claim 1, wherein the inert gas in step a) is one or more of helium, neon and argon; the volume percentage of the hydrogen and the inert gas is 5 to 20 percent.
4. The method according to claim 1, wherein the reducing agent in step B) is sodium borohydride; the dispersion of step B) is ultrasonic dispersion; the ultrasonic power is 80-100W; the ultrasonic time is 15-60 min.
5. The production method according to claim 1, wherein the ruthenium salt is a ruthenium halide; the molar ratio of the ruthenium salt to the reducing agent is 1: (5-40); the rutile type TiO having oxygen deficiency2The molar ratio of ruthenium salt to ruthenium salt is 1: (0.25-2).
6. The method according to claim 1, wherein the drying temperature in step C) is 50 ℃ to 80 ℃; the drying time is 6-24 h.
7. The method of claim 1, wherein the calcining of step C) is performed in a quartz boat; the calcination temperature is 300-400 ℃; the calcination time is 0.5-3 h.
8. Sea urchin-shaped RuO2/r-TiO2An oxygen evolution catalyst, characterized by being produced by the production method according to any one of claims 1 to 7.
9. Sea urchin-like RuO prepared by the preparation method of any one of claims 1 to 72/r-TiO2Application of oxygen evolution catalyst in anodic oxygen evolution of electrolyzed water.
10. A method of electrolyzing water, characterized by comprising sea urchin-like RuO prepared by the preparation method of any one of claims 1 to 72/r-TiO2Oxygen evolution catalyst.
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| CN111167440B (en) * | 2020-01-07 | 2023-05-02 | 郑州大学 | Catalyst for ammonia borane hydrolysis hydrogen evolution and preparation method thereof |
| CN111584800A (en) * | 2020-01-15 | 2020-08-25 | 武汉理工大学 | Oxygen-deficient titanium dioxide nanosheet modified lithium ion battery diaphragm and preparation method and application thereof |
| CN112458495B (en) * | 2020-11-27 | 2022-05-10 | 浙江大学衢州研究院 | Electrocatalyst of ruthenium-based transition metal oxide solid solution and preparation method and application thereof |
| CN112973680B (en) * | 2021-03-10 | 2022-09-06 | 中国科学院长春应用化学研究所 | Corrosion-resistant metal oxide-based composite material, preparation method and application thereof |
| CN113265682B (en) * | 2021-05-26 | 2023-06-20 | 山东科技大学 | Load-type RuO x /F-TiO 2 Oxygen evolution catalyst and preparation method and application thereof |
| CN114045528B (en) * | 2021-12-24 | 2022-11-25 | 上海交通大学 | Preparation method of anode catalyst for electrolyzing water in acidic medium |
| CN115786974B (en) * | 2022-12-20 | 2023-09-26 | 苏州擎动动力科技有限公司 | Catalyst for water electrolysis and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541423A (en) * | 2006-11-27 | 2009-09-23 | 住友化学株式会社 | Method for producing ruthenium oxide loaded body and method for producing chlorine |
| CN105032409A (en) * | 2015-07-03 | 2015-11-11 | 中国科学院过程工程研究所 | Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof |
| CN108212149A (en) * | 2017-04-22 | 2018-06-29 | 天津大学 | High dispersive type ruthenium oxide catalysts and its preparation method and application |
-
2018
- 2018-11-01 CN CN201811295042.7A patent/CN109289843B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541423A (en) * | 2006-11-27 | 2009-09-23 | 住友化学株式会社 | Method for producing ruthenium oxide loaded body and method for producing chlorine |
| CN105032409A (en) * | 2015-07-03 | 2015-11-11 | 中国科学院过程工程研究所 | Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof |
| CN108212149A (en) * | 2017-04-22 | 2018-06-29 | 天津大学 | High dispersive type ruthenium oxide catalysts and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Crystal phase effects on the structure and performance of ruthenium nanoparticles for CO2 hydrogenation;Qingquan Lin,et.al.;《Catal. Sci. Technol.》;20140312;第4卷;第2058-2063页 * |
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