CN114592210A - Co3O4-RuO2Preparation method and application of composite material - Google Patents
Co3O4-RuO2Preparation method and application of composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
This patent discloses a Co3O4‑RuO2The preparation method of the composite material and the application thereof, wherein the preparation method comprises the following steps: s1: ultrasonically dispersing cobalt zeolite (ZIF-67) in methanol; s2: adding RuCl3Dissolving in deionized water; s3: adding the step of adding the ZIF-67 suspension obtained in the step S1 intoThe solution obtained in the step S2 and deionized water are subjected to ultrasonic treatment and react in a reaction kettle, and after the reaction is finished, the solution is cooled, washed, dried, ground, calcined and cooled to obtain Co3O4‑RuO2A composite material. The preparation method is to obtain Co by a hydrothermal method3O4‑RuO2Composite material of Co3O4With RuO2The electron interaction exists to form a P-N heterojunction structure, and the synergistic effect of the two is beneficial to improving RuO2OER activity and stability under acidic environment. Co provided by the invention3O4‑RuO2The composite material shows better performance than commercial ruthenium dioxide under acidic condition, and can be used in the field of electrocatalytic oxygen evolution. The preparation method is simple and easy to control, and the electric oxygen evolution catalyst with good practical value, application prospect, high activity and high stability can be prepared.
Description
Technical Field
The invention belongs to the field of new material preparation and electrochemical catalysis, and particularly relates to Co3O4-RuO2A preparation method and application of the composite material.
Background
In order to solve the problem of environmental pollution caused by industrial development, renewable energy sources are further developed, so that the dependence of human society on fossil fuels can be effectively reduced. In recent years, a great deal of work has been focused on the research of hydrogen energy and carbon neutralization technologies, wherein hydrogen production by electrolysis of water is regarded as one of the most effective and environmentally friendly ways to realize sustainable development of energy. Especially proton exchange membrane water electrolysis (pempes) can produce hydrogen gas with high purity (> 99.99%) and high pressure (about 35 MPa). Furthermore, pempes have a compact structure with easy maintenance and rapid start-up/shut-down, which makes it promising for large-scale production of hydrogen at the Megawatt (MW) level, compared to alkaline water electrolyzers and solid oxide steam electrolyzers.
The two half-reactions of pempes generate an electroevolution hydrogen reaction (HER) and an electroevolution oxygen reaction (OER), respectively. However, the overall performance of pempes depends on the electrocatalyst used for each half-reaction. Compared with the cathodic hydrogen evolution reaction, the anodic oxygen evolution reaction involves a four-electron transfer process, and is lower than the cathodic two-electron hydrogen evolution reaction in the kinetic reaction rate, and the complex reaction process causes the anodic oxygen evolution reaction to overcome a higher reaction energy barrier in the thermodynamics. Therefore, the lack of highly active and stable OER electrocatalysts remains one of the major bottlenecks that hinder the development of electrocatalytic energy conversion reactions in acidic media. At present, commercial electroevolving oxygen catalysts are mainly iridium or ruthenium and corresponding oxides thereof, but the activity and stability of the catalysts still have great room for improvement. Therefore, how to improve the performance of iridium-based or ruthenium-based catalysts is of great significance to the optimization of pemves.
The commercial oxygen evolution catalyst mainly comprises RuO2And IrO2Research shows that RuO2The electrocatalytic activity of the acidic OER is higher than that of IrO2While the latter is significantly superior to the former in stability. However, ruthenium is not available in large quantities and is expensive, which prevents its widespread use on a large scale. Currently based on acidic IrO2The research of the electric oxygen evolution catalyst has made great progress, and a series of acidic IrO with higher activity and better stability2The electroevolving oxygen catalysts are reported sequentially. However, although both Ru and Ir are noble metals, Ir is much more expensive than Ru. Thus, RuO was developed2Acidic OER based electrocatalysts have received much attention.
RuO2Is an N-type semiconductor, but still has insufficient stability and catalytic activity; considering that the electronic structure of the control material can influence the stability and activity of the catalyst, we tried to construct a P-N junction structure and then combine Co3O4Has better oxygen evolution activity and is a P-type semiconductor, and the interaction between the P-type semiconductor and an N-type semiconductor is utilized to promote RuO2The electric oxygen evolution of (2) becomes a key to solve the above problems.
The invention content is as follows:
aiming at the defects of the existing research content, the invention aims to synthesize Co3O4-RuO2The composite material is applied to the acid oxygen evolution reaction.
In order to realize the purpose of the invention, the specific technical scheme is as follows:
co3O4-RuO2A method of making a composite material, the method comprising the steps of:
s1: preparation of ZIF-67 suspension: adding ZIF-67 into methanol, and performing ultrasonic dispersion uniformly;
S2：RuCl3preparation of the solution: adding RuCl3Adding into deionized water, stirring and dissolving;
S3：Co3O4-RuO2preparing a composite material:
s3.1: adding the final ZIF-67 suspension obtained in the step S1 into the RuCl obtained in the step S23Carrying out ultrasonic treatment on the solution and deionized water for 2-15 min;
s3.2: transferring the solution finally obtained in the step S3.1 into a reaction kettle, and reacting for 2-10h under the condition of preheating at 60-100 ℃;
s3.3: cooling the solution finally obtained in the step S3.2 by cold water, centrifuging the product at a high speed, washing the product by methanol, and drying the product at the temperature of 60-100 ℃;
s3.4: the final product obtained in the step S3.3 is added into N2And O2Calcining for 1-5h at the temperature of 500 ℃ under the atmosphere of mixed gas and 200-3O4-RuO2A composite material;
according to the scheme, in the step S1.1, 10-40mg of ZIF-67 is ultrasonically dispersed into 5-10mL of methanol;
according to the scheme, step S2 specifically includes mixing RuCl3The mass of the deionized water is 5-30mg, and the volume of the deionized water is 1-5 mL;
according to the above scheme, step S3.1, the RuCl is added3The volume of the solution is 0.5-5mL, and the volume of the deionized water is 0.5-2.5 mL;
according to the scheme, in the step S3.3, the speed of a centrifugal machine is 15000-21000 rpm, the time is 3-10min for one time, and the centrifugal washing is carried out for 3-6 times;
according to the above scheme, in step S3.4, N2And O2The mixing ratio of the mixed atmosphere is 99.5%/0.5% and the gas flow rate is 20-80 sccm, and the heating rate is 3-5 ℃/min;
co prepared by the preparation method3O4-RuO2The composite material is applied to the field of new material preparation and electrochemical catalysis.
The invention has the beneficial effects that: the preparation method is simple, and the P-N junction structure is constructed and then Co is combined3O4Has better oxygen evolution activity, is a P-type semiconductor, and promotes RuO by utilizing the interaction between the P-type semiconductor and an N-type semiconductor2The electrical oxygen evolution efficiency. Obtained Co3O4-RuO2Under the acidic condition, only 180mV of overpotential is needed to reach 10mA cm-2Current density, compared to pure Co3O4And RuO2The sample has a great degree of promotion.
Drawings
FIG. 1 shows the Co produced by the present invention3O4-RuO2High resolution transmission electron microscopy images of the composite;
FIG. 2 shows acid etched RuO prepared according to the present invention2Co synthesized by direct hydrolysis and calcination with ZIF-67 under the same conditions3O4And Co3O4-RuO2An X-ray diffraction pattern of the composite;
FIG. 3 is a graph of the Mott-Schottk test made in accordance with the present invention;
FIG. 4 shows RuO prepared according to the present invention2、Co3O4And RuO2-Co3O4Linear Sweep Voltammetry (LSV) profile of the composite;
FIG. 5 is Co3O4-RuO210000 times Cyclic Voltammetry (CV) test graph of the composite material;
FIG. 6 is Co3O4-RuO2A stability test chart of the composite material;
the specific implementation mode is as follows:
the present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1
S1: preparation of ZIF-67 suspension: adding 20mg of ZIF-67 into 1mL of methanol, and uniformly dispersing by ultrasonic;
S2：RuCl3preparation of the solution: 10mg of RuCl3Adding the mixture into 1mL of deionized water, and stirring for dissolving;
S3：Co3O4-RuO2preparing a composite material:
s3.1: adding 2mL of RuCl obtained in the step S2 into the ZIF-67 suspension finally obtained in the step S13Carrying out ultrasonic treatment on the solution and 1mL of deionized water for 5 min;
s3.2: transferring the solution finally obtained in the step S3.1 into a reaction kettle, and reacting for 6 hours under the condition of preheating at 80 ℃;
s3.3: and (3) cooling the solution finally obtained in the step S3.2 by cold water, centrifuging the product at a high speed of 18000rmp, washing the product for 3 times by using methanol, drying the product at 80 ℃, and collecting precipitate.
S3.4: the final product of step S3.3 is 99.5% N2/0.5％O2Calcining at 350 ℃ for 2h at the temperature rising rate of 4 ℃/min under the atmosphere of mixed gas and at the gas flow rate of 40sccm, and cooling to obtain Co3O4-RuO2A composite material;
FIG. 1 shows Co prepared in example 13O4-RuO2In the transmission electron microscope image of the composite material, the lattice fringes with lattice spacing d of 0.24nm and 0.20nm respectively corresponding to Co can be clearly observed in FIG. 1b3O4Crystal plane of (311) and RuO2The (210) crystal plane of (a), the results indicate that Co is present3O4And RuO2A heterojunction structure is formed between the two.
FIG. 2 shows RuO prepared in example 12、Co3O4And RuO2/Co3O4Powder X-ray diffraction Pattern of the composite further illustrating RuO2、Co3O4And RuO2-Co3O4And (4) successfully synthesizing the composite material.
Example 2
Co obtained by example 13O4-RuO2The composite material is further etched by using a 2M sulfuric acid solution with the temperature of 80 ℃, and the specific experiment is 20mg Co3O4-RuO2Dispersing in 20mL of 2M sulfuric acid solution, heating at 80 ℃ for 8h, after the reaction is finished, centrifuging, washing to be neutral, washing and drying to obtain RuO2。
Example 3
Co was obtained by direct hydrolysis and calcination with ZIF-67 under the same conditions as in example 13O4。
Example 4
The materials obtained in example 1, example 2 and example 3 and the electrochemical performances carried out thereon were tested by the following experiments.
The preparation process of the working electrode is as follows: weighing 5mg of Co3O4-RuO2The composite material is added into a 2.5mL liquid phase analysis bottle, 1mL absolute ethyl alcohol mixed solution containing 50 mu L of an anion is added, and ultrasonic dispersion is carried out for 30min to form catalyst dispersion slurry. And then, a liquid transfer gun sucks 100 mu L of the slurry to be uniformly coated on the surface of the carbon paper, and the carbon paper is naturally air-dried for 1h to be measured. The loading area of the catalyst is 0.5cm x 1cm, and the loading amount of the catalyst is 1mg/cm2. Electrochemical performance testing was performed at room temperature on a CHI760E workstation using a standard three-electrode system with graphite rods and Ag/AgCl as counter and reference electrodes, respectively. In all tests, the reference electrode potential was calibrated to the reference Reversible Hydrogen Electrode (RHE) by the method at H2In the saturated electrolyte, a platinum sheet is simultaneously used as a working electrode and a counter electrode for carrying out potential correction on a saturated calomel electrode, 2mV/s is used as a voltage scanning rate, and the average value of two potentials when current passes through zero is used as the thermodynamic potential of hydrogen electrode reaction. Unless specifically noted, potentials were calibrated to Reversible Hydrogen Electrode (RHE) using iR calibration: e (rhe) ═ e (sce) +0.059lg pH-iR, where R is the system series impedance obtained by the impedance test. Test electrolyte was 0.1M HClO4An aqueous solution of (a).
FIG. 3 is Co3O4And RuO2The graph of the Mott-Schottky test of (1) can determine the type of the semiconductor from the Mott-Schottky test result. From which Co is seen3O4Is less than 0, it can be judged thatIs a P-type semiconductor. RuO2The slope of (b) is greater than 0, and it can be judged as an N-type semiconductor. With reference to Co in FIG. 1b3O4And RuO2There is a heterojunction structure between, thus illustrating RuO2-Co3O4The composite catalyst has a P-N junction heterojunction structure.
FIG. 4 is RuO2、Co3O4And RuO2-Co3O4Linear Sweep Voltammetry (LSV) curves of composite materials, RuO2-Co3O4The catalyst is most effective, superior to pure Co3O4And RuO2And (3) sampling. RuO2-Co3O4The composite structure only needs 180mV overpotential to reach the same current density (10mA cm)-2)。
FIG. 5 is Co3O4-RuO2After 10000 times of Cyclic Voltammetry (CV) tests, the CV curve of the composite material is basically overlapped with the first test curve, which shows that the composite material RuO2-Co3O4Has excellent stability.
FIG. 6 is Co3O4-RuO2Stability testing of the composite materials by chronopotentiometry at a Current Density of 10mA cm-2When the material is used, the voltage basically has no obvious change within 12h, and the stability of the material is further illustrated.
Claims (5)
1. Co3O4-RuO2A method of making a composite material, the method comprising the steps of:
s1: preparation of ZIF-67 suspension: adding ZIF-67 into methanol, and performing ultrasonic dispersion uniformly;
S2：RuCl3preparation of the solution: adding RuCl3Adding into deionized water, stirring and dissolving;
S3：Co3O4-RuO2preparing a composite material:
s3.1: adding the final ZIF-67 suspension obtained in the step S1 into the RuCl obtained in the step S23Carrying out ultrasonic treatment on the solution and deionized water for 2-15 min;
s3.2: transferring the solution finally obtained in the step S3.1 into a reaction kettle, and reacting for 2-10h under the condition of preheating at 60-100 ℃;
s3.3: cooling the solution finally obtained in the step S3.2 by cold water, centrifuging the product at a high speed, washing the product by methanol, and drying the product at the temperature of 60-100 ℃;
s3.4: the final product obtained in the step S3.3 is added into N2And O2Calcining for 1-5h at the temperature of 500 ℃ under the atmosphere of mixed atmosphere and 200-3O4-RuO2A composite material.
2. Co of claim 13O4-RuO2The preparation method of the composite material is characterized in that in the step S1, 10-40mg of ZIF-67 is weighed and ultrasonically dispersed into 5-10mL of methanol; step S2, adding RuCl3The mass of the deionized water is 5-30mg, and the volume of the deionized water is 1-5 mL; step S3.1, the addition of RuCl3The volume of the solution is 0.5-5mL, and the volume of the deionized water is 0.5-2.5 mL.
3. Co according to claim 13O4-RuO2The preparation method of the composite material is characterized in that in the step S3.3, the speed of a centrifugal machine is 15000-21000 rpm, the time is 3-10min for one time, and the centrifugal washing is carried out for 3-6 times; in step S3.4, N is2And O2The mixing ratio of the mixed atmosphere is 99.5%/0.5% gas flow rate is 20-80 sccm, and the heating rate is 3-5 ℃/min.
4. Co obtained by the production method according to claims 1 to 33O4-RuO2A composite material.
5. Composite Co according to claims 1-43O4-RuO2Application of the electric Oxygen Evolution Reaction (OER) in an acidic environment.
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