CN110787810A - Preparation method and application of ruthenium-cobalt binary catalyst - Google Patents
Preparation method and application of ruthenium-cobalt binary catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
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- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 8
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011261 inert gas Substances 0.000 claims description 4
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- 239000003960 organic solvent Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- UNZSJASIKFONPS-UHFFFAOYSA-N C(C)(=O)N(C)C.[N].[N] Chemical compound C(C)(=O)N(C)C.[N].[N] UNZSJASIKFONPS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
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- 239000000243 solution Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 abstract 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of catalysts, in particular to a preparation method of a ruthenium-cobalt binary catalyst, which comprises the following steps: (1) dissolving and mixing nitrate and ruthenium chloride; (2) adding cobalt chloride into the mixed solution in the step (1); (3) evaporating the solvent from the solution obtained in the step (2) to dryness, and drying to obtain a solid matter; (4) activating the solid matter; (5) and centrifuging the activated solid to separate out the ruthenium-cobalt binary catalyst. The invention also provides an application of the ruthenium-cobalt binary catalyst in a hydrogen-rich water generating device. The preparation method of the ruthenium-cobalt binary catalyst provided by the invention is applied to a portable hydrogen-rich water generating device, can provide higher catalytic activity, reduces the working voltage of the hydrogen-rich water generating device, improves the hydrogen production efficiency, reduces the cost of the hydrogen-rich water generating device, and improves the market competitiveness of products.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a preparation method of a ruthenium-cobalt binary catalyst and application of the ruthenium-cobalt binary catalyst in a hydrogen-rich water generating device.
Background
Recent medical research indicates that many diseases and aging of human beings can be finally attributed to cell damage and aging, and the main cause of the disease is surplus malignant oxygen free radicals. Malignant oxygen free radicals attack normal cells and internal structures, can cause various inflammations, toxin deposition, cell damage, aging and even canceration, and bring great harm to human bodies. The human body has various ways of generating oxygen free radicals, and the oxygen free radicals can be generated when respiration, diet, ultraviolet rays, smoking, drinking, mobile phone electromagnetic radiation and emotional fluctuation are large. It is well known in the medical field that elimination of excess oxygen radicals is beneficial in reducing disease and delaying aging.
A long article "Hydrogen acts as an atherapeutic antioxidant by selective reduction of cytotoxic oxygen radials" was published by professor Taitian adult male, Japan medical university, 2007 in the world's famous journal "Nature medicine". He states that hydrogen is a selective antioxidant substance that can selectively scavenge the malignant free radicals of the human body. The hydrogen is colorless, tasteless, nontoxic and odorless gas, has small volume, strong reducibility and strong penetrability, can easily enter any parts such as cell nucleus, mitochondria and the like in cells to combine with oxygen free radicals to generate water, thereby eliminating redundant malignant oxygen free radicals. The unique property of hydrogen gas determines that it can be directly used for disease treatment of living body. From this, hydrogen has gone into people's visual field as a new tool against oxidation, and has raised the research enthusiasm of hydrogen molecular medicine internationally. Subsequently, medical research institutes in the united states, germany, france, sweden and korea, and doctors and researchers in a plurality of three hospitals in China are added into the research on the medical effect of hydrogen molecules. On 19 th 3 th 19 th 2014, the institute of molecular hydrogen biomedical sciences was officially established in Beijing by the Chinese medical council agency, and nearly 200 experts studied in molecular hydrogen biomedical science at home and abroad. By 8 months in 2018, the related projects of hydrogen molecular biology effect research have obtained the standing support limit of the national science fund project of 540 ten thousand yuan. As of 7 months in 2019, nearly 2500 papers on the medical effect of hydrogen molecules were published by more than 2000 researchers from 20 countries in the world. So far, clinical researches on more than ten diseases by hydrogen have been reported, namely type 2 diabetes, metabolic syndrome, hemodialysis, rheumatoid arthritis, Parkinson's disease, interstitial cystitis, life quality reduction caused by liver cancer radiotherapy, chronic hepatitis B, muscle diseases, cerebral ischemia, skin diseases and the like.
Hydrogen is safe to living bodies, and it is clearly specified by the Japan health and labor provinces that hydrogen can be used as a food additive. The national standard document for food safety (GB 31633-2014) of China also puts hydrogen in the safe food additive line. Compared with the conventional medicine, the hydrogen has extremely strong penetrability, can selectively resist malignant oxygen free radicals, has safe physiological action and has no toxic or side effect on human bodies. At present, no clear contraindications and contraindicated people are found.
A hydrogen-rich water generator is a device that can rapidly and portably prepare a hydrogen-rich water beverage, such as a hydrogen-rich water cup. Hydrogen-rich water cups currently on the market also exist: 1) the working voltage is too high, and ozone harmful to human bodies is easily generated; 2) the hydrogen production amount is small, and the hydrogen dissolved stock in water is low; 3) the adoption of noble metal platinum as a catalyst has a series of problems of high cost and the like, so a feasible scheme capable of effectively solving the problems is needed.
Disclosure of Invention
The invention aims to provide a preparation method of a ruthenium-cobalt binary catalyst, which is applied to a portable hydrogen-rich water generating device, can provide higher catalytic activity, reduce the working voltage of a hydrogen-rich water cup, improve the hydrogen production efficiency, reduce the cost of the hydrogen-rich water cup and improve the market competitiveness of products.
To achieve the above object, the present invention is realized by:
a preparation method of a ruthenium-cobalt binary catalyst comprises the following steps:
1) dissolving nitrate in deionized water at 40-60 ℃, adding ruthenium chloride, and stirring for 20min to fully react the nitrate with the ruthenium chloride to obtain a mixed solution A;
wherein the mass ratio of the nitrate to the ruthenium chloride is 20-40: 1;
2) keeping the temperature of the mixed solution A unchanged, adding 10-35% of cobalt oxalate into the mixed solution A by the addition amount of ruthenium chloride in the step 1), and continuously stirring for 20 minutes to obtain a mixed solution B;
3) heating the mixed solution B to 80-95 ℃, evaporating the solvent to dryness under strong mechanical stirring to obtain a solid A, putting the solid A into a vacuum drying oven, drying in vacuum at 60-80 ℃ for 12-24 h, taking out, and fully grinding by using an agate mortar to obtain a solid B;
4) putting the ground solid B into a ceramic dish and carrying out activation treatment in a tube furnace;
the activation treatment process comprises the following steps: heating the material from room temperature to 200 ℃ at the heating rate of 5 ℃/min; then heating the material to 300-700 ℃ at a heating rate of 2 ℃/min, preserving the heat for 1-3 h, and naturally cooling to room temperature;
the activation treatment process is carried out under the protection of inert gas;
5) and (3) putting the activated material in the step 4) into deionized water, accelerating the dissolving process by using ultrasonic oscillation, obtaining a ruthenium-cobalt binary catalyst suspension solution after white solid impurities are completely dissolved, separating by using an ultrahigh-speed centrifuge, pouring out supernatant liquid, washing the precipitate again by using deionized water and centrifuging, repeating the steps for 3-5 times, putting the obtained solid into a vacuum drying oven, and drying for 12 hours at the temperature of 60 ℃ to remove residual moisture to obtain the ruthenium-cobalt binary catalyst.
Preferably, the mass ratio of the nitrate to the deionized water in the step 1) is 2: 5.
Preferably, the nitrate is one of potassium nitrate, sodium nitrate, lithium nitrate, magnesium nitrate and zinc nitrate.
Preferably, the inert gas in step 4) is one of nitrogen, argon and helium.
Preferably, the centrifugation in step 5) is performed at 10000r/min for 10min at 25 ℃.
The invention also provides the application of the ruthenium-cobalt binary catalyst prepared by the preparation method of the ruthenium-cobalt binary catalyst in a hydrogen-rich water generating device.
The application method comprises the following steps:
1) adding the ruthenium-cobalt binary catalyst into one of organic solvents of ethanol, propanol, isopropanol, nitrogen-nitrogen dimethyl formamide and nitrogen-nitrogen dimethyl acetamide, and dispersing by ultrasonic oscillation;
2) adding nafion adhesive (DuPont, USA) with proton exchange function, continuing ultrasonic oscillation for 30 minutes to obtain mixed solution;
3) spraying the mixed solution obtained in the step 2) on one side of a proton exchange membrane to form a membrane electrode;
4) the membrane electrode is used for an electrolysis device diaphragm of a hydrogen-rich water generation device, and one side sprayed with the catalyst is in contact with an anode electrode plate.
Preferably, the solid-to-liquid ratio of the ruthenium-cobalt binary catalyst to the organic solvent in step 1) is 10 mg: 1 mL.
Preferably, the mass ratio of the binder to the ruthenium-cobalt binary catalyst is 1: 2-4.
Preferably, the spraying amount of the mixed solution in the step 3) is 1-5 mg/cm calculated by the ruthenium-cobalt binary catalyst2。
Compared with the prior art, the invention has the following beneficial effects:
1) the catalyst can greatly reduce the activation energy required by anodic oxidation in the electrolytic water reaction process, reduce the electrode reaction polarization overpotential, reduce the working voltage of the hydrogen-rich water cup, reduce the energy consumption and effectively avoid the generation of ozone;
2) can replace noble metal platinum catalyst, greatly reduce cost and improve market competitiveness of the product.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a polarization curve of the Ru-Co binary catalyst prepared in example 1 of the present invention measured in 0.5mol/L sulfuric acid aqueous solution, and the working electrode was a Ru-Co binary catalyst-coated glassy carbon electrode having a diameter of 3mm and a scanning rate of 2 mV/s.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following is a detailed description of specific embodiments.
Example 1
A preparation method of a ruthenium-cobalt binary catalyst specifically comprises the following steps:
1) weighing 20g of sodium nitrate, adding 100mL of deionized water, heating the mixed solution to 60 ℃, stirring to dissolve the sodium nitrate, maintaining the temperature of the solution at 60 ℃, adding 1g of ruthenium chloride, and stirring for 20min to obtain a mixed solution A;
2) while maintaining the temperature, 0.2g of cobalt oxalate (CoC) was added to the mixture A2O4) Continuously stirring for 20min to obtain a mixed solution B;
3) heating the mixed solution B to 90 ℃, evaporating the solvent to obtain a solid A, drying the solid A at 80 ℃ for 12 hours in vacuum, taking out, and fully grinding to obtain a solid B;
4) activating the ground solid B in a tube furnace,
the activation treatment process is as follows: heating the material from room temperature to 200 ℃ at the heating rate of 5 ℃/min; then heating the material to 450 ℃ at the heating rate of 2 ℃/min, preserving the heat for 1h at the temperature, and naturally cooling to room temperature;
the whole activation treatment process is carried out in an inert atmosphere under the protection of nitrogen;
5) and (3) putting the activated material into deionized water, dissolving white solids (the white solids are impurities) completely to obtain a suspension solution of the ruthenium-cobalt binary catalyst, centrifuging at 25 ℃ at a rotating speed of 10000r/min for 10min, pouring out supernatant, washing and centrifuging the residues for multiple times by using the deionized water to remove impurities, drying the obtained solid at 60 ℃ for 12h, and grinding to crush the solid to obtain the ruthenium-cobalt binary catalyst.
FIG. 1 shows the polarization curve of the Ru-Co binary catalyst prepared in this example in 0.5mol/L sulfuric acid solution, and the working electrode is a glassy carbon electrode coated with the Ru-Co binary catalyst and having a diameter of 3mm and a scanning rate of 2 mV/s.
The ruthenium-cobalt binary catalyst is applied to a hydrogen-rich water generating device, and the specific application method comprises the following steps:
1) adding 1g of the ruthenium-cobalt binary catalyst into 10mL of ethanol, and performing ultrasonic oscillation dispersion;
2) adding nafion adhesive (DuPont, USA) with proton exchange function, and continuing ultrasonic oscillation for 30min to obtain mixed solution;
wherein the mass ratio of the binder to the ruthenium-cobalt binary catalyst is 1: 3;
3) spraying the mixed solution on one side of a proton exchange membrane to form a membrane electrode;
wherein the spraying amount of the mixed solution is 3mg/cm calculated by the ruthenium-cobalt binary catalyst2；
4) The membrane electrode is cut into a round shape with the diameter of 30mm, and is used for an electrolysis device diaphragm of a hydrogen-rich water generation device, and one side sprayed with the catalyst is contacted with an anode electrode plate.
Example 2
1) Weighing 40g of potassium nitrate, adding 200mL of deionized water, heating the obtained mixed solution to 40 ℃, stirring to completely dissolve the potassium nitrate, maintaining the temperature of the solution at 40 ℃, adding 1g of ruthenium chloride, and stirring for 20min to obtain a mixed solution A;
2) while maintaining the temperature, 0.35g of cobalt oxalate (CoC) was added to the mixture A2O4) Continuously stirring for 20min to obtain a mixed solution B;
3) heating the mixed solution B to 80 ℃, evaporating the solvent to obtain a solid A, drying the solid A in vacuum at 60 ℃ for 24 hours, taking out and fully grinding the solid A to obtain a solid B;
4) activating the ground solid B in a tube furnace,
the activation treatment process is as follows: heating the material from room temperature to 200 ℃ at the heating rate of 5 ℃/min; then heating the material to 300 ℃ at the heating rate of 2 ℃/min, preserving the heat for 3 hours at the temperature, and naturally cooling to room temperature;
the whole activation treatment process is carried out in an inert atmosphere under the protection of helium;
5) and (3) putting the activated material into deionized water, dissolving white solids (the white solids are impurities) completely to obtain a suspension solution of the ruthenium-cobalt binary catalyst, centrifuging at 25 ℃ at a rotating speed of 10000r/min for 10min, pouring out supernatant, washing and centrifuging the residues for multiple times by using the deionized water to remove impurities, drying the obtained solid at 60 ℃ for 12h to remove water, and grinding to crush the solid to obtain the ruthenium-cobalt binary catalyst.
The ruthenium-cobalt binary catalyst is applied to a hydrogen-rich water generating device, and the specific application method comprises the following steps:
1) adding 2g of the ruthenium-cobalt binary catalyst into 200mL of propanol, and dispersing by ultrasonic oscillation;
2) adding nafion adhesive (DuPont, USA) with proton exchange function, and continuing ultrasonic oscillation for 30min to obtain mixed solution;
wherein the mass ratio of the binder to the ruthenium-cobalt binary catalyst is 1: 2;
3) spraying the mixed solution on one side of a proton exchange membrane to form a membrane electrode;
wherein the spraying amount of the mixed solution is 5mg/cm calculated by the ruthenium-cobalt binary catalyst2；
4) And cutting the membrane electrode into a round shape with the diameter of 30mm, applying the round shape to a diaphragm of a hydrogen-rich water cup electrolysis device, and enabling one side sprayed with the catalyst to be in contact with an anode electrode plate.
Example 3
1) Weighing 30g of magnesium nitrate, adding 150mL of deionized water, heating the obtained mixed solution to 50 ℃, stirring to completely dissolve the magnesium nitrate, maintaining the temperature of the solution at 50 ℃, adding 1g of ruthenium chloride, and stirring for 20min to obtain a mixed solution A;
2) while maintaining the temperature, 0.1g of cobalt oxalate (CoC) was added to the mixture A2O4) Continuously stirring for 20min to obtain a mixed solution B;
3) heating the mixed solution B to 95 ℃, evaporating the solvent to obtain a solid A, drying the solid A at 70 ℃ for 20 hours in vacuum, taking out, and fully grinding to obtain a solid B;
4) activating the ground solid B in a tube furnace,
the activation treatment process is as follows: heating the material from room temperature to 200 ℃ at the heating rate of 5 ℃/min; then heating the material to 700 ℃ at the heating rate of 2 ℃/min, preserving the heat for 1h at the temperature, and naturally cooling to room temperature;
the whole activation treatment process is carried out in an inert atmosphere under the protection of argon;
5) and (3) putting the activated material into deionized water, dissolving white solid (the white solid is part of impurities) completely to obtain a suspension solution of the ruthenium-cobalt binary catalyst, centrifuging at 25 ℃ at 10000r/min for 10min, pouring out supernatant, washing and centrifuging the remainder for multiple times by using deionized water to remove impurities, drying the obtained solid at 60 ℃ for 12h to remove water, and grinding to crush the solid to obtain the ruthenium-cobalt binary catalyst.
The ruthenium-cobalt binary catalyst is applied to a hydrogen-rich water generating device, and the specific application method comprises the following steps:
1) adding 0.5 of the ruthenium-cobalt binary catalyst into 50mL of nitrogen-nitrogen dimethyl formamide, and dispersing by ultrasonic oscillation;
2) adding nafion adhesive (DuPont, USA) with proton exchange function, and continuing ultrasonic oscillation for 30min to obtain mixed solution;
wherein the mass ratio of the binder to the ruthenium-cobalt binary catalyst is 1: 4;
3) spraying the mixed solution on one side of a proton exchange membrane to form a membrane electrode;
wherein the spraying amount of the mixed solution is 1mg/cm calculated by the ruthenium-cobalt binary catalyst2；
4) The membrane electrode is cut into a round shape with the diameter of 30mm, and is used for an electrolysis device diaphragm of a hydrogen-rich water generation device, and one side sprayed with the catalyst is contacted with an anode electrode plate.
Next, the operating voltage of the hydrogen-rich water generator provided in examples 1 to 3 was measured at a constant current, and the amount of hydrogen dissolved in water was measured after 5 minutes of energization, and compared with the existing commercially available products.
The results are shown in Table 1.
Table 1 measurement results of operating voltage and water-soluble hydrogen content of hydrogen-rich water generator and commercially available product provided in examples 1 to 3 of table 1
As can be seen from table 1, the hydrogen-rich water generation devices provided in embodiments 1 to 3 of the present application have lower operating voltages and can significantly reduce energy consumption compared to existing commercially available products; and the content of dissolved hydrogen in water is higher.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The preparation method of the ruthenium-cobalt binary catalyst is characterized by comprising the following steps of:
1) dissolving nitrate in deionized water at 40-60 ℃, and then adding ruthenium chloride to obtain a mixed solution A;
wherein the mass ratio of the nitrate to the ruthenium chloride is 20-40: 1;
2) adding 10-35% of cobalt oxalate into the mixed solution A by the amount of the ruthenium chloride added in the step 1), and uniformly mixing to obtain a mixed solution B;
3) heating the mixed solution B to 80-95 ℃, evaporating the solvent to dryness to obtain a solid A, drying the solid A and then crushing to obtain a solid B;
4) activating the crushed solid B;
the activation treatment process comprises the following steps: heating the material from room temperature to 200 ℃ at the heating rate of 5 ℃/min; then heating the material to 300-700 ℃ at a heating rate of 2 ℃/min, preserving the heat for 1-3 h, and naturally cooling to room temperature;
the activation treatment process is carried out under the protection of inert gas;
5) dissolving the activated material in the step 4) in deionized water, centrifuging to obtain a solid mixture, and sequentially washing and drying the solid mixture to obtain the ruthenium-cobalt binary catalyst.
2. The method for preparing the ruthenium-cobalt binary catalyst as claimed in claim 1, wherein the mass ratio of the nitrate to the deionized water in step 1) is 2: 5.
3. The method for preparing the ruthenium-cobalt binary catalyst as claimed in claim 1, wherein the nitrate is one of potassium nitrate, sodium nitrate, lithium nitrate, magnesium nitrate and zinc nitrate.
4. The method for preparing the ruthenium-cobalt binary catalyst according to claim 1, wherein the inert gas in the step 4) is one of nitrogen, argon and helium.
5. The method for preparing the ruthenium-cobalt binary catalyst according to claim 1, wherein the centrifugation in the step 5) is performed at 10000r/min for 10min at 25 ℃.
6. Use of the ruthenium cobalt binary catalyst prepared by the method of preparing a ruthenium cobalt binary catalyst according to any one of claims 1 to 5 in a hydrogen-rich water generating apparatus.
7. The application according to claim 6, characterized in that the application method comprises the following steps:
1) adding the ruthenium-cobalt binary catalyst into one of organic solvents of ethanol, propanol, isopropanol, nitrogen-nitrogen dimethyl formamide and nitrogen-nitrogen dimethyl acetamide, and oscillating and dispersing;
2) adding a binder with a proton exchange function, and performing ultrasonic oscillation for 30min to obtain a mixed solution;
3) spraying the mixed solution obtained in the step 2) on one side of a proton exchange membrane to form a membrane electrode;
4) the membrane electrode is used for an electrolysis device diaphragm of a hydrogen-rich water generation device, and one side sprayed with the catalyst is in contact with an anode electrode plate.
8. The use according to claim 7, wherein the solid-to-liquid ratio of the ruthenium-cobalt binary catalyst to the organic solvent in step 1) is 10 mg: 1 mL.
9. The use according to claim 7, wherein the mass ratio of the binder to the ruthenium-cobalt binary catalyst is 1: 2-4.
10. The use according to claim 7, wherein the spraying amount of the mixed solution in the step 3) is 1-5 mg/cm based on the ruthenium-cobalt binary catalyst2。
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