CN113699549B - Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof - Google Patents
Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN113699549B CN113699549B CN202111071894.XA CN202111071894A CN113699549B CN 113699549 B CN113699549 B CN 113699549B CN 202111071894 A CN202111071894 A CN 202111071894A CN 113699549 B CN113699549 B CN 113699549B
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/004—Oxides; Hydroxides
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- 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
- C25B1/27—Ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention belongs to the field of catalyst materials, and particularly relates to a ruthenium and tin bimetallic oxide electrocatalytic material, and a preparation method and application thereof. The catalyst is synthesized by a simple hydrothermal method: dissolving a tin oxide precursor in deionized water, fully stirring, adding urea, hydrochloric acid and ruthenium oxide precursor, transferring the solution to a stainless steel autoclave for hydrothermal reaction for a plurality of hours, filtering, washing and vacuum drying to obtain a final product. The ruthenium-tin bimetallic oxide catalyst has good stability and large specific surface area. The catalyst is dripped on carbon cloth to be used as a working electrode for electrocatalytic nitrogen reduction ammonia production, and the catalytic ammonia production effect is ideal. The preparation method of the catalytic material is simple, has high repeatability, and can be popularized and applied to other electrocatalytic directions.
Description
Technical Field
The invention belongs to the field of catalyst materials, and particularly relates to a ruthenium and tin bimetallic oxide electrocatalytic material, and a preparation method and application thereof.
Background
Ammonia is the second largest chemical in industrial production and is commonly used in pharmaceutical, synthetic fibers andchemical fertilizer production and other fields. Ammonia is H 2 Is also the only ideal storage medium for decomposing and not discharging CO 2 Is a carbon-free energy carrier. The Haber-Bosch process, which is currently used in industry, needs to be implemented under high temperature and pressure conditions, is energy intensive and highly dependent on fossil fuels, whose combustion is a major source of greenhouse gas emissions. The electrochemical reduction method can utilize renewable energy such as solar energy or wind energy to convert N 2 And conversion of water to NH 3 Provides a very promising method for nitrogen fixation under the condition of normal temperature and normal pressure. An effective nitrogen fixation catalyst should have sufficient active sites, optimized electronic structure, and be capable of selectively adsorbing and activating N 2 . In view of thermodynamic stability, acid resistance, HER inhibition and the like, snO is considered 2 Has good application prospect, but because of SnO 2 Low conductivity, weak adsorptivity, and thus exhibits limited catalytic activity. Ru is known as the second generation NH 3 Catalysts, but currently Ru has been less studied for electrochemical nitrogen fixation.
Disclosure of Invention
The invention aims to provide a preparation method of a ruthenium-tin bimetallic oxide catalytic material with simple synthesis method, good stability and large specific surface area.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the ruthenium and tin bimetallic oxide electrocatalytic material is prepared through simple hydrothermal reaction, dissolving tin oxide precursor in deionized water, stirring thoroughly, adding urea, hydrochloric acid and ruthenium oxide precursor, transferring the solution to a stainless steel autoclave for hydrothermal reaction for several hours, filtering, washing and vacuum drying to obtain the final product.
Ruthenium as described above&Tin bimetallic oxide electrocatalytic material, wherein the tin oxide precursor is SnCl 4 A solution; the ruthenium oxide precursor is RuCl 3 ·xH 2 O。
The mass ratio of the tin oxide precursor to the ruthenium oxide precursor is about 7-15:1.
the stirring time of the ruthenium-tin bimetallic oxide electrocatalytic material is 10-15min.
The ruthenium and tin bimetallic oxide electrocatalytic material is characterized in that the hydrochloric acid is concentrated hydrochloric acid with the concentration of 12 mol/L.
The reaction temperature of the hydrothermal reaction of the ruthenium and tin bimetallic oxide electrocatalytic material is 150-180 ℃ and the reaction time is 24 hours.
The ruthenium and tin bimetallic oxide electrocatalytic material adopts a vacuum filtration membrane of 0.22 μm or 0.45 μm mixed cellulose membrane during the suction filtration.
The application of any ruthenium and tin bimetallic oxide electrocatalytic material in electrocatalytic nitrogen reduction to produce ammonia.
The application method comprises the following steps: h-type electrolytic cell is used as an electrolytic tank, na 2 SO 4 The solution is used as electrolyte, and in the nitrogen atmosphere, electrocatalytic nitrogen reduction is carried out in a three-electrode system to produce ammonia. The three-electrode system is as follows: ruthenium (Ru)&The tin bimetallic electrocatalytic material is used as a working electrode, an Ag/AgCl (3.5 mol/LKCl) electrode is used as a reference electrode, and a carbon rod electrode is used as a counter electrode.
For the above application, the Na 2 SO 4 The concentration of the solution was 0.1mol/L.
The preparation method of the working electrode comprises the steps of taking ruthenium and tin bimetallic oxide in a centrifugal test tube, adding absolute ethyl alcohol and Nafion solution, performing ultrasonic dispersion, dropping the obtained dispersion on carbon cloth, and performing vacuum drying at 60 ℃ for 12 hours.
The beneficial effects of the invention are as follows: the invention provides a simple and feasible method for preparing a ruthenium-tin bimetallic oxide electrocatalytic material. The novel ruthenium and tin bimetallic oxide catalytic material obtained by the invention has the characteristics of good conductivity, large specific surface area, high stability and the like, and shows ideal catalytic ammonia production performance. The electrocatalytic material prepared by the method has wide application prospect in the aspect of electrocatalytic nitrogen reduction and ammonia production.
Drawings
FIG. 1 is an XPS diagram of a ruthenium & tin bimetallic oxide electrocatalytic material synthesized in example 1.
Fig. 2 is an SEM image of ruthenium & tin bi-metal oxide electrocatalytic materials synthesized in example 1.
FIG. 3 is an EDS diagram of ruthenium & tin bimetallic oxide electrocatalytic materials synthesized in example 1.
FIG. 4 is a graph of ammonia production efficiency of ruthenium & tin bi-metal oxide electrocatalytic materials for nitrogen reduction ammonia production of example 2.
Detailed Description
EXAMPLE 1 ruthenium & tin bimetallic oxide electrocatalytic Material
The preparation method comprises the following steps: ruO (Ruo) 2 @Sn-SnO 2 Preparation of the catalyst
0.69g of stannic chloride hydrate is dissolved in 40mL of deionized water and stirred for 10min, then 1.0g of urea and 2mL of concentrated hydrochloric acid with a concentration of 12mol/L are added to the solution. Subsequently, 0.07g RuCl was added to the aqueous solution 3 ·xH 2 O. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heated at 150℃for 24h. Cooling to room temperature, filtering and washing. The vacuum filtered membrane was a 0.22 μm or 0.45 μm mixed cellulose membrane. Finally, vacuum drying is carried out for 12 hours at 60 ℃ to obtain the final product.
(II) results of experiments
Fig. 1 is an XPS diagram of the ruthenium & tin bi-metal oxide electrocatalytic material prepared in example 1. As shown in the figure, the ruthenium and tin bimetallic nano-particles are successfully immobilized on the surface of the electrocatalytic material.
Fig. 2 is an SEM image of the ruthenium & tin bi-metal oxide electrocatalytic material prepared in example 1. As shown, the ruthenium and tin bimetallic nanoparticles are tightly bound together.
Fig. 3 is an EDS diagram of the ruthenium & tin bimetallic oxide electrocatalytic material prepared in example 1. As shown in the figure, the prepared ruthenium-tin bimetallic oxide electrocatalytic material comprises the following components in percentage by mass: sn=1:8.
Example 2 ruthenium & tin bimetallic oxide electrocatalytic nitrogen reduction ammonia production Performance test
1. Pretreatment of carbon cloth:
calcining carbon cloth (1 cm×1 cm) at 300deg.C for 1 hr, ultrasonic treating in 20wt% hydrochloric acid solution for 30min, washing with ethanol and distilled water several times, and drying in vacuum oven.
2. Preparation of working electrode
5mg of the ruthenium & tin bimetallic oxide catalyst was dispersed in 1mL of a solution (0.4 mL of absolute ethanol, 0.6mL of ultrapure water, and 10. Mu.L of a 0.5wt% Nafion solution) and sonicated for 1h to form a catalyst solution. The obtained catalyst dispersion solution was dropped on the pretreated carbon cloth.
3. Ammonia production performance test
Under the nitrogen atmosphere, an H-type electrolytic cell is selected as an electrolytic tank, and the electrolyte is 0.1mol/LNa 2 SO 4 The volume of the solution is 70mL, the proton exchange membrane is Nafion117 membrane, and the ruthenium&The tin bimetallic oxide electrocatalytic material is used as a working electrode, the reference electrode is Ag/AgCl (3.5 mol/LKCl), and the counter electrode is a carbon rod. In this process, nitrogen was continuously introduced at a gas flow rate of 25mL/min.
The product was analysed spectrophotometrically with Navier reagent. As shown in FIG. 4, ruthenium was detected at-0.2V&The ammonia production efficiency of the tin bimetallic oxide electrocatalytic material is highest, and the highest Faraday efficiency can reach 10.74%; the ammonia yield is also maximized at this timeThe catalytic material has higher electrocatalytic performance, which shows that the catalytic material has ideal development prospect in the field of electrocatalytic nitrogen reduction and ammonia production.
Claims (8)
1. The application of a ruthenium-tin bimetallic oxide electrocatalytic material in electrocatalytic nitrogen reduction to produce ammonia is characterized in that: the ruthenium-tin bimetallic oxide catalyst is prepared by dissolving a tin oxide precursor in deionized water, fully stirring, then adding urea, hydrochloric acid and the ruthenium oxide precursor, finally transferring the solution to a stainless steel autoclave for hydrothermal reaction for a plurality of hours, filtering and washing, and vacuum drying to obtain a final product;
the mass ratio of the tin oxide precursor to the ruthenium oxide precursor is 7-15:1.
2. The use according to claim 1, characterized in that: the tin oxide precursor is SnCl 4 A hydrate; the ruthenium oxide precursor is RuCl 3 •xH 2 O。
3. The use according to claim 2, characterized in that: the time of fully stirring is 10-15min.
4. A use according to claim 3, characterized in that: the hydrochloric acid is concentrated hydrochloric acid with the concentration of 12 mol/L.
5. The use according to claim 4, characterized in that: the reaction temperature of the hydrothermal reaction is 150-180 ℃ and the reaction time is 24h.
6. The use according to claim 5, characterized in that: the method comprises the following steps: h-type electrolytic cell is used as an electrolytic tank, na 2 SO 4 The solution is used as electrolyte, and electrocatalytic nitrogen reduction is carried out in a three-electrode system to produce ammonia in a nitrogen atmosphere, wherein the three-electrode system is as follows: ruthenium (Ru)&The tin bimetallic electrocatalytic material is used as a working electrode, an Ag/AgCl (3.5 mol/LKCl) electrode is used as a reference electrode, and a carbon rod electrode is used as a counter electrode.
7. The use according to claim 6, characterized in that: the Na is 2 SO 4 The concentration of the solution was 0.1mol/L.
8. The use according to claim 6, characterized in that: the preparation method of the working electrode comprises the following steps: taking ruthenium and tin double oxide, adding absolute ethyl alcohol and Nafion solution into a centrifugal test tube, performing ultrasonic dispersion, dripping the obtained dispersion on carbon cloth, and performing vacuum drying at 60 ℃ for 12 hours.
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| CN114669299B (en) * | 2022-03-14 | 2023-07-25 | 福州大学 | Mesoporous carbon-loaded copper-iron bimetallic catalyst and preparation method and application thereof |
| CN114622244B (en) * | 2022-03-15 | 2023-06-20 | 南京师范大学 | Ru-SnO 2 Hydrogen evolution reaction catalyst and preparation method thereof |
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| WO2019193594A1 (en) * | 2018-04-02 | 2019-10-10 | Ariel Scientific Innovations Ltd. | Electrocatalysts, the preparation thereof, and using the same for ammonia synthesis |
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