CN114622244B - Ru-SnO 2 Hydrogen evolution reaction catalyst and preparation method thereof - Google Patents
Ru-SnO 2 Hydrogen evolution reaction catalyst and preparation method thereof Download PDFInfo
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- CN114622244B CN114622244B CN202210252372.8A CN202210252372A CN114622244B CN 114622244 B CN114622244 B CN 114622244B CN 202210252372 A CN202210252372 A CN 202210252372A CN 114622244 B CN114622244 B CN 114622244B
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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
- 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
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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 discloses Ru-SnO 2 Hydrogen evolution reaction catalyst and preparation method thereof, wherein the catalyst carrier is active carbon loaded with ruthenium single atomWherein the molar ratio of Ru to Sn is 4: 4-9, the mass ratio of the active carbon to the ruthenium is 40:5 to 15; adding ruthenium trichloride and active carbon into water to prepare dispersion liquid, then adding stannous chloride aqueous solution, reacting at 10-30 ℃ for 5-20 hours, and finally vacuum drying; (2) Heating the product prepared in the step (1) to 200-500 ℃ in inert gas atmosphere, and calcining for 1-4 hours to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst; the catalyst is doped with monoatomic ruthenium in tin dioxide, has excellent catalytic activity, and has a current density of 10mA cm in a 1M KOH solution ‑2 The overpotential is 10-18 mV, and shows good stability in alkaline environments; the method is simple and quick to operate, and can realize large-scale production.
Description
Technical Field
The invention relates to a catalyst for electrolytic reaction, in particular to Ru-SnO 2 A hydrogen evolution reaction catalyst and a preparation method thereof.
Background
With the rapid consumption of fossil fuels and the increasing global energy demand, there is an urgent need to develop renewable clean energy, H 2 As a renewable energy source which is easy to store and transport, clean, pollution-free and high in energy density, the renewable energy source is considered as one of potential candidates of a future low-carbon energy system. Electrolytic water has received much attention in recent years as a zero-carbon hydrogen production process, H in the hydrogen economy cycle 2 The combustion releases energy while the regenerated water is the only starting molecule and byproduct in the hydrogen economy cycle.
Water splitting reaction (H) 2 O→H 2 +1/2O 2 ) Consists of two half reactions, namely an oxygen evolution reaction and a hydrogen evolution reaction. As with any chemical reaction, the water splitting reaction also requires overcoming a large energy barrier during the reaction. Therefore, we need to develop the suitableTo minimize overpotential for hydrogen and oxygen production.
Among the currently mainstream catalysts, although some metal-free and non-noble metal catalysts exhibit better catalytic performance, still exhibit higher overpotential and lower stability than platinum group metals. Ru is of great interest because of its better hydrolytic capacity than Pt, stronger bonding strength to H and OH, and relatively lower price. However, at the same time Ru-based catalysts also expose problems such as strong adsorption of Ru to OH for hydrogen evolution reactions, blocking the active sites, slowing down the reaction rate.
Disclosure of Invention
The invention aims to: the invention aims to provide Ru-SnO with excellent electrocatalytic activity and stability for hydrogen gas precipitation reaction 2 Hydrogen evolution reaction catalyst; it is another object of the present invention to provide a process for preparing the catalyst.
The technical scheme is as follows: ru-SnO of the invention 2 The carrier of the hydrogen evolution reaction catalyst is active carbon, and the carrier is loaded with ruthenium single-atom doped tin dioxide nano particles, wherein the molar ratio of Ru to Sn is 4: 4-9, the mass ratio of the active carbon to the ruthenium is 40:5 to 15.
Preferably, the molar ratio of Ru to Sn is 4:6-9. SnO (SnO) 2 The content of Ru is small, the catalytic effect is not obvious, and the active sites of Ru on the surface can be blocked too much.
Preferably, the mass ratio of the activated carbon to the ruthenium is 40:10-15. The active carbon is used as a conductive substrate, the consumption is small, and single-atom Ru doped SnO 2 The dispersion effect on the surface is poor, so that agglomeration is caused, and the overall catalytic performance is reduced; the dosage is small, and single atom Ru doped SnO 2 The distribution is too dispersed, and the catalyst with the same mass has fewer catalytic active sites on the surface, so that the catalytic performance is poor.
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) Adding ruthenium trichloride and active carbon into water to prepare dispersion liquid, then adding stannous chloride aqueous solution, reacting at 10-30 ℃ for 5-20 hours, and finally vacuum drying;
(2) Heating the product prepared in the step (1) to 200-500 ℃ in inert gas atmosphere, and calcining for 1-4 hours to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
The reaction process of the step (1) is based on thermodynamic data
Ru 3+ Can be coated with SnCl 2 Reduction of Sn 2+ Is easily oxidized in the oxidation reaction process, thereby being converted into SnO 2 . Notably, ru 3+ Is not reduced to Ru 0 Clusters, but in SnO 2 Sites formed on the surface of the nano particles and coordinated with Ru-O. This is because Ru-O bond strength is +.>
Ru-Ru bond strength is->
The former is more thermodynamically formed. After the reaction of the step (1), drying and calcining are carried out, and the surface structure of the synthesized catalyst is more stable through calcination annealing treatment.
Preferably, in the step (1), the reaction temperature is 20-30 ℃ and the reaction time is 10-12 hours. The reaction temperature is low, the reaction rate is too slow, the temperature is high, the reaction is severe, the product is easy to agglomerate, and the catalytic performance is poor.
In the step (1), the drying is vacuum drying, so that the contact with air is avoided, and the catalyst is prevented from being exposed to air and heated to be deactivated. The preferred drying temperature is 30 to 60 ℃.
Preferably, in the step (2), the temperature is raised to 300-500 ℃, the temperature raising rate is 1-5 ℃/min, and the calcination time is 1-2 hours. Too high a calcination temperature can cause particle agglomeration, reducing catalytic performance; the calcination temperature is too low and nickel hydroxide cannot be converted to nickel oxide. The nickel hydroxide is incompletely converted into nickel oxide after the calcination time is short, and the particle agglomeration is easy to cause after the calcination time is long.
The inert gas is any one of nitrogen, argon, helium or carbon dioxide.
The mechanism of the invention is as follows: in the Volmer step in the hydrogen evolution reaction,
plays an important role, and for Ru, ru is used for OH ad Is too strong to slow down the reaction rate, while we have introduced SnO 2 To solve this problem. SnO (SnO) 2 Has stronger adsorption of OH relative to Ru ad Is formed into a pair OH with Ru sites ad Is used for effectively relieving the competition adsorption of Ru to OH ad This facilitates the release of Ru active sites, improves the reaction progress of HER, and shows excellent catalytic activity and stability.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The catalyst is doped with monoatomic ruthenium in tin dioxide, has excellent catalytic activity, and has a current density of 10mA cm in a 1M KOH solution -2 The overpotential is 10-18 mV, and shows good stability in alkaline environments; (2) The method is simple and quick to operate, and can realize large-scale production.
Drawings
FIG. 1 is a TEM spectrum of the catalyst prepared in example 2;
FIG. 2 is a HAADF-STEM map of the catalyst prepared in example 2;
FIG. 3 is a graph showing the particle size distribution of the catalyst prepared in example 2;
FIG. 4 is an XRD pattern of the catalyst prepared in example 2;
FIG. 5 is an XPS spectrum of the catalyst prepared in example 2;
FIG. 6 HER curve of the catalyst prepared in example 2 versus a commercially available Pt/C catalyst in 1M KOH solution;
FIG. 7 is a mass activity curve of the catalyst prepared in example 2 versus a commercially available Pt/C catalyst in 1M KOH solution;
FIG. 8 a stability test curve of the catalyst prepared in example 2 in 1M KOH solution;
figure 9 HER curve of the catalyst prepared according to the invention in 1M KOH solution.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) 40mg of activated carbon was added to 2mL of RuCl 3 (0.025M) in water and sonicated for 1 hour, then 3mL of freshly prepared SnCl was added thereto 2 ·2H 2 O (0.025M) aqueous solution, reacting for 20 hours at 10 ℃, washing three times with deionized water, and vacuum drying at 30 ℃;
(2) Calcining the product obtained in the step (1) for 4 hours in a nitrogen atmosphere at 200 ℃ at a heating rate of 1 ℃/min to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
Example 2
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) 40mg of activated carbon was added to 4mL of RuCl 3 (0.025M) in water and sonicated for 1 hour, then 6mL of freshly prepared SnCl was added thereto 2 ·2H 2 O (0.025M) aqueous solution, reacting for 15 hours at 20 ℃, washing three times with deionized water, and vacuum drying at 40 ℃;
(2) Calcining the product obtained in the step (1) for 2 hours in a nitrogen atmosphere at 300 ℃ at a heating rate of 2 ℃/min to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
Example 3
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) 40mg of activated carbon was added to 6mL of RuCl 3 (0.025M) in water and sonicated for 1 hour, then 9mL of freshly prepared SnCl was added thereto 2 ·2H 2 O (0.025M) aqueous solution, reacting for 10 hours at 25 ℃, washing three times with deionized water, and vacuum drying at 60 ℃;
(2) Calcining the product obtained in the step (1) for 1h in a nitrogen atmosphere at 500 ℃ at a heating rate of 5 ℃/min to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
Example 4
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) 40mg of activated carbon was added to 6mL of RuCl 3 (0.025M) in water and sonicated for 1 hour, then 6mL of freshly prepared SnCl was added thereto 2 ·2H 2 O (0.025M) aqueous solution, reacting for 5 hours at 30 ℃, washing three times with deionized water, and vacuum drying at 40 ℃;
(2) Calcining the product obtained in the step (1) for 2 hours in a nitrogen atmosphere at 300 ℃ at a heating rate of 2 ℃/min to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
Example 5
Ru-SnO of the invention 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) 40mg of activated carbon was added to 4mL of RuCl 3 (0.025M) in water and sonicated for 1 hour, then 9mL of freshly prepared SnCl was added thereto 2 ·2H 2 O (0.025M) aqueous solution, reacting for 15 hours at 20 ℃, washing three times with deionized water, and vacuum drying at 40 ℃;
(2) Calcining the product obtained in the step (1) for 2 hours in an argon atmosphere at 300 ℃ and heating up at a rate of 2 ℃/min to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst.
Characterization of Performance
The catalyst prepared in example 2 was physically characterized using TEM, HAADF-STEM, XRD and XPS.
As can be seen from the TEM image (FIG. 1 a), snO 2 Supported by ultra-small nanoparticles on activated carbon, further enlargement (FIG. 1 b) can observe ordered lattice fringes with 0.348nm interplanar spacing on the particle surface, corresponding to SnO 2 110 crystal plane of (c).
As can be seen from the HAADF-STEM diagram (FIG. 2), ru is in SnO 2 The independent dispersion in the host demonstrated that Ru was present in the form of a single atom.
Obtained from particle size distribution (FIG. 3) spectrum 2 The average size of the nanoparticles was about 2.0nm.
As can be seen from XRD patterns (FIG. 4), the diffraction peaks of the material can be compared with those of SnO 2 The standard card was fully matched (JCPDS card, 41-1445), and no Ru peak was observed, indicating that Ru was present in amorphous form.
As can be obtained from XPS spectra (fig. 5), two elements Ru, sn coexist in the catalyst.
FIG. 6 is a graph showing the Hydrogen Evolution (HER) profile of the catalyst prepared in example 2 and a commercially available Pt/C catalyst in 1M KOH solution, as can be seen from the graph, the catalyst prepared in example 2 has a current density of 10mA cm -2 The overpotential was only 10mV, which is superior to the commercial Pt/C catalyst (21 mV). The catalyst prepared in example 2 had higher HER activity in alkaline electrolyte than the commercially available Pt/C catalyst, due mainly to SnO 2 Competing adsorption with Ru reduces poisoning of Ru sites "Ru-OH" and allows more active sites to be exposed.
FIG. 7 is a graph showing the mass activity of the catalyst prepared in example 2 and a commercially available Pt/C catalyst in 1M KOH solution, the mass activity of the catalyst prepared in example 2 at 25mV being 1262.7mA mg -1 Ru Is a commercial Pt/C catalyst (122.4 mA mg -1 Pt ) And shows a higher atomic utilization by a factor of 8.2.
FIG. 8 is a graph showing the stability test of the catalyst prepared in example 2 in 1M KOH solution, wherein the current does not change significantly after 27 hours of stable operation, thus proving that the catalyst prepared in accordance with the present invention has good stability in alkaline environments.
FIG. 9 is a graph of Hydrogen Evolution (HER) at a current density of 10mA cm in 1M KOH solution for catalysts prepared in examples 1, 3, 4 and 5 -2 The overpotential at the position is 18mV,17mV,11mV and 16mV respectively, and has better catalytic activity.
Claims (9)
1. Ru-SnO 2 The preparation method of the hydrogen evolution reaction catalyst comprises the following steps:
(1) Adding ruthenium trichloride and active carbon into water to prepare a dispersion liquid, then adding stannous chloride aqueous solution, reacting at 10-30 ℃ for 5-20 hours, and finally drying in vacuum;
(2) Heating the product prepared in the step (1) to 200-500 ℃ in an inert gas atmosphere, and calcining for 1-4 hours to obtain Ru-SnO 2 Hydrogen evolution reaction catalyst;
in the obtained catalyst, the molar ratio of Ru to Sn is 4: 4-9, wherein the mass ratio of the activated carbon to the ruthenium is 40: 5-15.
2. The method for preparing a catalyst according to claim 1, wherein in the step (1), the reaction temperature is 20 to 30 ℃ and the reaction time is 10 to 15 hours.
3. The method for preparing a catalyst according to claim 1, wherein in the step (1), the vacuum drying temperature is 30-60 ℃.
4. The method for preparing a catalyst according to claim 1, wherein in the step (2), the temperature is raised to 300 to 500 ℃ and the calcination time is 1 to 2 hours.
5. The method for preparing a catalyst according to claim 1, wherein in the step (2), the heating rate is 1-5 ℃/min.
6. The method for preparing a catalyst according to claim 1, wherein in the step (2), the inert gas is any one of nitrogen, argon and helium.
7. Ru-SnO prepared according to any one of the methods of claims 1-6 2 The hydrogen evolution reaction catalyst is characterized in that the carrier is active carbon and is loaded with tin dioxide nano particles doped with ruthenium monoatoms.
8. The catalyst of claim 7, wherein the Ru to Sn molar ratio is 4:6 to 9.
9. The catalyst according to claim 7, wherein the mass ratio of the activated carbon to ruthenium is 40:10-15.
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| CN101530797A (en) * | 2008-10-16 | 2009-09-16 | 郑州大学 | Catalyst with core-casing structure and preparation method thereof |
| CN103713016B (en) * | 2013-12-26 | 2016-06-22 | 武汉工程大学 | Palladium doping stannic oxide enveloped carbon nanometer tube and its preparation method and application |
| CN103657629B (en) * | 2013-12-30 | 2016-03-30 | 北京化工大学 | High dispersancy nano Pt-SnO 2the preparation method of/C catalyst |
| SG11201610165SA (en) * | 2014-06-05 | 2017-01-27 | Agency Science Tech & Res | Electrocatalyst for hydrogen production |
| KR102569084B1 (en) * | 2016-10-28 | 2023-08-22 | 바스프 에스이 | An electrocatalyst composition comprising a noble metal oxide supported on tin oxide |
| CN110152712B (en) * | 2019-06-06 | 2021-09-24 | 郑州大学 | Ru-based hydrogen evolution catalyst and preparation method and application thereof |
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| CN111001425A (en) * | 2019-12-05 | 2020-04-14 | 江南大学 | Ruthenium-loaded monoatomic electrolytic water catalytic material and preparation method thereof |
| CN113278990B (en) * | 2021-05-25 | 2023-08-22 | 中北大学 | Ruthenium quantum dot loaded carbon fiber hydrogen evolution catalyst and preparation method and application thereof |
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