CN108823602B - Ruthenium sulfide particle composite material, preparation method and application thereof - Google Patents
Ruthenium sulfide particle composite material, preparation method and application thereof Download PDFInfo
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- CN108823602B CN108823602B CN201810761757.0A CN201810761757A CN108823602B CN 108823602 B CN108823602 B CN 108823602B CN 201810761757 A CN201810761757 A CN 201810761757A CN 108823602 B CN108823602 B CN 108823602B
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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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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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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- 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
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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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 a ruthenium sulfide particle composite material which comprises a conductive substrate material and ruthenium sulfide particles growing on the conductive substrate material. The invention also discloses a preparation method of the ruthenium sulfide particle composite material and application of the ruthenium sulfide particle composite material in electrolyzing and water-separating hydrogen cathode material.
Description
Technical Field
The invention belongs to the technical field of inorganic advanced materials, and particularly relates to a preparation method and application of a ruthenium sulfide particle composite material.
Background
The continuous development and utilization of fossil resources accelerate the development of society, bring a lot of benefits to people and also provide great challenges to the sustainable development of society. The increasing aggravation of the problems of energy crisis, environmental pollution and the like causes people to have to vigorously develop clean energy. Hydrogen energy is a novel clean energy, and has attracted attention due to the advantages of high energy density of stored energy, zero emission of carbon dioxide, large earth reserve and the like. The hydrogen production process by water electrolysis is simple, the technical route is mature, and the method is a reliable method capable of producing hydrogen energy in large scale. However, the electrode catalyst material which is most applied in the water electrolysis hydrogen production industry is also a platinum-based material, and the large-scale application of the platinum is limited due to the limited storage amount and high price of the platinum. Non-noble metal materials are abundant and cheap, and researchers have made many efforts to replace platinum-based materials with non-noble metal materials in recent ten years, but most of the non-noble metal materials can only work under one condition (such as neutral, acidic or alkaline conditions) and have poor stability, rapid attenuation of catalytic performance and low hydrogen evolution efficiency, so that the current non-noble metal catalysts cannot meet the requirements of industrial application. Ruthenium is used as a transition noble metal element, the price of the ruthenium is only about 1/25 of platinum, and the ruthenium-containing material can have the performance similar to that of platinum and can stably work under neutral, acidic or alkaline conditions through regulation and control. The ruthenium-containing material is expected to replace platinum in the field of catalytic hydrogen evolution.
Disclosure of Invention
The invention firstly utilizes a one-step solvothermal method to prepare the ruthenium sulfide nanoparticle composite electrode material with ultrahigh activity and stability, and the ruthenium sulfide nanoparticle composite electrode material is used as an electrode material to produce hydrogen by electrolyzing water, thereby showing excellent performance.
The technical scheme of the invention is as follows:
in a first aspect, the present invention discloses a ruthenium sulfide particle composite material comprising a conductive base material and ruthenium sulfide particles grown on the conductive base material.
Preferably, the conductive base material is a carbon material.
Preferably, the carbon material is a graphene material.
Preferably, the ruthenium sulfide nanoparticles are amorphous.
Preferably, the ruthenium sulphide particles are nanoparticles.
Preferably, the nanoparticles have a particle size distribution of 1-500nm, more preferably 20-50 nm.
The second aspect of the invention discloses a preparation method of the ruthenium sulfide particle composite material, which comprises the following steps: adding a conductive substrate material into a solution containing a ruthenium source and a vulcanizing agent, heating in a closed state, carrying out solvothermal reaction under autogenous pressure, and separating and drying after the reaction is finished to obtain the ruthenium sulfide particle composite material.
Preferably, the conductive substrate material is a graphene material; the ruthenium source is one or more of ruthenium chloride, ruthenium sulfate or ruthenium nitrate; the vulcanizing agent is one or more of sodium sulfide, thiourea, thioacetamide or sulfur; the solvent used for the solution containing the ruthenium source and the sulfidizing agent is water, alcohol or a mixture thereof.
Preferably, the conditions of the solvothermal reaction are: the temperature is 80-300 ℃, and the reaction time is 15 minutes-24 hours.
In a third aspect the invention discloses the use of the ruthenium sulphide particle composite for electrode materials.
Preferably, the use of the ruthenium sulphide particulate composite material for the electrolysis of a water hydrogen evolution cathode material.
The invention has the beneficial effects that:
1. the ruthenium sulphide particle composite of the invention was prepared for the first time as shown in figure 1. The ruthenium sulfide is tightly combined with the substrate, so that the stability of the material is improved; meanwhile, because the ruthenium sulfide particles are amorphous, the structure of the ruthenium sulfide particles is disordered in a long range, more active sites can be exposed for electrochemical reaction, and the electrochemical reaction efficiency is improved. Preferably, the ruthenium sulfide particles are nanoparticles. When the ruthenium sulfide nanoparticles are nanoparticles, more active sites can be exposed for electrochemical reaction, and the electrochemical reaction efficiency can be improved more.
2. The substrate of the ruthenium sulfide particle composite material is a conductive graphene material. The composite material has low price, shows excellent performance in cathode materials for electrolyzing water and generating hydrogen under acidic, neutral or alkaline conditions, and is expected to replace platinum-based materials in application of electrode materials.
3. The preparation method is synthesized under the condition of simple solvothermal reaction, is simple and convenient, has low cost and good repeatability, is environment-friendly and is beneficial to industrial production. The preparation method is unique and ingenious, and provides a new idea for synthesizing the electrode material with high activity.
Drawings
FIG. 1 is a schematic representation of a ruthenium sulfide particle composite of the present invention.
FIG. 2 is a Transmission Electron Micrograph (TEM) of a ruthenium sulfide particle composite of example 1 of the present invention.
FIG. 3 is a selected area electron diffraction pattern of the ruthenium sulfide particle composite of example 1 of the present invention.
FIG. 4 is a graph of the elemental distribution of the ruthenium sulfide particle composite of example 1 of the invention.
FIG. 5 is an X-ray diffraction pattern (XRD) A of the ruthenium sulphide particle composite of example 1 of the invention and an X-ray diffraction pattern (XRD) B of graphene alone.
FIG. 6 is a Transmission Electron Micrograph (TEM) of a ruthenium sulfide particle composite of example 2 of the present invention.
FIG. 7 is a Transmission Electron Micrograph (TEM) of a ruthenium sulfide particle composite of example 3 of the present invention.
FIG. 8 is a Transmission Electron Micrograph (TEM) of a ruthenium sulfide particle composite of example 4 of the present invention.
FIG. 9 shows a ruthenium sulfide particle composite material in accordance with example 1 of the present invention0.5mol/L of H2SO4Polarization curve (solid line) in the solution (pH 0) of (c), and H at 0.5mol/L of commercial platinum carbon2SO4The polarization curve (dotted line) in the solution (pH ═ 0) of (a).
Fig. 10 is a graph showing the polarization curve (solid line) of the ruthenium sulfide particle composite material of example 1 of the present invention in a phosphoric acid buffer solution (pH 7) and the polarization curve (dotted line) of commercial platinum carbon in a phosphoric acid buffer solution (pH 7).
Fig. 11 is a graph of the polarization curve (solid line) of the ruthenium sulfide particle composite of example 1 of the present invention in a solution of 1.0mol/L KOH (pH 14) and the polarization curve (dotted line) of commercial platinum carbon in a solution of 1.0mol/L KOH (pH 14).
FIG. 12 shows the concentration of H at 0.5mol/L in the ruthenium sulfide particle composite of example 1 of the present invention2SO4In a solution of (A) (pH 0), a stability curve (A) at a current density of 50 milliamperes per square centimeter, and H at 0.5mol/L for commercial platinum-carbon2SO4At a current density of 50 milliamperes per square centimeter in the solution (pH 0) (graph (B)).
Fig. 13 is a graph of the stability curve (a) at a current density of 50 ma/cm in a phosphoric acid buffer solution (pH 7) for the ruthenium sulfide particle composite of example 1 of the present invention and the stability curve (B) at a current density of 50 ma/cm in a phosphoric acid buffer solution (pH 7) for commercial platinum carbon.
Fig. 14 is a graph of the stability curve (a) for 50 milliamps per square centimeter current density in a 1.0mol/L KOH solution (pH 14) for the ruthenium sulfide particle composite of example 1 of the present invention, and the stability curve (B) for 50 milliamps per square centimeter current density in a 1.0mol/L KOH solution (pH 14) for commercial platinum carbon.
Detailed Description
The invention is further illustrated by the following examples. The embodiments are merely illustrative and not restrictive.
Example 1
40 ml of an aqueous solution containing 0.5 mmol/l of ruthenium chloride and 10 mmol/l of thioacetamide was prepared and added to the reaction vessel, and then 20 mg of graphene powder was added to the reaction vessel and stirred uniformly. The reaction vessel was then closed, warmed to 150 ℃ and held under autogenous pressure for 6 hours for solvothermal reaction. And naturally cooling after the reaction is finished, centrifugally washing and drying to obtain the ruthenium sulfide particle composite material with the graphene as the substrate.
The obtained ruthenium sulfide particle composite material has a transmission electron microscope image as shown in figure 2, an electron diffraction image as shown in figure 3, an element distribution image as shown in figure 4 and an XRD (X-ray diffraction) spectrum as shown in figure 5. From fig. 2, it can be seen that the ruthenium sulfide particles are uniformly distributed on the graphene, and the particle size is 20-50 nm; FIG. 3 shows the diffraction ring with only graphene, without the diffraction ring with ruthenium sulfide, so ruthenium sulfide is amorphous; fig. 4 illustrates that the particles on the surface of graphene are ruthenium sulfide nanoparticles; fig. 5 also shows that ruthenium sulfide has no X-ray diffraction peak, confirming that it is amorphous.
Example 2
Referring to the procedure in example 1, thioacetamide was replaced by thiourea and the solvothermal reaction conditions were changed to: the temperature was 150 ℃ and the reaction time was 6 hours.
A transmission electron micrograph of the resulting ruthenium sulfide particulate composite material is shown in FIG. 6.
Example 3
Referring to the procedure in example 1, water was replaced by ethanol and the solvothermal reaction conditions were changed to: the temperature was 150 ℃ and the reaction time was 6 hours.
A transmission electron micrograph of the resulting ruthenium sulfide particulate composite material is shown in FIG. 7.
Example 4
Referring to the procedure in example 1, the solvothermal conditions were changed to: the temperature was 180 ℃ and the reaction time was 4 hours.
A transmission electron micrograph of the resulting ruthenium sulfide particulate composite is shown in FIG. 8.
Example 5
The performance of the ruthenium sulphide particle composite of the invention for hydrogen evolution by electrolysis in water was tested with a three-electrode system and compared with commercial platinum carbon: the reference electrode is a calomel electrode, the counter electrode is a carbon electrode, and the working electrode is the ruthenium sulfide particle composite material with the substrate of graphene obtained in example 1 or commercial platinum carbon. The polarization curves obtained by performing the test in a 0.5M sulfuric acid solution, or a phosphoric acid buffer solution, or a 1.0M potassium hydroxide solution are shown in FIG. 9, FIG. 10, and FIG. 11, respectively. From FIGS. 9 to 11, it can be seen that the ruthenium sulfide particle composite obtained in example 1 has a good hydrogen evolution performance by electrolysis of water (solid line), which is comparable to that of commercial platinum carbon (dotted line); the current hardly decayed (curve a of fig. 12, 13, and 14) at a current density of 50 milliamps per square centimeter for 12 hours, which was more stable than platinum carbon (curve B of fig. 12, 13, and 14). This demonstrates that the ruthenium sulfide particle composite of the present invention is excellent in stability of hydrogen evolution by electrolysis of water. Particularly, when the ruthenium sulfide particles are nanoparticles, the hydrogen evolution performance and stability of the electrolyzed water are more excellent.
The above examples fully demonstrate the feasibility of the one-step solvothermal method of the present invention to prepare a graphene-based ruthenium sulfide particle composite. The ruthenium sulfide nanoparticles have an amorphous structure and show excellent electrochemical reaction performance.
Claims (3)
1. A method of preparing a ruthenium sulfide particle composite, the ruthenium sulfide particle composite comprising: the conductive substrate comprises a conductive substrate material and ruthenium sulfide particles growing on the conductive substrate material, wherein the ruthenium sulfide particles are in an amorphous state, the ruthenium sulfide particles are nanoparticles, and the conductive substrate material is a graphene material;
the preparation method of the ruthenium sulfide particle composite material comprises the following steps: adding a conductive substrate material into a solution containing a ruthenium source and a vulcanizing agent, heating in a closed state, carrying out solvothermal reaction under autogenous pressure, and separating and drying after the reaction is finished to obtain the ruthenium sulfide particle composite material;
the ruthenium source is one or more of ruthenium chloride, ruthenium sulfate or ruthenium nitrate; the vulcanizing agent is one or more of sodium sulfide, thiourea, thioacetamide or sulfur; the solvent used for the solution containing the ruthenium source and the sulfidizing agent is water, alcohol or a mixture thereof.
2. The method according to claim 1, wherein the solvothermal reaction is carried out under the following conditions: the temperature is 80-300 ℃, and the reaction time is 15 minutes-24 hours.
3. Use of the ruthenium sulphide particle composite produced by the method of producing a ruthenium sulphide particle composite according to claim 1 as a cathode material for the electrowinning of hydrogen under acidic, neutral or alkaline conditions.
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| CN111463439B (en) * | 2019-01-21 | 2022-02-18 | 中国科学院福建物质结构研究所 | Composite, bifunctional catalyst containing composite and electrochemical neutralization energy battery |
| CN111939941B (en) * | 2020-07-03 | 2022-12-09 | 南方科技大学 | Ruthenium-based catalyst and preparation method and application thereof |
| CN111939940B (en) * | 2020-07-03 | 2023-05-16 | 南方科技大学 | Ruthenium-based catalyst, and preparation method and application thereof |
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| US7879753B2 (en) * | 2003-05-27 | 2011-02-01 | Industrie De Nora S.P.A. | Catalyst for oxygen reduction |
| CN100428988C (en) * | 2004-01-28 | 2008-10-29 | 德·诺拉电极股份公司 | Synthesis of noble metal sulphide catalysts in a sulphide ion-free aqueous environment |
| CN1325385C (en) * | 2005-03-31 | 2007-07-11 | 南京大学 | Process for preparing ruthenium sulfide nanopartical |
| CN1325384C (en) * | 2005-03-31 | 2007-07-11 | 南京大学 | Multipore ruthenium sulfide nanoball and its preparation process |
| CN1820850A (en) * | 2006-03-16 | 2006-08-23 | 上海师范大学 | Non-crystalline alloy catalyst of uniform grain size and its preparing method |
| US9315912B2 (en) * | 2006-11-29 | 2016-04-19 | Industrie De Nora S.P.A. | Carbon-supported metal sulphide catalyst for electrochemical oxygen reduction |
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