CN111068717B - Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof - Google Patents
Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 22
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 15
- 230000010355 oscillation Effects 0.000 claims abstract description 15
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- 239000011593 sulfur Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 239000007772 electrode material Substances 0.000 description 4
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- 238000005054 agglomeration Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
A ruthenium simple substance modified sulfur-doped graphene two-dimensional material and a preparation method and application thereof are prepared by mixing RuCl3·6H2Adding O and graphene oxide into deionized water, adjusting the pH value to 0-6, uniformly dispersing by ultrasonic oscillation, and then freeze-drying to remove a solvent to obtain a solid; and roasting the solid at high temperature in an inert atmosphere, cooling to room temperature, performing acid leaching, washing with water, and drying to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance. The sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance prepared by the invention has good conductivity, and the ruthenium simple substance is uniformly distributed as an active center; the sulfur-doped graphene two-dimensional material modified by the elementary ruthenium can be used as a catalyst for analyzing hydrogen by electrocatalytic water decomposition, and has the characteristics of low overpotential, high catalytic activity and long catalytic life.
Description
Technical Field
The invention relates to a two-dimensional material, in particular to a sulfur-doped graphene two-dimensional material modified by a ruthenium simple substance, and preparation and application thereof.
Background
Hydrogen energy is considered to be the most promising secondary energy source in the 21 st century. The hydrogen element is the most common element in the nature, has the highest specific energy density, and is as high as 142.35 kJ.kg-1The energy generated by burning each kilogram of hydrogen is about 3 times of that generated by burning gasoline, 3.9 times of that generated by burning alcohol and 4.5 times of that generated by burning coke; and secondly, the product water of hydrogen combustion is the raw material for preparing hydrogen, so that the resource can be recycled, and no greenhouse gas and pollutant are generated in the process. Therefore, hydrogen gas is used as a clean energy carrier for decompositionThe method has important significance for solving the problems of energy and pollution. And the development of an efficient and stable catalyst for hydrogen production by water decomposition is very important.
For the hydrogen production by water electrolysis, how to improve the activity of the electrode catalytic material, reduce the hydrogen evolution overpotential and improve the stability of the electrode material is the key point and key point of the research in the field of electrocatalysis. Graphene is a hexagonal honeycomb-shaped two-dimensional carbon nanomaterial consisting of carbon atoms in sp2 hybridized orbitals, has important application prospects in the fields of catalysis, energy storage, electronic devices and the like due to the characteristics of good mechanical properties, light weight, high conductivity and the like, and is considered to be a revolutionary material in the future. It is well known that metallic ruthenium has suitable metal-hydrogen adsorption and desorption capabilities, and that electrocatalysts based on metallic ruthenium show good catalytic activity and stability in electrocatalytic hydrogen evolution reactions.
So far, the electrocatalytic hydrogen evolution material based on metal ruthenium still has more problems, one of which is the stability and the cyclability of the electrode, especially the poor stability in alkaline solution, and the catalytic efficiency of the catalyst is reduced; the second is that the reported electrode material still has higher overpotential, and the third is that the current electrode material preparation method is more complicated. Therefore, how to design and prepare an electrocatalytic water-decomposition hydrogen-analysis material with high catalytic activity and good stability is a problem to be solved at present.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a sulfur-doped graphene two-dimensional material modified by a ruthenium simple substance, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a sulfur-doped graphene two-dimensional material modified by a ruthenium simple substance comprises the following steps:
1) adding RuCl3·6H2Adding O and graphene oxide into deionized water, adjusting the pH value to 0-6 by using sulfuric acid, uniformly dispersing by ultrasonic oscillation, and then removing a solvent by freeze drying to obtain a solid;
2) and roasting the solid at high temperature in an inert atmosphere, cooling to room temperature, performing acid leaching, washing with water, and drying to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
A further development of the invention is that, in step 1), RuCl3·6H2The mass ratio of O to graphene oxide is 1: 2 to 10.
The invention is further improved in that the pH value is 1-3.
The invention has the further improvement that the time of ultrasonic oscillation is 3-4 hours.
A further development of the invention is that RuCl3·6H2The mass ratio of O to graphene oxide is 1: 4.
the further improvement of the method is that in the step 1), the ratio of the graphene oxide to the water is 10-30 mg: 10-30 mL.
The further improvement of the invention is that the ratio of graphene oxide to water is 20 mg: 10 mL.
The further improvement of the invention is that in the step 1), the time of ultrasonic oscillation is 2-6 hours.
In a further improvement of the invention, in step 2), the inert atmosphere is nitrogen, argon or helium.
The further improvement of the invention is that in the step 2), the high-temperature roasting temperature is 500-1000 ℃, and the time is 1-5 hours.
The further improvement of the invention is that the high-temperature roasting temperature is 600-800 ℃, and the time is 2-3 hours.
The further improvement of the invention is that in the step 2), the acid leaching solution is 0.01-1 mol/L hydrochloric acid solution, and the acid leaching time is 3-10 hours.
The invention has the further improvement that the acid leaching solution is 0.05-0.2 mol/L hydrochloric acid solution, and the acid leaching time is 4-6 hours.
The elementary ruthenium modified sulfur-doped graphene two-dimensional material is prepared according to the method.
The application of the elementary ruthenium modified sulfur-doped graphene two-dimensional material prepared by the method as a catalyst for analyzing hydrogen by electrocatalytic water decomposition.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance is prepared by taking graphene oxide as a substrate through the processes of ultrasonic dispersion, freeze drying, high-temperature roasting, acid leaching and the like. Compared with the prior art, the method has the advantages of simple process, low cost, easy control of reaction process, high yield and the like, and is suitable for industrial large-scale production.
(2) The sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance prepared by the invention has good conductivity, and the ruthenium simple substance is uniformly distributed as an active center; the sulfur-doped graphene two-dimensional material modified by the elementary ruthenium can be used as a catalyst for analyzing hydrogen by electrocatalytic water decomposition, and has the characteristics of low overpotential, high catalytic activity and long catalytic life.
(3) According to the invention, graphene oxide is selected as a substrate, a ruthenium simple substance is loaded on the surface of the graphene oxide, and oxygen-containing functional groups on the surface of the graphene oxide are beneficial to dispersing and depositing the ruthenium simple substance and can effectively inhibit the aggregation of the ruthenium simple substance. The uniformly dispersed ultrafine particle elementary ruthenium is a key factor of the two-dimensional material prepared by the invention for efficiently decomposing water into hydrogen by electrocatalysis.
(4) According to the invention, graphene oxide is selected as a substrate, sulfuric acid is added in the preparation process, and the graphene oxide and sulfur are simultaneously reduced in the roasting process, so that the graphene containing sulfur element is successfully prepared. The introduction of sulfur improves the conductivity of the two-dimensional material prepared by the invention.
(5) The invention successfully prepares the two-dimensional composite material with good metal ruthenium dispersibility and stable chemical property by fully utilizing the good conductivity of the sulfur-doped graphene and the excellent hydrogen evolution performance of the ruthenium simple substance. The sulfur-doped graphene two-dimensional material modified by the elemental ruthenium prepared by the invention has the characteristics of controllable morphology and performance, and the sulfur element and the loaded elemental ruthenium are doped on the surface of the graphene oxide serving as the substrate, so that the agglomeration and stacking of the elemental ruthenium nanoparticles are effectively inhibited while the conductivity is improved, and the conductivity and the hydrogen analysis performance of electrocatalytic water are improved. The sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance, which is prepared by the invention, is expected to be used as a promising high-performance hydrogen evolution electrode material and widely applied in the field of energy sources, so that the material has good development and application values and an optimistic development prospect, and is worthy of being popularized in laboratory work and industrial processes.
Drawings
Figure 1 is a preparation scheme.
FIG. 2 is a transmission electron micrograph of the product of example 1.
FIG. 3 is a transmission electron micrograph of the product of example 2.
FIG. 4 is a transmission electron micrograph of the product of example 3.
FIG. 5 is a scanning electron micrograph of the product of example 1.
FIG. 6 is an X-ray photoelectron spectrum of the product of example 1.
FIG. 7 is an EDX mapping plot of the product of example 1. Wherein, (a) is HAADF-STEM (high angle annular dark field image) diagram, (b) is element C, (C) is element Ru, (d) is element S, and (e) is element O.
FIG. 8 shows the results of example 1, example 2 and example 3 at 0.5mol/L H2SO4Linear voltammograms in aqueous solution.
FIG. 9 is a linear voltammogram of the products of example 1, example 2 and example 3 in 1.0mol/L aqueous KOH.
FIG. 10 is an electrolytic diagram of the product of example 1 in 1.0mol/L aqueous KOH.
Detailed Description
The following examples further illustrate embodiments of the present invention, but are not intended to limit the scope of the invention.
According to the invention, the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance is prepared by taking graphene oxide as a substrate through the processes of ultrasonic dispersion, freeze drying, high-temperature roasting, acid leaching and the like. And analyzing the particle morphology, the crystal structure, the element valence state and the distribution of the prepared sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance through a transmission electron microscope, a scanning electron microscope, an X-ray photoelectron energy spectrum, an X-ray diffraction spectrum and the like. And detecting the hydrogen analysis performance of the prepared elemental ruthenium modified sulfur-doped graphene two-dimensional material through an electrochemical linear volt-ampere experiment and an electrolysis experiment.
Referring to fig. 1, the present invention comprises the steps of:
1) weighing a certain amount of RuCl3·6H2Adding O and graphene oxide into deionized water, adjusting the pH value of the solution to acidity by sulfuric acid, and carrying out ultrasonic oscillation for a period of time to uniformly disperse the two substances in the solution.
2) The solution was freeze dried to remove the solvent.
3) The obtained solid is roasted at high temperature at the heating rate of 3-10 ℃/min under the inert atmosphere.
4) After cooling to room temperature, pickling is carried out for a certain period of time.
5) And washing the obtained solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Step 1) RuCl3·6H2The mass ratio of O to graphene oxide is 1: 10-1: 2, with preferred values of 1: 4.
the ratio of graphene oxide to water in step 1) is 30 mg: 10 mL-10 mg: 30mL, with preferred values of 20 mg: 10 mL.
The pH value range in the step 1) is 0-6, and the preferred value is 1-3.
The ultrasonic oscillation time in the step 1) is 2-6 hours, and the preferred value is 3-4 hours.
The inert atmosphere in the step 3) can be nitrogen, argon or helium.
And 3) roasting at a high temperature of 500-1000 ℃, wherein the preferred value is 600-800 ℃.
And 3) roasting at high temperature for 1-5 hours, wherein the preferred value is 2-3 hours.
The acid leaching solution in the step 4) is hydrochloric acid solution, the concentration is 0.01-1 mol/L, and the optimal value is 0.05-0.2 mol/L.
The acid leaching time in the step 4) is 3-10 hours, and the optimal value is 4-6 hours.
The following are specific examples.
Example 1
Weighing 5mg of RuCl3·6H2O andadding 20mg of graphene oxide into 10mL of deionized water, adjusting the pH value of the solution to 2 by using sulfuric acid, and performing ultrasonic oscillation for 4 hours to uniformly disperse the two substances in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 5 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) was increased to 700 ℃ and the mixture was calcined for 2 hours. After cooling to room temperature, the mixture was immersed in 0.1mol/L hydrochloric acid for 5 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Example 2
Weighing 2.5mg RuCl3·6H2O and 20mg of graphene oxide are added into 10mL of deionized water, the pH value of the solution is adjusted to 3 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 3 hours, so that the two substances are uniformly dispersed in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 10 deg.C for min under argon atmosphere-1The temperature rising rate of (2) was increased to 600 ℃ and the mixture was calcined for 1.5 hours. After cooling to room temperature, the mixture was immersed in 0.05mol/L hydrochloric acid for 3 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Example 3
Weighing 10mg RuCl3·6H2O and 20mg of graphene oxide are added into 10mL of deionized water, the pH value of the solution is adjusted to 1 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 6 hours, so that the two substances are uniformly dispersed in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 3 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) is increased to 800 ℃ and the mixture is roasted for 3 hours. After cooling to room temperature, the mixture was immersed in 0.8mol/L hydrochloric acid for 8 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
The test results of example 1, example 2 and example 3 are as follows:
(1) SEM and TEM test results show that: the prepared composite material has a unique two-dimensional structure, and crystalline nanoparticles of elemental ruthenium can be seen on the surface thereof, as shown in fig. 2, fig. 3, fig. 4 and fig. 5. The oxygen on the graphene oxide precursor can enable the ruthenium to be dispersed more uniformly, and the agglomeration of the ruthenium is inhibited, so that the ruthenium with catalytic activity is fully exposed.
(2) The EDX mapping test results indicated the presence of ruthenium and sulfur elements, as shown in figure 7; the XPS test results further demonstrate that the valence state of ruthenium is 0, namely, the ruthenium is simple substance, as shown in FIG. 6.
(3) The sulfur-doped graphene two-dimensional material modified by the elementary ruthenium prepared by the steps can be used as an electrocatalyst to perform a test of water electrolysis and hydrogen evolution in 0.5mol/L sulfuric acid and 1.0mol/L KOH. Electrochemical test results show that the sulfur-doped graphene two-dimensional material modified by the elementary ruthenium has excellent hydrogen evolution catalytic activity.
Example 4
Weighing 5mg of RuCl3·6H2O and 20mg of graphene oxide are added into 10mL of deionized water, the pH value of the solution is adjusted to 0 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 2 hours, so that the two substances are uniformly dispersed in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 5 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) is increased to 500 ℃ and the mixture is roasted for 5 hours. After cooling to room temperature, the mixture was immersed in 0.01mol/L hydrochloric acid for 10 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Example 5
Weighing 5mg of RuCl3·6H2O and 10mg of graphene oxide are added into 30mL of deionized water, the pH value of the solution is adjusted to 6 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 3 hours, so that the two substances are uniformly dispersed in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 5 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) was increased to 1000 ℃ and the mixture was calcined for 2 hours. After cooling to room temperature, the mixture was further immersed in 0.05mol/L hydrochloric acid for 6 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Example 6
Weighing 5mg of RuCl3·6H2O and 50mg of graphene oxide are added into 50mL of deionized water, the pH value of the solution is adjusted to 1 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 4 hours, so that the two substances are uniformly dispersed in the solution. Will dissolveAnd (5) liquid-cooling, freeze-drying and removing the solvent. The obtained solid was heated at 5 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) was increased to 600 ℃ and the mixture was calcined for 3 hours. After cooling to room temperature, the mixture was immersed in 0.2mol/L hydrochloric acid for 4 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
Example 7
Weighing 5mg of RuCl3·6H2O and 30mg of graphene oxide are added into 10mL of deionized water, the pH value of the solution is adjusted to 3 by sulfuric acid, and the solution is subjected to ultrasonic oscillation for 6 hours, so that the two substances are uniformly dispersed in the solution. The solution was freeze dried to remove the solvent. The obtained solid was heated at 5 deg.C for min under nitrogen atmosphere-1The temperature rising rate of (2) is increased to 800 ℃ and the mixture is roasted for 2 hours. After cooling to room temperature, the mixture was immersed in 1mol/L hydrochloric acid for 3 hours. And finally, washing the solid to be neutral, and drying in vacuum to obtain the sulfur-doped graphene two-dimensional material modified by the ruthenium simple substance.
The following is an application of the ruthenium simple substance modified sulfur-doped graphene two-dimensional material prepared by the invention as a catalyst for hydrogen analysis by electrocatalytic water decomposition.
5mg of the product obtained in example 1, example 2 or example 3 and 100. mu.L of a 5 wt% Nafion solution were added to 1000. mu.L of a 1:1 mixture of water and ethanol, respectively, and sonicated for two hours to obtain a uniformly dispersed ink. Spreading 30 μ L of the above ink drop on 0.5 × 0.5cm carbon paper, and drying at room temperature to obtain hydrogen evolution electrode.
The hydrogen evolution electrode is taken as a working electrode, Ag/AgCl is taken as a reference electrode, a graphite rod is taken as an auxiliary electrode, and the concentration is 0.5mol/LH2SO4Linear voltammetric scanning was performed in aqueous solution. As the voltage increases negatively, the current begins to increase, evidencing the occurrence of an electrocatalytic hydrogen evolution reaction. It can be seen from fig. 8 that the two-dimensional material prepared in example 1 has the lowest overpotential.
An electrode prepared from a hydrogen evolution electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite rod is used as an auxiliary electrode, and linear voltammetry scanning is carried out in a 1.0mol/L KOH aqueous solution. As the voltage increases negatively, the current begins to increase, evidencing the occurrence of an electrocatalytic hydrogen evolution reaction. It can be seen from fig. 9 that the two-dimensional material prepared in example 1 has the lowest overpotential.
As can be seen from fig. 2 to 4, the two-dimensional material prepared in example 1 has small ruthenium particles, uniform distribution and larger loading amount compared with examples 2 and 3.
An electrolysis experiment was performed in a 1.0mol/L KOH aqueous solution using the two-dimensional material hydrogen evolution electrode prepared in example 1 as a working electrode, Ag/AgCl as a reference electrode, and a graphite rod as an auxiliary electrode. As shown in fig. 10, the current did not change significantly with time, demonstrating that the two-dimensional material prepared by the present invention has excellent stability in the electrocatalytic hydrogen evolution reaction.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (8)
1. A preparation method of a sulfur-doped graphene two-dimensional material modified by a ruthenium simple substance is characterized by comprising the following steps:
1) adding RuCl3·6H2Adding O and graphene oxide into deionized water, adjusting the pH value to 0-6 by using sulfuric acid, uniformly dispersing by ultrasonic oscillation, and then removing a solvent by freeze drying to obtain a solid; wherein, RuCl3·6H2The mass ratio of O to graphene oxide is 1: 2-10;
2) roasting the solid at high temperature in an inert atmosphere, cooling to room temperature, performing acid leaching, washing with water, and drying to obtain a sulfur-doped graphene two-dimensional material modified by a ruthenium simple substance; the sulfur-doped graphene two-dimensional material modified by the elementary ruthenium is used as a catalyst for hydrogen analysis through electrocatalytic water decomposition, and is roasted at a high temperature of 500-1000 ℃; the high-temperature roasting time is 1-5 hours.
2. The preparation method of the elemental ruthenium modified sulfur-doped graphene two-dimensional material according to claim 1, wherein in the step 1), the ratio of graphene oxide to water is 10-30 mg: 10-30 mL.
3. The preparation method of the elemental ruthenium modified sulfur-doped graphene two-dimensional material according to claim 1, wherein in the step 1), the ultrasonic oscillation time is 2-6 hours.
4. The method for preparing the elemental ruthenium-modified sulfur-doped graphene two-dimensional material according to claim 1, wherein in the step 2), the inert atmosphere is nitrogen, argon or helium.
5. The preparation method of the elemental ruthenium modified sulfur-doped graphene two-dimensional material according to claim 1, wherein in the step 2), the high-temperature roasting time is 2-3 hours.
6. The method for preparing the elemental ruthenium-modified sulfur-doped graphene two-dimensional material according to claim 1, wherein in the step 2), the acid leaching solution is 0.01-1 mol/L hydrochloric acid solution, and the acid leaching time is 3-10 hours.
7. The elementary ruthenium modified sulfur-doped graphene two-dimensional material prepared by the method of any one of claims 1 to 6.
8. The application of the elementary ruthenium modified sulfur-doped graphene two-dimensional material prepared by the method in any one of claims 1 to 6 as a catalyst for hydrogen analysis by electrocatalytic water decomposition.
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