CN114318362B - Ruthenium nanocluster hydrogen evolution electrocatalyst and super-assembly method thereof - Google Patents
Ruthenium nanocluster hydrogen evolution electrocatalyst and super-assembly method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of porous materials, and provides a ruthenium nanocluster hydrogen evolution electrocatalyst and a super-assembly method thereof. The prepared ruthenium nanocluster hydrogen evolution electrocatalyst has the advantages of excellent performance, high activity and excellent stability, and meanwhile, the price of ruthenium is far lower than that of platinum, so that the catalyst has extremely high economic benefit.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a ruthenium nanocluster hydrogen evolution electrocatalyst and a super-assembly method thereof.
Background
Global energy consumption has grown exponentially over the last decades, with 56% expected to grow by 2040 years. Currently, 80% of the world's energy consumption comes from fossil fuels, leading to serious energy crisis and serious global warming. These problems have prompted scientists to develop environmentally friendly energy sources for our daily lives, hydrogen being considered a real fossil fuel alternative in the future due to its highest mass specific energy density and zero carbon dioxide emissions. The electrochemical pyrolysis water has the advantages of simple process, high product purity, good reproducibility and the like, and is an attractive hydrogen production method. However, hydrogen Evolution Reactions (HER) require highly active electrocatalysts. Platinum-based compounds remain the most advanced HER electrocatalyst at present, but due to their high material costs and scarce reserves, sustainable hydrogen supply is not guaranteed. Regardless of the challenges, the development of an efficient, durable, low cost electrocatalyst is an urgent need for sustainable and large-scale implementation of clean energy plants.
Disclosure of Invention
The invention aims to solve the problems and provide a ruthenium nanocluster hydrogen evolution electrocatalyst and a super-assembly preparation method thereof.
The invention provides a super-assembly preparation method of a ruthenium nanocluster hydrogen evolution electrocatalyst, which has the characteristics that the method comprises the following steps: step 1, placing a zinc zeolite imidazole frame in a tube furnace and carbonizing at high temperature in a hydrogen-argon mixed gas to obtain a nitrogen-doped carbon nano frame; step 2, soaking the nitrogen-doped carbon nano-frame in a phytic acid solution, stirring, transferring to an evaporation container, and evaporating to induce self-assembly to obtain the phytic acid modified nitrogen-doped carbon nano-frame; and 3, soaking the nitrogen-doped carbon nano-frame modified by the phytic acid into a hydrated ruthenium trichloride solution, and stirring to obtain the ruthenium nanocluster hydrogen evolution electrocatalyst.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: wherein, the step 1 comprises the following substeps: step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution; step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution; step 1-3, quickly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution; and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: wherein, the mol ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1:4-1:5, the concentration of imidazole methanol solution is 10-25%, and the concentration of zinc methanol solution is 2-6%.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: in the step 1, the concentration of hydrogen in the hydrogen-argon mixture is 5% -10%.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: wherein, in the step 1, the high-temperature carbonization temperature is 900-1100 ℃, the time is 2-4 hours, and the heating rate is 5 ℃/min.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: in the step 2, the concentration of the phytic acid solution is 1% -4%.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: in the step 2, the mixture is transferred to an evaporation dish after ultrasonic stirring, self-assembly is induced by evaporation, the temperature during evaporation is controlled at 80-100 ℃, and the evaporation time is 8-12 hours.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: in the step 3, the ruthenium nanocluster hydrogen evolution electrocatalyst is obtained after ultrasonic stirring, and the reaction temperature is controlled to be 50-60 ℃ and the reaction time is controlled to be 12-16 hours when the ultrasonic stirring is carried out.
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst provided by the invention can also have the following characteristics: wherein, in the step 3, the concentration of the hydrated ruthenium trichloride solution is 1mg/mL.
The invention also provides a ruthenium nanocluster hydrogen evolution electrocatalyst, which has the characteristics, and is prepared by a super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst.
Effects and effects of the invention
According to the ruthenium nanocluster hydrogen evolution electrocatalyst and the super-assembly preparation method thereof, the production process is simple, the nitrogen-doped carbon nano-frame is obtained by carbonizing the zinc zeolite imidazole frame at high temperature, then the frame is mixed with the phytic acid solution to obtain the phytic acid modified nitrogen-doped carbon nano-frame, the modified nano-frame is used as a carrier to be mixed with the hydrated ruthenium trichloride solution, metal ions in the solution are chelated through phosphate groups in the surface-modified phytic acid molecular structure of the nano-frame in the reaction process, the ruthenium nanocluster is formed, and finally the corresponding ruthenium nanocluster hydrogen evolution electrocatalyst is obtained. The prepared ruthenium nanocluster hydrogen evolution electrocatalyst has the advantages of excellent performance, high activity and excellent stability, and meanwhile, the price of ruthenium is far lower than that of platinum, so that the catalyst has extremely high economic benefit.
According to the invention, the nitrogen-doped carbon nano-frame modified by phytic acid is used as a carrier, and a phosphate radical in the phytic acid molecular structure on the surface of the carrier can chelate metal ions in a solution, so that ruthenium nanoclusters are obtained on the surface of the frame, and finally, the ruthenium nanocluster hydrogen evolution electrocatalyst is obtained. The preparation method of the material is simple and is expected to be applied to industrial production.
Drawings
FIG. 1 is a transmission electron microscopic view of a ruthenium nanocluster hydrogen evolution electrocatalyst according to example 1 of the invention;
FIG. 2 is a spherical aberration correcting high resolution transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst of the present embodiment 1 of the invention;
FIG. 3 is an X-ray photoelectron spectrum of ruthenium (Ru) of the ruthenium nanocluster hydrogen evolution electrocatalyst of the present embodiment 1 of the invention;
FIG. 4 is a graph of linear sweep voltammetry of hydrogen evolution of a ruthenium nanocluster hydrogen evolution electrocatalyst according to example 1 of the invention in 1M KOH electrolyte;
FIG. 5 is a graph showing the stability test of the ruthenium nanocluster hydrogen evolution electrocatalyst according to example 1 of the invention;
FIG. 6 is a high power transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst according to example 2 of the invention;
FIG. 7 is a high power transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst according to example 3 of the present invention.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the invention easy to understand, the ruthenium nanocluster hydrogen evolution electrocatalyst and the super-assembly preparation method thereof are specifically described below with reference to examples and drawings.
The processes in the examples of the present invention are conventional processes unless otherwise indicated, and the starting materials in the examples of the present invention are commercially available from the public sources unless otherwise indicated.
The invention relates to a super-assembly preparation method of a ruthenium nanocluster hydrogen evolution electrocatalyst, which specifically comprises the following steps:
step 1, placing a zinc zeolite imidazole frame in a tube furnace and carbonizing at high temperature in a hydrogen-argon mixed gas to obtain a nitrogen-doped carbon nano frame;
step 2, immersing the nitrogen-doped carbon nano-frame in a phytic acid solution, ultrasonically stirring, transferring to an evaporation container (evaporation dish), and evaporating to induce self-assembly to obtain the phytic acid modified nitrogen-doped carbon nano-frame;
and 3, soaking the nitrogen-doped carbon nano-frame modified by the phytic acid into a hydrated ruthenium trichloride solution, and carrying out ultrasonic stirring to obtain the ruthenium nanocluster hydrogen evolution electrocatalyst.
Step 1 is to synthesize a zinc zeolite imidazole framework which is a metal organic framework material, and specifically comprises the following substeps:
step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution;
step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution;
step 1-3, quickly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution;
and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
The mol ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1:4-1:5, the concentration of imidazole methanol solution is 10% -25%, and the concentration of zinc methanol solution is 2% -6%.
In the step 1, the concentration of hydrogen in the hydrogen-argon mixture is 5% -10%; the high-temperature carbonization temperature is 900-1100 ℃, the time is 2-4 hours, and the heating rate is 5 ℃/min.
In the step 2, the concentration of the phytic acid solution is 1% -4%; the temperature during evaporation is controlled at 80-100 ℃ and the evaporation time is 8-12 hours.
In the step 3, when ultrasonic stirring is carried out, the reaction temperature is controlled to be 50-60 ℃ and the reaction time is controlled to be 12-16 hours. The concentration of the hydrated ruthenium trichloride solution was 1mg/mL.
Example 1 ]
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst of the embodiment comprises the following steps:
and step 1, placing the zinc zeolite imidazole framework in a tube furnace and carbonizing at high temperature in hydrogen-argon mixed gas to obtain the nitrogen-doped carbon nano framework.
The step 1 comprises the following substeps:
step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution;
step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution;
step 1-3, quickly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution;
and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
The mol ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1:4, the concentration of imidazole methanol solution is 10%, and the concentration of zinc methanol solution is 2%.
In step 1, the concentration of the hydrogen-argon mixture was 5%.
In the step 1, the high-temperature carbonization temperature is 1000 ℃, the time is 3 hours, and the heating rate is 5 ℃/min.
And 2, soaking the nitrogen-doped carbon nano frame in a phytic acid solution, and evaporating the solution.
In step 2, the concentration of the phytic acid solution was 4%.
In step 2, the evaporation temperature is controlled at 100 ℃ and the evaporation time is 12 hours.
And 3, soaking the nitrogen-doped nano-framework modified by the phytic acid in a hydrated ruthenium trichloride solution, and carrying out ultrasonic stirring to obtain the ruthenium nanocluster hydrogen evolution electrocatalyst.
In the step 3, when ultrasonic stirring is carried out, the reaction temperature is controlled to be 50 ℃, and the reaction time is 16 hours.
In step 3, the concentration of ruthenium trichloride hydrate was 1mg/mL.
The ruthenium nanocluster hydrogen evolution electrocatalyst is prepared by a super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst.
FIG. 1 is a transmission electron microscope image of a ruthenium nanocluster hydrogen evolution electrocatalyst in the present example.
As shown in FIG. 1, the ruthenium nanocluster hydrogen evolution electrocatalyst is a rhombic dodecahedron with relatively uniform size.
FIG. 2 is a spherical aberration correcting high resolution transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst of the present example.
As shown in fig. 2, the ruthenium nanocluster hydrogen evolution electrocatalyst can observe many ruthenium nanoclusters under a spherical aberration correcting high resolution transmission electron microscope, wherein the dark portion represents a phytic acid modified nitrogen-doped carbon support and the bright block is a supported ruthenium nanocluster.
FIG. 3 is an X-ray photoelectron spectrum of ruthenium (Ru) of the ruthenium nanocluster hydrogen evolution electrocatalyst of the present example.
As shown in fig. 3, the X-ray photoelectron spectrum of ruthenium (Ru) of the ruthenium nanocluster hydrogen evolution electrocatalyst shows that most of the valence states of Ru in the material are 0.
In the embodiment, the ruthenium nanocluster hydrogen evolution electrocatalyst is ground into powder to prepare ink with certain concentration, a small amount of ink is taken to be dripped on the surface of a platinum carbon electrode, after the ink is naturally air-dried, a glassy carbon electrode coated with the ink, a mercury oxide electrode, a graphite rod and an electrolytic cell filled with electrolyte are assembled into a three-electrode electrolyzed water testing system, and the electrocatalytic performance of the three-electrode electrolyzed water testing system is tested by using an electrochemical workstation.
FIG. 4 is a graph of linear sweep voltammetry of hydrogen evolution of the ruthenium nanocluster hydrogen evolution electrocatalyst of this example in a 1M KOH electrolyte.
As shown in FIG. 4, when the catalyst of the electrolyzed water testing system is a ruthenium nanocluster hydrogen evolution electrocatalyst in a 1M KOH solution, the current density of the reaction system can reach 10mA cm only by low overpotential of 11mV -2 Is superior to commercial platinum carbon (Pt/C) catalysts and commercial ruthenium carbon (Ru/C) catalysts. Meanwhile, with the increase of current density, the difference of the three catalysts is larger and larger, and the advantages of the ruthenium nanocluster hydrogen evolution electrocatalyst are more and more obvious.
Fig. 5 is a graph of stability test of the ruthenium nanocluster hydrogen evolution electrocatalyst of the present example.
As shown in FIG. 5Shown, at 10mA cm -2 Under the current density, the ruthenium nanocluster hydrogen evolution electrocatalyst can ensure that the catalytic activity is almost free from attenuation within 24 hours, which shows that the ruthenium nanocluster hydrogen evolution electrocatalyst has excellent practical application potential.
Example 2 ]
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst of the embodiment comprises the following steps:
and step 1, placing the zinc zeolite imidazole framework in a tube furnace and carbonizing at high temperature in hydrogen-argon mixed gas to obtain the nitrogen-doped carbon nano framework.
The step 1 comprises the following substeps:
step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution;
step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution;
step 1-3, quickly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution;
and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
The mol ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1:4, the concentration of imidazole methanol solution is 15%, and the concentration of zinc methanol solution is 4%.
In step 1, the concentration of the hydrogen-argon mixture was 5%.
In the step 1, the high-temperature carbonization temperature is 900 ℃, the time is 4 hours, and the heating rate is 5 ℃/min.
And 2, soaking the nitrogen-doped carbon nano frame in a phytic acid solution, and evaporating the solution.
In step 2, the concentration of the phytic acid solution was 2%.
In step 2, the evaporation temperature was controlled at 90℃and the evaporation time was 10 hours.
And 3, soaking the nitrogen-doped nano-framework modified by the phytic acid in a hydrated ruthenium trichloride solution, and carrying out ultrasonic stirring to obtain the ruthenium nanocluster hydrogen evolution electrocatalyst.
In the step 3, when ultrasonic stirring is carried out, the reaction temperature is controlled to be 55 ℃, and the reaction time is 16 hours.
In step 3, the concentration of ruthenium trichloride hydrate was 1mg/mL.
The ruthenium nanocluster hydrogen evolution electrocatalyst is prepared by a super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst.
FIG. 6 is a high power transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst in the present example.
As shown in fig. 6, the ruthenium nanocluster hydrogen evolution electrocatalyst can observe many ruthenium nanoclusters with deeper contrast under high power transmission electron microscopy.
Example 3 ]
The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst of the embodiment comprises the following steps:
and step 1, placing the zinc zeolite imidazole framework in a tube furnace and carbonizing at high temperature in hydrogen-argon mixed gas to obtain the nitrogen-doped carbon nano framework.
The step 1 comprises the following substeps:
step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution;
step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution;
step 1-3, quickly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution;
and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
The mol ratio of zinc nitrate hexahydrate to dimethyl imidazole is 1:5, the concentration of imidazole methanol solution is 25%, and the concentration of zinc methanol solution is 6%.
In step 1, the concentration of the hydrogen-argon mixture was 10%.
In the step 1, the high-temperature carbonization temperature is 1100 ℃, the time is 2 hours, and the heating rate is 5 ℃/min.
And 2, soaking the nitrogen-doped carbon nano frame in a phytic acid solution, and evaporating the solution.
In step 2, the concentration of the phytic acid solution was 1%.
In step 2, the evaporation temperature was controlled at 80℃and the evaporation time was 8 hours.
And 3, soaking the nitrogen-doped nano-framework modified by the phytic acid in a hydrated ruthenium trichloride solution, and carrying out ultrasonic stirring to obtain the ruthenium nanocluster hydrogen evolution electrocatalyst.
In the step 3, when ultrasonic stirring is carried out, the reaction temperature is controlled to be 60 ℃, and the reaction time is 16 hours.
In step 3, the concentration of ruthenium trichloride hydrate was 1mg/mL.
The ruthenium nanocluster hydrogen evolution electrocatalyst is prepared by a super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst.
FIG. 7 is a high power transmission electron microscope image of the ruthenium nanocluster hydrogen evolution electrocatalyst in the present example.
As shown in fig. 7, the ruthenium nanocluster hydrogen evolution electrocatalyst can observe many ruthenium nanoclusters with deeper contrast under high power transmission electron microscopy.
Effects and effects of the examples
According to the ruthenium nanocluster hydrogen evolution electrocatalyst and the super-assembly preparation method thereof, which are related to the embodiment of the invention, the production process is simple, the nitrogen-doped carbon nanocluster is obtained by carbonizing the zinc zeolite imidazole framework at high temperature, then the framework is soaked in a phytic acid solution, the nitrogen-doped carbon nanocluster modified by phytic acid is obtained by evaporation-induced self-assembly, then the modified framework is soaked in a hydrated ruthenium trichloride solution, and the phosphate radical in the phytic acid structure on the surface of the framework can chelate metal ions in the solution in the reaction process to form ruthenium nanoclusters, so that the corresponding ruthenium nanocluster hydrogen evolution electrocatalyst is finally obtained. The prepared ruthenium nanocluster hydrogen evolution electrocatalyst has the advantages of excellent performance, high activity and excellent stability, and meanwhile, the price of ruthenium is much lower than that of platinum, so that the catalyst has extremely high economic benefit.
According to the embodiment of the invention, the nitrogen-doped carbon nano-frame modified by the phytic acid is used as a carrier, and the phosphate radical in the phytic acid molecular structure on the surface of the carrier can chelate metal ions in the solution, so that the ruthenium nano-cluster is obtained on the surface of the frame, and finally the ruthenium nano-cluster hydrogen evolution electrocatalyst is obtained. The preparation method of the material is simple and is expected to be applied to industrial production.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (6)
1. The super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst is characterized by comprising the following steps of:
step 1, placing a zinc zeolite imidazole frame in a tube furnace and carbonizing at high temperature in a hydrogen-argon mixed gas to obtain a nitrogen-doped carbon nano frame;
step 2, soaking the nitrogen-doped carbon nano-frame in a phytic acid solution, stirring, transferring to an evaporation container, and evaporating to induce self-assembly to obtain the phytic acid modified nitrogen-doped carbon nano-frame;
step 3, soaking the phytic acid modified nitrogen-doped carbon nano-frame into a hydrated ruthenium trichloride solution, stirring to obtain a ruthenium nanocluster hydrogen evolution electrocatalyst,
in the step 2, the concentration of the phytic acid solution is 1% -4%, the phytic acid solution is transferred into an evaporation dish after ultrasonic stirring, self-assembly is induced by evaporation, the temperature during evaporation is controlled to be 80 ℃ -100 ℃, the evaporation time is 8-12 hours,
in the step 3, the ruthenium nanocluster hydrogen evolution electrocatalyst is obtained after ultrasonic stirring, the reaction temperature is controlled to be 50-60 ℃ and the reaction time is controlled to be 12-16 hours when the ultrasonic stirring is carried out, and the concentration of the hydrated ruthenium trichloride solution is 1mg/mL.
2. The method for preparing the ruthenium nanocluster hydrogen evolution electrocatalyst according to claim 1, wherein the method comprises the steps of:
wherein, the step 1 comprises the following substeps:
step 1-1, ultrasonically dissolving dimethyl imidazole in methanol to obtain an imidazole methanol solution;
step 1-2, ultrasonically dissolving zinc nitrate hexahydrate in methanol to obtain zinc methanol solution;
step 1-3, rapidly pouring the imidazole methanol solution into the zinc methanol solution to obtain a mixed solution;
and step 1-4, stirring the mixed solution at room temperature for 24 hours, and obtaining the zinc zeolite imidazole framework after centrifugation and vacuum drying.
3. The method for preparing the ruthenium nanocluster hydrogen evolution electrocatalyst according to claim 2, wherein the method comprises the steps of:
wherein the mol ratio of the zinc nitrate hexahydrate to the dimethylimidazole is 1:4-1:5,
the concentration of the imidazole methanol solution is 10% -25%,
the concentration of the zinc methanol solution is 2% -6%.
4. The method for preparing the ruthenium nanocluster hydrogen evolution electrocatalyst according to claim 1, wherein the method comprises the steps of:
in the step 1, the concentration of hydrogen in the hydrogen-argon mixture is 5% -10%.
5. The method for preparing the ruthenium nanocluster hydrogen evolution electrocatalyst according to claim 1, wherein the method comprises the steps of:
in the step 1, the high-temperature carbonization temperature is 900-1100 ℃, the time is 2-4 hours, and the heating rate is 5 ℃/min.
6. The ruthenium nanocluster hydrogen evolution electrocatalyst according to any one of claims 1 to 5, wherein the ruthenium nanocluster hydrogen evolution electrocatalyst is prepared by a super-assembly preparation method of the ruthenium nanocluster hydrogen evolution electrocatalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111569928A (en) * | 2020-05-12 | 2020-08-25 | 武汉理工大学 | MOFs-derived carbon-based material anchored high-dispersion metal Pt nanocluster and preparation method and application thereof |
| CN113437314A (en) * | 2021-06-29 | 2021-09-24 | 青岛科技大学 | Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof |
| CN113617349A (en) * | 2021-05-27 | 2021-11-09 | 中国科学院金属研究所 | Nano carbon solid acid catalyst, preparation thereof and application thereof in preparation of olefin through catalytic dehydration of alcohol |
| CN113684502A (en) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | Preparation method of nitrogen-doped carbon-based supported ruthenium catalyst for hydrogen electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569928A (en) * | 2020-05-12 | 2020-08-25 | 武汉理工大学 | MOFs-derived carbon-based material anchored high-dispersion metal Pt nanocluster and preparation method and application thereof |
| CN113617349A (en) * | 2021-05-27 | 2021-11-09 | 中国科学院金属研究所 | Nano carbon solid acid catalyst, preparation thereof and application thereof in preparation of olefin through catalytic dehydration of alcohol |
| CN113437314A (en) * | 2021-06-29 | 2021-09-24 | 青岛科技大学 | Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof |
| CN113684502A (en) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | Preparation method of nitrogen-doped carbon-based supported ruthenium catalyst for hydrogen electrolysis |
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