CN110620242A - Iron/nitrogen binary doped carbon catalyst loaded with ruthenium nanoparticles and preparation method thereof - Google Patents
Iron/nitrogen binary doped carbon catalyst loaded with ruthenium nanoparticles and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
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Abstract
The invention relates to an iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, dissolving glucose, dicyandiamide and ferric chloride in deionized water, adding a silicon dioxide aqueous solution, stirring to form a mixed solution, then adding ruthenium chloride into the mixed solution, stirring the mixed solution added with the ruthenium chloride, and heating. And (2) carrying out heat treatment on the mixture obtained after the solvent evaporation in an inert gas to ensure that ferric chloride and dicyandiamide are codoped in the glucose carbonization process, heating and reducing ruthenium chloride into ruthenium nano particles to obtain a heat-treated product, sequentially baking and soaking the heat-treated product in a sodium hydroxide solution and stirring the heat-treated product in sulfuric acid, respectively carrying out cleaning and centrifuging procedures, and putting the centrifuged product into an oven for drying. And grinding the dried product to obtain the iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of preparation of carbon nano materials, in particular to an iron/nitrogen binary doped carbon nano material loaded with ruthenium nano particles and a preparation method thereof.
[ background of the invention ]
The carbon material has wide sources, low cost and good stability, and has freely movable delocalized pi electrons, the delocalized pi electrons are favorable for the electrochemical reaction, and although the electronic structure of the carbon material is stable, the carbon material does not have the electrocatalytic capacity generally.
Platinum-based catalysts are currently used in various chemical reactions and industrial fields of fuel cells, but there are still many problems to be solved with platinum-based catalysts, such as the use of platinum in a Polymer Electrolyte Fuel Cell (PEFC) or an air cell, which causes a corresponding increase in the cost of the cell, and the occurrence of chemical reactions, such as the decomposition of an electrolyte solution, in the cell due to the use of platinum. Therefore, platinum-based catalysts pose a major obstacle to technological breakthrough in the development of next-generation batteries.
The technology of doping heterogeneous atoms in the carbon material has been proved by a plurality of research results to influence the charge density distribution of a carbon material system and the spin density distribution of the carbon atoms, thereby changing the electronic structure of the carbon material, and the carbon material doped with the heterogeneous atoms shows certain electrocatalytic activity. Among them, the transition metal (mainly iron and cobalt) and nitrogen binary doped nano carbon catalyst is considered to be the most organic to replace the platinum-based catalyst to be applied to the cathode oxygen reduction process of the fuel cell due to the higher activity and stability, so the design and preparation of the supported nano noble metal heterogeneous catalyst have been receiving more and more attention from make internal disorder or usurp people.
So far, relatively few studies and reports have been made on metallic ruthenium as a hydrogen evolution catalyst, but the bonding strength of metallic ruthenium and hydrogen is about 65kcal/mol, the bonding strength of metallic ruthenium and hydrogen and the bonding strength of platinum/hydrogen are quite close, the price of metallic ruthenium is cheaper than that of platinum, and the price of metallic ruthenium is only one-fifteenth of that of platinum, so that it is feasible to replace platinum with metallic ruthenium as a hydrogen evolution catalyst, and the manufacturing cost can be greatly reduced.
[ summary of the invention ]
In view of the above, the invention provides an iron/nitrogen binary doped nanocarbon catalyst loading ruthenium nanoparticles and a preparation method thereof, and due to the synergistic effect of the iron/nitrogen binary doped nanocarbon matrix and the ruthenium nanoparticles, the catalytic activity of the catalyst prepared by the invention is obviously improved, so that the catalyst provided by the invention can actually replace the platinum-based catalyst in the prior art, and can be further applied to electrocatalytic hydrogen evolution greatly.
In order to solve the problems in the prior art, the invention provides a preparation method of an iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles, which comprises the following steps: firstly, dissolving glucose, dicyandiamide and ferric chloride in deionized water, adding a silicon dioxide aqueous solution, stirring to form a mixed solution, then adding ruthenium chloride into the mixed solution, stirring the mixed solution added with the ruthenium chloride, and heating. And (3) carrying out heat treatment on the mixture obtained after the solvent evaporation in an inert gas to enable ferric chloride and dicyandiamide to generate co-doping in the glucose carbonization process, and heating and reducing ruthenium chloride into ruthenium nanoparticles to obtain a heat-treated product. And (3) baking and soaking the heat-treated product in a sodium hydroxide solution, then carrying out cleaning and centrifuging procedures, subsequently stirring the centrifuged product in sulfuric acid, then carrying out cleaning and centrifuging procedures, and putting the centrifuged product into an oven for drying. And finally, grinding the dried product to obtain the iron/nitrogen binary doped nano carbon catalyst loaded with the ruthenium nano particles.
Preferably, in the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles, as described above, in the step of soaking the heat-treated product in the sodium hydroxide solution, and then performing the cleaning and centrifuging procedures, the molar concentration of the sodium hydroxide solution is 2M, the working temperature of the sodium hydroxide solution is 90 ℃, the soaking time of the heat-treated product in the sodium hydroxide solution is 8 hours, and the cleaning procedure is performed using deionized water and ethanol.
Preferably, in the preparation method of the iron/nitrogen binary-doped nanocarbon catalyst loaded with ruthenium nanoparticles, as described above, in the step of stirring the centrifuged product in sulfuric acid, and then performing the washing and centrifuging procedures, the molar concentration of the sulfuric acid is 0.5M, the working temperature of the sulfuric acid is 60 ℃, the time of stirring the centrifuged product in the sulfuric acid is 2 hours, and the washing procedure is performed using deionized water and ethanol.
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is as described above, wherein the temperature of the oven is 90 ℃ in the step of drying the centrifuged product in the oven.
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is as described above, wherein the mass ratio of glucose to silica is (0.5 g-2 g): (1 gram-6 grams).
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is as described above, wherein the mass ratio of glucose, dicyandiamide to ferric chloride is (0.5 g-2 g): (0 g-2 g): (0 g-0.3 g).
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is as described above, wherein the mass ratio of glucose to ruthenium chloride is (0.5 g-2 g): (0 g-0.3 g).
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is adopted, wherein the temperature range of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 1-6 hours.
Preferably, the preparation method of the iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is as described above, wherein the inert gas is argon, nitrogen, hydrogen-argon mixture gas or hydrogen-nitrogen mixture gas.
The invention also provides an iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles, which is prepared by the preparation method.
Compared with the prior art, the preparation process has the advantages of simple steps, low cost and low equipment requirement, and is very easy for large-scale production. The invention adopts ruthenium chloride, glucose, dicyandiamide and ferric chloride as raw materials, takes silicon dioxide as a template, and carries out heat treatment under the protection of inert gas at a certain temperature, the obtained nanocarbon catalyst has excellent electrocatalytic oxygen reduction characteristics, and the hydrogen evolution performance of ruthenium nanoparticles is greatly improved due to the synergistic effect between the iron/nitrogen binary doped nanocarbon matrix and the ruthenium nanoparticles, and the ruthenium metal nanoparticles have uniform size and uniform dispersion. Therefore, the iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles can replace expensive platinum-based catalyst in the technical field of electrocatalytic hydrogen evolution.
The specific techniques employed in the present invention will be further illustrated by the following examples and accompanying drawings.
[ description of the drawings ]
Fig. 1 is a flowchart illustrating steps of a method for preparing an iron/nitrogen binary doped carbon catalyst loaded with ruthenium nanoparticles according to an embodiment of the present invention.
Fig. 2 is a high-resolution transmission electron microscope image of the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) prepared according to an embodiment of the present invention.
Fig. 3a is a photoelectron spectrum of ruthenium element in the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) prepared according to an embodiment of the present invention.
Fig. 3b is a photoelectron spectrum of iron element in the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) according to an embodiment of the present invention.
Fig. 3C is a photoelectron spectrum of nitrogen element in the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) according to an embodiment of the present invention.
FIG. 4a is a graph of the electrocatalytic hydrogen evolution performance of the iron/nitrogen binary doped nanocarbon catalyst (Fe-N-C), the ruthenium nanoparticle-supported nitrogen-doped nanocarbon catalyst (Ru/N-C), the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) and the commercial 40% Pt/C catalyst in a 1M Phosphate Buffer Saline (PBS) solution, prepared according to an embodiment of the present invention.
FIG. 4b is a graph of the electrocatalytic hydrogen evolution performance of the iron/nitrogen binary doped nanocarbon catalyst (Fe-N-C), the ruthenium nanoparticle-supported nitrogen-doped nanocarbon catalyst (Ru/N-C), the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) and the commercial 40% Pt/C catalyst in 0.1M potassium hydroxide (KOH) solution, prepared according to an embodiment of the present invention.
FIG. 4C shows an example of a binary Fe/N doped nanocarbon catalyst (Fe-N-C), a ruthenium nanoparticle supported N doped nanocarbon catalyst (Ru/N-C), a ruthenium nanoparticle supported binary Fe/N doped nanocarbon catalyst (Ru/Fe-N-C) and a commercial 40% Pt/C catalyst prepared according to an embodiment of the present invention in 0.5M sulfuric acid (H)2SO4) Electrocatalytic hydrogen evolution performance diagram in solution.
[ detailed description ] embodiments
The present invention will be further described with reference to the following examples and accompanying drawings, which are provided for the purpose of illustrating the detailed embodiments and the specific operation thereof, and are not intended to limit the scope of the present invention.
As shown in fig. 1, a flow chart of steps of a preparation method of the ruthenium nanoparticle-supported iron/nitrogen binary-doped carbon catalyst according to an embodiment of the present invention includes the following steps:
step 110: glucose, dicyandiamide, and ferric chloride are dissolved in deionized water, and then a silicon dioxide aqueous solution is added, and a mixed solution is formed by magnetic stirring, but it is obvious to those skilled in the art that any suitable stirring method can be adopted, and the magnetic stirring method disclosed in this embodiment is not limited thereto. In addition, this example discloses that the mass ratio of glucose and silica is (0.5 g) to 2 g (g)): (1-6 g), or the mass ratio of glucose, dicyandiamide to ferric chloride is (0.5-2 g): (0 grams (g) -2 grams (g)): (0 grams (g) -0.3 grams (g));
step 120: ruthenium chloride is added to the mixed solution, and after the mixed solution added with the ruthenium chloride is stirred for a period of time, the temperature is raised to 110 ℃ again, and the solvent is evaporated. In this embodiment, the mass ratio of glucose to ruthenium chloride is (0.5-2 g): (0 grams (g) -0.3 grams (g));
step 130: and (3) carrying out heat treatment on the mixture obtained after the solvent evaporation in an inert gas to enable ferric chloride and dicyandiamide to generate co-doping in the glucose carbonization process, and heating and reducing ruthenium chloride into ruthenium nanoparticles to obtain a heat-treated product. Wherein the heat treatment temperature range of the step is between 600-1000 ℃, the heat treatment time range is 1-6 hours, and the inert gas can be argon, nitrogen, a hydrogen-argon mixed gas containing 5% of hydrogen or a hydrogen-nitrogen mixed gas containing 5% of hydrogen. One skilled in the art can select the optimal heat treatment temperature, heat treatment time and inert gas type according to the actual process conditions, and is not limited to the process parameters disclosed in this step;
step 140: and (3) baking and soaking the heat-treated product in a sodium hydroxide (NaOH) solution, and then carrying out cleaning and centrifuging procedures. Wherein the molar concentration of the sodium hydroxide solution adopted in the step is 2M, the working temperature of the sodium hydroxide solution is 90 ℃, the soaking time of the heat-treated product in the sodium hydroxide solution is 8 hours, and deionized water and ethanol are used for cleaning;
step 150: the centrifuged product is washed with sulfuric acid (H)2SO4) Stirring, washing and centrifuging. Wherein, the molar concentration of the sulfuric acid adopted in the step is 0.5M, the working temperature of the sulfuric acid is 60 ℃, the stirring time of the centrifuged product in the sulfuric acid is 2 hours, and deionized water and ethanol are used for cleaning;
step 160: drying the centrifuged product in a drying oven at 90 ℃;
step 170: and grinding the dried product to obtain the iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles. It is worth to be noted that the ruthenium particles prepared by the method have the size of only 1-2 nanometers (nm), are uniformly distributed on the iron/nitrogen-doped carbon material, the nitrogen-doped carbon material has a stable chemical structure and large specific surface area and pore volume, and the doping of nitrogen atoms is also helpful for enhancing the electron transport of the carrier and modulating the chemical and electronic properties of the supported phase, so that the effects of stabilizing and dispersing the active centers are achieved.
The following three examples are presented to further illustrate the preparation method of the present invention, and it should be noted that the parameters of the specific preparation method and the like exemplified below are only examples in suitable ranges, and are not intended to limit the specific process values of the present invention, and those skilled in the art can make the best choice within the suitable parameter ranges according to the actual process conditions through the description of the present application.
[ example 1]
1 gram (g) of glucose, 1 gram (g) of dicyandiamide and 0.15 gram (g) of ferric chloride are dissolved in 25 milliliters (ml) of deionized water, 4 grams (g) of aqueous silica solution are added, and a uniform mixed solution is formed by magnetic stirring, and then the mixed solution is heated to 110 ℃ to evaporate the solvent in the solution. Subsequently, the product after the evaporation of the above solvent was put into a tube furnace protected with argon (Ar) to be heat-treated at 800 ℃ for 2 hours. Then, the heat-treated product is dried and soaked in sodium hydroxide (NaOH) solution with the working temperature of 90 ℃ and the molar concentration of 2M for 8 hours, and then the obtained product is washed and centrifuged by deionized water and ethanol. Then the product after centrifugation is treated with 0.5M sulfuric acid (H) at 60 deg.C2SO4) Stirring for 2 hours, washing and centrifuging the obtained product by using deionized water and ethanol. And drying the centrifuged product in an oven at 90 ℃, and finally grinding the dried product to obtain the iron/nitrogen binary doped nanocarbon catalyst (Fe-N-C).
[ example 2]
1 gram (g) of glucose and 1 gram (g) of dicyandiamide were dissolved in 25 milliliters (ml) of deionized water, and 4 grams (g) of aqueous silica solution was added and magnetically stirred to form a uniform mixed solution. Then, 10 ml (ml) of an aqueous ruthenium chloride solution (concentration: 0.01g/ml) was added to the above mixed solution, stirred for 30 minutes, and then heated to 110 ℃ to evaporate the solvent in the solution. Subsequently, the product after the evaporation of the above solvent was put into a tube furnace protected with argon (Ar) to be heat-treated at 800 ℃ for 2 hours. Then, the heat-treated product is dried and soaked in sodium hydroxide (NaOH) solution with the working temperature of 90 ℃ and the molar concentration of 2M for 8 hours, and then the obtained product is washed and centrifuged by deionized water and ethanol. Then the centrifuged product is processed at 60℃,0.5M molar sulfuric acid (H)2SO4) Stirring for 2 hours, washing and centrifuging the obtained product by using deionized water and ethanol. And drying the centrifuged product in an oven at 90 ℃, and finally grinding the dried product to obtain the nitrogen-doped nano carbon catalyst (Ru/N-C) loaded with the ruthenium nanoparticles.
[ example 3]
1 gram (g) of glucose, 1 gram (g) of dicyandiamide, and 0.15 gram (g) of ferric chloride were dissolved in 25 milliliters (ml) of deionized water, and 4 grams (g) of aqueous silica solution was added and magnetically stirred to form a uniform mixed solution. Then, 10 ml (ml) of an aqueous ruthenium chloride solution (concentration: 0.01g/ml) was added to the above mixed solution, stirred for 30 minutes, and then heated to 110 ℃ to evaporate the solvent in the solution. Subsequently, the product after the evaporation of the above solvent was put into a tube furnace protected with argon (Ar) to be heat-treated at 800 ℃ for 2 hours. Then, the heat-treated product is dried and soaked in sodium hydroxide (NaOH) solution with the working temperature of 90 ℃ and the molar concentration of 2M for 8 hours, and then the obtained product is washed and centrifuged by deionized water and ethanol. Then the product after centrifugation is treated with 0.5M sulfuric acid (H) at 60 deg.C2SO4) Stirring for 2 hours, washing and centrifuging the obtained product by using deionized water and ethanol. And drying the centrifuged product in an oven at 90 ℃, and finally grinding the dried product to obtain the iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) loaded with ruthenium nanoparticles.
Referring to fig. 2, fig. 2 is a high-resolution transmission electron microscope image of the ruthenium nanoparticle-supported binary Fe/N doped nanocarbon catalyst (Ru/Fe-N-C) according to an embodiment of the invention. As is clear from FIG. 2, ruthenium nanoparticles have been successfully supported on a nanocarbon matrix, and it is apparent that the heterogeneous catalyst of the present invention is actually supported with metallic ruthenium particles.
FIG. 3a is a high resolution X-ray photoelectron spectrum of the ruthenium (Ru) element in the Ru/N binary doped nanocarbon catalyst (Ru/Fe-N-C) loaded with Ru nanoparticles according to an embodiment of the invention; FIG. 3b is a high resolution X-ray photoelectron spectrum of iron (Fe) element in the Ru/N binary doped nanocarbon catalyst (Ru/Fe-N-C) loaded with Ru nanoparticles according to an embodiment of the present invention; and fig. 3C is a high-resolution X-ray photoelectron spectrum of nitrogen (N) element in the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) prepared according to an embodiment of the present invention.
As is clear from FIGS. 3 a-3C, the metallic ruthenium (Ru) in the resulting Ru/Fe-N-C catalyst is predominantly Ru0Exists in the form that peaks at the positions 463.1eV and 485.3eV correspond to Ru3p3/2And Ru3p1/2(as shown in FIG. 3 a); fe2p3/2Peak and Fe2p1/2The presence of the peak demonstrates successful doping of iron (Fe) in the nanocarbon catalyst (as shown in fig. 3 b); nitrogen (N) is present in the form of pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and nitrogen oxides, which fully demonstrates the successful doping of nitrogen in nanocarbon catalysts (as shown in fig. 3 c).
FIG. 4a is a graph showing the performance of electrocatalytic hydrogen evolution of the iron/nitrogen binary doped nanocarbon catalyst (Fe-N-C), the nitrogen doped nanocarbon catalyst (Ru/N-C) supporting ruthenium nanoparticles and the iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) supporting ruthenium nanoparticles obtained in the above examples 1-3 in a 1M Phosphate Buffered Saline (PBS) solution; FIG. 4b is a graph showing the performance of electrocatalytic hydrogen evolution of the Fe/N binary doped nanocarbon catalyst (Fe-N-C), the Ru nanoparticle-supported N doped nanocarbon catalyst (Ru/N-C) and the Ru nanoparticle-supported Fe/N binary doped nanocarbon catalyst (Ru/Fe-N-C) obtained in examples 1-3 in a 1M potassium hydroxide (KOH) solution; FIG. 4C shows the results of examples 1-3, wherein the iron/nitrogen binary doped nanocarbon catalyst (Fe-N-C), the ruthenium nanoparticle-supported nitrogen-doped nanocarbon catalyst (Ru/N-C) and the ruthenium nanoparticle-supported iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) were treated with sulfuric acid (H) of 0.5M2SO4) Electrocatalytic hydrogen evolution performance diagram in solution.
As is clear from FIGS. 4a to 4c, when the current density is 10mA/cm2In the meantime, the iron/nitrogen binary doped nano carbon catalyst (Fe-N-C), the nitrogen doped nano carbon catalyst (Ru/N-C) supporting the ruthenium nano particle and the iron/nitrogen binary doped nano carbon catalyst (Ru/Fe-N-C) supporting the ruthenium nano particleThe overpotential is reduced in sequence; in an alkaline electrolyte (potassium hydroxide solution), the reaction activity of the iron/nitrogen binary doped nano-carbon catalyst (Ru/Fe-N-C) loaded with ruthenium nano-particles is close to that of a commercial 40% Pt/C catalyst; in a neutral electrolyte (PBS solution), the catalytic activity of the ruthenium nanoparticle-loaded iron/nitrogen binary doped nanocarbon catalyst (Ru/Fe-N-C) is even superior to that of a commercial Pt/C catalyst, and the ruthenium nanoparticle-loaded iron/nitrogen binary doped nanocarbon catalyst shows excellent hydrogen evolution performance.
In summary, the preparation method of the present invention mixes the metal ruthenium salt, the iron salt, the organic carbon precursor, the nitrogen source, and the silica nanoparticles, and further pyrolyzes and removes the silica particles in the inert gas at a high temperature to obtain the iron/nitrogen co-doped carbon catalyst. The preparation method has the advantages of simple and stable preparation process, low cost, low equipment requirement and extremely high repeatability, is very easy to carry out large-scale production, and is quite suitable for industrial production. The ruthenium particles prepared by the method have uniform size which is only 1-2 nanometers (nm), and the ruthenium metal particles are uniformly distributed on the iron/nitrogen co-doped carbon material, so that the catalyst prepared by the preparation method has excellent performance of electrolyzing water to produce hydrogen, and has good application prospect.
Although the present invention has been described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form, construction, features, methods and quantities may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of an iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles is characterized by comprising the following steps:
dissolving glucose, dicyandiamide and ferric chloride in deionized water, adding a silicon dioxide aqueous solution, and stirring to form a mixed solution;
adding ruthenium chloride into the mixed solution, and stirring and heating the mixed solution added with the ruthenium chloride;
carrying out heat treatment on the mixture obtained after the solvent evaporation in an inert gas to enable the ferric chloride and the dicyandiamide to be co-doped in the glucose carbonization process, and heating and reducing the ruthenium chloride into ruthenium nanoparticles to obtain a heat-treated product;
baking and soaking the heat-treated product in a sodium hydroxide solution, and then carrying out cleaning and centrifuging procedures;
stirring the centrifuged product in sulfuric acid, and then carrying out cleaning and centrifuging procedures;
putting the centrifuged product into an oven for drying; and
and grinding the dried product to obtain the iron/nitrogen binary doped nano carbon catalyst loaded with ruthenium nano particles.
2. The method of claim 1, wherein in the step of soaking the heat-treated product in a sodium hydroxide solution, and then performing the washing and centrifugation procedure, the molar concentration of the sodium hydroxide solution is 2M, the operating temperature of the sodium hydroxide solution is 90 ℃, the soaking time of the heat-treated product in the sodium hydroxide solution is 8 hours, and the washing procedure is performed using deionized water and ethanol.
3. The method of claim 1, wherein in the step of stirring the centrifuged product in sulfuric acid, and then performing the washing and centrifuging processes, the molar concentration of the sulfuric acid is 0.5M, the working temperature of the sulfuric acid is 60 ℃, the time of stirring the centrifuged product in the sulfuric acid is 2 hours, and the washing processes are performed using deionized water and ethanol.
4. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst according to claim 1, wherein the temperature of the oven is 90 ℃ in the step of drying the centrifuged product in the oven.
5. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst according to claim 1, wherein the mass ratio of the glucose to the silica is (0.5-2 g): (1 gram-6 grams).
6. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst according to claim 1, wherein the mass ratio of the glucose, the dicyandiamide and the ferric chloride is (0.5-2 g): (0 g-2 g): (0 g-0.3 g).
7. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst as claimed in claim 1, 5 or 6, wherein the mass ratio of the glucose to the ruthenium chloride is (0.5-2 g): (0 g-0.3 g).
8. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst as claimed in claim 1, wherein the temperature of the heat treatment is in the range of 600 ℃ to 1000 ℃ and the time of the heat treatment is in the range of 1 to 6 hours.
9. The method for preparing the ruthenium nanoparticle-supported iron/nitrogen binary-doped nanocarbon catalyst as claimed in claim 1, wherein the inert gas is argon, nitrogen, a hydrogen-argon mixture gas or a hydrogen-nitrogen mixture gas.
10. An iron/nitrogen binary doped nanocarbon catalyst loaded with ruthenium nanoparticles, which is prepared by the preparation method of any one of claims 1 to 9.
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