CN117187859A - Electro-catalyst with adjustable ruthenium monoatomic and ruthenium cluster proportion and preparation method thereof - Google Patents
Electro-catalyst with adjustable ruthenium monoatomic and ruthenium cluster proportion and preparation method thereof Download PDFInfo
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- CN117187859A CN117187859A CN202310974256.1A CN202310974256A CN117187859A CN 117187859 A CN117187859 A CN 117187859A CN 202310974256 A CN202310974256 A CN 202310974256A CN 117187859 A CN117187859 A CN 117187859A
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- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 111
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 72
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 38
- 239000011258 core-shell material Substances 0.000 claims abstract description 37
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 37
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 238000003763 carbonization Methods 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 18
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 20
- -1 polypropylene Polymers 0.000 claims description 16
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000001523 electrospinning Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 28
- 239000001257 hydrogen Substances 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
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- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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Abstract
The application discloses an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion and a preparation method thereof. The preparation method comprises the following steps: dissolving ruthenium salt and a fiber framework in a first solvent, and stirring the first solvent to obtain a first solution; dissolving a thermoplastic high molecular polymer in a second solvent, and stirring the second solvent to obtain a second solution; respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by using the spinning device to generate core-shell polymer fibers; the core-shell polymer fiber is subjected to oxidation treatment to obtain a ruthenium mixture, and the ruthenium mixture is subjected to carbonization treatment to obtain the hollow carbon nanofiber electrocatalyst. The application aims to solve the problems of high cost and high energy consumption of the existing water electrolysis hydrogen production method, and solves the problems that ruthenium monoatoms and ruthenium clusters in an electrocatalyst are difficult to coexist and the proportion is difficult to regulate.
Description
Technical Field
The application relates to the technical field of material preparation, in particular to an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion and a preparation method thereof.
Background
The problems of environmental pollution and energy shortage due to the widespread use of fossil fuels are increasingly serious. The hydrogen energy has the characteristics of rich resources, high heat efficiency, environmental friendliness and the like, and is considered as one of the alternative energy sources of the traditional fossil fuel. Compared with the hydrogen production by non-renewable fossil fuels such as coal, petroleum, natural gas and the like, the raw material of water pyrolysis is rich water resource on the earth, and the electrolyzed water has the advantages of simple process, stable work and high hydrogen production purity and is considered as the hydrogen production process with the most development prospect. However, industrial water electrolysis for hydrogen production is costly and energy consuming due to the high overpotential barrier.
Therefore, there is a need to prepare a high activity electrocatalyst for the water electrolysis hydrogen production to reduce the cost and energy consumption of the water electrolysis hydrogen production.
Disclosure of Invention
The application provides an electrocatalyst with adjustable ruthenium monoatoms and ruthenium clusters and a preparation method thereof, and the method aims to solve the problems of high cost and high energy consumption of the existing water electrolysis hydrogen production method and solve the problems that the ruthenium monoatoms and the ruthenium clusters in the electrocatalyst are difficult to coexist and the proportion is difficult to regulate.
In one aspect, the application provides a method for preparing an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion, which comprises the following steps:
adding ruthenium salt and a fiber skeleton into a first solvent to dissolve the ruthenium salt and the fiber skeleton in the first solvent, and stirring the first solvent to obtain a first solution;
adding a thermoplastic high molecular polymer into a second solvent to dissolve the thermoplastic high molecular polymer in the second solvent, and stirring the second solvent to obtain a second solution;
respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device to generate core-shell polymer fibers;
the core-shell polymer fibers are oxidized to obtain a ruthenium mixture, and the ruthenium mixture is carbonized to obtain a hollow carbon nanofiber electrocatalyst comprising ruthenium monoatoms and ruthenium clusters in a target ratio.
In the preparation method of the present application, the adding the first solution and the second solution to the spinning device respectively includes:
adding the first solution to the spinning device at a first flow rate and adding the second solution to the spinning device at a second flow rate; wherein the ratio of the first flow rate to the second flow rate is 3:1.
In the preparation method of the present application, the electrospinning the first solution and the second solution by using the spinning device to generate core-shell polymer fibers comprises:
and setting electrostatic spinning parameters, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device according to the electrostatic spinning parameters to form fiber filaments so as to generate core-shell polymer fibers.
In the preparation method of the application, the electrostatic spinning parameters comprise electrostatic spinning voltage and electrostatic spinning duration, wherein the electrostatic spinning voltage is 11kV, and the electrostatic spinning duration is 10 hours.
In the preparation method of the present application, the oxidizing treatment of the core-shell polymer fiber to obtain ruthenium mixture comprises:
and placing the core-shell polymer fiber in a heating device, and carrying out oxidation treatment on the core-shell polymer fiber according to preset oxidation parameters to obtain a ruthenium mixture, wherein the ruthenium mixture comprises ruthenium salt and ruthenium oxide.
In the preparation method of the application, the preset oxidation parameters comprise an oxidation temperature and an oxidation time; the oxidation temperature is 100-220 ℃, and the oxidation time is 2 hours.
In the preparation method of the present application, the carbonizing treatment of the ruthenium mixture to obtain the hollow carbon nanofiber electrocatalyst comprises:
carbonizing the ruthenium mixture by using a heating device according to preset carbonization parameters to obtain hollow carbon nanofibers;
and taking the hollow carbon nanofiber as a matrix, and loading ruthenium monoatoms and ruthenium clusters with target proportions on the matrix to obtain the hollow carbon nanofiber electrocatalyst.
In the preparation method of the application, the preset carbonization parameters comprise carbonization temperature and carbonization time; the carbonization temperature is 600-1100 ℃, and the carbonization time is 2 hours.
In the preparation method of the application, the ruthenium salt comprises aqueous ruthenium acetate; the fiber skeleton comprises polypropylene, polyethylene, polyamide, polyether ketone or polyethylene terephthalate; the thermoplastic high molecular polymer comprises polymethyl methacrylate, polylactic acid, polycaprolactone, polyvinyl alcohol, polymethyl acrylate or polyethylene terephthalate; the first solvent and the second solvent comprise dimethylformamide or acetone.
On the other hand, the application also provides an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion, which is prepared by the preparation method.
The embodiment of the application provides an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion and a preparation method thereof, wherein ruthenium salt and a fiber framework are added into a first solvent, so that the ruthenium salt and the fiber framework are dissolved in the first solvent, and the first solvent is stirred to obtain a first solution; adding a thermoplastic high molecular polymer into a second solvent to dissolve the thermoplastic high molecular polymer in the second solvent, and stirring the second solvent to obtain a second solution; respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device to generate core-shell polymer fibers; the core-shell polymer fibers are oxidized to obtain a ruthenium mixture, and the ruthenium mixture is carbonized to obtain a hollow carbon nanofiber electrocatalyst comprising ruthenium monoatoms and ruthenium clusters in a target ratio. Therefore, the problem that ruthenium monoatoms and ruthenium clusters in the electrocatalyst are difficult to coexist is solved, the proportion of the ruthenium monoatoms and the ruthenium clusters in the electrocatalyst is regulated and controlled, and the target proportion of the ruthenium monoatoms and the ruthenium clusters are regulated and controlled, so that the prepared electrocatalyst for the reduction hydrogen evolution reaction has the advantages of high activity, high stability and low ruthenium content, and the electrocatalyst can also be applied to full-pH electrolyte and has important significance in expanding the practical application range of electrolyzed water and reducing the cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing an electrocatalyst with adjustable ratio of ruthenium monoatoms to ruthenium clusters according to an embodiment of the application;
FIG. 2 is an X-ray diffraction pattern of a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application;
FIG. 3 (a) shows a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application and a comparative Pt/C catalyst at 0.5. 0.5M H 2 SO 4 Linear scanning curve for hydrogen evolution reaction under electrolyteA line graph;
FIG. 3 (b) is a linear scan graph showing hydrogen evolution reactions of hollow carbon nanofiber electrocatalysts prepared at various oxidation temperatures and comparative Pt/C catalysts under a 1M KOH electrolyte according to an embodiment of the present application;
FIG. 4 (a) shows a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application and a comparative Pt/C catalyst at 0.5. 0.5M H 2 SO 4 Tafel plot of hydrogen evolution reaction under electrolyte;
FIG. 4 (b) is a Tafil plot showing hydrogen evolution reactions of hollow carbon nanofiber electrocatalysts prepared at various oxidation temperatures and comparative Pt/C catalysts under a 1M KOH electrolyte according to an embodiment of the present application;
FIG. 5 (a) is a HRTEM diagram of a hollow carbon nanofiber electrocatalyst prepared at 160℃and according to an embodiment of the application under a spherical aberration electron microscope;
fig. 5 (b) is an AC-STEM diagram of a hollow carbon nanofiber electrocatalyst prepared at an oxidation temperature of 160 ℃ under a spherical aberration electron microscope according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Some embodiments of the present application are described in detail below with reference to the accompanying drawings. The following embodiments and features of the embodiments may be combined with each other without conflict.
Electrolytic water hydrogen production is performed by a reductive hydrogen evolution reaction (Hydrogen Evolution Reaction, HER) on the cathode, wherein most water-splitting electrocatalysts are more prone to exhibit higher HER activity in acidic media, as a large amount of h+ in the acid can immediately convert and release hydrogen without hydrolysis; in alkaline electrolyte, the catalyst needs to catalyze the dissociation of water molecules to obtain more hydrogen protons before catalyzing to generate hydrogen, so that more energy is consumed.
Currently, commercially used HER catalysts remain noble metal Pt/C catalysts, pt, while having better acidic HER catalytic ability, has very limited ability to promote hydrolytic cleavage in the alkaline, resulting in its basic HER performance in general. Moreover, the scarce reserves of Pt noble metals, high costs and poor cycling stability greatly limit their commercial application.
The application provides an electrocatalyst with adjustable ratio of ruthenium monoatoms and ruthenium clusters and a preparation method thereof, which solve the problem that the ruthenium monoatoms and the ruthenium clusters in the electrocatalyst are difficult to coexist, and realize the regulation and control of the ratio of the ruthenium monoatoms and the ruthenium clusters in the electrocatalyst, thereby regulating and controlling the ruthenium monoatoms and the ruthenium clusters with target ratio, so that the prepared electrocatalyst for the reduction hydrogen evolution reaction has the advantages of high activity, high stability and low ruthenium content, and the electrocatalyst can also be suitable for full pH electrolyte and has important significance for expanding the practical application range of electrolyzed water and reducing the cost.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing an electrocatalyst with adjustable ratio of ruthenium monoatoms and ruthenium clusters according to an embodiment of the application. The preparation method can prepare the reduction hydrogen evolution reaction electrocatalyst with high activity, high stability and low ruthenium content.
As shown in FIG. 1, the preparation method of the electrocatalyst with adjustable ruthenium monoatoms and ruthenium clusters comprises the following steps: step S101 to step S104.
S101, adding ruthenium salt and a fiber skeleton into a first solvent to enable the ruthenium salt and the fiber skeleton to be dissolved in the first solvent, and stirring the first solvent to obtain a first solution.
The ruthenium (Ru) salt may be a compound containing ruthenium ions, for example, aqueous ruthenium acetate (Ru (COOH) 3. XH2O) or the like. The fibrous skeleton may be Polypropylene (PAN), polyethylene, polyamide, polyetherketone, or polyethylene terephthalate (PET), or the like. The first solvent may be Dimethylformamide (DMF), acetone, or the like. The first solution may be a shell solution obtained by dissolving a ruthenium salt and a fibrous skeleton in a first solvent.
Specifically, a ruthenium salt and a fiber skeleton are added to a first solvent so that the ruthenium salt and the fiber skeleton are dissolved in the first solvent, and the first solvent is placed on a stirring table and is stirred for more than 12 hours, so that the ruthenium salt and the fiber skeleton are sufficiently fused with the first solvent, and a first solution is obtained.
For example, aqueous ruthenium acetate and polypropylene may be added to N, N-Dimethylformamide (DMF) to dissolve the aqueous ruthenium acetate and polypropylene in DMF solvent, and the DMF solvent placed on a stirring bench and stirred for more than 12 hours to allow the aqueous ruthenium acetate and polypropylene to fuse sufficiently with the DMF solvent to give a shell solution.
Illustratively, the ratio of the molar mass of Ru (COOH) 3. XH2O to PAN added may be 1:83-1:87, DMF solvent may be 4-6g.
S102, adding the thermoplastic high molecular polymer into a second solvent to enable the thermoplastic high molecular polymer to be dissolved in the second solvent, and stirring the second solvent to obtain a second solution.
The thermoplastic high polymer can be used for hollow electrostatic spinning, and can be polymethyl methacrylate (PMMA), polylactic acid (PLA), polycaprolactone (PCL), polyvinyl alcohol (PVA), polymethyl acrylate (PBA) or polyethylene terephthalate (PET). The second solvent may be Dimethylformamide (DMF), acetone, or the like. The second solution may be a core layer solution obtained by dissolving a thermoplastic high molecular polymer in a second solvent.
Specifically, the thermoplastic high molecular polymer is added into a second solvent so as to dissolve the thermoplastic high molecular polymer in the second solvent, and the second solvent is placed on a stirring table and is stirred for more than 12 hours, so that the thermoplastic high molecular polymer and the second solvent are fully fused, and a second solution is obtained.
For example, polymethyl methacrylate (PMMA) may be added to N, N-Dimethylformamide (DMF) to dissolve the polymethyl methacrylate in DMF solvent, and the DMF solvent is placed on a stirring table and stirred for more than 12 hours, thereby sufficiently fusing the polymethyl methacrylate with the DMF solvent to obtain the core solution.
Illustratively, the polymethyl methacrylate may be added in an amount of 2-3g and the DMF solvent in an amount of 4-6g.
And S103, respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device to generate the core-shell polymer fiber.
Wherein the spinning device can be used for electrostatic spinning. The core-shell polymer fiber may be a fibrous structure formed of high molecular chains doped with ruthenium (Ru), a product.
In some embodiments, the first solution is added to the spinning device at a first flow rate and the second solution is added to the spinning device at a second flow rate; wherein the ratio of the first flow rate to the second flow rate is 3:1. Thus, the effect of electrostatic spinning is better, and the core-shell polymer fiber is produced.
Wherein the first flow rate is the flow rate of the first solution entering the spinning device; the second flow rate is the flow rate of the second solution into the spinning device. The first flow rate and the second flow rate may be determined according to practical situations, and the electrospinning effect is best when the speed ratio of the first flow rate to the second flow rate is 3:1, and the values of the first flow rate and the second flow rate are not particularly limited herein.
Specifically, the first solution and the second solution can be added into the spinning device through different channels, the first solution is added into the spinning device at a first flow rate, and the second solution is added into the spinning device at a second flow rate, so that the electrostatic spinning effect is better, and the core-shell polymer fiber is produced.
For example, the first solution and the second solution may be fed into the spinning device through different channels, and the first solution is fed into the spinning device at a flow rate of 9m/s, and the second solution is fed into the spinning device at a flow rate of 3 m/s.
In some embodiments, electrospinning parameters are set and the first solution and the second solution are electrospun with the spinning device according to the electrospinning parameters to form filaments, thereby producing core-shell polymer fibers. The first solution and the second solution can be electrospun through specific electrospinning parameters, so that the effect of electrospinning is optimal.
The electrostatic spinning parameters comprise electrostatic spinning voltage and electrostatic spinning duration, wherein the electrostatic spinning voltage can be any voltage value, for example, 11kV, and the electrostatic spinning duration can be any duration, for example, 10 hours.
Specifically, an electrostatic spinning voltage and an electrostatic spinning time length in the electrostatic spinning parameters are set, and a spinning device is started according to the set electrostatic spinning parameters so as to carry out electrostatic spinning on the first solution and the second solution to form fiber filaments, and further core-shell polymer fibers are generated.
For example, when the electrostatic spinning voltage in the electrostatic spinning parameter is set to 11kV and the electrostatic spinning time period is set to 10 hours, the first solution and the second solution are subjected to electrostatic spinning by using a spinning device according to the electrostatic spinning parameter to form fiber filaments, so that core-shell polymer fibers are generated, the effect of electrostatic spinning under the electrostatic spinning parameter is the best, and the generated core-shell polymer fibers are the best.
S104, oxidizing the core-shell polymer fiber to obtain a ruthenium mixture, and carbonizing the ruthenium mixture to obtain the hollow carbon nanofiber electrocatalyst, wherein the hollow carbon nanofiber electrocatalyst comprises ruthenium monoatoms and ruthenium clusters with target proportion.
The hollow carbon nanofiber electrocatalyst is a HER catalyst, has high activity, high stability and low ruthenium content, and can be also suitable for all-pH electrolyte. The hollow carbon nanofiber electrocatalyst comprises ruthenium monoatoms and ruthenium clusters with target proportions, and the catalysis effect of the electrocatalyst can be optimized through the ruthenium monoatoms and the ruthenium clusters with the target proportions.
The target ratio may be any ratio, and may be adjusted according to actual conditions, and is not particularly limited herein.
In some embodiments, the core-shell polymer fiber is placed in a heating device, and the core-shell polymer fiber is subjected to oxidation treatment according to preset oxidation parameters to obtain a ruthenium mixture, wherein the ruthenium mixture comprises ruthenium salt and ruthenium oxide. The core-shell polymer fibers can thus be subjected to an oxidation treatment by means of preset oxidation parameters in order to obtain an optimum proportion of ruthenium mixture.
The heating device can be a muffle furnace, an electric furnace and other heating devices. The ruthenium mixture includes a ruthenium salt, which is a non-oxidized portion of the ruthenium mixture, and a ruthenium oxide, which is an oxidized portion of the ruthenium mixture, which can be oxidized to ruthenium dioxide.
Specifically, the preset oxidation parameters may include an oxidation temperature and an oxidation time; the oxidation temperature may be set to 100-220 ℃, for example, 120 ℃, 140 ℃, 160 ℃, 180 ℃ or 200 ℃, and the oxidation time may be set to 2 hours.
For example, the core-shell polymer fiber may be subjected to an oxidation treatment in a muffle furnace with an oxidation temperature of 120 ℃ and an oxidation time of 2 hours in a preset oxidation parameter to obtain a ruthenium mixture having a first proportion of ruthenium oxide.
For example, the core-shell polymer fiber may be subjected to an oxidation treatment in a muffle furnace with an oxidation temperature of 140 ℃ and an oxidation time of 2 hours in a preset oxidation parameter to obtain a ruthenium mixture having a ruthenium oxide content of a second ratio.
For example, the core-shell polymer fiber may be subjected to an oxidation treatment in a muffle furnace with an oxidation temperature of 160 ℃ and an oxidation time of 2 hours in a preset oxidation parameter to obtain a ruthenium mixture having a ruthenium oxide content of a third ratio.
For example, the core-shell polymer fiber may be subjected to an oxidation treatment in a muffle furnace with an oxidation temperature of 180 ℃ and an oxidation time of 2 hours in a preset oxidation parameter to obtain a ruthenium mixture having a fourth proportion of ruthenium oxide.
For example, the core-shell polymer fiber may be subjected to an oxidation treatment in a muffle furnace with an oxidation temperature of 200 ℃ and an oxidation time of 2 hours in a preset oxidation parameter to obtain a ruthenium mixture having a fifth ratio of ruthenium oxide content.
Wherein fifth ratio > fourth ratio > third ratio > second ratio > first ratio.
When the ruthenium content is constant, the higher the oxidation temperature, the higher the ratio of ruthenium acetate to ruthenium dioxide, that is, the higher the ruthenium oxide content in the ruthenium mixture.
In some embodiments, carbonizing the ruthenium mixture with a heating device according to preset carbonization parameters to obtain hollow carbon nanofibers; and taking the hollow carbon nanofiber as a matrix, and loading ruthenium monoatoms and ruthenium clusters with target proportions on the matrix to obtain the hollow carbon nanofiber electrocatalyst. Thus, the hollow carbon nanofiber electrocatalyst with the target proportion of ruthenium monoatoms and ruthenium clusters can be prepared by carbonization.
The heating device can be a muffle furnace, an electric furnace and other heating devices. The hollow carbon nanofibers can be used as a matrix for ruthenium monoatoms and clusters, in particular, by spotting the core layer of a ruthenium mixture.
Specifically, the preset carbonization parameters include carbonization temperature and carbonization time; the carbonization temperature may be set according to actual conditions, and generally the carbonization temperature may be set to 600-1100 ℃, for example, 800 ℃, and the carbonization time may be set according to actual conditions, for example, 2 hours, without being limited thereto.
Wherein, when the carbonization temperature is 800 ℃ and the carbonization time is 2 hours, the carbonization effect is optimal, and the ruthenium salt in the ruthenium mixture can be carbonized into ruthenium monoatoms and ruthenium oxide can be carbonized into ruthenium clusters.
Specifically, the ruthenium mixture is carbonized by a heating device, a core layer in the ruthenium mixture can be spotted, and then an outer layer (namely a shell layer) is left, so that the hollow carbon nanofiber is obtained; and the hollow carbon nanofiber is used as a matrix, and ruthenium salt and ruthenium oxide in the ruthenium mixture are carbonized, so that the ruthenium salt and the ruthenium salt can be carbonized into ruthenium monoatoms, the ruthenium oxide is carbonized into ruthenium clusters, and the ruthenium monoatoms and the ruthenium clusters with target proportion are loaded on the matrix, so that the hollow carbon nanofiber electrocatalyst is obtained.
The ratio of ruthenium monoatoms and ruthenium clusters in the hollow carbon nanofiber electrocatalyst was substantially the same as the ratio of ruthenium salts and ruthenium oxides in the ruthenium mixture.
As shown in fig. 2, fig. 2 is an X-ray diffraction pattern of a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application.
As can be seen from fig. 2, the corresponding ruthenium diffraction peaks show a tendency to be gradually enhanced with increasing oxidation temperature. That is, the higher the oxidation temperature, the higher the ratio of ruthenium acetate to ruthenium dioxide, that is, the higher the content of ruthenium oxide in the ruthenium mixture, and the higher the ratio of ruthenium carbide to ruthenium clusters.
However, the higher the proportion of the non-ruthenium clusters is, the higher the hydrogen evolution catalytic activity and the stability of the hollow carbon nanofiber electrocatalyst prepared by the method are, so that the oxidation temperature needs to be regulated and controlled within a proper range, the proportion of ruthenium monoatoms and ruthenium clusters in the hollow carbon nanofiber is favorably regulated and controlled, the synergistic effect of the ruthenium monoatoms and the ruthenium clusters is fully exerted, and the superior hydrogen evolution catalytic activity is obtained.
As shown in FIG. 3 (a) and FIG. 3 (b), FIG. 3 (a) shows a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application and a comparative Pt/C catalyst at 0.5. 0.5M H 2 SO 4 Linear scan plot of hydrogen evolution reaction under electrolyte; FIG. 3 (b) is a linear scan graph showing hydrogen evolution reactions of hollow carbon nanofiber electrocatalysts prepared at various oxidation temperatures and comparative Pt/C catalysts under 1M KOH electrolyte, according to an embodiment of the present application.
As can be seen from the experiment and FIGS. 3 (a) and 3 (b), the hollow carbon nanofiber electrocatalyst prepared can reach 10mAcm in an acidic environment as well as in an alkaline environment when the oxidation temperature is 120 DEG C -2 The required overpotential is 131mV and 157mV, respectively; when the oxidation temperature is 140 ℃, the prepared hollow carbon nanofiber electrocatalyst can reach 10mAcm in an acidic environment and an alkaline environment -2 The required overpotential is 36.2mV and 99mV, respectively; when the oxidation temperature is 160 ℃, the prepared hollow carbon nanofiber electrocatalyst can be in an acidic environmentUp to 10mAcm in alkaline environment -2 The required overpotential is 25mV and 32mV, respectively; when the oxidation temperature is 180 ℃, the prepared hollow carbon nanofiber electrocatalyst can reach 10mAcm in an acidic environment and an alkaline environment -2 The required overpotential is 51mV and 70mV, respectively; when the oxidation temperature is 200 ℃, the prepared hollow carbon nanofiber electrocatalyst can reach 10mAcm in an acidic environment and an alkaline environment -2 The required overpotential is 99mV and 122mV, respectively; the commercial platinum-carbon catalyst with the platinum mass fraction of 20% can reach 10mAcm in an acidic environment and an alkaline environment -2 The required overpotential is 33mV and 57mV, respectively.
From the above analysis, it is known that when the oxidation temperature is 160 ℃, the hollow carbon nanofiber electrocatalyst prepared at the oxidation temperature needs low overpotential in both an acidic environment and an alkaline environment, so that the hollow carbon nanofiber electrocatalyst prepared at the oxidation temperature has high activity, high stability and low ruthenium content and can be also applied to all-pH electrolyte.
As shown in FIG. 4 (a) and FIG. 4 (b), FIG. 4 (a) shows a hollow carbon nanofiber electrocatalyst prepared at various oxidation temperatures according to an embodiment of the application and a comparative Pt/C catalyst at 0.5. 0.5M H 2 SO 4 Tafel plot of hydrogen evolution reaction under electrolyte; FIG. 4 (b) is a Tafil plot showing hydrogen evolution reactions of hollow carbon nanofiber electrocatalysts prepared at various oxidation temperatures and comparative Pt/C catalysts under a 1M KOH electrolyte, according to an embodiment of the application.
As can be seen from fig. 4 (a) and 4 (b), when the oxidation temperature is 160 ℃, the hollow carbon nanofiber electrocatalyst prepared at the oxidation temperature requires a low overpotential, whether in an acidic environment or an alkaline environment, so that the hollow carbon nanofiber electrocatalyst prepared at the oxidation temperature has high activity, high stability and low ruthenium content and can be also applied to a full pH electrolyte.
As shown in fig. 5 (a) and fig. 5 (b), fig. 5 (a) is an HRTEM image of a hollow carbon nanofiber electrocatalyst prepared at 160 ℃ oxidation temperature under a spherical aberration electron microscope according to an embodiment of the present application; fig. 5 (b) is an AC-STEM diagram of a hollow carbon nanofiber electrocatalyst prepared at an oxidation temperature of 160 ℃ under a spherical aberration electron microscope according to an embodiment of the present application.
In the prior art, no electrocatalyst is capable of achieving coexistence of ruthenium monoatoms and ruthenium clusters. As can be seen from fig. 5 (a) and 5 (b), the two figures are characterization diagrams corresponding to the hollow carbon nanofiber electrocatalyst, and it can be explained that ruthenium monoatoms and ruthenium clusters exist in the prepared hollow carbon nanofiber electrocatalyst. Thus, coexistence of ruthenium monoatoms and ruthenium clusters can be realized in the prepared electrocatalyst.
The embodiment of the application provides an electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion and a preparation method thereof, wherein ruthenium salt and a fiber framework are added into a first solvent, so that the ruthenium salt and the fiber framework are dissolved in the first solvent, and the first solvent is stirred to obtain a first solution; adding a thermoplastic high molecular polymer into a second solvent to dissolve the thermoplastic high molecular polymer in the second solvent, and stirring the second solvent to obtain a second solution; respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device to generate core-shell polymer fibers; the core-shell polymer fibers are oxidized to obtain a ruthenium mixture, and the ruthenium mixture is carbonized to obtain a hollow carbon nanofiber electrocatalyst comprising ruthenium monoatoms and ruthenium clusters in a target ratio. Therefore, the problem that ruthenium monoatoms and ruthenium clusters in the electrocatalyst are difficult to coexist is solved, the proportion of the ruthenium monoatoms and the ruthenium clusters in the electrocatalyst is regulated and controlled, and the target proportion of the ruthenium monoatoms and the ruthenium clusters are regulated and controlled, so that the prepared electrocatalyst for the reduction hydrogen evolution reaction has the advantages of high activity, high stability and low ruthenium content, the electrocatalyst can also be applied to all-pH electrolyte, and the preparation method has simple steps and easily obtained materials, and has important significance in expanding the practical application range of electrolyzed water and reducing the cost.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the electrocatalyst with adjustable ruthenium monoatoms and ruthenium cluster proportion is characterized by comprising the following steps:
adding ruthenium salt and a fiber skeleton into a first solvent to dissolve the ruthenium salt and the fiber skeleton in the first solvent, and stirring the first solvent to obtain a first solution;
adding a thermoplastic high molecular polymer into a second solvent to dissolve the thermoplastic high molecular polymer in the second solvent, and stirring the second solvent to obtain a second solution;
respectively adding the first solution and the second solution into a spinning device, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device to generate core-shell polymer fibers;
the core-shell polymer fibers are oxidized to obtain a ruthenium mixture, and the ruthenium mixture is carbonized to obtain a hollow carbon nanofiber electrocatalyst comprising ruthenium monoatoms and ruthenium clusters in a target ratio.
2. The method of claim 1, wherein the adding the first solution and the second solution to the spinning device comprises:
adding the first solution to the spinning device at a first flow rate and adding the second solution to the spinning device at a second flow rate; wherein the ratio of the first flow rate to the second flow rate is 3:1.
3. The method of claim 1, wherein electrospinning the first solution and the second solution using the spinning device to produce core-shell polymer fibers comprises:
and setting electrostatic spinning parameters, and carrying out electrostatic spinning on the first solution and the second solution by utilizing the spinning device according to the electrostatic spinning parameters to form fiber filaments so as to generate core-shell polymer fibers.
4. The method of claim 3, wherein the electrospinning parameters comprise an electrospinning voltage and an electrospinning duration, the electrospinning voltage being 11kV and the electrospinning duration being 10 hours.
5. The method of claim 1, wherein the oxidizing the core-shell polymer fiber to obtain a ruthenium mixture comprises:
and placing the core-shell polymer fiber in a heating device, and carrying out oxidation treatment on the core-shell polymer fiber according to preset oxidation parameters to obtain a ruthenium mixture, wherein the ruthenium mixture comprises ruthenium salt and ruthenium oxide.
6. The method of claim 5, wherein the predetermined oxidation parameters include an oxidation temperature and an oxidation time; the oxidation temperature is 100-220 ℃, and the oxidation time is 2 hours.
7. The method of claim 1, wherein carbonizing the ruthenium mixture to obtain a hollow carbon nanofiber electrocatalyst comprises:
carbonizing the ruthenium mixture by using a heating device according to preset carbonization parameters to obtain hollow carbon nanofibers;
and taking the hollow carbon nanofiber as a matrix, and loading ruthenium monoatoms and ruthenium clusters with target proportions on the matrix to obtain the hollow carbon nanofiber electrocatalyst.
8. The method of claim 7, wherein the predetermined carbonization parameters include carbonization temperature and carbonization time; the carbonization temperature is 600-1100 ℃, and the carbonization time is 2 hours.
9. The method of any one of claims 1-8, wherein the ruthenium salt comprises aqueous ruthenium acetate; the fiber skeleton comprises polypropylene, polyethylene, polyamide, polyether ketone or polyethylene terephthalate; the thermoplastic high molecular polymer comprises polymethyl methacrylate, polylactic acid, polycaprolactone, polyvinyl alcohol, polymethyl acrylate or polyethylene terephthalate; the first solvent and the second solvent comprise dimethylformamide or acetone.
10. An electrocatalyst with an adjustable ratio of ruthenium monoatoms to ruthenium clusters, characterized in that it is prepared by using the preparation method according to any one of claims 1 to 9.
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