CN114635155A - Self-supporting core-shell structure catalyst and preparation method and application thereof - Google Patents
Self-supporting core-shell structure catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000011258 core-shell material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000011257 shell material Substances 0.000 claims abstract description 15
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 89
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011162 core material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- 239000007787 solid Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229940000207 selenious acid Drugs 0.000 claims description 2
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 claims description 2
- 229960005265 selenium sulfide Drugs 0.000 claims description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 abstract description 23
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/8605—Porous electrodes
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- H01M4/00—Electrodes
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- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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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Abstract
The invention discloses a self-supporting core-shell structure catalyst, and a preparation method and application thereof, and belongs to the technical field of preparation of electrocatalysis materials. The invention solves the problem of poor activity and stability of the existing urea oxidation catalyst. According to the invention, nickel sulfide grown in situ on the self-supporting substrate is taken as a core, and the nickel sulfide is completely wrapped by sulfide, so that the Fermi level of a shell material is improved by a heterojunction formed by the nickel sulfide and the sulfide, and the catalytic activity is improved; and a built-in electric field at the interface provides a higher electron barrier to prevent electrons from entering a nuclear part, so that nickel sulfide is protectedThe structure can not be damaged in the electrochemical reaction, the catalyst can work for a long time, and the unification of high activity and high stability of the catalyst is realized, so that the catalyst has high urea oxidation catalytic activity and excellent stability at 10mA cm‑2Only 1.33V is needed at the current density of (2), and the activity is not obviously changed after the continuous operation for 24 hours.
Description
Technical Field
The invention relates to a self-supporting core-shell structure catalyst, a preparation method and application thereof, and belongs to the technical field of preparation of electrocatalysis materials.
Background
Fossil fuels have brought scientific culture to human beings, but they also bring environmental pollution and greenhouse effect. The use of fossil fuels by mankind is now on the rise daily, and the urgency for developing new clean energy sources is self-evident. The traditional primary fossil fuel (coal, petroleum, natural gas and the like) is still used as a main application energy source in the world to date, and particularly has an extremely high energy source proportion in developing countries. The problems of high use cost, low energy efficiency and high pollution caused by the method are used as an energy restriction bottleneck, the industrial development is greatly limited, and the inevitable influence on the global economy is generated.
The urea oxidation reaction is an anode reaction of direct urea fuel cells and a cathode reaction of urea electrolysis, the urea oxidation reaction can directly use urea as a fuel source of the fuel cells, the urea oxidation reaction provides a method for producing hydrogen by electrolysis, the urea oxidation reaction and the urea electrolysis reaction belong to novel energy technologies, and the urea oxidation reaction is a key for determining the performances of the urea oxidation reaction and the urea electrolysis reaction. Noble metal catalysts are generally considered the benchmark for urea oxidation, but with recent advances, non-noble metal catalysts stand out and the relatively lower cost can match or even exceed the performance of noble metal catalysts. However, the increased performance is still difficult to meet the current demand, and one reason for limiting the performance of the catalyst is derived from the number of catalytically active sites and the stability of the catalyst itself. The current mainstream urea oxidation catalysts mainly comprise nickel-based catalysts such as nickel phosphide, nickel nitride and the like, but their oxidation potential is still high and is accompanied by poor stability.
In order to enhance the activity of the catalyst, a great deal of researchers find that the activity of the catalyst can be improved by introducing the dissimilar metal elements, such as a nickel-molybdenum catalyst and a nickel-cobalt catalyst, the catalytic approach of the bimetal is helpful for improving the catalytic activity of urea oxidation, but the different activities among the metals always bring lower catalytic stability along with the rapid corrosion of materials.
In summary, it is important to provide a catalyst which has high catalytic activity for urea oxidation and does not cause structural damage in an electrochemical reaction and can be operated for a long period of time.
Disclosure of Invention
The invention provides a self-supporting core-shell structure catalyst, a preparation method and application thereof, aiming at solving the problems in the prior art.
The technical scheme of the invention is as follows:
a self-supporting core-shell structure catalyst takes foam nickel as a substrate, nano linear core-shell structure particles are attached to the surface of the substrate, nickel sulfide is taken as a core material in the core-shell structure, and one or more than two materials of molybdenum sulfide, tungsten sulfide, selenium sulfide, copper sulfide or manganese sulfide are taken as a shell material in the core-shell structure.
Further defined, the shell material thickness is between 5 and 50 nm.
The preparation method of the self-supporting core-shell structure catalyst comprises the following steps:
and 2, adding a vulcanizing agent and a shell material precursor, carrying out ultrasonic dispersion treatment for 10-30min until solid powder is completely dissolved, sealing the polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, heating for reaction to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and airing the foamed nickel substrate product in the air to obtain the self-supporting core-shell structure catalyst.
Further limiting, the area of the foam nickel cut in the step 1 is 1cm2-30cm2The thickness is 1mm-5 mm.
Further limiting, the heating reaction conditions in the step 2 are as follows: the temperature is 220 ℃ and 250 ℃, and the heat preservation time is 12-24 h.
Further limited, the vulcanizing agent in the step 2 is thiourea, sulfur monochloride or sulfur.
Further limiting, the mass ratio of the adding amount of the vulcanizing agent to the foamed nickel in the step 2 is 1: (0.7-7).
And further limiting, in the step 2, the precursor of the shell layer material is one or more of sodium molybdate, sodium tungstate, selenious acid, copper oxide and manganese oxide which are mixed in any proportion.
Further limiting, in the step 2, the mass ratio of the added amount of the precursor of the shell layer material to the foamed nickel is 1: (1-10).
The self-supporting core-shell structure catalyst is applied to preparing electrodes.
The invention has the following beneficial effects:
according to the invention, nickel sulfide growing in situ on the self-supporting substrate is taken as a core, and the nickel sulfide is completely wrapped by sulfide, so that the Fermi level of a shell material is improved by a heterojunction formed by the nickel sulfide and the sulfide, and the catalytic activity is improved; and a built-in electric field at the interface provides a higher electron barrier, prevents electrons from entering a nuclear part, protects nickel sulfide, prevents the structure from being damaged in an electrochemical reaction, and ensures that the catalyst can work for a long time. The self-supporting substrate foamed nickel has a large specific surface area, a large number of active sites are provided for urea oxidation, the defects that the specific surface area of the existing commercial catalyst in a powder form is small and a large number of conductive carbon is needed to be supplemented are overcome, the unification of high activity and high stability is realized, so that the catalyst has high urea oxidation catalytic activity and excellent stability, and the urea oxidation catalytic activity is 10mAcm-2Only needs 1.33V under the current density of (2), and is continuously operatedThe activity did not change significantly after 24 h. In addition, the preparation method of the catalyst provided by the invention is simple and feasible, convenient to collect and suitable for large-scale production.
Drawings
FIG. 1 is an SEM photograph of a self-supported core-shell catalyst obtained in example 1;
FIG. 2 is a TEM photograph of a self-supported core-shell catalyst obtained in example 1;
FIG. 3 is a graph comparing electrochemical performance of the self-supported core-shell catalyst obtained in example 1 and the catalyst obtained in comparative example, wherein a is a linear voltammogram comparison graph, b is an electrochemical impedance comparison graph at 1.35V, c is a Tafel curve comparison graph, and d is a current density of 10mAcm-2Electrochemical stability comparison graph below.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea and 60mg of sodium molybdate, carrying out ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and airing the foamed nickel substrate product in the air to obtain a self-supporting core-shell structure catalyst, namely Ni for short3S2@MoS2CS。
The nickel sulfide core material of the self-supporting core-shell structure catalyst obtained in the embodiment is of a nanowire structure, the diameter of the nanowire structure is about 80nm, and the thickness of the molybdenum sulfide shell material is about 20 nm.
The microstructure characterization results of the self-supported core-shell structure catalyst obtained in this example are shown in fig. 1 and 2, and it can be seen from fig. 1 that the obtained catalystThe oxidant presents a nano-wire structure and is stably and uniformly distributed on the surface of the foamed nickel, and the nano-wire Ni can be known from the graph of 2a-b3S2@MoS2The CS sample presents a remarkable core-shell structure, and only MoS is contained in the shell layer of the outer layer as can be seen from FIGS. 2c-f2And (4) distribution. As can be seen from FIGS. 2g-h, comparative sample Ni3S2The nanowire-like structure is also present, indicating that the loaded outer sulfide does not change the shape of the core material.
Example 2:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea and 600mg of sodium molybdate, carrying out ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning for 3-5 times by using ultrapure water, and airing in the air to obtain the self-supporting core-shell structure catalyst.
Comparative example 1:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea, performing ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and drying the foamed nickel substrate product in the air to obtain a self-supporting core-shell structure catalyst, namely Ni for short3S2。
Comparative example 2:
(1) mixing 600mg of sodium molybdate with 200mg of thiourea, adding 60ml of water, and carrying out ultrasonic treatment for 30min until the solid is completely dissolved;
(2) sealing the mixed solution obtained in the step 1 in a 100ml polytetrafluoroethylene lining, transferring the mixed solution into a constant-temperature oven, and continuously reacting for 18h at 240 ℃;
(3) centrifuging the product obtained in the step 2 by using water and absolute ethyl alcoholCleaning, collecting, and drying at 60 deg.C in vacuum oven to obtain powder catalyst, MoS for short2。
Effect example 1:
for the self-supporting core-shell structure catalyst obtained in example 1, Ni obtained in comparative example 13S2And MoS obtained in comparative example 22The electrochemical properties of the catalyst are characterized and compared, and the results are shown as a and b in fig. 3, it can be known from the graph a that the sample curves of the examples 1 and 2 are more than the comparative examples 1 and 2 in the linear sweep voltammetry curve, the catalytic activity is greatly improved compared with that of the core material and the shell material which are independent, and the urea oxidation capability of the catalyst is greatly improved due to the core-shell structure formed by the samples of the examples 1 and 2. As can be seen from fig. b, the charge transfer resistance of the catalyst forming the core-shell structure is smaller than that of the sample of the comparative example, which indicates that the core-shell structure contributes to the rapid transfer of charges during the catalytic reaction.
For the self-supporting core-shell structure catalyst obtained in example 1, Ni obtained in comparative example 13S2And MoS obtained in comparative example 22The catalytic performance of the catalyst is characterized and compared, the results are shown as c and d in fig. 3, the Tafel slope of the core-shell structure catalyst is far smaller than that of the comparative example, which shows that the core-shell structure catalyst is more beneficial to urea oxidation reaction in the reaction process, and the core-shell structure catalyst has excellent electrochemical stability at 10 mA/cm-2After 24 hours of continuous operation at current density, no significant voltage decay occurred, and the performance was more stable than the two samples of the comparative example.
Effect example 2:
the electrochemical properties and the catalytic properties of the catalysts obtained in example 1, example 2, comparative example 1 and comparative example 2 were compared, and the results are shown in the following table:
as is clear from the table, examples 1 and 2 exhibited a current density of 10mAcm-2The potential is much lower than that of comparative examples 1 and 2, which shows that the energy required for the catalyst of the example to start the catalytic reaction is much lower; the electrochemical impedance of the examples at 1.35vvs. rhe is much lower than the comparative sample, indicating that the charge transfer rate is higher on the example sample at this voltage; the Tafel slopes of examples 1, 2 are lower than comparative examples 1, 2, indicating that urea oxidation reactions are more likely to occur on the example samples.
Claims (10)
1. The self-supporting core-shell structure catalyst is characterized in that foam nickel is used as a substrate, nano linear core-shell structure particles are attached to the surface of the substrate, nickel sulfide is used as a core material of the core-shell structure, and one or more than two materials of molybdenum sulfide, tungsten sulfide, selenium sulfide, copper sulfide or manganese sulfide are used as shell materials of the core-shell structure.
2. The self-supporting core-shell structured catalyst according to claim 1, wherein the shell material has a thickness of 5 to 50 nm.
3. A process for the preparation of a self-supporting core-shell structured catalyst according to claim 1, comprising the steps of:
step 1, placing the cut foam nickel into a cleaning agent for ultrasonic dispersion treatment for 30-60min, taking out the foam nickel, vertically placing the foam nickel into a polytetrafluoroethylene lining, adding ultrapure water which submerges the top end of the foam nickel, and keeping the solution to reach 60% -80% of the total volume of the polytetrafluoroethylene lining;
and 2, adding a vulcanizing agent and a shell material precursor, performing ultrasonic dispersion treatment for 10-30min until solid powder is completely dissolved, sealing the polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, performing heating reaction to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and drying the foamed nickel substrate product in the air to obtain the self-supporting core-shell structure catalyst.
4. The method for preparing the self-supporting core-shell structure catalyst according to claim 3, wherein the area of the foam nickel cut in the step 1 is 1cm2-30 cm2The thickness is 1mm-5 mm.
5. The preparation method of the self-supporting core-shell structure catalyst according to claim 3, wherein the heating reaction conditions in the step 2 are as follows: the temperature is 220 ℃ and 250 ℃, and the heat preservation time is 12-24 h.
6. The method for preparing a self-supporting core-shell structure catalyst according to claim 3, wherein the vulcanizing agent in the step 2 is thiourea, sulfur monochloride or sulfur.
7. The preparation method of the self-supporting core-shell structure catalyst according to claim 3 or 6, wherein the mass ratio of the addition amount of the vulcanizing agent to the nickel foam is 1: (0.7-7).
8. The method for preparing a self-supporting core-shell catalyst according to claim 3, wherein the precursor of the shell layer material in the step 2 is sodium molybdate, and one or more of sodium tungstate, selenious acid, copper oxide and manganese oxide are mixed in any proportion.
9. The preparation method of the self-supporting core-shell structure catalyst according to claim 3 or 8, wherein the mass ratio of the addition amount of the precursor of the shell layer material to the nickel foam in the step 2 is 1 (1-10).
10. Use of a self-supporting core-shell structured catalyst according to claim 1 for the preparation of an electrode.
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