CN115491710A - Co rich in sulfur vacancy 3 S 4 Nano catalyst and preparation method and application thereof - Google Patents
Co rich in sulfur vacancy 3 S 4 Nano catalyst and preparation method and application thereof Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 60
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 40
- 239000011593 sulfur Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 13
- 239000011029 spinel Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 34
- 239000012498 ultrapure water Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000010411 electrocatalyst Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 238000004073 vulcanization Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002057 nanoflower Substances 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 23
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 238000002386 leaching Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/031—Porous electrodes
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The invention discloses Co rich in sulfur vacancy 3 S 4 A nano catalyst and a preparation method and application thereof. Co is synthesized by taking cobalt chloride, ammonium fluoride and urea as raw materials through a hydrothermal method 3 S 4 The nano catalyst has low cost of raw materials and simple preparation method. Then obtaining Co with spinel structure rich in sulfur vacancy by a reduction method 3 S 4 The nanoflower shows good activity and product selectivity in electrocatalytic oxygen and hydrogen evolution reactions by controlling the reduction time to increase more active area and expose more active sites.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to Co rich in sulfur vacancy 3 S 4 A nano catalyst and a preparation method and application thereof.
Background
Under the large background that the energy crisis is increasingly aggravated and the environmental pollution is increasingly serious, the novel energy development and conversion technologies such as electrolytic water and the like can provide powerful support for the implementation of the sustainable energy development strategy in the future for all mankind. However, there are many constraints on the large-scale commercialization of water electrolysis technologies, the greatest of which is the lack of efficient, inexpensive, stable, non-noble metal-based OER and HER electrocatalysts.
Thio spinel (AB) 2 S 4 ) Has precise structure and composition, abundant electronic configuration and valence state and unique electronic structure, has catalytic activity equivalent to that of noble metal-based catalysts, and is considered to be one of the most promising non-noble metal catalysts. However, due to the structural limitation of the spinel, the active sites of the spinel are not sufficiently exposed, and the catalytic activity of the spinel cannot be utilized to the maximum extent due to poor material transmission performance and electrical conductivity. In recent years, researchers regulate and control the electronic structure of spinel by means of atom doping, vacancy introduction or heterojunction construction and the like, and improve catalytic activity, so that the application range of spinel is expanded. The introduction of the anion vacancy into the crystal lattice structure can obviously improve the conductivity of the catalyst, and the introduction of the vacancy into the spinel structure can accelerate charge transfer and electron transmission and generate more active sites, so that the structure and the electronic characteristics of the catalyst are optimized, the activity and the stability of the catalyst are improved, and the method becomes one of effective means for improving the electrocatalytic performance of the spinel.
Therefore, the development of a general strategy for designing a spinel catalyst rich in sulfur vacancies, which has a simple synthesis method, cheap precursor, high efficiency and stability, is urgent and is full of challenges. .
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Accordingly, it is an object of the present invention to overcome the disadvantages of the prior art and to provide a sulfur vacancy rich Co 3 S 4 A preparation method of a nano catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dissolving cobalt chloride, ammonium fluoride and urea in deionized water, and stirring at normal temperature to form a mixed solution;
preparing a Co precursor by performing hydrothermal reaction on the pretreated nickel foam and the mixed solution;
sulfurizing the Co precursor to obtain Co 3 S 4 A nano-catalyst;
Co 3 S 4 soaking in NaBH 4 Reducing in water solution;
drying after the reaction is finished to obtain Co rich in sulfur vacancy 3 S 4 And (3) a nano catalyst.
Co as said sulfur vacancy-rich material of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the molar weight of the cobalt chloride is 1-4 mmoL, the molar weight of the ammonium fluoride is 2-5 mmoL, and the molar weight of the urea is 3-6 mmoL.
Co as said sulfur vacancy-rich material of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the pretreatment of the foamed nickel comprises the steps of respectively cleaning the foamed nickel with acetone, ethanol and ultrapure water, and then drying in vacuum.
Co as said sulfur vacancy-rich material of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the hydrothermal reaction is carried out at the temperature of 100-150 DEG CThe time is 10 to 20 hours.
Co as said sulfur vacancy-rich compound of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: and (3) carrying out vulcanization treatment, wherein the treatment temperature is 150-200 ℃, and the treatment time is 10-20 h.
Co as said sulfur vacancy-rich material of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the Co 3 S 4 Soaking in NaBH 4 Reduction in aqueous solution, in which NaBH is present 4 The concentration is 0.1-0.5 mol/L, and the reduction time is 5-30 min.
It is another object of the present invention to overcome the disadvantages of the prior art and to provide a sulfur vacancy rich Co 3 S 4 Spinel type Co prepared by preparation method of nano catalyst 3 S 4 And (3) a nano catalyst.
It is a further object of the present invention to overcome the deficiencies of the prior art and to provide a Co enriched with sulfur vacancies 3 S 4 Application of nano catalyst.
Co as said sulfur vacancy-rich compound of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the use includes use as an electrocatalyst in the electrolysis of water.
Co as said sulfur vacancy-rich material of the present invention 3 S 4 A preferred embodiment of the process for preparing the nanocatalyst, wherein: the Co 3 S 4 The nano catalyst is used as a working electrode in a three-electrode system, wherein the concentration of the nano catalyst is 100mA/cm -2 The OER overpotential is only 245mV at the current density of (1); at 10mA/cm -2 HER overpotential was only 45mV at current density of (a).
Co as said sulfur vacancy-rich compound of the present invention 3 S 4 A preferable embodiment of the preparation method of the nanocatalyst, wherein: the Co 3 S 4 The nano catalyst is used as a cathode and an anode in a two-electrode system, and when the nano catalyst is applied to total hydrolysis, only 1.53V is needed, and 20mA/cm can be achieved -2 The current density of (2).
The invention has the beneficial effects that:
(1) The invention synthesizes Co by using cobalt chloride, ammonium fluoride and urea as raw materials 3 S 4 The nano catalyst has the advantages of low cost of raw materials, simple preparation method and obvious advantages in practical application.
(2) The invention is carried out by NaBH 4 Reduction of Co 3 S 4 Nano catalyst for preparing spinel type Co rich in S vacancy 3 S 4 The nano-catalyst is reduced at normal temperature without an additional device in the process, the method is simple and effective, and the defects that other synthetic methods in the prior art are complex and difficult to prepare on a large scale are overcome.
(3) The electrocatalyst prepared and synthesized by the method has excellent performance, and the active area of the catalyst is controlled by controlling the reduction time, so that the catalyst shows the optimal catalytic activity and product selectivity in the electrocatalytic oxygen evolution and hydrogen evolution reactions.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 shows V obtained in example 1 of the present invention s -Co 3 S 4 The XRD pattern of @ NF electrocatalyst.
FIG. 2 shows V obtained in example 1 of the present invention s -Co 3 S 4 HRTEM image of @ NF electrocatalyst.
FIG. 3 shows V obtained in example 1 of the present invention s -Co 3 S 4 @ NF LSV plot of OER performance in a three-electrode system.
FIG. 4 shows V obtained in example 1 of the present invention s -Co 3 S 4 @ NF LSV plot of HER performance in a three-electrode system.
FIG. 5 shows V obtained in example 1 of the present invention s -Co 3 S 4 @ NF in the two electrodesLSV plot of perhydrolysis performance in the system.
FIG. 6 is a graph comparing OER performance of products obtained in examples 1 to 7 of the present invention and comparative examples 1 and 2 in a three-electrode system.
Fig. 7 is a graph comparing HER performance of products prepared in examples 1 to 7 of the present invention and comparative examples 1 and 2 in a three-electrode system.
FIG. 8 is a graph showing a comparison of the total hydrolysis performance of the products obtained in examples 1 to 7 of the present invention and comparative examples 1 and 2 in a two-electrode system.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The starting materials used in the present invention are, unless otherwise specified, those which are commonly commercially available.
The correspondence between the names of the raw materials used in the present invention and the chemical formula is shown in table 1.
TABLE 1 chemical name correspondence table
| Cobalt chloride | CoCl 2 ·6H 2 O |
| Ammonium fluoride | NH 4 F |
| Urea | CO(NH 2 ) 2 |
| Sodium sulfide | Na 2 S |
Example 1
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction, wherein the reaction temperature is 120 ℃, the reaction time is 15h, vacuum drying is carried out for 6h at 60 ℃ after the reaction is finished, and a Co precursor is obtained, and the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 15h, leaching the solution with ethanol and ultrapure water respectively after the reaction is finished, and vacuum-drying the solution at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted as Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH with concentration of 0.2mol/L 4 Carrying out reduction reaction in the aqueous solution for 10min, leaching the product after the reaction is finished by ultrapure water, and drying the product for 6h in vacuum at 60 ℃ to obtain Co rich in sulfur vacancy 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
FIG. 1 and FIG. 2 show the V prepared in this example s -Co 3 S 4 XRD pattern and HR TEM pattern of @ NF electrocatalyst, from which V can be clearly seen s -Co 3 S 4 Lattice fringes of @ NF electrocatalyst, corresponding to Co 3 S 4 While some lattice disorder was observed, indicating successful introduction of sulfur vacancies into Co 3 S 4 In the electrocatalyst, surface V s -Co 3 S 4 Successful preparation of @ NF electrocatalysts.
Example 2
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction at 120 ℃ for 15h, and vacuum drying at 60 ℃ for 6h after the reaction is finished to obtain a Co precursor, wherein the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 15h, leaching the solution with ethanol and ultrapure water respectively after the reaction is finished, and vacuum-drying the solution at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted as Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH of 0.2mol/L concentration 4 Carrying out reduction reaction in the aqueous solution for 5min, leaching the product after the reaction is finished with ultrapure water, and drying the product for 6h in vacuum at 60 ℃ to obtain Co rich in sulfur vacancies 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
Example 3
Cutting foamed nickel into 12cm 2 Respectively ultrasonic treating the small blocks in acetone, ethanol and ultrapure water 3Drying in vacuum at 60 ℃ after 0min, and recording the product as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction at 120 ℃ for 15h, and vacuum drying at 60 ℃ for 6h after the reaction is finished to obtain a Co precursor, wherein the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 15h, leaching the solution with ethanol and ultrapure water respectively after the reaction is finished, and vacuum-drying the solution at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH with concentration of 0.2mol/L 4 Carrying out reduction reaction in the aqueous solution for 15min, leaching the product after the reaction is finished with ultrapure water, and drying the product for 6h in vacuum at 60 ℃ to obtain Co rich in sulfur vacancies 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
Example 4
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction, wherein the reaction temperature is 120 ℃, the reaction time is 15h, vacuum drying is carried out for 6h at 60 ℃ after the reaction is finished, and a Co precursor is obtained, and the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 15h, leaching with ethanol and ultrapure water respectively after the reaction is finished, and vacuum drying at 60 ℃ for 6h to obtain the sodium sulfideCo 3 S 4 Nanocatalyst, noted Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH with concentration of 0.2mol/L 4 Carrying out reduction reaction in the aqueous solution for 20min, leaching the product after the reaction is finished with ultrapure water, and drying the product in vacuum at 60 ℃ for 6h to obtain Co rich in sulfur vacancies 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
Example 5
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction at 120 ℃ for 15h, and vacuum drying at 60 ℃ for 6h after the reaction is finished to obtain a Co precursor, wherein the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 5h, leaching the solution with ethanol and ultrapure water respectively after the reaction is finished, and vacuum-drying the solution at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH with concentration of 0.2mol/L 4 Carrying out reduction reaction in the aqueous solution for 10min, leaching the product after the reaction is finished with ultrapure water, and drying the product in vacuum at 60 ℃ for 6h to obtain Co rich in sulfur vacancies 3 S 4 Nano catalyst, marked as Vs-Co 3 S 4 @NF。
Example 6
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction at 120 ℃ for 15h, and vacuum drying at 60 ℃ for 6h after the reaction is finished to obtain a Co precursor, wherein the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 10h, leaching with ethanol and ultrapure water respectively after the reaction is finished, and vacuum drying at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH of 0.2mol/L concentration 4 Carrying out reduction reaction in the aqueous solution for 10min, leaching the product after the reaction is finished with ultrapure water, and drying the product in vacuum at 60 ℃ for 6h to obtain Co rich in sulfur vacancies 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
Example 7
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction at 120 ℃ for 15h, and vacuum drying at 60 ℃ for 6h after the reaction is finished to obtain a Co precursor, wherein the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 20h, leaching the solution with ethanol and ultrapure water respectively after the reaction is finished, and vacuum-drying the solution at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted as Co 3 S 4 @NF；
Mixing Co 3 S 4 @ NF soaking in NaBH with concentration of 0.2mol/L 4 Carrying out reduction reaction in the aqueous solution for 10min, leaching the product after the reaction is finished with ultrapure water, and drying the product in vacuum at 60 ℃ for 6h to obtain Co rich in sulfur vacancies 3 S 4 Nanocatalyst, designated as Vs-Co 3 S 4 @NF。
Comparative example 1
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
and (3) immersing NF in the mixed solution for hydrothermal reaction, wherein the reaction temperature is 120 ℃, the reaction time is 15h, vacuum drying is carried out for 6h at 60 ℃ after the reaction is finished, and a Co precursor is obtained, and the product is marked as Co-P @ NF.
Comparative example 2
Cutting foamed nickel into 12cm 2 Respectively carrying out ultrasonic treatment on the small blocks in acetone, ethanol and ultrapure water for 30min, and then drying in vacuum at 60 ℃, wherein the product is marked as NF;
respectively weighing 1mmol of cobalt chloride, 2mmol of urea and 3mmol of ammonium fluoride, sequentially dissolving in 30mL of deionized water, and stirring at normal temperature to form a mixed solution;
immersing NF in the mixed solution for hydrothermal reaction, wherein the reaction temperature is 120 ℃, the reaction time is 15h, vacuum drying is carried out for 6h at 60 ℃ after the reaction is finished, and a Co precursor is obtained, and the product is marked as Co-P @ NF;
weighing 0.2mmol of sodium sulfide, dissolving the sodium sulfide in 30mL of ultrapure water, stirring for 10min to obtain a sodium sulfide solution, placing Co-P @ NF in the solution to carry out vulcanization treatment at 160 ℃ for 15h, cooling to room temperature after the reaction is finished, leaching with ethanol and ultrapure water, and vacuum-drying at 60 ℃ for 6h to obtain Co 3 S 4 Nanocatalyst, noted Co 3 S 4 @NF。
The products prepared by the embodiments and the comparative examples are used as catalysts in electrocatalytic reactions.
In a three-electrode system, a product catalyst is used as a working electrode, an Hg/HgO electrode and a carbon rod are respectively used as a reference electrode and a counter electrode, the OER and HER performances of the three-electrode system are tested in 1MKOH, the LSV curve scan number is 5mV/s, and the EIS range is 0.01-100 KHz;
in a two-electrode system, the product catalyst is respectively used as an anode and a cathode to assemble an electrolytic cell, the total hydrolysis performance of the electrolytic cell is tested in 1MKOH, and the sweep number of an LSV curve is 5mV/s.
FIGS. 3 to 5 are views showing V obtained in example 1 of the present invention s -Co 3 S 4 @ NF LSV plot of OER performance in three-electrode system, LSV plot of HER performance, and LSV plot of perhydrolysis performance in two-electrode system.
As shown in FIGS. 3 to 5, 100mA/cm was observed in the three-electrode system -2 The OER overpotential is only 245mV at the current density of (1); at 10mA/cm -2 HER overpotential was only 45mV at current density of (d); only 1.53V is needed in the test of the total hydrolysis performance, and 20mA/cm can be reached -2 The current density of (2).
The above test results show that the electrocatalyst prepared by the invention has excellent OER, HER and total hydrolysis performance.
FIG. 6 is a graph comparing OER performance of the product catalysts of examples 1 to 7 of the present invention and comparative examples 1 and 2 in a three-electrode system, from left to right, of 100mA/cm in a three-electrode system, of examples 1 to 7, comparative examples 1 and 2 -2 The OER overpotentials of the product catalysts of each example are 245mV, 300mV, 259mV, 380mV, 358mV, 302mV, 289mV, 500mV, 330mV, respectively;
FIG. 7 is a graph showing a comparison of HER performance of product catalysts of examples 1 to 7 and comparative examples 1 and 2 of the present invention in a three-electrode system, wherein the results are shown from left to right in the order of example 1 to 7, comparative example 1 and comparative example 2, and 10mA/cm in the three-electrode system -2 At a current density of (a), the HER overpotentials for the product catalysts of each example were 45mV, 156mV, 101mV, 201mV, 263mV, 226mV, 189mV, 306mV, 240mV, respectively;
as can be seen from FIGS. 6 and 7The invention provides Co rich in sulfur vacancy 3 S 4 Nanocatalysts compared to unsulfided Co catalysts and Co without sulfur vacancies 3 S 4 The nano-catalyst shows more excellent OER and HER performances, and simultaneously, the method controls the active area of the catalyst by controlling the reduction time, so that the catalyst shows the optimal catalytic activity in electrocatalytic oxygen evolution and hydrogen evolution reactions.
FIG. 8 is a graph comparing the total hydrolysis performance of the product catalysts of examples 1 to 7 of the present invention and comparative examples 1 and 2, in which each example reached 20mA/cm at 1.53V, 1.95V, 1.78V, 1.89V, 1.91V, 1.79V, 1.75V, 2.05V, and 1.61V, respectively -2 The current density shows that the catalyst prepared by the method still has good performance when being applied to total hydrolysis.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. Co rich in sulfur vacancy 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: comprises the steps of (a) preparing a substrate,
dissolving cobalt chloride, ammonium fluoride and urea in deionized water, and stirring at normal temperature to form a mixed solution;
preparing a Co precursor by performing hydrothermal reaction on the pretreated nickel foam and the mixed solution;
sulfurizing the Co precursor to obtain Co 3 S 4 A nano-catalyst;
Co 3 S 4 soaking in NaBH 4 Reducing in water solution;
drying after the reaction is finished to obtain Co rich in sulfur vacancy 3 S 4 A nano-catalyst.
2. Co enriched in sulfur vacancies as claimed in claim 1 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: the molar weight of the cobalt chloride is 1-4 mmoL, the molar weight of the ammonium fluoride is 2-5 mmoL, and the molar weight of the urea is 3-6 mmoL.
3. Co enriched in sulfur vacancies as claimed in claim 1 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: the pretreatment of the foamed nickel comprises the steps of respectively washing the foamed nickel with acetone, ethanol and ultrapure water, and then drying in vacuum.
4. Co enriched in sulfur vacancies as claimed in claim 1 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: the hydrothermal reaction is carried out, wherein the reaction temperature is 100-150 ℃, and the reaction time is 10-20 h.
5. Co enriched in sulfur vacancies as claimed in claim 1 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: and (3) carrying out vulcanization treatment, wherein the treatment temperature is 150-200 ℃, and the treatment time is 10-20 h.
6. Co enriched in sulfur vacancies as claimed in claim 1 3 S 4 The preparation method of the nano catalyst is characterized by comprising the following steps: the Co 3 S 4 Soaking in NaBH 4 Reduction in aqueous solution, in which NaBH is present 4 The concentration is 0.1-0.5 mol/L, and the reduction time is 5-30 min.
7. Co rich in sulfur vacancies produced by the process as set forth in any one of claims 1 to 6 3 S 4 A nanocatalyst characterized by: the Co 3 S 4 The nano-catalyst is spinel type rich in sulfur vacancy.
8. Co enriched in sulfur vacancies as claimed in claim 7 3 S 4 The application of the nano-catalyst is characterized in that: the applicationThe catalyst is used as an electrocatalyst in electrolyzed water.
9. Co enriched in sulfur vacancies as claimed in claim 8 3 S 4 The application of the nano-catalyst is characterized in that: the Co 3 S 4 The nano catalyst is used as a working electrode in a three-electrode system, wherein the concentration of the nano catalyst is 100mA/cm -2 The OER overpotential is only 245mV at the current density of (1); at 10mA/cm -2 HER overpotential was only 45mV at the current density of (2).
10. Co enriched in sulfur vacancies as claimed in claim 8 3 S 4 The application of the nano-catalyst is characterized in that: the Co 3 S 4 The nano catalyst is used as a cathode and an anode in a two-electrode system, and when the nano catalyst is applied to total hydrolysis, only 1.53V is needed, and 20mA/cm can be achieved -2 The current density of (2).
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