CN114438616A - Preparation method of transition metal phosphorus sulfide nano-fiber, prepared product and application thereof - Google Patents
Preparation method of transition metal phosphorus sulfide nano-fiber, prepared product and application thereof Download PDFInfo
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- CN114438616A CN114438616A CN202210223367.4A CN202210223367A CN114438616A CN 114438616 A CN114438616 A CN 114438616A CN 202210223367 A CN202210223367 A CN 202210223367A CN 114438616 A CN114438616 A CN 114438616A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 94
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 47
- -1 transition metal phosphorus sulfide Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 claims description 19
- 229910000796 S alloy Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000003624 transition metals Chemical group 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 claims description 7
- 239000010411 electrocatalyst Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 239000000919 ceramic Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 3
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229910005896 NiPS3 Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method of transition metal phosphosulfide nano-fibers, which relates to the technical field of material science, engineering technology and chemistry. The diameter of the nano fiber is about 200-400 nm, and the nano fiber has excellent flexibility. The invention has the beneficial effects that: the transition metal phosphorus sulfide nanofiber provided by the invention has the advantages of high specific surface area, high conductivity, high flexibility, high stability, abundant active sites and the like, and has remarkable advantages when being used as a water decomposition catalyst.
Description
Technical Field
The invention relates to the technical field of material science, engineering technology and chemistry, in particular to a preparation method of transition metal phosphorus sulfide nano-fibers, a prepared product and application thereof.
Background
With the urgent need for changing the conventional energy system, the development of renewable energy is imminent. Hydrogen is a clean, environment-friendly and renewable new energy source and is undoubtedly an alternative energy source, and the electrolyzed water has high efficiency,Simple operation and no pollution are regarded as the most effective hydrogen production technology. As a semi-reaction to electrolyze water, the efficiency of OER technology directly affects the performance of electrolyzed water, traditional noble metal oxide catalysts such as IrO2And RuO2Is the most efficient OER catalyst at present, however, the further development of OER is seriously hindered by the scarcity and the high cost of the materials, and the requirement of large-scale production of hydrogen cannot be met. The development of a novel OER catalyst with the advantages of low cost, high conversion efficiency, good electrochemical stability, strong corrosion resistance and the like is the current research focus. In recent years, ternary transition metal phosphorous sulfide MPSx(M ═ Fe, Co, Ni, Cu, etc.; (x ═ 1 or 3) shows good stability and catalytic activity in electrocatalysis, and shows potential to replace noble metal catalysts. Ma et al synthesized porous carbon-coated ultrafine CoPS nanoparticles with ZIF-67 and carbon black as precursors, exhibiting high catalytic activity and long stability in OER reactions (Ma, j.et al.j.mater. chem.a,2018,6, 10433). Liu et al synthesized two-dimensional CoPS nanosheets by hydrothermal synthesis, which when used as OER catalysts exhibited a lower Tafel slope (50.2mV/dec) (Liu, P.et al. ChemElectrochem 2019,6, 2852-2859). NiPS prepared by Schuhmann through liquid phase stripping3The nanoplatelets have a lower overpotential (Schuhman, W.et al. ACS Catal.2017, 7, 229-. However, most of the existing methods for synthesizing transition metal phosphosulfide are liquid phase methods, the yield is limited, and the morphology is difficult to control accurately. Most of transition metal phosphorus sulfides reported at present are nanoparticles and nanosheets, have the defects of small specific surface area and few active sites, and limit the catalytic activity and stability of the material. For example, patent application publication No. CN112877712A discloses a transition metal phosphorous sulfide, and a preparation method and application thereof, but the electrochemical activity of the transition metal phosphorous sulfide is still to be further improved.
Disclosure of Invention
The technical problem to be solved by the invention is that the electrochemical activity of the transition metal phosphorus sulfide in the prior art is still to be further improved, and the electrostatic spinning method is provided and utilized to obtain the transition metal phosphorus sulfide nanofiber and the application thereof, and the transition metal phosphorus sulfide nanofiber has excellent catalytic activity and flexibility.
The invention solves the technical problems through the following technical means:
a preparation method of transition metal phosphorus sulfide nano-fiber comprises the following steps:
(1) dissolving metal salt and a conductive high polymer material in an organic solvent to prepare a metal precursor solution; the conductive polymer material is polyacrylonitrile or polyvinylpyrrolidone; the metal atom in the metal salt is a transition metal;
(2) processing the metal precursor solution obtained in the step (1) by an electrostatic spinning method to obtain metal salt nano fibers;
(3) calcining a phosphorus source and a sulfur source in an inert atmosphere to obtain a phosphorus-sulfur alloy;
(4) and (3) calcining the phosphorus-sulfur alloy and the nanofiber obtained in the step (2) in an inert atmosphere to obtain the transition metal phosphorus sulfide nanofiber.
Has the advantages that: compared with the prior art for preparing nano particles and nano sheets, the size and the shape of the nano fiber prepared by the method are easy to control, the average diameter is about 200-400 nm, and the nano fiber can be prepared in a large scale and is suitable for various ternary transition metal phosphorus sulfides.
The transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of large specific surface area, abundant active sites, good conductivity and structural stability. Meanwhile, due to the use of polyacrylonitrile, the nanofiber has excellent flexibility. When used as an electrocatalyst, the catalyst has excellent catalytic activity.
Preferably, in the step (1), the metal salt is chloride, nitrate or acetate, and the transition metal is one of Fe, Mn, Cu, Co and Ni.
The metal salt is more preferably a chloride salt. The conductive polymer material is more preferably polyacrylonitrile.
Preferably, the organic solvent in step (1) is N, N-dimethylformamide.
Preferably, the mass ratio of the metal salt to the conductive polymer material is 1: (0.5-2), wherein the content of the metal salt and the conductive polymer in the solvent per unit volume is 0.15-0.3 g.
Preferably, the volume of the syringe used in the electrospinning method described in step (2) is 5 to 20ml, and more preferably 5 to 10 ml. The type of the syringe needle is 16-22G, and more preferably 19-21G. And a high-voltage direct-current power supply is used, wherein the positive voltage of the connecting syringe needle is 13-25 kV, and more preferably 12-16 kV. The negative pressure of a receiving plate connected with the electrospinning device is-3 to-1 kV, and the most preferable negative pressure is-1 kV. The distance between the needle head and the receiving plate is 10-20 cm, and more preferably 10-15 cm.
Preferably, the metal nano-fiber obtained in the step (2) is transferred to an oven and dried, wherein the drying temperature is 60-80 ℃, and the drying time is 12 hours.
Preferably, the phosphorus source and the sulfur source in step (3) are red phosphorus and sublimed sulfur powder respectively, and the mass ratio of the phosphorus powder to the sulfur powder is 1: (1-3).
Preferably, the inert atmosphere in the step (3) is Ar or N2Preferably Ar. The calcination temperature is 300 ℃, the heating rate is 10-20 ℃/min, more preferably 15-20 ℃/min, and the calcination time is 10-30 min.
Preferably, the phosphorus-sulfur alloy obtained in the step (3) is placed in a ceramic boat, the ceramic boat is transferred to the upstream of a tube furnace, the nano-fiber obtained in the step (2) is placed in another ceramic boat, and then the nano-fiber is calcined in an inert atmosphere, so that the phosphorus-sulfur alloy and the nano-fiber react to successfully obtain the transition metal phosphorus-sulfur nano-fiber. The distance between the two ceramic boats is preferably 12-15 cm.
Preferably, the inert atmosphere in the step (4) is Ar or N2Preferably Ar. The calcination temperature is 500-800 ℃, the heating rate is 5-10 ℃/min, the calcination time is 1-3 h, and the mass ratio of the phosphorus-sulfur alloy to the nanofiber is (10-50): 1, more preferably 50: 1.
The transition metal phosphorus sulfide nanofiber prepared by the method has an average diameter of 200-400 nm and flexibility.
Has the advantages that: the transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of large specific surface area, abundant active sites, good conductivity and structural stability. And has excellent flexibility.
The transition metal phosphorus sulfide nanofiber prepared by the method is used as a water decomposition electrocatalyst.
Has the advantages that: the transition metal phosphorus sulfide nano-fiber prepared by the invention has excellent catalytic activity when being used as an electrocatalyst.
The invention has the advantages that: compared with the prior art for preparing nano particles and nano sheets, the size and the shape of the nano fiber prepared by the method are easy to control, the average diameter is about 200-400 nm, and the nano fiber can be prepared in a large scale and is suitable for various ternary transition metal phosphorus sulfides.
The transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of large specific surface area, abundant active sites, good conductivity and structural stability. Meanwhile, due to the use of polyacrylonitrile, the nanofiber has excellent flexibility. When used as an electrocatalyst, the catalyst has excellent catalytic activity.
Drawings
FIG. 1 is an XRD pattern of a CoPS nanofiber as synthesized in example 1 of the present invention;
FIG. 2 is an SEM image of CoPS nanofibers synthesized in example 1 of the present invention;
FIG. 3 is a photograph of a CoPS nanofiber synthesized in example 1 of the present invention;
FIG. 4 is a graph of the catalytic performance of CoPS nanofibers synthesized in example 1 of the present invention;
FIG. 5 shows CuPS synthesized in example 2 of the present invention3XRD pattern of nanofibers;
FIG. 6 shows CuPS synthesized in example 2 of the present invention3A nanofiber SEM image;
FIG. 7 shows NiPS synthesized in example 3 of the present invention3A nanofiber XRD picture;
FIG. 8 shows NiPS synthesized in example 3 of the present invention3SEM image of nanofibers.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the transition metal phosphorus sulfide nanofiber specifically comprises the following steps:
(1) first, 0.8g of polyacrylonitrile (chemical reagent, Inc., of the national drug group) was added to 10ml of N, N-dimethylformamide solvent (chemical reagent, Inc., of the national drug group), and stirred to be sufficiently dissolved, and the solution was labeled as solution A. Then 1g of cobalt chloride hexahydrate powder (the purity is more than or equal to 99 percent, of chemical reagents of national drug group, Inc.) is weighed and dissolved in the solution A by stirring to prepare a metal precursor solution B for electrostatic spinning.
(2) Sucking the solution B by using a 10mL syringe, placing the solution B on a syringe pump (Baoding Lange constant flow pump Co., Ltd., LSP01-1A), installing a 21G needle, connecting the needle with a positive electrode, connecting a receiving plate with a negative electrode, respectively setting the voltages of the positive electrode and the negative electrode to be 12kV and-1 kV, setting the distance between the needle and the receiving plate to be 15cm, setting the liquid inlet speed to be 1mL/h, starting electrostatic spinning, and successfully obtaining the nanofiber. And after spinning is finished, collecting the nano fibers, transferring the nano fibers into an oven, and drying the nano fibers at 80 ℃ for 12 hours to obtain the nano fibers.
(3) Balance500mg of red phosphorus and 500mg of sublimed sulfur powder were uniformly mixed, introduced into a ceramic boat, and then transferred into a tube furnace (Beick, 1200 ℃ micro box furnace, MF-1200℃) to be calcined under Ar atmosphere. Firstly, heating the tube furnace from room temperature to 300 ℃ at the heating rate of 15 ℃/min, preserving heat for 10min, and then naturally cooling to obtain the phosphorus-sulfur alloy PxSyAnd (3) powder.
(4) And (3) respectively placing the phosphorus-sulfur alloy obtained in the step (3) and the nano-fiber obtained in the step (2) into two ceramic boats, and then placing the ceramic boats at the upstream and central positions of the tube furnace, wherein the ceramic boats are arranged in parallel, and the vertical distance between the centers of the two ceramic boats is 12 cm. Heating to 500 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1h to enable the phosphorus-sulfur alloy and the nano-fiber to generate phosphorus-sulfur reaction. And naturally cooling to room temperature after the reaction is finished to obtain the CoPS/C flexible nanofiber, namely the transition metal phosphorus sulfide nanofiber.
Phase analysis was performed on the product obtained in example 1 by X-ray diffraction, and fig. 1 is an XRD pattern of the CoPS/C nanofibers prepared in example 1 of the present invention, which is consistent with the standard card CoPS PDF # 27-0139. The successful synthesis of the CoPS material in inventive example 1 was demonstrated. The morphology of the article obtained in example 1 was characterized by a scanning electron microscope, and as shown in fig. 2, the CoPS/C nanofibers prepared in example 1 of the present invention were uniform in size and about 300nm in diameter. FIG. 3 is a photograph of CoPS/C nanofibers obtained in example 1, which exhibit excellent bendability, demonstrating excellent flexibility.
5mg of CoPS/C nanofibers were weighed, ground to a powder and placed in 1mL of a mixed solution consisting of ethanol, deionized water and Nafion solution (V)Ethanol：VDeionized water： VNafion640:320:40) and stirring and ultrasonic processing are carried out until uniformly mixed ink is obtained for standby. Measuring 3 mu L of the solution by using a liquid transfer gun, dropwise adding the solution to the surface of a glassy carbon electrode, naturally drying, and testing the electrocatalytic performance of the glassy carbon electrode. FIG. 4 is a linear scan curve obtained by OER reaction of the CoPS/C nanofibers prepared in example 1 in 1M KOH solution, and it can be obtained from the graph that the current density is 10mA/cm2When the electrode is over-potentialIt was 344 mV.
Example 2
The preparation method of the transition metal phosphorus sulfide nanofiber specifically comprises the following steps:
(1) first, 0.8g of polyacrylonitrile (chemical reagent, Inc., of the national drug group) was added to 10ml of N, N-dimethylformamide solvent (chemical reagent, Inc., of the national drug group), and stirred to be sufficiently dissolved, and the solution was labeled as solution A. Then 1g of copper chloride dihydrate powder (the purity is more than or equal to 99 percent, of chemical reagents of national drug group, Inc.) is weighed and dissolved in the solution A by stirring to prepare a metal precursor solution B for electrostatic spinning.
(2) Sucking the solution B by using a 10mL syringe, then placing the solution B on an injection pump (Baoding Lange constant flow pump Co., Ltd., LSP01-1A), installing a 21G needle, connecting the needle with a positive electrode, connecting a receiving plate with a negative electrode, wherein the voltages of the positive electrode and the negative electrode are respectively 15kV and-1 kV, the distance between the needle and the receiving plate is 15cm, the liquid inlet speed is 0.8mL/h, setting a corresponding program, starting electrostatic spinning, and successfully obtaining the nanofiber. And after spinning is finished, collecting the nano fibers, transferring the nano fibers into an oven, and drying the nano fibers at 80 ℃ for 12 hours to obtain the nano fibers.
(3) 500mg of red phosphorus and 500mg of sublimed sulfur powder were weighed, uniformly mixed, introduced into a ceramic boat, and then transferred into a tube furnace (beiike, 1200 ℃ micro box furnace, MF-1200C) to be calcined under an Ar atmosphere. Firstly, heating the tube furnace from room temperature to 300 ℃ at the heating rate of 15 ℃/min, preserving heat for 10min, and then naturally cooling to obtain the phosphorus-sulfur alloy PxSyAnd (3) powder.
(4) And (3) respectively placing the phosphorus-sulfur alloy obtained in the step (3) and the nano-fiber obtained in the step (2) in two boats, and then placing the boats at the upstream and central positions of the tube furnace, wherein the distance between the ceramic boats is 15 cm. Heating to 600 ℃ at the heating rate of 5 ℃/min under Ar atmosphere, and preserving heat for 2h to enable the phosphorus-sulfur alloy and the nano-fiber to generate phosphorus-sulfur reaction. Naturally cooling to room temperature after the reaction is finished to obtain CuPS3the/C flexible nano fiber is the transition metal phosphorus sulfide nano fiber.
FIG. 5 shows CuPS prepared according to example 2 of the present invention3/C nano fiberXRD pattern of vitamin, and standard card CuPS3PDF #48-1236 was fully matched, and FIG. 6 shows the CuPS prepared in example 2 of the present invention3The scanning electron microscope photo of the/C nano fiber has uniform nano fiber size and average diameter of about 350-400 nm, and is consistent with the expected result.
Example 3
The preparation method of the transition metal phosphosulfide nano-fiber specifically comprises the following steps:
(1) first, 0.8g of polyacrylonitrile (chemical reagent, Inc., of the national drug group) was added to 10ml of N, N-dimethylformamide solvent (chemical reagent, Inc., of the national drug group), and stirred to be sufficiently dissolved, and the solution was labeled as solution A. Then 1g of nickel chloride hexahydrate powder (the purity is more than or equal to 99 percent of chemical reagents of national drug group, Inc.) is weighed and dissolved in the solution A by stirring to prepare a metal precursor solution B for electrostatic spinning.
(2) Sucking the solution B by using a 10mL syringe, placing the solution B on a syringe pump (Baoding Lange constant flow pump Co., Ltd., LSP01-1A), installing a 21G needle, connecting the needle with a positive electrode, connecting a receiving plate with a negative electrode, respectively setting the voltages of the positive electrode and the negative electrode to be 12kV and-1 kV, setting the distance between the needle and the receiving plate to be 15cm, setting the liquid inlet speed to be 1mL/h, starting electrostatic spinning, and successfully obtaining the nanofiber. After spinning is finished, collecting the nano fibers, transferring the nano fibers into an oven, and drying the nano fibers at 80 ℃ for 12 hours to obtain the nano fibers
(3) 500mg of red phosphorus and 500mg of sublimed sulfur powder were weighed, uniformly mixed, introduced into a ceramic boat, and then transferred into a tube furnace (beiike, 1200 ℃ micro box furnace, MF-1200C) to be calcined under an Ar atmosphere. Firstly, heating the tube furnace from room temperature to 300 ℃ at the heating rate of 15 ℃/min, preserving heat for 10min, and then naturally cooling to obtain the phosphorus-sulfur alloy PxSyAnd (3) powder.
(4) And (3) respectively placing the phosphorus-sulfur alloy obtained in the step (3) and the nano-fiber obtained in the step (2) in two boats, and then placing the boats at the upstream and central positions of the tube furnace, wherein the distance between the ceramic boats is 12 cm. Heating to 500 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1h to ensure that the phosphorus-sulfur alloy and the nano-fiber generate phosphorus-sulfurAnd (4) carrying out a reaction. Naturally cooling to room temperature after the reaction is finished to obtain NiPS3the/C flexible nano fiber is the transition metal phosphorus sulfide nano fiber.
FIG. 7 shows the NiPS prepared in example 33XRD pattern of/C nanofibers, FIG. 8 shows NiPS prepared in example 33Scanning electron microscope pictures of/C nanofibers demonstrate that example 3 successfully prepares NiPS3a/C nanofiber.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of transition metal phosphorus sulfide nano-fiber is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving metal salt and a conductive high polymer material in an organic solvent to prepare a metal precursor solution; the conductive polymer material is polyacrylonitrile or polyvinylpyrrolidone; the metal atom in the metal salt is a transition metal;
(2) processing the metal precursor solution obtained in the step (1) by an electrostatic spinning method to obtain metal salt nano fibers;
(3) calcining a phosphorus source and a sulfur source in an inert atmosphere to obtain a phosphorus-sulfur alloy;
(4) and (3) calcining the phosphorus-sulfur alloy and the nanofiber obtained in the step (2) in an inert atmosphere to obtain the transition metal phosphorus sulfide nanofiber.
2. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: in the step (1), the metal salt is chloride, nitrate or acetate, and the transition metal is one of Fe, Mn, Cu, Co and Ni.
3. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: in the step (1), the organic solvent is N, N-dimethylformamide.
4. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: the mass ratio of the metal salt to the conductive polymer material is 1: (0.5-2), wherein the content of the metal salt and the conductive polymer in the solvent per unit volume is 0.15-0.3 g.
5. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: the volume of the syringe used in the electrostatic spinning method in the step (2) is 5-20 ml, the type of the syringe needle is 16-22G, and a high-voltage direct-current power supply is used, wherein the positive pressure connected with the syringe needle is 13-25 kV, the negative pressure connected with a receiving plate of an electrospinning device is-3-1 kV, and the distance between the syringe needle and the receiving plate is 10-20 cm.
6. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: and (3) the phosphorus source and the sulfur source are red phosphorus and sublimed sulfur powder respectively, and the mass ratio of the phosphorus powder to the sulfur powder is 1: (1-3).
7. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: the inert atmosphere in the step (3) is Ar or N2The calcination temperature is 300 ℃, the heating rate is 10-20 ℃/min, and the calcination time is 10-30 min.
8. The method of preparing transition metal phosphosulfide nanofibers according to claim 1, characterized in that: in the step (4), the inert atmosphere is Ar or N2The calcination temperature is 500-800 ℃, the heating rate is 5-10 ℃/min, the calcination time is 1-3 h, and phosphorus is addedThe mass ratio of the sulfur alloy to the nano-fibers is (10-50): 1.
9. the transition metal phosphosulfide nanofiber prepared by the preparation method according to any one of claims 1 to 8, wherein: the average diameter of the transition metal phosphorus sulfide nanofiber is 200-400 nm, and the transition metal phosphorus sulfide nanofiber has flexibility.
10. Use of transition metal phospho-sulfide nanofibres prepared with the preparation method according to any of claims 1-8 as water-splitting electrocatalysts.
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