CN114438616B - Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof - Google Patents
Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof Download PDFInfo
- Publication number
- CN114438616B CN114438616B CN202210223367.4A CN202210223367A CN114438616B CN 114438616 B CN114438616 B CN 114438616B CN 202210223367 A CN202210223367 A CN 202210223367A CN 114438616 B CN114438616 B CN 114438616B
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- transition metal
- phosphorus
- phosphosulfide
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 89
- 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 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims description 25
- 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 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000796 S alloy Inorganic materials 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 9
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UAQJVNPFHGOEAH-UHFFFAOYSA-N oxido-oxo-phosphosulfanylphosphanium Chemical compound O=P(=O)SP(=O)=O UAQJVNPFHGOEAH-UHFFFAOYSA-N 0.000 description 4
- 241000434830 Cleopomiarus micros Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy 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
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 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
- 239000003153 chemical reaction reagent 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture 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
- 238000004626 scanning electron microscopy Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- 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 phosphorus sulfide nanofiber, which relates to the fields of material science, engineering technology and chemical technology. The diameter of the nanofiber is about 200-400 nm, and the nanofiber 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, rich active sites and the like, and has remarkable advantages when being used as a water splitting catalyst.
Description
Technical Field
The invention relates to the technical fields of material science and engineering technology and chemistry, in particular to a preparation method of transition metal phosphorus sulfide nanofiber, a prepared product and application thereof.
Background
With the urgent need for modification of traditional energy systems, the development of renewable energy is urgent. Hydrogen is certainly an alternative energy source as a clean, environment-friendly and renewable new energy source, and electrolyzed water is regarded as the most effective hydrogen production technology due to higher efficiency, simple operation and no pollution. As a half-reaction of electrolyzed water, the efficiency of OER technology directly affects the performance of electrolyzed water, a conventional noble metal oxide catalyst such as IrO 2 And RuO (Ruo) 2 Is the most efficient OER catalyst at present, however, the scarcity and the high cost of the materials seriously prevent the further development of OER, and cannot meet the requirement of mass production of hydrogen. 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 key point of the research. In recent years, ternary transition metal phosphorus sulfide MPS x (m= Fe, co, ni, cu, etc.; x=1 or 3) shows better stability and catalytic activity in electrocatalysis, showing the potential to replace noble metal catalysts. Ma et al synthesized porous carbon-coated ultrafine CoPS nanoparticles using 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 alTwo-dimensional CoPS nanoplatelets were synthesized by hydrothermal method and showed a low Taphil slope (50.2 mV/dec) when used as OER catalysts (Liu, P.et al. Chem Electrochem 2019,6,2852-2859). NiPS prepared by Schuhmann through liquid phase stripping 3 The nanoplatelets have a lower overpotential (Schuhman, w.et al acs catalyst.2017, 7, 229-237). However, most of the current methods for synthesizing transition metal phosphosulfide are liquid phase methods, the yield is limited, and the morphology is difficult to control accurately. The transition metal phosphosulfide reported at present is mostly nano particles and nano sheets, has the defects of small specific surface area and few active sites, and limits the catalytic activity and stability of the material. For example, patent application publication No. CN112877712A discloses a transition metal phosphosulfide, a preparation method and application thereof, but the electrochemical activity of the transition metal phosphosulfide is still to be further improved.
Disclosure of Invention
The technical problem to be solved by the invention is that the electrochemical activity of transition metal phosphosulfide in the prior art is still to be further improved, and an electrostatic spinning method is proposed and utilized to obtain the transition metal phosphosulfide nanofiber and the application thereof, wherein the transition metal phosphosulfide nanofiber has excellent catalytic activity and flexibility.
The invention solves the technical problems by the following technical means:
a method for preparing transition metal phosphosulfide nano-fiber, which comprises the following steps:
(1) Dissolving metal salt and conductive polymer material in an organic solvent to prepare a metal precursor solution; the conductive polymer material is polyacrylonitrile or polyvinylpyrrolidone; the metal atoms in the metal salt are transition metals;
(2) Treating the metal precursor solution obtained in the step (1) by an electrostatic spinning method to obtain metal salt nanofibers;
(3) Calcining a phosphorus source and a sulfur source in an inert atmosphere to obtain a phosphorus-sulfur alloy;
(4) 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.
The beneficial effects are that: compared with the prior art for preparing nano particles and nano sheets, the nano fiber prepared by the method has the advantages of easy control of size and morphology, average diameter of about 200-400 nm, large-scale preparation and suitability for various ternary transition metal phosphorus sulfides.
The transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of larger specific surface area, rich 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, the metal salt in step (1) is chloride, nitrate or acetate, and the transition metal is one of Fe, mn, cu, co, 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 electrostatic spinning method described in step (2) uses a syringe volume of 5 to 20ml, more preferably 5 to 10ml. The syringe needle is 16 to 22G in size, more preferably 19 to 21G. And a high voltage direct current power supply is used in which the positive voltage to which the syringe needle is connected is 13 to 25kV, more preferably 12 to 16kV. The negative pressure of the receiving plate connected with the electrospinning device is-3 to-1 kV, and most preferably-1 kV. The distance between the needle and the receiving plate is 10-20 cm, more preferably 10-15 cm.
Preferably, the metal nanofiber obtained in the step (2) is transferred to an oven, and is dried at a drying temperature of 60-80 ℃ for 12 hours.
Preferably, in the step (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).
Preferably, the inert atmosphere in step (3) is Ar or N 2 Ar is preferred. 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 phosphosulfide Jin Fang obtained in the step (3) is placed in a ceramic boat, transferred to the upstream of a tube furnace, the nanofiber obtained in the step (2) is placed in another ceramic boat, and then calcined under an inert atmosphere to react the phosphosulfide alloy with the nanofiber, so that the transition metal phosphosulfide nanofiber is successfully obtained. The distance between the two ceramic boats is preferably 12-15 cm.
Preferably, the inert atmosphere in step (4) is Ar or N 2 Ar is preferred. The calcination temperature is 500-800 ℃, the temperature rising 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 phosphosulfide nanofiber prepared by the method has the average diameter of 200-400 nm and has flexibility.
The beneficial effects are that: the transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of larger specific surface area, rich active sites, good conductivity and structural stability. While having excellent flexibility.
The transition metal phosphosulfide nanofiber prepared by the method is applied to a water decomposition electrocatalyst.
The beneficial effects are that: when the transition metal phosphosulfide nanofiber prepared by the method is used as an electrocatalyst, the catalyst has excellent catalytic activity.
The invention has the advantages that: compared with the prior art for preparing nano particles and nano sheets, the nano fiber prepared by the method has the advantages of easy control of size and morphology, average diameter of about 200-400 nm, large-scale preparation and suitability for various ternary transition metal phosphorus sulfides.
The transition metal phosphorus sulfide nanofiber prepared by the method has the advantages of larger specific surface area, rich 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 CoPS nanofibers synthesized in example 1 of the present invention;
FIG. 2 is an SEM image of synthesized CoPS nanofibers of example 1 of the present invention;
FIG. 3 is a photograph of a real object of the CoPS nanofiber synthesized in example 1 of the present invention;
FIG. 4 is a graph showing the catalytic performance of the CoPS nanofibers synthesized in example 1 of the present invention;
FIG. 5 is a CuPS synthesized in example 2 of the present invention 3 XRD pattern of nanofibers;
FIG. 6 is a CuPS synthesized in example 2 of the present invention 3 Nanofiber SEM images;
FIG. 7 shows NiPS synthesized in example 3 of the present invention 3 Nanofiber XRD pattern;
FIG. 8 shows NiPS synthesized in example 3 of the present invention 3 SEM image of nanofibers.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
The preparation method of the transition metal phosphosulfide nanofiber specifically comprises the following steps:
(1) First, 0.8g of polyacrylonitrile (national medicine group chemical Co., ltd.) was added to 10ml of N, N-dimethylformamide solvent (national medicine group chemical Co., ltd.) and stirred to be sufficiently dissolved, and labeled as solution A. Then, 1g of cobalt chloride hexahydrate powder (purity: 99% or more, national medicine group chemical reagent Co., ltd.) was weighed and dissolved in the solution A with stirring to prepare a metal precursor solution B for electrospinning.
(2) The solution B is sucked by a 10mL syringe, then the solution B is placed on a syringe pump (LSP 01-1A of Baoding Lange constant flow pump Co., ltd.), a 21G needle is installed, then the needle is connected with the anode, a receiving plate is connected with the cathode, the voltages of the anode and the cathode are respectively 12kV and-1 kV, the distance between the needle and the receiving plate is 15cm, the liquid inlet speed is 1mL/h, and after a corresponding program is set, electrostatic spinning is started, so that the nanofiber is successfully obtained. After spinning, the nanofibers were collected and transferred to an oven, and dried at 80 ℃ for 12h to obtain nanofibers.
(3) 500mg of red phosphorus and 500mg of sublimed sulfur powder were weighed, mixed uniformly, introduced into a ceramic boat, transferred into a tube furnace (Bei Yi g, 1200 ℃ C. Micro box furnace, MF-1200℃), and calcined under Ar atmosphere. Firstly, heating a tube furnace from room temperature to 300 ℃ at a heating rate of 15 ℃/min, preserving heat for 10min, and naturally cooling to obtain a phosphorus-sulfur alloy P x S y And (3) powder.
(4) And (3) respectively placing the phosphorus-sulfur alloy obtained in the step (3) and the nanofiber obtained in the step (2) in two ceramic boats, and then placing the ceramic boats at the upstream and central positions of a tube furnace, wherein the ceramic boats are arranged in parallel, and the vertical distance between the centers of the two ceramic boats is 12cm. Heating to 500 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, and preserving heat for 1h to enable the phosphorus-sulfur alloy and the nanofiber to undergo phosphorus vulcanization reaction. And naturally cooling to room temperature after the reaction is finished, so as to obtain the CoPS/C flexible nanofiber, namely the transition metal phosphosulfide nanofiber.
The product obtained in example 1 was subjected to phase analysis by X-ray diffraction, and FIG. 1 shows the XRD pattern of the CoPS/C nanofiber 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 example 1 of the present invention was demonstrated. The article obtained in example 1 was characterized in morphology by scanning electron microscopy, and the CoPS/C nanofibers prepared in example 1 of the present invention were uniform in size and about 300nm in diameter, as shown in FIG. 2. FIG. 3 is a photograph of the CoPS/C nanofiber obtained in example 1, showing excellent bendability, demonstrating excellent flexibility.
Weighing 5mg of CoPS/C nanofiber, grinding into powder, and adding into 1mL of mixed solution composed of ethanol, deionized water and Nafion solution (V Ethanol ：V Deionized water ： V Nafion =640:320:40), and ultrasonic agitation until a uniform mixture of ink is obtained for use. 3 mu L of the solution is measured by a liquid-transferring gun and is dripped on the surface of the glassy carbon electrode, and after natural drying, the electrocatalytic performance of the solution is tested. FIG. 4 is a graph showing a linear scan curve obtained by OER reaction of the CoPS/C nanofiber prepared in example 1 in 1M KOH solution at a current density of 10mA/cm 2 At this time, the electrode overpotential was 344mV.
Example 2
The preparation method of the transition metal phosphosulfide nanofiber specifically comprises the following steps:
(1) First, 0.8g of polyacrylonitrile (national medicine group chemical Co., ltd.) was added to 10ml of N, N-dimethylformamide solvent (national medicine group chemical Co., ltd.) and stirred to be sufficiently dissolved, and labeled as solution A. Then, 1g of copper chloride dihydrate powder (purity: 99% or more, national pharmaceutical chemicals Co., ltd.) was weighed and dissolved in the solution A with stirring to prepare a metal precursor solution B for electrospinning.
(2) The solution B is sucked by a 10mL syringe, then the solution B is placed on a syringe pump (LSP 01-1A of Baoding Lange constant flow pump Co., ltd.), a 21G needle is installed, then the needle is connected with the anode, a receiving plate is connected with the cathode, the voltages of the anode and the cathode 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, and after the corresponding program is set, the electrostatic spinning is started, so that the nanofiber is successfully obtained. After spinning, collecting and transferring the nanofiber into an oven, and drying at 80 ℃ for 12 hours to obtain the nanofiber.
(3) 500mg of red phosphorus and 500mg of sublimed sulfur powder were weighed, mixed uniformly, introduced into a ceramic boat, transferred into a tube furnace (Bei Yi g, 1200 ℃ C. Micro box furnace, MF-1200℃), and calcined under Ar atmosphere. Firstly, heating a tube furnace from room temperature to 300 ℃ at a heating rate of 15 ℃/min, preserving heat for 10min, and naturally cooling to obtain a phosphorus-sulfur alloy P x S y And (3) powder.
(4) The phosphorus-sulfur alloy obtained in (3) and the nanofiber obtained in (2) were placed in two boats respectively, and then placed in the upstream and central positions of a tube furnace, the distance of the ceramic boat being 15cm. Heating to 600 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, and preserving heat for 2 hours to enable the phosphosulfide alloy and the nanofiber to undergo phosphosulfide reaction. Naturally cooling to room temperature after the reaction is completed to obtain CuPS 3 And (3) the flexible nanofiber is the transition metal phosphosulfide nanofiber.
FIG. 5 shows CuPS prepared in example 2 of the present invention 3 XRD pattern of C nanofiber, and standard card CuPS 3 PDF#48-1236 is completely identical and FIG. 6 shows CuPS prepared in example 2 of the present invention 3 and/C scanning electron microscope pictures of the nanofibers, the nanofibers are uniform in size and have an average diameter of about 350-400 nm, consistent with the expected results.
Example 3
The preparation method of the transition metal phosphosulfide nanofiber specifically comprises the following steps:
(1) First, 0.8g of polyacrylonitrile (national medicine group chemical Co., ltd.) was added to 10ml of N, N-dimethylformamide solvent (national medicine group chemical Co., ltd.) and stirred to be sufficiently dissolved, and labeled as solution A. Then, 1g of nickel chloride hexahydrate powder (purity: 99% or more, national medicine group chemical reagent Co., ltd.) was weighed and dissolved in the solution A with stirring to prepare a metal precursor solution B for electrospinning.
(2) The solution B is sucked by a 10mL syringe, then the solution B is placed on a syringe pump (LSP 01-1A of Baoding Lange constant flow pump Co., ltd.), a 21G needle is installed, then the needle is connected with the anode, a receiving plate is connected with the cathode, the voltages of the anode and the cathode are respectively 12kV and-1 kV, the distance between the needle and the receiving plate is 15cm, the liquid inlet speed is 1mL/h, and after a corresponding program is set, electrostatic spinning is started, so that the nanofiber is successfully obtained. After spinning, collecting and transferring the nanofiber into a baking oven, and drying 12h at 80 ℃ to obtain the nanofiber
(3) 500mg of red phosphorus and 500mg of sublimed sulfur powder were weighed, mixed uniformly, introduced into a ceramic boat, transferred into a tube furnace (Bei Yi g, 1200 ℃ C. Micro box furnace, MF-1200℃), and calcined under Ar atmosphere. Firstly, heating a tube furnace from room temperature to 300 ℃ at a heating rate of 15 ℃/min, preserving heat for 10min, and naturally cooling to obtain a phosphorus-sulfur alloy P x S y And (3) powder.
(4) The phosphorus-sulfur alloy obtained in (3) and the nanofiber obtained in (2) were placed in two boats respectively, then placed in the upstream and central positions of a tube furnace, and the distance of the ceramic boat was 12cm. Heating to 500 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, and preserving heat for 1h to enable the phosphorus-sulfur alloy and the nanofiber to undergo phosphorus vulcanization reaction. Naturally cooling to room temperature after the reaction is completed to obtain NiPS 3 And (3) the flexible nanofiber is the transition metal phosphosulfide nanofiber.
FIG. 7 shows NiPS prepared in example 3 3 XRD patterns of the C nanofibers, FIG. 8 is NiPS prepared in example 3 3 Scanning electron microscope pictures of/C nanofibers demonstrated that this example 3 successfully produced NiPS 3 and/C nanofibers.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of transition metal phosphorus sulfide nanofiber is characterized by comprising the following steps of: the method comprises the following steps:
(1) Dissolving metal salt and conductive polymer material in an organic solvent to prepare a metal precursor solution; the conductive polymer material is polyacrylonitrile or polyvinylpyrrolidone; the metal atoms in the metal salt are transition metals; the metal salt is chloride, nitrate or acetate, and the transition metal is one of Fe, mn, cu, co, ni;
(2) Treating the metal precursor solution obtained in the step (1) by an electrostatic spinning method to obtain metal salt nanofibers;
(3) Calcining a phosphorus source and a sulfur source in an inert atmosphere to obtain a phosphorus-sulfur alloy;
(4) Calcining the phosphorus-sulfur alloy and the nanofiber obtained in the step (2) in an inert atmosphere to obtain the transition metal phosphorus-sulfur compound nanofiber, wherein the specific operation is that the phosphorus-sulfur compound Jin Fang is placed in a ceramic boat and is transferred to the upstream of a tube furnace, the nanofiber obtained in the step (2) is placed in another ceramic boat, and then the calcination is carried out in the inert atmosphere to enable the phosphorus-sulfur alloy and the nanofiber to react, so that the transition metal phosphorus-sulfur nanofiber is successfully obtained.
2. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: the organic solvent in the step (1) is N, N-dimethylformamide.
3. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: 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.
4. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: the electrostatic spinning method in the step (2) uses a syringe with a volume of 5-20 ml, a syringe needle with a model of 16-22G and a high-voltage direct current power supply, wherein the positive pressure of the syringe needle is 13-25 kV, the negative pressure of a receiving plate connected with an electrostatic spinning device is-3 to-1 kV, and the distance between the syringe needle and the receiving plate is 10-20 cm.
5. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: the phosphorus source and the sulfur source in the 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).
6. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: the inert atmosphere in the step (3) is Ar or N 2 The calcination temperature is 300 ℃, the temperature rising rate is 10-20 ℃/min, and the calcination time is 10-30 min.
7. The method for preparing the transition metal phosphosulfide nanofiber according to claim 1, wherein: the inert atmosphere in the step (4) is Ar or N 2 The calcination temperature is 500-800 ℃, the temperature rising 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.
8. a transition metal phosphosulfide nanofiber prepared by the preparation method of any one of claims 1 to 7, characterized in that: the average diameter of the transition metal phosphosulfide nanofiber is 200-400 nm, and the transition metal phosphosulfide nanofiber has flexibility.
9. Use of a transition metal phosphosulfide nanofiber prepared by the preparation method of any one of claims 1-7 as a water-splitting electrocatalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223367.4A CN114438616B (en) | 2022-03-07 | 2022-03-07 | Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223367.4A CN114438616B (en) | 2022-03-07 | 2022-03-07 | Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114438616A CN114438616A (en) | 2022-05-06 |
| CN114438616B true CN114438616B (en) | 2023-10-31 |
Family
ID=81358779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210223367.4A Active CN114438616B (en) | 2022-03-07 | 2022-03-07 | Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114438616B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010063244A2 (en) * | 2008-12-03 | 2010-06-10 | Elmarco S.R.O. | A method for production of nanofibres and/or nanofibrous structures of phospho-olivines, nanofibres of phospho-olivines and nanofibrous structure formed of nanofibres of phospho-olivines |
| CN106430122A (en) * | 2016-10-11 | 2017-02-22 | 中国科学技术大学 | NiSe2 transition metal chalcogenide nanosheet as well as preparation method and application thereof |
| CN107376958A (en) * | 2017-06-05 | 2017-11-24 | 国家纳米科学中心 | The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use |
| EP3597800A1 (en) * | 2018-07-16 | 2020-01-22 | Freie Universität Berlin | Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN112599777A (en) * | 2020-12-14 | 2021-04-02 | 河北工业大学 | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11033888B2 (en) * | 2017-08-30 | 2021-06-15 | Uchicago Argonne, Llc | Nanofiber electrocatalyst |
-
2022
- 2022-03-07 CN CN202210223367.4A patent/CN114438616B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010063244A2 (en) * | 2008-12-03 | 2010-06-10 | Elmarco S.R.O. | A method for production of nanofibres and/or nanofibrous structures of phospho-olivines, nanofibres of phospho-olivines and nanofibrous structure formed of nanofibres of phospho-olivines |
| CN106430122A (en) * | 2016-10-11 | 2017-02-22 | 中国科学技术大学 | NiSe2 transition metal chalcogenide nanosheet as well as preparation method and application thereof |
| CN107376958A (en) * | 2017-06-05 | 2017-11-24 | 国家纳米科学中心 | The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use |
| EP3597800A1 (en) * | 2018-07-16 | 2020-01-22 | Freie Universität Berlin | Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN112599777A (en) * | 2020-12-14 | 2021-04-02 | 河北工业大学 | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114438616A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108816258B (en) | Hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, preparation method and application of hollow carbon material in hydrogen production by catalytic electrolysis of water | |
| CN113371693B (en) | Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof | |
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| CN107649160B (en) | Graphene-loaded transition group metal monodisperse atomic catalyst and preparation method and application thereof | |
| Cao et al. | Improved hydrogen generation via a urea-assisted method over 3D hierarchical NiMo-based composite microrod arrays | |
| CN111346640B (en) | Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN111483999B (en) | Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube | |
| CN109621969B (en) | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN1986047A (en) | Noble metal electrocatalyst based on nano carbon fiber and its preparing method | |
| CN110961162A (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
| CN111185201B (en) | Rhenium-doped molybdenum sulfide nanosheet/carbon cloth composite material, preparation method thereof and application thereof in hydrogen production by electrocatalysis of water | |
| CN113060770A (en) | Preparation method of heterojunction CoO/CoS porous nanorod, obtained material and application | |
| CN110575840B (en) | Preparation method of two-dimensional molybdenum carbide/graphene nanosheet composite material | |
| Liu et al. | Electrospun Fe2C-loaded carbon nanofibers as efficient electrocatalysts for oxygen reduction reaction | |
| Yu et al. | Assembled cobalt phosphide nanoparticles on carbon nanofibers as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction | |
| CN108479809B (en) | MnS/Ni3S4Composite material and preparation method and application thereof | |
| CN112599806B (en) | Preparation method and application of carbon nanofiber-based electrocatalyst | |
| CN111804313B (en) | Fe 2 O 3 @Co 9 S 8 Preparation method and application of double-hollow core-shell structure nano composite material | |
| CN111389430B (en) | Catalyst CoP for hydrogen production by water electrolysis x S y MWCNTs and preparation method thereof | |
| CN114438616B (en) | Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof | |
| CN113417032B (en) | Preparation method of nitrogen-doped mesoporous carbon fiber-based non-noble metal electrocatalyst | |
| CN113174612B (en) | Carbon tube composite material loaded with Ni nano-particles and preparation method and application thereof | |
| CN115261915A (en) | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |