CN114016162A - Preparation method of bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution - Google Patents
Preparation method of bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 70
- 239000002121 nanofiber Substances 0.000 title claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 14
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 11
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000001354 calcination Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 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
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- D01F1/10—Other agents for modifying properties
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
Abstract
The invention discloses a preparation method of a bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution, which comprises the following steps: growing regular dodecahedral ZIF-67 by taking the tetragonal ZIF-8 nano-particles as a core to obtain core-shell ZIF-8@ ZIF-67 nano-particles; adding ZIF-8@ ZIF-67 nano particles and polyacrylonitrile into an N, N-dimethylformamide solution to prepare an electrostatic spinning solution, and performing electrostatic spinning to obtain a ZIF-8@ ZIF-67/PAN electrostatic spinning membrane; and then carbonizing and reducing the obtained electrostatic spinning film to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles, and then sequentially oxidizing and phosphorizing to obtain the target product, namely the bubble-shaped nanofiber embedded with the cobalt phosphide nanoparticles. The preparation method has the advantages of easy obtaining, easy repetition, high yield, uniform product structure and the like, and the prepared material has excellent electro-catalytic hydrogen evolution capability.
Description
Technical Field
The invention relates to a preparation method of a bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution, belonging to the technical field of functional nano materials.
Background
The nano material has the characteristics of large specific surface area, large pore structure, clear pore structure and uniform distribution of active sites, is an ideal catalyst material, and has attracted wide attention in electrocatalytic water splitting because the nano material not only represents a clean and efficient hydrogen production technology, but also can be easily combined with other intermittent energy sources, such as wind energy and solar energy. To date, platinum-based metals are the most effective HER electrocatalysts, but the scarcity and high cost of these precious metals severely hamper their widespread use in commercial electrolysis of water. In order to find an alternative to noble metal HER catalysts, various materials are based on non-noble metal transition metals, of which Transition Metal Phosphides (TMPs) have attracted considerable attention in terms of suitable electronic configuration and excellent activity. And electronic regulation of electrocatalytic active sites by heteroatom doping has been widely recognized as a powerful strategy to further improve the intrinsic activity of TMP catalysts. The Metal Organic Framework (MOF) material has a periodic metal atom organic matter connection structure, a large specific surface area and an adjustable pore structure, and is an ideal precursor for further synthesizing TMP by high-temperature carbonization. The synthesis of highly dispersed TMP nanoparticles embedded in Co, N and P multi-doped carbon frameworks (adv. mater.2020,32,2003649) based on MOFs opens up a new approach to the design of efficient catalysts for the electrolysis of water.
At present, a low-cost and convenient preparation method is needed to obtain a material with a unique structure, and the material is required to have better stability and higher yield so as to meet the application of the material in the fields of electrocatalysis, energy sources and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution, and the technical problem to be solved is to provide the preparation method with the advantages of easy obtaining, easy repetition, high yield and the like, so that the prepared material has excellent electrocatalytic hydrogen evolution capability.
The invention solves the technical problem and adopts the following technical scheme:
a preparation method of bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution is characterized by comprising the following steps: growing regular dodecahedral ZIF-67 by taking the tetragonal ZIF-8 nano-particles as a core to obtain core-shell ZIF-8@ ZIF-67 nano-particles; adding the ZIF-8@ ZIF-67 nano particles and polyacrylonitrile into an N, N-dimethylformamide solution to prepare an electrostatic spinning solution, and performing electrostatic spinning to obtain a ZIF-8@ ZIF-67/PAN electrostatic spinning membrane; and then carbonizing and reducing the obtained electrostatic spinning film to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles, and then sequentially oxidizing and phosphorizing to obtain the target product, namely the bubble-shaped nanofiber embedded with the cobalt phosphide nanoparticles. Comprises the following steps
Step 1, adding 10-11 g of dimethyl imidazole into 80-100 mL of water, adding 50-55 mg of CTAB into 10-15 mL of water, and adding 0.7-0.8 g of zinc nitrate hexahydrate into 80-100 mL of water;
uniformly mixing aqueous solutions of dimethylimidazole, CTAB and zinc nitrate hexahydrate, and reacting under magnetic stirring; after the reaction is finished, standing, performing centrifugal separation, washing the obtained precipitate with methanol to obtain cube-shaped ZIF-8 nano particles;
step 2, dispersing the ZIF-8 nano particles obtained in the step 1 in 80-100 mL of methanol to obtain a suspension; respectively dissolving 3-4 g of cobalt chloride hexahydrate and 8-9 g of dimethyl imidazole in 20-40 mL of methanol, then sequentially pouring into the suspension, and reacting under magnetic stirring; after the reaction is finished, performing centrifugal separation, and washing the obtained precipitate by sequentially using methanol and N, N-dimethylformamide to obtain a ZIF-8@ ZIF-67 nano particle with a core-shell structure;
step 3, dispersing the ZIF-8@ ZIF-67 nanoparticles in 4-5 mL of N, N-dimethylformamide, adding 0.4-0.5 g of polyacrylonitrile, magnetically stirring until the mixture is uniformly mixed to obtain an electrostatic spinning solution, and then obtaining a ZIF-8@ ZIF-67/PAN electrostatic spinning membrane through electrostatic spinning;
step 4, enabling the electrostatic spinning membrane to be 5% H2Calcining in a 95% Ar atmosphere to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles;
step 5, calcining and oxidizing the bubble-shaped nanofiber embedded with the metal Co nanoparticles in air to obtain the Co-containing nanofiber3O4Nanoparticle embedded bubble-like nanofibers;
step 6, adding the catalyst Co3O4And respectively placing the bubble-shaped nano fiber embedded with the nano particles and sodium hypophosphite at the mass ratio of 1: 5-50 at the downstream and upstream of a flowing argon atmosphere for calcining and phosphating to obtain the bubble-shaped nano fiber embedded with the cobalt phosphide nano particles.
Preferably, in the step 1, the magnetic stirring time is 5-10 min, the rotating speed is 250-350 rpm, the standing time is 20-40 min, the rotating speed of centrifugal separation is 11000-12000 rpm, and the centrifugal time is 5-15 min.
Preferably, in the step 2, the magnetic stirring time is 8-12 h, the rotating speed is 250-350 rpm, the rotating speed of centrifugal separation is 5000-8000 rpm, and the centrifugal time is 5-15 min.
Preferably, in the step 3, the voltage of the electrostatic spinning is 14-16 KV, the flow rate is 0.2-0.3 mL/h, and the distance from the needle to the receiving screen is 7-14 cm.
Preferably, in step 4, the calcination is two-step gradient temperature-rising calcination, and the method comprises the following steps: firstly, heating to 150-200 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation calcination for 1-2 h; and then heating to 700-1000 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation and calcination for 2-4 h.
Preferably, in the step 5, the temperature of the calcination oxidation is 340-370 ℃, the temperature rise rate is 5 ℃/min, and the calcination time is 10-60 min.
Preferably, in the step 6, the temperature of the calcination and the phosphorization is 340-370 ℃, the heating rate is 2 ℃/min, and the calcination time is 1-3 h.
The obtained bubble-shaped nanofiber embedded with the cobalt phosphide nanoparticles can be used as an electrocatalytic hydrogen evolution material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles, which has the advantages of easily obtained raw materials, easiness in repetition, high yield and uniform product structure, and compared with a porous carbon nanomaterial derived from traditional nanoparticle calcination, the product obtained by the method has larger specific surface area and more excellent electrocatalytic performance.
2. Compared with the zero-dimensional ZIF-8@ ZIF-67 particles, the product obtained by the invention is used as an electrocatalytic hydrogen evolution material, so that the electron transfer is enhanced, and the stability and high activity of the catalyst are ensured.
3. Compared with the traditional catalyst, the material obtained by the invention is non-noble metal, has low price and wide application prospect.
Drawings
FIG. 1 is a transmission electron microscope image of tetragonal ZIF-8 nanoparticles obtained in step 1 of example 1;
FIG. 2 is a transmission electron microscope image of the core-shell structured ZIF-8@ ZIF-67 nanoparticles obtained in step 2 of example 1;
FIG. 3 is a scanning electron micrograph of a ZIF-8@ ZIF-67/PAN fiber film obtained in step 3 of example 1;
FIG. 4 is a transmission electron microscope image of the bubble-like nanofibers embedded with metallic Co nanoparticles obtained in step 4 of example 1.
FIG. 5 shows the results of step 5 of example 1 with Co3O4Transmission electron microscopy of nanoparticle embedded bubble-like nanofibers.
FIG. 6 is a transmission electron microscope image of the target product obtained in example 1, in which the cobalt phosphide nanoparticles are embedded in the bubble-like nanofibers.
FIG. 7 is a graph showing the performance of electrocatalytic hydrogen evolution of the target product obtained in example 1, i.e., the bubbled nanofibers with embedded cobalt phosphide nanoparticles, and the comparative bubbled nanofibers with embedded metallic Co nanoparticles.
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The electrospinning direct current high voltage power source used in the following examples was provided by EST705 high precision high stability electrostatic high voltage generator (0-60KV) produced by beijing, the double injection pump used in the experiment was KI-602 injection pump produced by beijing kojiu mechanical engineering ltd, the centrifuge was Anke TGL-10B produced by shanghai pavilion scientific instruments factory, the magnetic stirrer was RT-10 multi-point magnetic stirrer produced by guangzhou instrumental laboratory technology ltd, the calciner was OTF-1200X produced by mixcrystal materials technology ltd, the scanning electron microscope was Zeiss ra sup40 produced by germany, and the transmission electron microscope was JEOL-F2010 produced by japan. The drugs used in the following examples were purchased and used without any treatment.
Example 1
This example prepares a bubble-like nanofiber with embedded cobalt phosphide nanoparticles as follows:
step 1, adding 10.8g of 2-methylimidazole into 100mL of water, adding 52mg of CTAB into 14.4mL of water, and adding 0.7g of zinc nitrate hexahydrate into 100mL of water; uniformly mixing aqueous solutions of dimethylimidazole, CTAB and zinc nitrate hexahydrate, and reacting under magnetic stirring (the rotating speed is 300rpm, and the stirring time is 5 min); after the reaction was completed, the mixture was left to stand for 30min, centrifuged (centrifugation rate 12000rpm, centrifugation time 10min), and the resulting precipitate was washed with methanol to obtain tetragonal ZIF-8 nanoparticles.
Step 2, ultrasonically dispersing the ZIF-8 nano particles in 100mL of methanol to obtain a suspension(ii) a 3.28g CoCl2·6H2O and 8.9g of dimethylimidazole are respectively dissolved in 30mL of methanol, then are poured into the suspension in sequence, and react under magnetic stirring (the stirring speed is 300rpm, and the stirring time is 10 hours); and after the reaction is finished, performing centrifugal separation (the centrifugal rate is 8000rpm, and the centrifugal time is 10min), and washing the obtained precipitate by sequentially using methanol and N, N-dimethylformamide to obtain the core-shell structure ZIF-8@ ZIF-67 nano particles.
And 3, ultrasonically dispersing the obtained ZIF-8@ ZIF-67 nano particles in 5mL of N, N-dimethylformamide solution, adding 0.45g of polyacrylonitrile, and uniformly mixing under magnetic stirring (the stirring speed is 300rpm, and the stirring time is 12 hours) to obtain the electrostatic spinning solution. Transferring the electrostatic spinning solution into a 10mL injector for electrostatic spinning, and setting the flow rate to be 0.3mL/h, the high-voltage direct current voltage to be 15KV and the distance from the copper mesh to the needle head to be 10 cm. And collecting the ZIF-8@ ZIF-67/PAN electrostatic spinning membrane on a copper net.
Step 4, the obtained electrostatic spinning membrane is 5% H2Heating to 200 ℃ at the heating rate of 1 ℃/min in the atmosphere of 95% Ar, preserving heat for 2h, then continuously heating to 900 ℃ at the heating rate of 2 ℃/min, and preserving heat for 4h to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles.
Step 5, heating the bubble-shaped nanofiber embedded with the metal Co nanoparticles to 360 ℃ at a speed of 5 ℃/min in the air, and preserving the temperature for 30min for oxidation to obtain the Co-containing nanofiber3O4Nanoparticles embedded in bubble-like nanofibers.
Step 6, will have Co3O4And (3) placing the bubble-shaped nano-fiber embedded with the nano-particles in a porcelain boat at a lower air inlet, placing sodium hypophosphite in a porcelain boat at an upper air inlet (the mass ratio of the bubble-shaped nano-fiber to the sodium hypophosphite is 1:10), and heating to 350 ℃ at a heating rate of 2 ℃/min in a flowing argon atmosphere for heat preservation for 2h to obtain the bubble-shaped nano-fiber embedded with the cobalt phosphide nano-particles.
FIG. 1 is a transmission electron microscope photograph of the tetragonal ZIF-8 nanoparticles obtained in step 1 of this example, which had a particle size of about 50nm, relatively dispersed particles and uniform size.
FIG. 2 is a transmission electron microscope image of the core-shell structure ZIF-8@ ZIF-67 nanoparticles obtained in step 2 of this example, wherein the particle size is about 120nm, and the particles are relatively dispersed and uniform in size.
FIG. 3 is a scanning electron microscope image of the ZIF-8@ ZIF-67/PAN electrospun membrane obtained in step 3 of this example, which shows that the ZIF-8@ ZIF-67 particles are distributed relatively uniformly in the fiber, and the fiber diameter is 600 nm.
Fig. 4 is a transmission electron microscope image of the metal Co nanoparticle-embedded bubble-shaped nanofiber obtained in step 4 of this example, it can be seen that the bubble-shaped hollow structures are uniformly distributed on the fiber, and the metal Co nanoparticles are embedded in the nanofiber.
FIG. 5 shows the Co-containing residue obtained in step 5 of this example3O4Transmission electron microscopy of nanoparticle-embedded bubble-like nanofibers shows that metallic Co nanoparticles are oxidized to hollow Co3O4Nano particles and better material appearance retention.
Fig. 6 is a transmission electron microscope image of the target product obtained in this embodiment of the bubble-shaped nanofibers with cobalt phosphide nanoparticles embedded therein, which shows that the morphology of the fibers after calcination and phosphating is well maintained.
The electrocatalytic performance of the resulting bubble-like nanofibers with embedded CoP nanoparticles of this example was tested as follows: electrochemical workstation electrochemical testing was performed using a three-electrode system, the working electrode being a 5mm diameter glassy carbon disk electrode (area of disk 0.196 cm)2) The reference electrode is an Ag/AgCl electrode and the carbon electrode is used as a counter electrode. 5mg of the obtained nanofibers were dispersed in 500. mu.L of ethanol, sonicated for 5 hours, and 10. mu.L of the resulting nanofibers were applied to the surface of a glass carbon using a microinjector. Before testing, N was passed through the electrolyte (1M KOH solution)2For at least half an hour, keeping the electrolyte at N2A saturated state. During the test, the rotating disk electrode was set at 1600rpm, and the sweep rate was 5 mV/s.
FIG. 7 is a graph showing the performance of electrocatalytic hydrogen evolution of the target product obtained in this example (solid line) and the comparative metal Co nanoparticle-embedded bubble-like nanofibers (dashed line), and it can be seen that the overpotential of the target product is 156mV (at 10 mA/cm)-2At), much lower than the overpotential of 227mV for the control (at 10mA cm)-2At (c).
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution is characterized by comprising the following steps: growing regular dodecahedral ZIF-67 by taking the tetragonal ZIF-8 nano-particles as a core to obtain core-shell ZIF-8@ ZIF-67 nano-particles; adding the ZIF-8@ ZIF-67 nano particles and polyacrylonitrile into an N, N-dimethylformamide solution to prepare an electrostatic spinning solution, and performing electrostatic spinning to obtain a ZIF-8@ ZIF-67/PAN electrostatic spinning membrane; and then carbonizing and reducing the obtained electrostatic spinning film to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles, and then sequentially oxidizing and phosphorizing to obtain the target product, namely the bubble-shaped nanofiber embedded with the cobalt phosphide nanoparticles.
2. The method of claim 1, comprising the steps of:
step 1, adding 10-11 g of dimethyl imidazole into 80-100 mL of water, adding 50-55 mg of CTAB into 10-15 mL of water, and adding 0.7-0.8 g of zinc nitrate hexahydrate into 80-100 mL of water;
uniformly mixing aqueous solutions of dimethylimidazole, CTAB and zinc nitrate hexahydrate, and reacting under magnetic stirring; after the reaction is finished, standing, performing centrifugal separation, washing the obtained precipitate with methanol to obtain cube-shaped ZIF-8 nano particles;
step 2, dispersing the ZIF-8 nano particles obtained in the step 1 in 80-100 mL of methanol to obtain a suspension; respectively dissolving 3-4 g of cobalt chloride hexahydrate and 8-9 g of dimethyl imidazole in 20-40 mL of methanol, then sequentially pouring into the suspension, and reacting under magnetic stirring; after the reaction is finished, performing centrifugal separation, and washing the obtained precipitate by sequentially using methanol and N, N-dimethylformamide to obtain a ZIF-8@ ZIF-67 nano particle with a core-shell structure;
step 3, dispersing the ZIF-8@ ZIF-67 nanoparticles in 4-5 mL of N, N-dimethylformamide, adding 0.4-0.5 g of polyacrylonitrile, magnetically stirring until the mixture is uniformly mixed to obtain an electrostatic spinning solution, and then obtaining a ZIF-8@ ZIF-67/PAN electrostatic spinning membrane through electrostatic spinning;
step 4, enabling the electrostatic spinning membrane to be 5% H2Calcining in a 95% Ar atmosphere to obtain the bubble-shaped nanofiber embedded with the metal Co nanoparticles;
step 5, calcining and oxidizing the bubble-shaped nanofiber embedded with the metal Co nanoparticles in air to obtain the Co-containing nanofiber3O4Nanoparticle embedded bubble-like nanofibers;
step 6, adding the catalyst Co3O4And respectively placing the bubble-shaped nano fiber embedded with the nano particles and sodium hypophosphite at the mass ratio of 1: 5-50 at the downstream and upstream of a flowing argon atmosphere for calcining and phosphating to obtain the bubble-shaped nano fiber embedded with the cobalt phosphide nano particles.
3. The method of claim 2, wherein: in the step 1, the magnetic stirring time is 5-10 min, the rotating speed is 250-350 rpm, the standing time is 20-40 min, the rotating speed of centrifugal separation is 11000-12000 rpm, and the centrifugal time is 5-15 min.
4. The method of claim 2, wherein: in the step 2, the magnetic stirring time is 8-12 h, the rotating speed is 250-350 rpm, the rotating speed of centrifugal separation is 5000-8000 rpm, and the centrifugal time is 5-15 min.
5. The method of claim 2, wherein: in the step 3, the voltage of the electrostatic spinning is 14-16 KV, the flow rate is 0.2-0.3 mL/h, and the distance from the needle head to the receiving screen is 7-14 cm.
6. The method of claim 2, wherein: in step 4, the calcination is two-step gradient temperature rise calcination, and the method comprises the following steps: firstly, heating to 150-200 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation calcination for 1-2 h; and then heating to 700-1000 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation and calcination for 2-4 h.
7. The method of claim 2, wherein: in the step 5, the calcining oxidation temperature is 340-370 ℃, the heating rate is 5 ℃/min, and the calcining time is 10-60 min.
8. The method of claim 2, wherein: in the step 6, the temperature of the calcination and phosphorization is 340-370 ℃, the heating rate is 2 ℃/min, and the calcination time is 1-3 h.
9. A bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles, obtained by the preparation method of any one of claims 1 to 8.
10. Use of the nanofibers embedded with cobalt phosphide nanoparticles as claimed in claim 9, wherein: used as electrocatalytic hydrogen evolution material.
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