CN111068734A - Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis - Google Patents
Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis Download PDFInfo
- Publication number
- CN111068734A CN111068734A CN201911350565.1A CN201911350565A CN111068734A CN 111068734 A CN111068734 A CN 111068734A CN 201911350565 A CN201911350565 A CN 201911350565A CN 111068734 A CN111068734 A CN 111068734A
- Authority
- CN
- China
- Prior art keywords
- fiber
- bamboo
- btc
- nano
- nitrogen
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 10
- 239000000956 alloy Substances 0.000 title claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 230000001588 bifunctional effect Effects 0.000 title description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 239000002121 nanofiber Substances 0.000 claims abstract description 19
- 229920002223 polystyrene Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 7
- 239000004917 carbon fiber Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005054 agglomeration Methods 0.000 claims abstract description 4
- 230000002776 aggregation Effects 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 32
- 239000012621 metal-organic framework Substances 0.000 claims description 15
- 229910000531 Co alloy Inorganic materials 0.000 claims description 10
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 229920005594 polymer fiber Polymers 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 12
- 238000001523 electrospinning Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- -1 carbon nano-fiber transition metal Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle electrocatalytic material and efficient electrocatalytic oxygen reduction and oxygen evolution performances of the electrocatalytic material. By electrospinning technique, PS fiber or PAN fiber is mixed with CoXNiY-BTC binding ofThe preparation method is characterized in that MOFs @ PS or MOFs @ PAN nano-fibers are designed and synthesized, and the electric catalytic material of the bamboo-like nitrogen-doped carbon nano-fiber coated transition metal alloy nano-particles is synthesized through high-temperature carbonization. By controlling different Co/Ni molar ratios, nano-scale precursor Co is preparedXNiYBTC, Co formation by coating with polystyrene or polyacrylonitrileXNiY-BTC @ PS or CoXNiY-BTC @ PAN nanofibers. The PS fiber or PAN fiber is used as a template and is converted into carbon fiber with good conductivity in the high-temperature carbonization process, the Co/Ni bimetallic alloy avoids the corrosion of electrolyte and slows down the agglomeration of the electrolyte in the reaction process under the coating of a uniform carbon-nitrogen structure, and the electrocatalytic oxygen reduction and oxygen evolution activity of the material are obviously enhanced under the synergistic action of the metal phase and the carbon fiber.
Description
Technical Field
The invention relates to a preparation method of a bamboo-like nitrogen-doped carbon nanofiber-coated Co/Ni alloy nanoparticle electrocatalytic material and efficient electrocatalytic oxygen reduction and oxygen evolution performances of the material. PS fibers or PAN fibers and spherical Co with different Co/Ni molar ratios by a simple electrostatic spinning technologyXNiYCombined with BTC, the bamboo joint Co with more uniformity is reasonably designed and synthesizedXNiY-BTC @ PS or CoXNiYthe-BTC @ PAN nano-fiber is carbonized at high temperature to synthesize a series of bamboo-like nitrogen-doped carbon nano-fiber Co/Ni alloy nano-particle electro-catalytic materials with efficient electro-catalytic oxygen reduction and oxygen evolution performances.
Background
With the rapid development of global economy, human energy demand has increased dramatically. The current energy structure mainly depends on fossil energy such as petroleum, natural gas, coal and the like, and the excessive exploitation and use of the energy cause the problems of serious shortage of the fossil energy, environmental pollution and the like worldwide. To change this situation, the development of green and sustainable new energy is a necessary choice for the global economic development. Solar energy, wind energy, ocean energy and the like are used as sustainable novel energy sources, and the sustainable novel energy sources are influenced by regions or environments and the like in the using process, so that the sustainable novel energy sources have intermittency and instability. Abundant water resources reserved on the earth are converted into products (hydrogen, oxygen and the like) with higher values through an electrochemical conversion way, and the products are taken as a potential sustainable new energy development direction and are widely concerned by scientific researchers. The development and utilization of the energy can realize an energy conversion system taking water, hydrogen and oxygen as cyclic utilization, and realize zero emission in the true sense. There are several important energy conversion technologies in this energy conversion system, including hydrogen fuel cell technology, reversible metal-air cell technology, and hydrogen production by electrolysis of water. How to improve the efficient utilization of the energy devices becomes an urgent problem to be solved by scientific researchers. Research finds that several core reactions exist in the technologies, including Oxygen Reduction Reaction (ORR), Oxygen Evolution Reaction (OER), Hydrogen Evolution Reaction (HER) and Hydrogen Oxidation Reaction (HOR), and the slow kinetics of the reactions and the excessively high reaction energy barrier reduce the chemical reaction rate and the energy conversion efficiency, which restrict the large-scale application of the energy devices. Therefore, the development of the high-activity and high-stability electrocatalyst can accelerate the chemical reaction rate and reduce the energy loss in the reaction process, and is a necessary way for promoting the large-scale application of technologies such as hydrogen fuel cells, metal-air cells, hydrogen production by water electrolysis and the like.
The preparation of inorganic nano-materials by using MOFs as templates or precursors has attracted great interest of researchers. Due to the periodic arrangement of metal ions and organic ligands in the MOFs, the nano material obtained by converting the MOFs has a definite structure and chemical composition. In addition, because the metal ions and organic ligands composing the MOFs are various in variety, and the coordination strength and thermal stability between the components in the MOFs are also different, various types of nanomaterials can be synthesized by selecting different MOFs precursors or adjusting different reaction conditions. Researchers have found that pyrolysis of MOFs can produce a wide variety of porous carbon nanomaterials, including metal oxide/metal sulfide/metal phosphide-based porous carbon composites, and the like. In addition, functional materials with excellent performance can also be obtained by modifying the MOFs. The MOFs-based nano material has good application prospect in the fields of photo/electro-catalysis, energy storage, sensors, adsorption and the like. Therefore, MOFs-based materials have become a research hotspot in the fields of chemistry and novel functional materials.
In fact, compared with the traditional porous carbon material, the MOFs-based derivative with unique advantages opens up a way for preparing various porous carbon materials, MOFs precursors have various forms, and the MOFs precursors are reasonably designed, so that the MOFs-derived porous carbon catalytic material which is free of metal or transition metal doping and has high catalytic activity can be obtained. The carbonization strategy can result in a functionally desirable chemical structure with synergistic effects between the metal and carbon matrix components, thereby achieving higher electrocatalytic performance.
The invention adopts simple electrostatic spinning technology to mix PS fiber or PAN fiber with spherical CoXNiYCombined with BTC, bamboo-like Co is reasonably designed and synthesizedXNiY-BTC @ PS or CoXNiYthe-BTC @ PAN nano-fiber is carbonized at high temperatures of different temperatures to synthesize a series of bamboo-shaped nitrogen-doped carbon nano-fiber transition metal alloy nano-particle electro-catalytic materials. By controlling different Co/Ni molar ratios, the nanometer-scale precursor Co with uniform spherical morphology is preparedXNiYBTC, formed by coating polystyrene or polyacrylonitrile to form relatively uniform bamboo-shaped CoXNiY-BTC @ PS or CoXNiY-BTC @ PAN nanofibers. The PS fiber or PAN fiber serving as an excellent template is converted into carbon fiber with good conductivity in the high-temperature carbonization process, the bimetal alloy formed by the Co/Ni in the optimal proportion can be well protected under the coating of a uniform carbon-nitrogen structure, the corrosion of electrolyte is avoided, the agglomeration of the electrolyte in the reaction process is slowed down, and the electrocatalytic oxygen reduction and oxygen evolution activity of the electrocatalytic material are obviously enhanced under the synergistic action of the metal phase and the carbon fiber.
Disclosure of Invention
The experiment uses PS fiber or PAN fiber and spherical Co with different Co/Ni molar ratios through simple electrostatic spinning technologyXNiYCombined with BTC, the bamboo joint Co with more uniformity is reasonably designed and synthesizedXNiY-BTC @ PS or CoXNiY-BTC @ PAN nanofibers viaCarbonizing at a high temperature to synthesize a series of bamboo-shaped nitrogen-doped carbon nanofiber Co/Ni alloy nanoparticle-coated electrocatalytic materials. The Co/Ni alloy can be well protected under the cladding of a uniform carbon-nitrogen structure, the corrosion of electrolyte is avoided, the agglomeration of the electrolyte in the reaction process is slowed down, and the electrocatalytic oxygen reduction and oxygen evolution activity of the electrocatalytic material are obviously enhanced under the synergistic action of the metal phase and the carbon fiber. The operation steps are as follows:
(1) weighing Co (NO) at different Co/Ni molar ratios3)2·6H2O and Ni (NO)3)2·6H2O960 mg in total, 300 mg of trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours. (2) Co/Ni BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature. Co/NiBTC @ PS or Co/Ni BTC @ PAN nanofibers with different Co/Ni molar ratios were prepared using exactly the same experimental procedure. (3) Co/Ni BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature.Co/Ni BTC @ PS or Co/Ni BTC @ PAN nanofibers with different Co/Ni molar ratios were prepared using exactly the same experimental procedure. (4) Spreading the prepared Co/Ni BTC @ PS or Co/Ni BTC @ PAN nano-fiber in a porcelain boat, fixing, transferring into a muffle furnace, and heating at 2 deg.C for min-1The temperature rising rate of (2) was increased from room temperature to 280 ℃ and maintained for 1 hour. Subsequently, the nanofibers were protected with ultra pure Ar gas at the target temperatures (700, 800 and 900 ℃) for 5 ℃ min-1The heating rate of (3) is carbonized for 3 hours. And after naturally cooling to room temperature, marking the obtained electrocatalytic materials of the bamboo-shaped nitrogen-doped carbon nanofiber coating Co/Ni alloy nano particles as Co/Ni @ N-CNFs-700, Co/Ni @ N-CNFs-800 and Co/Ni @ N-CNFs-900 respectively. (5) Co/Ni @ N-CNFs-Ts (T =700,800,900 ℃) with different Co/Ni molar ratios tests the electrocatalytic oxygen reduction and oxygen evolution performances in alkaline solution, and shows excellent bifunctional electrocatalytic activity and stability. The different Co/Ni molar ratios and carbonization temperatures greatly influence the electrocatalytic oxygen reduction and oxygen evolution performances of the prepared CoNi @ N-CNFs-Ts electrocatalytic material.
Drawings
FIG. 1 is a scanning electron micrograph of Co/Ni BTC prepared according to an example of the present invention.
FIG. 2 is a scanning electron microscope image of Co/Ni @ N-CNFs-800 prepared in the example of the present invention.
FIG. 3 is a comparative XRD plot of Co/Ni @ N-CNFs-Ts prepared in accordance with examples of the present invention.
FIG. 4 is a Raman comparison of Co/Ni @ N-CNFs-Ts prepared according to examples of the present invention.
FIG. 5 is a diagram of the electrocatalytic oxygen reduction performance of Co/Ni @ N-CNFs-800 prepared in the examples of the present invention.
FIG. 6 is a diagram showing the electrocatalytic oxygen reduction stability of Co/Ni @ N-CNFs-800 prepared in the examples of the present invention.
FIG. 7 is a graph of the electrocatalytic oxygen evolution stability of Co/Ni @ N-CNFs-800 prepared in the examples of the present invention.
Detailed Description
The invention is described in further detail by means of specific examples:
example 1: weighing 960 mg Co (NO)3)2·6H2O, 300 mg trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours.
Example 2: weighing 960 mg Ni (NO)3)2·6H2O, 300 mg trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours.
Example 3: weighing 480 mg Co (NO)3)2·6H2O and 480 mg Ni (NO)3)2·6H2O, 300 mg trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours.
Example 4: 369 mg of Co (NO) are weighed out3)2·6H2O and 111 mg Ni (NO)3)2·6H2O, 300 mg trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours.
Example 5: 267 mg Co (NO) are weighed out3)2·6H2O and213 mg Ni(NO3)2·6H2o, 300 mg trimesic acid (H)3BTC) and 2 g polyvinylpyrrolidone (PVP, MW 58000) were dissolved in 60mL DMF solution. The resulting mixture was magnetically stirred for 30 minutes to ensure complete dissolution of the reactants, which were then transferred to a stainless steel autoclave and held in an oven at 150 ℃ for 6 hours. The precipitate was centrifuged and washed several times with DMF and ethanol, and then dried in vacuo at 60 ℃ for 24 hours.
Example 6: Co-BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature.
Example 7: Ni-BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature.
Example 8: CoNi-0.3-BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) at a Co/Ni molar ratio of 0.3 to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature.
Example 9: CoNi-0.8-BTC was stirred and ultrasonically dispersed in N, N-Dimethylformamide (DMF) at a Co/Ni molar ratio of 0.8 to form a homogeneous suspension. 1g of Polystyrene (PS) or 1g of Polyacrylonitrile (PAN) powder was slowly added to the suspension with continuous stirring, and then subjected to ultrasonic treatment, and after stirring at 60 ℃ for 18 hours, a uniformly dispersed viscous solution was formed. The viscous solution was then poured into a 10 mL plastic syringe equipped with a stainless steel needle with an inner diameter of 0.80 mm and connected to a Direct Current (DC) high voltage power supply. Electrospinning was carried out at room temperature.
Example 10: spreading the prepared Co/Ni BTC @ PS or Co/Ni BTC @ PAN nano-fiber in a porcelain boat, fixing, transferring into a muffle furnace, and heating at 2 deg.C for min-1The temperature rising rate of (2) was increased from room temperature to 280 ℃ and maintained for 1 hour. Subsequently, the nanofibers were protected with ultra pure Ar gas at a target temperature of 700 ℃ for 5 min-1The heating rate of (3) is carbonized for 3 hours. And after naturally cooling to room temperature, respectively marking the obtained electrocatalytic material of the bamboo-shaped nitrogen-doped carbon nanofiber coated Co/Ni alloy nanoparticles as Co/Ni @ N-CNFs-700.
Example 11: spreading the prepared Co/Ni BTC @ PS or Co/Ni BTC @ PAN nano-fiber in a porcelain boat, fixing, transferring into a muffle furnace, and heating at 2 deg.C for min-1The temperature rising rate of (2) was increased from room temperature to 280 ℃ and maintained for 1 hour. Subsequently, the nanofibers were protected with ultra pure Ar gas at a target temperature of 800 ℃ for 5 ℃ min-1The heating rate of (3) is carbonized for 3 hours. And after naturally cooling to room temperature, marking the obtained electrocatalytic material of the bamboo-shaped nitrogen-doped carbon nanofiber coated Co/Ni alloy nanoparticles as Co/Ni @ N-CNFs-800 respectively.
Example 12: spreading the prepared Co/Ni BTC @ PS or Co/Ni BTC @ PAN nano-fiber in a porcelain boat, fixing, transferring into a muffle furnace, and heating at 2 deg.C for min-1The temperature rising rate of (2) was increased from room temperature to 280 ℃ and maintained for 1 hour. Subsequently, the nanofibers were protected with ultra pure Ar gas at a target temperature of 900 ℃ for 5 ℃ min-1The heating rate of (3) is carbonized for 3 hours. Naturally cooling to room temperature, and then carrying out electrocatalysis on the obtained bamboo-shaped nitrogen-doped carbon nanofiber coated Co/Ni alloy nanoparticlesThe materials are respectively marked as Co/Ni @ N-CNFs-900.
Claims (4)
1. A preparation method of a bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle electro-catalytic material is characterized by comprising the following steps: the polymer fiber and the spherical MOFs are combined through an electrostatic spinning technology, bamboo-shaped MOFs @ polymer nano-fiber is reasonably designed and synthesized, wherein the polymer fiber is used as an excellent template and is converted into carbon fiber with good conductivity in a high-temperature carbonization process, and a series of electrocatalytic materials of bamboo-shaped nitrogen-doped carbon nano-fiber coated transition metal alloy nano-particles are synthesized through high-temperature carbonization at different temperatures.
2. The method of claim 1, wherein: by simple electrostatic spinning technology, Co is mixedXNiYCombining BTC with Polystyrene (PS) or Polyacrylonitrile (PAN) to prepare bamboo-shaped MOFs @ PS or MOFs @ PAN nano-fibers, and synthesizing the bamboo-shaped nitrogen-doped carbon nano-fiber-coated Co/Ni alloy nano-particle electro-catalytic material through high-temperature carbonization.
3. The method of claim 1, wherein: by controlling different Co/Ni molar ratio (0.1-1 mol%), nano-scale precursor Co with uniform spherical morphology is preparedXNiYBTC, with different masses (0.5-2 g) of polystyrene or polyacrylonitrile, forming a more uniform bamboo-like Co coatingXNiY-BTC @ PS or CoXNiY-BTC @ PAN nanofibers.
4. The method of claim 1, further comprising: in the electrocatalytic material of bamboo-shaped nitrogen-doped carbon nanofiber coated Co/Ni alloy nanoparticles, the bimetallic alloy formed by the Co/Ni in the optimal proportion can be well protected under the coating of a uniform carbon-nitrogen structure, so that the corrosion of electrolyte is avoided, the agglomeration of the electrolyte in the reaction process is slowed down, and the electrocatalytic oxygen reduction and oxygen evolution activity of the electrocatalytic material are obviously enhanced under the synergistic action of the metal phase and the carbon fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911350565.1A CN111068734A (en) | 2019-12-24 | 2019-12-24 | Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911350565.1A CN111068734A (en) | 2019-12-24 | 2019-12-24 | Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111068734A true CN111068734A (en) | 2020-04-28 |
Family
ID=70317364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911350565.1A Pending CN111068734A (en) | 2019-12-24 | 2019-12-24 | Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111068734A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112071623A (en) * | 2020-09-17 | 2020-12-11 | 杭州肄康新材料有限公司 | Preparation method of soft magnetic material for high frequency |
| CN114400339A (en) * | 2021-12-06 | 2022-04-26 | 江苏大学 | Heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber |
| CN114502278A (en) * | 2021-08-26 | 2022-05-13 | 北京航空航天大学 | Metal atom supported carbon nanofiber catalyst and preparation method and application thereof |
| CN115976543A (en) * | 2023-02-02 | 2023-04-18 | 郑州大学 | Multicomponent nano-structure metal oxide electrocatalyst material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140093790A1 (en) * | 2012-09-28 | 2014-04-03 | Di-Jia Liu | Nanofibrous electrocatalysts |
| CN106835362A (en) * | 2017-01-16 | 2017-06-13 | 中国科学院长春应用化学研究所 | Micron ball carbon fibre composite of codope and preparation method thereof |
| CN108722460A (en) * | 2018-04-08 | 2018-11-02 | 湖北大学 | NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof |
| CN110201696A (en) * | 2019-05-06 | 2019-09-06 | 武汉理工大学 | A kind of porous carbon fiber supports the preparation method of high dispersive noble metal nano particles |
-
2019
- 2019-12-24 CN CN201911350565.1A patent/CN111068734A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140093790A1 (en) * | 2012-09-28 | 2014-04-03 | Di-Jia Liu | Nanofibrous electrocatalysts |
| CN106835362A (en) * | 2017-01-16 | 2017-06-13 | 中国科学院长春应用化学研究所 | Micron ball carbon fibre composite of codope and preparation method thereof |
| CN108722460A (en) * | 2018-04-08 | 2018-11-02 | 湖北大学 | NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof |
| CN110201696A (en) * | 2019-05-06 | 2019-09-06 | 武汉理工大学 | A kind of porous carbon fiber supports the preparation method of high dispersive noble metal nano particles |
Non-Patent Citations (2)
| Title |
|---|
| KANGJONG KIM ET AL.: "Carbon-wrapped Bimetallic Co/Ni Catalysts (C@CoxNi1−x) Derived from Co/Ni-MOF for Bifunctional Catalysts in Rechargeable Zn-Air Batteries", 《BULLETIN OF THE KOREAN CHEMICAL SOCIETY》 * |
| QING BAI ET AL.: "obalt@Nitrogen-Doped Porous Carbon Fiber Derived from the Electrospun Fiber of Bimetal-Organic Framework for Highly Active Oxygen Reduction", 《SMALL METHOD》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112071623A (en) * | 2020-09-17 | 2020-12-11 | 杭州肄康新材料有限公司 | Preparation method of soft magnetic material for high frequency |
| CN114502278A (en) * | 2021-08-26 | 2022-05-13 | 北京航空航天大学 | Metal atom supported carbon nanofiber catalyst and preparation method and application thereof |
| WO2023024031A1 (en) * | 2021-08-26 | 2023-03-02 | 北京航空航天大学 | Metal-atom-supported carbon nanofiber catalyst, and preparation method therefor and use thereof |
| CN114400339A (en) * | 2021-12-06 | 2022-04-26 | 江苏大学 | Heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber |
| CN114400339B (en) * | 2021-12-06 | 2023-09-12 | 江苏大学 | heteropolyacid@MOFs/polymer electrostatic spinning nanofiber |
| CN115976543A (en) * | 2023-02-02 | 2023-04-18 | 郑州大学 | Multicomponent nano-structure metal oxide electrocatalyst material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | The application of CeO 2-based materials in electrocatalysis | |
| CN111068734A (en) | Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis | |
| CN109248703B (en) | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof | |
| Cao et al. | Improved hydrogen generation via a urea-assisted method over 3D hierarchical NiMo-based composite microrod arrays | |
| CN110479329B (en) | Preparation and application of phosphorus-doped cobalt telluride nano material | |
| CN110124713B (en) | Nitrogen-doped carbon nanofiber loaded hollow structure Co3O4/CeO2Preparation method and application of nanoparticle material | |
| CN111659439B (en) | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof | |
| Yu et al. | Self-supported Co–Mo sulfide in electrospun carbon nanofibers as electrocatalysts for hydrogen evolution reaction in alkaline medium | |
| CN114497585A (en) | Preparation method of platinum-based synergistic catalyst with structure coupling effect | |
| CN111346640A (en) | Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| Dong et al. | MnO2 nanowires/CNTs composites as efficient non-precious metal catalyst for oxygen reduction reaction | |
| CN111229280A (en) | Preparation method and application of cobalt-nickel-nitrogen co-doped carbon nanotube catalyst | |
| CN113322473B (en) | Loaded Ni-CeO 2 Preparation method and application of heterojunction nitrogen-doped porous carbon nanofiber material | |
| CN112962109B (en) | Preparation method and application of antimony-doped copper/cuprous oxide electro-catalytic material | |
| CN108543541B (en) | Nickel-cobalt-phosphorus/amino carbon nanotube catalyst and preparation method and application thereof | |
| CN112599806B (en) | Preparation method and application of carbon nanofiber-based electrocatalyst | |
| CN113417032B (en) | Preparation method of nitrogen-doped mesoporous carbon fiber-based non-noble metal electrocatalyst | |
| CN116404179A (en) | Preparation method and application of zinc-loaded single-atom porous carbon nanotube | |
| CN110586104A (en) | Titanium dioxide, copper oxide and cobalt titanate composite nanofiber and preparation method thereof | |
| CN115305496A (en) | Preparation method and application of rare earth cerium-doped cobalt phosphide/iron phosphide heterogeneous material | |
| Li et al. | Advances in Understanding Carbon Composite Catalysts Based on Cathode for Microbial Fuel Cells | |
| CN114016162A (en) | Preparation method of bubble-shaped nanofiber embedded with cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution | |
| Liu et al. | Mo2C nanoparticles coated tubular carbon nanofibers as a highly efficient electrocatalyst for the hydrogen evolution reaction | |
| CN114824327A (en) | Iron-nitrogen double-doped carbon nanocomposite and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200428 |
|
| WD01 | Invention patent application deemed withdrawn after publication |