CN112439402B - Preparation method of carbon nanotube loaded with iron-based nanoparticle, carbon nanotube loaded with iron-based nanoparticle and application of carbon nanotube - Google Patents
Preparation method of carbon nanotube loaded with iron-based nanoparticle, carbon nanotube loaded with iron-based nanoparticle and application of carbon nanotube Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 283
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 98
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 98
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 89
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 239000004964 aerogel Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 14
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000007710 freezing Methods 0.000 description 17
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- 239000010411 electrocatalyst Substances 0.000 description 3
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 1
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- 230000010757 Reduction Activity Effects 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- 150000001247 metal acetylides Chemical class 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
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Classifications
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- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a carbon nano tube loaded with iron-based nano particles, the carbon nano tube loaded with the iron-based nano particles and application thereof, wherein the preparation method comprises the following steps: adding acetic acid aqueous solution of chitosan into aqueous solution of potassium ferricyanide, performing ultrasonic treatment to form sol, and performing freeze drying to obtain aerogel; placing aerogel in inert atmosphere, and heating to react to obtain porous carbon nano-sheets loaded with iron-based nano-particles; and (3) putting the porous carbon nano-sheets into air for heat treatment to obtain the carbon nano-tubes loaded with the iron-based nano-particles. The preparation method of the invention has low cost, is simple and universal, and the prepared material is a three-dimensional carbon pipe network structure formed by crosslinking carbon nano tubes, and Fe/Fe 3 C/Fe 2 O 3 The hollow nano particles are loaded on the carbon nano tubes, simple substance Fe is uniformly embedded in the carbon nano tubes, and the material can be used as an oxygen reduction electrocatalytic material and an air cathode catalytic material of a zinc-air battery, and has high activity and excellent stability.
Description
Technical Field
The present invention belongs to oxygen reduction catalysisThe technical field of agents, in particular to a method for loading iron-based nano particles (Fe, fe) 3 C、Fe 2 O 3 ) A preparation method of the carbon nano tube, the prepared carbon nano tube loaded with the iron-based nano particles and application thereof.
Background
With the consumption of global fossil energy and the increasing environmental pollution problem, the search for renewable green new energy storage and conversion modes has become an important and challenging research topic. Electrocatalytic oxygen reduction (ORR) is a core of fuel cells, metal cells, whose electrocatalytic process is directly related to the cell performance. The traditional noble metal catalyst greatly limits the large-scale commercialization process of new energy technology due to high price, rare reserves and slow catalytic dynamics. Therefore, research and development of non-noble metal catalysts with high catalytic activity and economical durability to replace noble metal catalysts is a key to solve the problems.
The excellent ORR activity is due to the addition of metal-containing active sites on the conductive carbon matrix. In general, interactions between the carbon support, transition metal and doped nitrogen in the composite material play a critical role in forming active sites that facilitate ORR. While transition metal Fe-based materials, alloys thereof and compound materials thereof have also been demonstrated to have good electrocatalytic oxygen reduction properties, such as carbides, oxides, nitrides, etc., have also been reported in great numbers for the development of nanocomposite materials, such as nanotubes, nanoplatelets and three-dimensional nanonetworks, which have considerable catalytic activity for the electrocatalytic reduction of oxygen. The one-dimensional nanotube structure is favorable for the transmission of electrons and substances, so that the reaction rate of oxygen reduction is improved, and the three-dimensional nano-network structure has the advantages of dispersing catalytic active sites, cross-linked pore channel structures and higher mechanical stability, so that the electrocatalytic performance is improved. Thus, combining these synergistic advantages, the synthesis of heteroatom doped iron loaded carbon oxide nanoparticle carbon nanomaterials is a sensible strategy. However, the synthesis process in the prior art is relatively complex, and the structural advantage cannot be better utilized to improve the performance of electrocatalytic oxygen reduction.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of the carbon nano tube loaded with the iron-based nano particles, which is simple and universal, low in cost and capable of preparing the loaded Fe/Fe 3 C/Fe 2 O 3 The carbon nanotubes of the hollow nanoparticles exhibit excellent activity and stability as oxygen-reducing electrocatalyst materials.
The invention also provides a product prepared by the preparation method of the carbon nanotube loaded with the iron-based nano particles, and the carbon nanotube loaded with the iron-based nano particles and application thereof.
The technical scheme is as follows: in order to achieve the above object, the preparation method of the carbon nanotube loaded with the iron-based nanoparticle of the present invention comprises the following steps:
(1) Adding acetic acid aqueous solution of chitosan into potassium ferricyanide aqueous solution, forming sol after ultrasonic treatment, and obtaining aerogel after freeze drying;
(2) Heating aerogel to 700-900 ℃ under the protection of inert atmosphere, and reacting after high-temperature calcination to obtain porous nano-sheets loaded with iron-based nano-particles;
(3) And heating the porous nano sheet loaded with the iron-based nano particles to 200-400 ℃ in air, and calcining at a high temperature to obtain the carbon nano tube material loaded with the iron-based nano particles.
Wherein the concentration of the potassium ferricyanide aqueous solution is 0.002-0.006 mol/L.
Wherein the concentration of the acetic acid aqueous solution of the chitosan is 10-30 mg/mL.
Wherein the inert atmosphere is at least one of nitrogen, argon, helium and carbon dioxide.
Wherein the heating rate of the heating in the steps (2) and (3) is 1 ℃/min-20 ℃/min, and the heat treatment time is 2-4 h.
The invention relates to a carbon nano tube loaded with iron-based nano particles, in particular to a Fe/Fe loaded carbon nano tube prepared by the preparation method 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Wherein the loadThe iron-based nanoparticle comprises Fe, fe 3 C. And Fe (Fe) 2 O 3 。
The invention relates to an application of a carbon nano tube loaded with iron-based nano particles in preparing an alkaline oxygen reduction catalyst.
The mixed catalyst of the carbon nano tube loaded with the iron-based nano particles comprises RuO 2 。
The mixed catalyst provided by the invention is applied to the preparation of zinc-air batteries as an air cathode.
The reaction principle of the invention is as follows: taking potassium ferricyanide as a metal source, taking chitosan as a carbon nitrogen source, forming hydrogel through ultrasound, freeze-drying to obtain aerogel, and calcining in a high-temperature inert atmosphere for the first step to obtain loaded Fe and Fe 3 C、Fe 2 O 3 The carbon nano-sheets of the three nano-particles are subjected to a second step of calcination in an air atmosphere, and a one-dimensional carbon nano-tube is obtained by catalyzing part of elemental iron, so that part of Fe nano-particles are coated in the carbon nano-tube, and the rest of Fe and Fe are 3 C、Fe 2 O 3 The three particles form hollow nano particles containing the three iron-based particles due to the Kelvin effect, and are loaded on the carbon nano tube. The material has regular morphology, and one-dimensional carbon nanotubes are produced by catalysis of elemental iron, which is beneficial to transfer of electrons and transport of substances, wherein Fe/Fe 3 C/Fe 2 O 3 The nano particles have a certain hollow structure, and the synergistic effect among three substances can improve the activity of catalyzing the oxygen reduction reaction. In addition, the carbon nano tube contains a certain amount of N element, and can form Fe-N active sites with Fe element to catalyze oxygen reduction reaction. The formed one-dimensional carbon nano tubes are mutually crosslinked to form a three-dimensional network structure and active substances Fe and Fe 3 C、Fe 2 O 3 The components and the structure have the advantages that the obtained material has higher oxygen reduction activity and excellent stability, can be used as an alkaline oxygen reduction reaction catalyst, and can be matched with RuO 2 The composite mixed catalyst is assembled into an air cathode of a metal-air battery together, and shows good cyclic charge-discharge performance.
The invention obtains the load three substances (Fe, fe) by simply mixing raw materials and then calcining at two steps of high temperature 3 C、Fe 2 O 3 ) The carbon nano tube of the hollow nano particle is formed into a special morphology, and the one-dimensional carbon nano tube is crosslinked to form a three-dimensional network structure, so that the carbon nano tube is beneficial to electron transmission and substance transfer, and also enhances mechanical stability, and the components and morphology of the carbon nano tube act cooperatively, so that the carbon nano tube has higher activity.
The invention provides a loaded iron-based nanoparticle (Fe, fe) 3 C、Fe 2 O 3 ) Has the following advantages:
1) Fe/Fe of smaller particle size formed by the iron precursor and chitosan in high temperature calcination 3 C/Fe 2 O 3 The hollow nano particles have excellent electrochemical activity and more catalytic active sites due to the synergistic effect among three substances;
2) The three-dimensional carbon pipe network structure formed by crosslinking the one-dimensional carbon nano tubes ensures that the catalyst material has larger specific surface area, and simultaneously, the pore channel structure formed by the gaps of the carbon tubes can effectively promote the contact between the electrolyte and the catalyst, thereby being beneficial to the occurrence of reaction;
3) The one-dimensional carbon nanotube structure can directionally promote the rapid transmission of electrons and ions, improve the catalytic reaction rate and promote the reaction of reactants and the rapid output of products.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1) The method is simple and convenient, and can realize large-scale production to prepare the one-dimensional carbon tube loaded iron-based metal particles;
2) Compared with the traditional method for preparing the oxygen reduction electrocatalyst material, such as an electrodeposition method, a solvothermal method and the like, the selected chitosan is cheap and easy to obtain, and the method has the advantages of simple and feasible process, low cost, simple operation and capability of realizing large-scale production;
3) The prepared product has regular shape, and has the characteristics of multiple active sites, good stability, one-dimensional composite structure and the like,compared with the conventional Fe-based alloy material, the prepared loaded Fe/Fe 3 C/Fe 2 O 3 The carbon nano tube of the hollow nano particle has more excellent structural characteristics and component advantages, is an oxygen reduction electrocatalyst material with great potential, and is expected to have wide application prospect in the future energy industry.
Drawings
FIG. 1 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Low-magnification SEM profile of carbon nanotubes of hollow nanoparticles;
FIG. 2 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 An enlarged SEM profile of carbon nanotubes of the hollow nanoparticles;
FIG. 3 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 TEM profile of carbon nanotubes of hollow nanoparticles;
FIG. 4 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 TEM profile of carbon nanotubes of hollow nanoparticles;
FIG. 5 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 HRTEM spectra of carbon nanotubes of hollow nanoparticles;
FIG. 6 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 HRTEM spectra of carbon nanotubes of hollow nanoparticles;
FIG. 7 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 XRD pattern of carbon nanotubes of the hollow nanoparticles;
FIG. 8 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Raman spectra of carbon nanotubes of hollow nanoparticles;
FIG. 9 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 LSV curve of carbon nanotubes of hollow nanoparticles;
FIG. 10 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Tafel curves of carbon nanotubes of hollow nanoparticles;
FIG. 11 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 I-t curve of carbon nanotubes of hollow nanoparticles;
FIG. 12 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Carbon nanotubes and RuO of hollow nanoparticles 2 Open circuit voltage curve of the cathode of the mixed catalyst catalytic zinc-air battery;
FIG. 13 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Carbon nanotubes and RuO of hollow nanoparticles 2 A discharge electrode polarization curve and a corresponding power density curve of a cathode of the mixed catalyst catalytic zinc-air battery;
FIG. 14 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Carbon nanotubes and RuO of hollow nanoparticles 2 Cathode of zinc-air battery catalyzed by mixed catalyst at 5mA cm -2 Constant current discharge curve under current density;
FIG. 15 is a supported Fe/Fe prepared according to example 1 of the present invention 3 C/Fe 2 O 3 Carbon nanotubes and RuO of hollow nanoparticles 2 Cathode of zinc-air battery catalyzed by mixed catalyst at 10mA cm -2 Long-term cyclic charge-discharge diagram under current density.
FIG. 16 is a supported Fe/Fe prepared according to comparative example 1 3 C/Fe 2 O 3 TEM images of carbon nanoplatelets of nanoparticles (non-hollow structures).
Detailed Description
The invention is further described below with reference to specific embodiments and figures.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, addingAdding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.% acetic acid volume fraction in water: 1%), performing ultrasonic treatment in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18 ℃ for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in an inert atmosphere, heating to 850 ℃, preserving heat for 3h at a heating rate of 2 ℃/min, heating to 300 ℃ in air, preserving heat for 3h at a heating rate of 2 ℃/min, and obtaining the loaded Fe/Fe 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 2
Will be 0.01mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 300 ℃ in air for 3h at 2 ℃/min, and obtaining Fe/Fe-loaded aerogel 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 3
Will be 0.03mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 300 ℃ in air for 3h at 2 ℃/min, and obtaining Fe/Fe-loaded aerogel 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 4
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolved in 5mL deionized water, followed by 1.0mL of 10mg/mL chitosan (mw=150000) acetic acid aqueous solution (1 vol.%) was added, sonicated in an ultrasonic cell disruptor for 4min,standing for 20min, freezing at-18deg.C for 12 hr, drying in a freeze dryer for 24 hr, placing the obtained aerogel in inert atmosphere, programmed heating to 850deg.C, maintaining for 3 hr at a heating rate of 2deg.C/min, programmed heating to 300deg.C in air for 3 hr at a heating rate of 2deg.C/min to obtain loaded Fe/Fe 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 5
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL 30mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 300 deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 6
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 25mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 300 deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 7
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 15mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, and programming to 850 deg.CKeeping the temperature for 3 hours at the temperature of 2 ℃/min, then keeping the temperature for 3 hours in the air after the temperature is programmed to 300 ℃, and obtaining the loaded Fe/Fe with the temperature rising rate of 2 ℃/min 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 8
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 800 deg.C, maintaining for 3h at a heating rate of 2 ℃/min, heating to 300 deg.C in air for 3h at a heating rate of still 2 ℃/min, and obtaining the loaded Fe/Fe 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 9
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 900deg.C, maintaining for 3h at a heating rate of 2 ℃/min, heating to 300 deg.C in air for 3h at a heating rate of still 2 ℃/min, and obtaining the loaded Fe/Fe 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 10
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 750deg.C, maintaining for 3h at 2 ℃/min, heating to 300deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 11
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 700deg.C, maintaining for 3h at a heating rate of 2 ℃/min, heating to 300deg.C in air for 3h at a heating rate of 2 ℃/min, and obtaining Fe/Fe-loaded aerogel 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 12
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 200deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 13
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 400 deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 14
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 250deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 15
Will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, heating to 850deg.C, maintaining for 3h at 2 ℃/min, heating to 350deg.C in air for 3h at 2 ℃/min, and loading Fe/Fe to obtain the final product 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 16
Will be 0.01mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL 10mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%, acetic acid volume fraction 1% in water), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, programming to 700deg.C, maintaining for 4h at a temperature rate of 1deg.C/min, and maintaining in air at a temperature of 200deg.C for 4h at a temperature rate of 1deg.C/min to obtain Fe/Fe-loaded aerogel 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Example 17
Will be 0.03mmol of K 3 [Fe(CN) 6 ]Dissolved in 5mL of deionized water, followed by 1.0mL of the solution30mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%, acetic acid volume fraction in water: 1%) is sonicated in an ultrasonic cell pulverizer for 4min, then left to stand for 20min, frozen at-18 ℃ for 12h, then dried in a freeze dryer for 24h, the obtained aerogel is placed in an inert atmosphere, the temperature is programmed to 900 ℃, the temperature is kept for 2h, the temperature is programmed to 20 ℃/min, the temperature is programmed to 400 ℃ in air, the temperature is kept for 2h, the temperature is still 20 ℃/min, and the loaded Fe/Fe is obtained 3 C/Fe 2 O 3 Carbon nanotubes of hollow nanoparticles.
Comparative example 1
Preparation of supported Fe/Fe in the same manner as in example 1 3 C/Fe 2 O 3 The porous carbon nanoplatelets of the carbon nanotubes of the hollow nanoparticles were different only in that the third step of calcination in air was not performed in this comparative example. The method comprises the following steps: will be 0.02mmol of K 3 [Fe(CN) 6 ]Dissolving in 5mL deionized water, adding 1.0mL of 20mg/mL chitosan (Mw=150000) acetic acid aqueous solution (1 vol.%), ultrasonic treating in an ultrasonic cell pulverizer for 4min, standing for 20min, freezing at-18deg.C for 12h, drying in a freeze dryer for 24h, placing the obtained aerogel in inert atmosphere, programming to 850 deg.C, maintaining for 3h at a heating rate of 2 ℃/min to obtain Fe/Fe-loaded aerogel 3 C/Fe 2 O 3 Porous carbon nanoplatelets of nanoparticles (non-hollow structures).
The supported Fe/Fe prepared in example 1 above was subjected to the processes of TEM, SEM, XRD, raman and TG and the like 3 C/Fe 2 O 3 The carbon nanotubes of the hollow nanoparticles are physically characterized. As can be seen from SEM (FIGS. 1 and 2) and TEM (FIGS. 3 and 4) maps, the catalyst prepared according to the method described in example 1 is a supported Fe/Fe catalyst 3 C/Fe 2 O 3 The carbon nanotubes of the hollow nano particles are mutually crosslinked and wound, and the one-dimensional carbon nanotubes with certain fold structures on the tube walls form a three-dimensional network structure, so that larger specific surface area and more active sites can be provided, and the transmission and diffusion of electrolyte are facilitated. Comparative example 1, however, did not undergo the second calcination in an oxygen atmosphere, and thus, as can be seen from a TEM image (FIG. 16), did not have carbon nanotubesAnd the formation of hollow nanoparticles. FIG. 5 shows lattice fringes of hollow nanoparticles, fe can be seen 3 C、Fe 2 O 3 Three species are present on the hollow nanoparticle. Fig. 6 is a lattice fringe of elemental Fe at one end of a carbon nanotube, demonstrating that the carbon nanotube is produced by catalysis of elemental Fe. FIG. 7 is a supported Fe/Fe 3 C/Fe 2 O 3 XRD patterns of carbon nanotubes of the hollow nano particles are compared with standard patterns, and diffraction peaks of the carbon nanotubes are compared with Fe 2 O 3 (PDF#39-1346)、Fe 3 The standard cards of C (PDF#65-2411) and Fe (PDF#06-0696) are completely identical, demonstrating the presence of all three species in the carbon nanotubes. FIG. 8 is a prepared supported Fe/Fe 3 C/Fe 2 O 3 The Raman spectrum of the carbon nanotube of the hollow nanoparticle shows that the graphitization degree is higher, so that the carbon nanotube has good conductivity and is beneficial to improving the activity of catalyzing oxygen reduction reaction.
FIG. 9 is a supported Fe/Fe 3 C/Fe 2 O 3 The LSV curve obtained by the oxygen reduction performance test of the carbon nano tube of the hollow nano particle in the oxygen saturated 0.1M KOH solution has an initial potential of about 0.985V and a half-wave potential of about 0.890V, which shows that the LSV curve has excellent oxygen reduction catalytic activity. FIG. 10 is a supported Fe/Fe 3 C/Fe 2 O 3 The Tafel curve of the hollow nano-particle carbon nano-tube is made according to the LSV curve, which shows that the hollow nano-particle carbon nano-tube has good catalytic dynamics. FIG. 11I-t curve from a chronoamperometric test at 0.5V shows the loading of Fe/Fe 3 C/Fe 2 O 3 The carbon nanotubes of the hollow nanoparticles have excellent stability.
Will be loaded with Fe/Fe 3 C/Fe 2 O 3 Hollow nanoparticle carbon nanotubes and RuO 2 (1:1 ratio by mass) as an air cathode catalyst for a zinc air cell, the open circuit voltage curve of fig. 12 shows that it has a stable and high open circuit voltage (1.434V), and the maximum power density of the mixed catalyst is 126.7mW cm calculated from the discharge electrode curve of fig. 13 and the corresponding power density curve -2 At 5mA cm -2 In constant current discharge test of (2), voltage levelThe battery specific capacity calculated from this was 733mAh g at 1.23V Zn -1 And an energy density of 885Wh kg Zn -1 (FIG. 14).
Loaded with Fe/Fe 3 C/Fe 2 O 3 Hollow nanoparticle carbon nanotubes and RuO 2 (the mass ratio of the two is 1:1) and the charge and discharge current density of the battery catalyzed by the mixed catalyst is 10mA cm -2 Long-range cycle performance testing was performed down, running steadily for 210 cycles (4200 minutes) (twenty minutes per cycle). Showing an outstanding long cycle life (fig. 15). These excellent properties are mainly attributed to Fe/Fe loading 3 C/Fe 2 O 3 The carbon nanotubes of the hollow nanoparticles have stable structure and composition. The material has wide application prospect as an oxygen reduction catalyst and an air cathode catalyst of a zinc-air battery.
Claims (10)
1. The preparation method of the carbon nanotube loaded with the iron-based nanoparticle is characterized by comprising the following steps of:
(1) Adding acetic acid aqueous solution of chitosan into potassium ferricyanide aqueous solution, forming sol after ultrasonic treatment, and obtaining aerogel after freeze drying;
(2) Heating aerogel to 700-900 ℃ under the protection of inert atmosphere, and calcining at high temperature to obtain porous nanosheets loaded with iron-based nanoparticles;
(3) And heating the porous nano sheet loaded with the iron-based nano particles to 200-400 ℃ in air, and calcining to obtain the carbon nano tube material loaded with the iron-based nano particles.
2. The method for preparing the iron-based nanoparticle-supported carbon nanotube according to claim 1, wherein the concentration of the aqueous solution of potassium ferricyanide is 0.002-0.006 mol/L.
3. The method for preparing the iron-based nanoparticle-supported carbon nanotube according to claim 1, wherein the concentration of the aqueous acetic acid solution of chitosan is 10-30 mg/mL.
4. The method for preparing iron-based nanoparticle-supported carbon nanotubes according to claim 1, wherein the inert atmosphere is at least one of nitrogen, argon, helium, and carbon dioxide.
5. The method for preparing the carbon nanotube loaded with the iron-based nanoparticle according to claim 1, wherein the heating rate of the heating in the steps (2) and (3) is 1 ℃/min to 20 ℃/min, and the heat treatment time is 2 to 4 hours.
6. An iron-based nanoparticle-loaded carbon nanotube produced by the production method of any one of claims 1 to 5.
7. The iron-based nanoparticle-supported carbon nanotube of claim 6, wherein the iron-based nanoparticle comprises Fe, fe 3 C. And Fe (Fe) 2 O 3 。
8. Use of the iron-based nanoparticle-supported carbon nanotube according to claim 6 or 7 for preparing an alkaline oxygen reduction catalyst.
9. A mixed catalyst comprising the iron-based nanoparticle-supported carbon nanotube according to claim 6 or 7, wherein the mixed catalyst further comprises RuO 2 。
10. Use of the mixed catalyst of claim 9 as an air cathode in the preparation of zinc air cells.
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