CN112563519A - Intermetallic compound-carbon nanotube composite material and preparation method and application thereof - Google Patents
Intermetallic compound-carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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- 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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention discloses an intermetallic compound-carbon nanotube composite material and a preparation method and application thereof. The preparation method comprises the following steps: (1) providing a carbon nanotube network macroscopic body; (2) activating the carbon nano tube network macroscopic body to obtain a nitrogen-doped carbon nano tube network macroscopic body; (3) dipping the nitrogen-doped carbon nanotube network macroscopic body in a metal precursor solution, and then drying to obtain a metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body; (4) and carrying out transient high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body to obtain the intermetallic compound-carbon nanotube composite material. The intermetallic compound-carbon nanotube composite material is prepared by the transient high temperature technology, wherein the grain size of the intermetallic compound is less than 3nm, and the intermetallic compound has excellent oxygen reduction and oxygen precipitation catalytic performance, and has good application prospect in the field of oxygen catalysis or metal air batteries.
Description
Technical Field
The invention belongs to the technical field of energy and cleaning, and relates to an intermetallic compound-carbon nanotube composite material, a preparation method thereof and application of the composite material in preparation of a metal-air battery (oxygen catalytic electrode).
Background
Currently, the most promising zero-pollution battery for electric vehicles is a metal-air battery with outstanding advantages of high efficiency, cleanliness, high energy density, etc. The core component of a metal-air battery is a bifunctional catalyst that drives an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER). However, the currently reported catalysts have the problems of slow kinetics, poor cycle stability and the like. In recent years, breakthrough of the bifunctional catalyst technology of the reversible metal-air battery has focused on noble metals and non-noble metals, and the non-noble metals are most prominently shown to be transition metal-based and non-metal carbon-based. The ORR catalytic performance of the transition metal-based catalyst is poor, and the battery performance is ensured by loading a large amount of catalysts, so that the concept of light weight of the metal-air battery is greatly violated, and the transition metal-based catalyst is easy to fall off in the battery operation process to influence the battery stability. Non-metallic carbon based Catalysts are limited by their intrinsic activity, have lower ORR and OER catalytic properties, and do not meet the practical application of Metal-Air Batteries (Cheng F, Chen J. ChemInform Abstract: Metal-Air Batteries: From Oxygen Reduction to catalyst Catalysts [ J ]. Chemical Society Reviews,2012,41(6):2172-2192.Tiwari A, Kim D, Kim Y, et al. Bifuntional Oxen electrochemical catalysis From Chemical Bonding of Transition Metal charogenides Conductive Carbons [ J ]. Advanced Energy Materials,2017: 1607: 1602225.). At present, the catalytic mechanism of the two non-noble metal catalysts is fuzzy, and a great distance is provided for researching and developing the bifunctional catalyst with excellent performance. Platinum-based catalysts have very Excellent ORR catalytic properties and are currently the most systematically and widely used catalysts, such as (Zhuo S, Sohlberg K. platinum Dioxide Phases: Relative Thermokinetic Stablility and Kinetics of Inter-conversion from First-Principles [ J ] Physica B,2006,381(1-2):12-19.He D S, He D, Wang J, et al. ultra Ichain synthesis Pt-enhanced Nanocage with ex Reduction Activity [ J ] Journal of the American Chemical Society,2016,138(5): 1497.).
A great deal of research proves that after the transition metal is doped into the crystal lattice of the platinum, the content of the platinum in the alloy can be effectively reduced and the catalytic performance of the alloy can be improved by adjusting the electronic structure and the geometric structure of the platinum. For example, Shi-Gang Sun et al prepared a PtCo alloy catalyst with a catalytic activity 8.6 times that of Pt/C by a one-pot method and greatly increased the stability of the catalyst by adding a trace amount of Au. (Wang Y, Slater J, Gerard M, Alan M, Roseman, C, Neil P, Angus I, Candae I, Sarah J. imaging Three-Dimensional electric induction in Pt-Ninanoparticies Using spectral Single Particle reaction [ J ]. Nano Letter,2019,19(2):732-738.Wang Y, Dual J, ZHao Y, Yang X, Tang Q. Ternary hybrid M @ excitation [ M ═ Ni, FeNi) counter electrodes for electronic-sensory cells [ J ]. electrochemical micron, Ptch. Acta,2018,291:114-123.Lu B, Sheng T, Ti, Zrard M, Zhang N, X, Mg, X, Mg, Z, Mg, Z, Cu, Mg, and the catalyst also has unique ordered effect and uniform active sites, and is beneficial to designing and preparing high-performance electrochemical catalysts. For example, Sun et al, the disordered fcc-PtFe/C alloy is treated at high temperature to promote the atoms to move, so as to prepare long-range ordered PtFe/C-IMCs, and the ORR performance of the long-range ordered PtFe/C-IMCs is obviously superior to that of the corresponding disordered alloy. (Kim J, Lee Y, Sun S, structured FePt nanoparticles and the element enhanced catalysis for the oxygen reduction reaction [ J ], Journal of the American Chemical Society,2010,132(14):4996-
It is generally believed that: the catalytic reaction takes place on the surface of the catalyst, and reducing the size of the multi-platinum-based intermetallic compound particles can increase the specific surface area thereof, thereby improving the activity. Small-sized nanoparticles have exceptionally active chemical activities, good catalytic properties and reaction selectivity compared to corresponding bulk materials, such as (Liu J, Shi W, Ni B, Yang Y, Li S, Zhuang J, Wang X.Adoration of regulators with inorganic materials through the Nature Chemistry,2019,11(9):839-845.Takamasa T, Tetsuya K, Aiko N, Takane I, Kimihisa Y.At-hybridization for synthesis of metals [ J ] Nature Communications,2018,9(1): 3873) nano-platinum-based intermetallic compounds have multiple structural features that further enhance the catalytic performance. However, the preparation of the multi-nano platinum-based intermetallic compound requires high temperature treatment to overcome the energy barrier for the transition of disordered structure to ordered structure, and drives the atom movement to obtain long-range order, which inevitably results in severe particle agglomeration, oswald ripening, etc., resulting in particle enlargement and wide particle size distribution. At present, the preparation method of the multi-element nano platinum-based intermetallic compound can be classified into two main types: solid phase methods and liquid phase methods. The solid phase method generally refers to various methods for synthesizing an ordered phase by a non-liquid phase method, for example, a method for reducing a metal under a non-liquid phase condition such as metal powder melting, an immersion method, chemical vapor deposition, and the like. The liquid phase method refers to a method of synthesizing an alloy or an intermetallic compound by a liquid phase, such as a liquid phase reduction deposition method, an oleic acid oleylamine method, a polyol method, and the like. Compared with the liquid phase method, the solid phase method is simple and can directly obtain an ordered structure, but the obtained particle size is generally larger. For example, PtBi/PtPd-IMCs bulk materials are respectively prepared by a metal powder melting method by Hector D.Abruna et al, and the advantages of platinum cannot be fully exerted due to the large size and low utilization rate of the IMCs, so that the PtBi/PtPd-IMCs bulk materials are not beneficial to large-scale application (Volpe D J, Casado-river E, Alden L, Lind C, Hagerdon K, Downie C, Korzeniewski C, Surface Treatment Effects on the electrochemical Activity and modification of interfacial pharmaceuticals [ J ] J.Electrochem.Soc.,2004,151(7): A971-A977.). The liquid phase method for preparing the platinum-based intermetallic compound has the advantage that the reduction of a liquid phase reducing agent is low, so that the ordered structure can be obtained only by high-temperature post-treatment, which easily causes serious particle agglomeration. PtNi alloys are prepared by liquid phase reduction deposition method such as Francis J.Disalvo, etc., PtNi-IMCs are formed by high temperature, however, after high temperature treatment, PtNi undergoes obvious particle agglomeration, and part of the particle size increases from the original 2-3nm to 15-20nm (Leonard B, Zhou Q, Wu D, Disalvo F, medicine Synthesis of PtNi Intermetallic Nanoparticles: influx of Reducing Agent and catalysts on electrochemical Activity [ J ], chem.Mater.,2011,23(5): 1136-1146.). This group then employs methods such as capping agents, KCl matrix confinement, etc. to mitigate particle growth during high temperature post-treatment, but inevitably increases the difficulty of their preparation. For example, Taehwan Hyeon et al converts PtFe into an ordered structure under high temperature conditions by dopamine coating, and the average size of the dopamine coated samples is 6.5nm, which is significantly smaller than that of samples without dopamine coating (Chung D, Jun S, Yoon G, Kwon S, Shin D, Seo P, Yoo J, Shin H, Chung Y, Kim H, Mun B, Lee K, Lee N, Yoo S, Lim D, Kang K, Sung Y, Hyeon T, high reusable and Active PtFe Nanocatalyst for Electrochemical Oxygen Reduction Reaction [ J ], Jam m Soc,2015,137(49): 15478-). It should be noted that the use of carbon/oxide as the coating and the confinement of the ordered channels in the support can alleviate the particle agglomeration to some extent, but the coating may affect the exposure of active sites on the particle surface, thereby affecting the catalytic activity, and the removal of the coating increases the difficulty and cost of preparation.
Existing platinum-based catalysts lack Oxygen Evolution (OER) catalytic performance. The currently developed intermetallic compound preparation process is complex and time-consuming, and in addition, high-temperature treatment is required to overcome the energy barrier of the disordered structure to the ordered structure for preparing the intermetallic compound, and the atoms are driven to move to obtain long-range order, which inevitably causes serious particle agglomeration, Oswald ripening and the like, leads to particle enlargement and wide particle size distribution, and cannot ensure the preparation of the nano intermetallic compound with uniform particles. Therefore, how to provide a simple and rapid preparation method for preparing a multi-element nano intermetallic compound with excellent ORR and OER bifunctional catalytic performance and uniform particle size is an urgent problem to be solved.
Disclosure of Invention
The main objective of the present invention is to provide an intermetallic compound/carbon nanotube composite material, and a preparation method and an application thereof, so as to overcome the disadvantages of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an intermetallic compound-carbon nanotube composite material, which comprises the following steps:
(1) providing a carbon nanotube network macroscopic body;
(2) activating the carbon nano tube network macroscopic body to obtain a nitrogen-doped carbon nano tube network macroscopic body;
(3) dipping the nitrogen-doped carbon nanotube network macroscopic body in a metal precursor solution, and then drying to obtain the nitrogen-doped carbon nanotube network macroscopic body loaded with a metal precursor, wherein the metal in the metal precursor solution comprises three and/or more transition metals, and the transition metals comprise any one or the combination of two or more of Pt, Pd, Cr, Mn, Fe, Co, Ni, Cu and Zn;
(4) and carrying out transient high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body to obtain the intermetallic compound-carbon nanotube composite material.
The embodiment of the invention also provides the intermetallic compound-carbon nanotube composite material prepared by the method, wherein intermetallic compounds in the composite material are uniformly dispersed in the nitrogen-doped carbon nanotube network macroscopic body, the types of metal elements in the intermetallic compounds are more than or equal to 3, the particle size of the intermetallic compounds in the composite material is less than 3nm, and atoms in the intermetallic compounds are in ordered arrangement.
The embodiment of the invention also provides application of the intermetallic compound-carbon nanotube composite material in the field of oxygen catalysis or metal-air batteries.
For example, embodiments of the present invention also provide an oxygen-functional electrocatalyst, which includes the intermetallic compound-carbon nanotube composite material described above.
Embodiments of the present invention also provide an oxygen-functional electrocatalytic electrode (oxygen electrode) comprising the foregoing intermetallic compound-carbon nanotube composite material or the foregoing oxygen-functional electrocatalyst.
The embodiment of the invention also provides a metal-air battery, which at least comprises the oxygen electrode.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method provided by the invention has the advantages of low cost, simplicity, practicability and short time consumption, and the preparation process of the transient high-temperature alloying only needs less than one second;
(2) the intermetallic compound size in the multi-element intermetallic compound-carbon nanotube composite material (namely the intermetallic compound-carbon nanotube composite material) prepared by the invention is less than 3nm, and the particle size distribution is uniform;
(3) according to the scheme, the nitrogen-doped carbon nanotube is utilized to anchor the multi-element metal, the small-size nano intermetallic compound is obtained by the transient electric heating technology and is dispersed in the functionalized carbon nanotube network, the bonding acting force between the carbon nanotube and the metal alloy nanoparticles is strong, and the catalytic performance and the stability of the carbon nanotube network are excellent;
(4) the intermetallic compound prepared by the invention has excellent oxygen reduction (ORR) and Oxygen Evolution (OER) catalytic performances, has the effect of filling up the blank of the platinum-based catalyst in the OER field, can effectively promote the oxygen dual-function research of the platinum-based catalyst, and further promotes the research and application of the metal-air battery.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart illustrating the preparation of an exemplary embodiment of the present invention;
FIG. 2 is a schematic view of a transient electric heating apparatus according to an exemplary embodiment of the present invention;
FIG. 3 is a STEM chart of PdFeNi-NCNTs prepared in example 4 of the present invention;
FIGS. 4a-4b are schematic diagrams of a spherical aberration electron microscope and a crystal plane of PtFeNi prepared in inventive example 2, respectively
FIG. 5 is a graph of ORR and OER performance of PtFeNi-NCNTs prepared in example 2 of the present invention.
FIG. 6 is an electron micrograph of a PtFeNi alloy obtained by a conventional tube furnace annealing method according to comparative example 1.
Detailed Description
In view of the defects of the prior art, the present inventors have conducted extensive studies and extensive practices to provide a technical solution of the present invention, which is to simply and rapidly prepare an intermetallic compound-carbon nanotube composite material mainly using a transient high temperature technique, wherein the intermetallic compound has a uniform particle size and excellent oxygen reduction (ORR) and Oxygen Evolution (OER) catalytic properties.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical solution, its implementation and principles, etc. will be further explained as follows.
It is to be noted that the definitions of the terms mentioned in the description of the present invention are known to those skilled in the art. For example, some of the terms are defined as follows:
1. oxygen functional electrocatalytic electrode: an electrode for generating oxygen catalytic reaction comprises a catalyst, a carbon carrier and a porous electrode.
One aspect of an embodiment of the present invention provides a method for preparing an intermetallic compound-carbon nanotube composite material, including:
(1) providing a carbon nanotube network macroscopic body;
(2) activating the carbon nano tube network macroscopic body to obtain a nitrogen-doped carbon nano tube network macroscopic body;
(3) dipping the nitrogen-doped carbon nanotube network macroscopic body in a metal precursor solution, and then drying to obtain the nitrogen-doped carbon nanotube network macroscopic body loaded with a metal precursor, wherein the metal in the metal precursor solution comprises three and/or more transition metals, and the transition metals comprise any one or the combination of two or more of Pt, Pd, Cr, Mn, Fe, Co, Ni, Cu and Zn;
(4) and carrying out transient high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body to obtain the intermetallic compound-carbon nanotube composite material.
In the present invention, the preparation process of the intermetallic compound-carbon nanotube composite material is shown in fig. 1.
In some more specific embodiments, the preparation method comprises: the carbon nano tube network macroscopic body is prepared by adopting any one of a chemical vapor deposition method or a floating catalytic chemical vapor deposition method of an Fe-based catalyst.
Further, the carbon nanotube network macroscopic body includes any one or a combination of two or more of a carbon nanotube film, a carbon nanotube fiber, a carbon nanotube aerogel and a carbon nanotube foam, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: and performing activated nitrogen doping treatment on the carbon nano tube network macroscopic body by at least adopting a hydrothermal method or a calcination method to obtain the nitrogen-doped carbon nano tube network macroscopic body.
Further, the calcination method comprises: and calcining the carbon nano tube network macroscopic body at the temperature of 400-500 ℃ for 1-2h in the nitrogen source atmosphere to obtain the nitrogen-doped carbon nano tube network macroscopic body.
In some more specific embodiments, the hydrothermal process comprises: carrying out hydrothermal reaction on the carbon nano tube network macroscopic body in an ammonia water solution containing 40% of volume concentration at 120-180 ℃ for 12-24h to obtain a nitrogen-doped carbon nano tube network macroscopic body;
further, the nitrogen source atmosphere comprises ammonia gas and inert gas.
Further, the volume ratio of the ammonia gas to the inert gas is 1: 1-6.
Further, the inert gas includes argon, and is not limited thereto.
In some more specific embodiments, the preparation method further comprises: before the activation treatment, the carbon nano tube network macroscopic body is subjected to vacuum iron removal treatment at 1800-2400 ℃.
In some more specific embodiments, the preparation method further comprises: before the activation treatment, the obtained carbon nano tube network macroscopic body is subjected to CV circulation in a sulfuric acid solution of 0.5-1mol/L for 40-60 circles to remove iron simple substance impurities.
In some more specific embodiments, the metal precursor solution in step (3) includes any one or a combination of two or more of a chloroplatinic acid solution, a chloroauric acid solution, a chloroiridic acid solution, and a salt solution of a transition metal, but is not limited thereto.
Further, the concentration of the metal precursor solution is 10-30 mmol/L.
Further, the metal in the metal precursor solution includes Pt and/or Pd and two or more transition metals including any one or a combination of two or more of Cr, Mn, Fe, Co, Ni, Cu, and Zn, but is not limited thereto.
Further, the mass loading amount of the metal precursor in the metal precursor loaded nitrogen-doped carbon nanotube network macroscopic body is 3-10 wt%.
In some more specific embodiments, the nitrogen-doped carbon nanotube network macroscopic body is immersed in the metal precursor solution for 1 to 2 hours.
In some more specific embodiments, the drying treatment mode includes any one of atmospheric drying, freeze drying and supercritical drying.
Further, the temperature of the drying treatment is 20-50 ℃.
In some more specific embodiments, step (4) specifically includes: and under a protective atmosphere, carrying out transient electric heating high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body at 750-950 ℃ for 100-500ms to obtain the intermetallic compound-carbon nanotube composite material.
Further, the current density of the transient electric heating is 0.1-2.5A/cm2。
Further, the current of the transient electric heating is a direct current constant current.
Furthermore, the current is 0.1-2.5A.
Further, the potential of the transient electric heating is a direct current constant potential.
Furthermore, the potential is 1-60V.
Further, the protective atmosphere includes a nitrogen atmosphere or an inert gas atmosphere.
In some more specific embodiments, the method for preparing the platinum-based intermetallic compound-carbon nanotube composite material includes:
(1) preparing a carbon nano tube network macroscopic body by a floating catalytic chemical vapor deposition method, removing iron simple substance impurities from the obtained carbon nano tube network macroscopic body in a 1800 ℃ vacuum graphite furnace, and calcining the obtained carbon nano tube network macroscopic body in a tube furnace containing 40% of ammonia gas and 60% of argon gas at 500 ℃ for 2 hours to obtain a nitrogen-doped carbon nano tube network macroscopic body;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into platinum salt and transition metal (Cr, Mn, Fe, Co, Ni, Cu, Zn and the like) salt precursor solutions with different concentrations for a plurality of hours, and freeze-drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor, (comprehensively considering the catalytic performance and the economic benefit, controlling the metal loading amount of a sample to be regulated to be between 3 and 10 percent, and drying the soaked nitrogen-doped carbon nanotube network macroscopic body at room temperature);
(3) FIG. 2 is a schematic view of a transient electric heating device used in the present invention, wherein the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor after drying treatment is connected with a copper foil, and placed in a quartz tube saturated with argon, and constant current (current density: 0.1-2.5A/cm) is applied to both ends2) And performing transient annealing on the sample at the temperature of 750-950 ℃, and electrifying for 100-500ms to obtain the platinum-based intermetallic compound-carbon nanotube composite material. The formation of the platinum-based multi-element intermetallic compound is promoted by the process of instantaneous temperature rise-drop caused by the joule heat effect.
The invention prepares and obtains the multi-element nanometer intermetallic compound-carbon nanotube composite material based on the transient high temperature preparation technology, and achieves the intermetallic compound with particles less than 3nm and uniform particle size based on the anchoring effect of the transient high temperature annealing and nitrogen-doped carbon nanotube macroscopic body on the metal particles; the intermetallic compound is distinguished from a metal (platinum-based) alloy, which has only excellent oxygen reduction performance, whereas the intermetallic compound of the present invention has excellent oxygen reduction and oxygen precipitation dual-functional catalytic performance.
Another aspect of the embodiments of the present invention also provides an intermetallic compound-carbon nanotube composite material prepared by the foregoing method, in which the intermetallic compound is uniformly dispersed in the macroscopic body of the nitrogen-doped carbon nanotube network, the kind of the metal element in the intermetallic compound is greater than or equal to 3, the particle size of the intermetallic compound in the composite material is less than 3nm, and the atoms in the intermetallic compound are in an ordered arrangement.
Further, the composite material has oxygen reduction and oxygen evolution catalytic properties.
Another aspect of the embodiments of the present invention also provides an application of the intermetallic compound-carbon nanotube composite material in the field of oxygen catalysis or metal air batteries.
For example, one aspect of an embodiment of the present invention provides an oxygen-functional electrocatalyst comprising the intermetallic compound-carbon nanotube composite material described above.
Further, the oxygen functional electrocatalyst comprises an oxygen reduction electrocatalyst or an oxygen reduction and oxygen evolution bi-functional electrocatalyst.
Another aspect of an embodiment of the present invention also provides an oxygen-functional electrocatalytic electrode (oxygen electrode) comprising the foregoing intermetallic compound-carbon nanotube composite material or the foregoing oxygen-functional electrocatalyst.
Another aspect of an embodiment of the present invention also provides a metal-air battery including the oxygen electrode described above.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) The carbon nano tube network prepared by the floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to iron simple substance impurity removal in a vacuum graphite furnace at 2000 ℃, and is calcined for 1.5 hours at 450 ℃ in a tubular furnace containing 40% of ammonia gas and 60% of argon gas, so that the nitrogen-doped carbon nano tube network macroscopic body is obtained;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into a platinum salt (with the concentration of 15mmol/L) and transition metal (Cr, Mn) salt precursor solution for 1.5h (with the concentrations of Cr and Mn of 15mmol/L and 15mmol/L respectively), and then drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor;
(3) FIG. 2 is a schematic view of a transient electric heating device used in the present invention, wherein a dried metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is connected with a copper foil, placed in an argon-saturated quartz tube, applied with a constant potential (potential: 30V) at both ends, subjected to transient annealing treatment at 800 ℃, and electrified for 300ms to obtain a platinum-based intermetallic compound-carbon nanotube composite material (PtCrMn-NCNTs).
Example 2
(1) The carbon nano tube network prepared by adopting a floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to iron simple substance impurity removal in a 1800 ℃ vacuum graphite furnace, and is calcined for 2 hours at 400 ℃ in a tubular furnace containing 50% of ammonia gas and 50% of argon gas, so that the nitrogen-doped carbon nano tube network macroscopic body is obtained;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into a platinum salt (with the concentration of 10mmol/L) and transition metal (Fe, Ni) salt precursor solution for 2h (with the concentrations of 10mmol/L and 10mmol/L respectively), and then drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor;
(3) FIG. 2 is a schematic view of a transient electric heating device used in the present invention, wherein a dried metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is connected with a copper foil, the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is placed in a quartz tube saturated with argon, a constant voltage (voltage: 20V) is applied to both ends of the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body, the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is subjected to transient annealing treatment at 750 ℃ and is electrified for 500ms, so as to obtain a platinum-based intermetallic compound-carbon nanotube composite material (PtFeNi-NCNTs), a spherical aberration electron microscope diagram and a crystal plane diagram of the platinum-based intermetallic compound-.
Example 3
(1) The carbon nano tube network prepared by the floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to CV circulation in a 0.5mol/L sulfuric acid solution for 40-60 circles to remove the iron simple substance impurities, and the nitrogen-doped carbon nano tube network macroscopic body is obtained by hydrothermal reaction at 120 ℃ for 24 hours in an ammonia water solution and contains 50% volume concentration;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into a palladium salt (with the concentration of 30mmol/L) and transition metal (Fe, Ni) salt precursor solution for 1h (with the concentrations of Fe and Ni being respectively (30mmol/L and 30mmol/L), and then drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor;
(3) FIG. 2 is a schematic view of a transient electric heating apparatus used in the present invention, wherein the nitrogen-doped carbon nanotube network macro body loaded with a metal precursor after drying treatment is connected with a copper foil, placed in a quartz tube saturated with argon, applied with a constant potential (potential: 60V) at both ends, subjected to transient annealing treatment at 950 ℃, and energized for 50ms to obtain palladium-based intermetallic compound-carbon nanotube composite materials (PdFeNi-NCNTs).
Example 4
(1) The carbon nano tube network prepared by the floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to CV circulation in 1mol/L sulfuric acid solution for 40-60 circles to remove the iron simple substance impurities, and the carbon nano tube network macroscopic body containing 40% volume concentration is subjected to hydrothermal reaction in ammonia water solution at 180 ℃ for 12 hours to obtain the nitrogen-doped carbon nano tube network macroscopic body;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into a palladium salt (with the concentration of 10mmol/L) and transition metal (Fe, Ni) salt precursor solution for 2h (with the concentrations of 15mmol/L and 15mmol/L respectively), and then drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor;
(3) FIG. 2 is a schematic view of a transient electric heating apparatus used in the present invention, wherein a dried metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is connected to a copper foil, placed in an argon-saturated quartz tube, subjected to transient annealing treatment at 800 ℃ for 200ms by applying a constant voltage (voltage: 40V) to both ends, and energized to obtain a palladium-based intermetallic compound-carbon nanotube composite (PdFeNi-NCNTs), and a STEM thereof is shown in FIG. 3.
Example 5
(1) The carbon nano tube network prepared by adopting a floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to iron simple substance impurity removal in a vacuum graphite furnace at 2400 ℃, and is calcined for 1h at 500 ℃ in a tubular furnace containing 50% of ammonia gas and 50% of argon gas, so that the nitrogen-doped carbon nano tube network macroscopic body is obtained;
(2) soaking the nitrogen-doped carbon nanotube network macroscopic body into a platinum salt (with the concentration of 30mmol/L) and transition metal (Co, Zn) salt precursor solution for 2h (with the concentrations of Co and Zn of 20mmol/L and 20mmol/L respectively), and then drying the nitrogen-doped carbon nanotube network macroscopic body loaded with the metal precursor;
(3) FIG. 2 is a schematic view of a transient electric heating apparatus used in the present invention, wherein the nitrogen-doped carbon nanotube network macroscopic body loaded with a metal precursor after drying treatment is connected with a copper foil, and is placed in a quartz tube saturated with argon, a constant voltage (voltage: 35V) is applied to both ends of the quartz tube, and the quartz tube is subjected to transient annealing treatment at 850 ℃ and energized for 200ms to obtain a platinum-based intermetallic compound-carbon nanotube composite material (PtCoZn-NCNTs).
Comparative example 1
(1) The carbon nano tube network prepared by the floating catalytic chemical vapor deposition method contains trace iron simple substance impurities, the obtained carbon nano tube network macroscopic body is subjected to CV circulation in 1mol/L sulfuric acid solution for 40-60 circles to remove the iron simple substance impurities, and the carbon nano tube network macroscopic body contains 40% volume concentration and is subjected to 120 ℃ hydrothermal reaction in ammonia water solution for 12 hours to obtain the nitrogen-doped carbon nano tube network macroscopic body;
(3) and (3) placing the dried metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body in a quartz tube saturated by argon, heating to 800 ℃, and preserving heat for 1s to obtain the palladium-based alloy-carbon nanotube composite material, wherein the alloying effect is poor, and the intermetallic compound cannot be obtained.
FIG. 6 is an electron microscope image of the PtFeNi alloy obtained by the conventional tube furnace annealing method in comparative example 1.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (17)
1. A method for preparing an intermetallic compound-carbon nanotube composite material is characterized by comprising the following steps:
(1) providing a carbon nanotube network macroscopic body;
(2) activating the carbon nano tube network macroscopic body to obtain a nitrogen-doped carbon nano tube network macroscopic body;
(3) dipping the nitrogen-doped carbon nanotube network macroscopic body in a metal precursor solution, and then drying to obtain the nitrogen-doped carbon nanotube network macroscopic body loaded with a metal precursor, wherein the metal in the metal precursor solution comprises three and/or more transition metals, and the transition metals comprise any one or the combination of two or more of Pt, Pd, Cr, Mn, Fe, Co, Ni, Cu and Zn;
(4) and carrying out transient high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body to obtain the intermetallic compound-carbon nanotube composite material.
2. The production method according to claim 1, characterized by comprising: preparing the carbon nano tube network macroscopic body by adopting any one of a chemical vapor deposition method or a floating catalytic chemical vapor deposition method of an Fe-based catalyst; preferably, the carbon nanotube network macroscopic body comprises any one or a combination of more than two of carbon nanotube films, carbon nanotube fibers, carbon nanotube aerogels and carbon nanotube foams.
3. The production method according to claim 1, characterized by comprising: and performing activated nitrogen doping treatment on the carbon nano tube network macroscopic body by at least adopting a hydrothermal method or a calcination method to obtain the nitrogen-doped carbon nano tube network macroscopic body.
4. The production method according to claim 3, characterized by comprising: calcining the carbon nano tube network macroscopic body at 400-500 ℃ for 1-2h in the nitrogen source atmosphere to obtain the nitrogen-doped carbon nano tube network macroscopic body; preferably, the nitrogen source atmosphere comprises ammonia gas and inert gas; preferably, the volume ratio of the ammonia gas to the inert gas is 1: 1-6; preferably, the inert gas comprises argon.
5. The method of claim 1, further comprising: before the activation treatment, the carbon nano tube network macroscopic body is subjected to vacuum iron removal treatment at 1800-2400 ℃.
6. The method of claim 1, wherein: the metal precursor solution in the step (3) comprises any one or combination of more than two of chloroplatinic acid solution, chloroauric acid solution, chloroiridic acid solution and transition metal salt solution; preferably, the concentration of the metal precursor solution is 10-30 mmol/L;
and/or the metal in the metal precursor solution comprises Pt and/or Pd and two or more transition metals, wherein the transition metals comprise any one or combination of two or more of Cr, Mn, Fe, Co, Ni, Cu and Zn;
and/or the mass loading amount of the metal precursor in the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body is 3-10 wt%.
7. The method of claim 1, wherein: the time for soaking the nitrogen-doped carbon nanotube network macroscopic body in the metal precursor solution is 1-2 h.
8. The method of claim 1, wherein: the drying treatment mode comprises any one of normal pressure drying, freeze drying and supercritical drying; preferably, the temperature of the drying treatment is 20-50 ℃.
9. The method according to claim 1, wherein the step (4) specifically comprises: and under a protective atmosphere, carrying out transient electric heating high-temperature annealing treatment on the metal precursor-loaded nitrogen-doped carbon nanotube network macroscopic body at 750-950 ℃ for 100-500ms to obtain the intermetallic compound-carbon nanotube composite material.
10. The method of claim 9, wherein: the current density of the transient electric heating is 0.1-2.5A/cm2；
And/or the current of the transient electric heating is direct current constant current; preferably, the current is 0.1-2.5A;
and/or the potential of the transient electric heating is direct current constant potential; preferably, the potential is 1-60V.
11. The method of claim 9, wherein: the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere.
12. An intermetallic-carbon nanotube composite prepared by the process of any one of claims 1-11, in which the intermetallic compounds are homogeneously dispersed in the nitrogen-doped carbon nanotube network macrostructure, the species of the metallic element in the intermetallic compound being 3 or more, the particle size of the intermetallic compound in the composite being less than 3nm, the atoms in the intermetallic compound being in an ordered arrangement.
13. The intermetallic-carbon nanotube composite of claim 12, characterized by: the composite material has oxygen reduction and oxygen evolution catalytic properties.
14. Use of the intermetallic compound-carbon nanotube composite material according to any one of claims 12 to 13 in the field of oxygen catalysis or metal air batteries.
15. An oxygen-functional electrocatalyst characterized by comprising the intermetallic compound-carbon nanotube composite material according to any one of claims 12 to 13; preferably, the oxygen functional electrocatalyst comprises an oxygen reduction electrocatalyst or an oxygen reduction and oxygen evolution bi-functional electrocatalyst.
16. An oxygen electrode, characterized by comprising the intermetallic compound-carbon nanotube composite material according to any one of claims 12 to 13 or the oxygen functional electrocatalyst according to claim 15.
17. A metal-air battery characterized by comprising the oxygen electrode according to claim 16.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151861A (en) * | 2021-04-28 | 2021-07-23 | 中国科学技术大学 | Method for synthesizing carbon-supported monatomic catalyst through thermal shock and carbon-supported monatomic catalyst |
| CN113394410A (en) * | 2021-05-08 | 2021-09-14 | 南京师范大学 | Nitrogen-doped carbon nanosheet composite material anchored with NiPd/Ni and preparation method and application thereof |
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436722A (en) * | 2003-03-21 | 2003-08-20 | 清华大学 | Vacuum high-temperature process of purifying carbon nanotube |
| CN101062478A (en) * | 2006-04-26 | 2007-10-31 | 中国科学院大连化学物理研究所 | Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof |
| CN101395747A (en) * | 2006-01-10 | 2009-03-25 | 卡伯特公司 | Alloy catalyst compositions and processes for making and using same |
| US20090317289A1 (en) * | 2006-06-30 | 2009-12-24 | N.E. Chemcat Corporation | Process for producing metal nanoparticle and metal nanoparticle produced by the process |
| CN103352189A (en) * | 2013-07-02 | 2013-10-16 | 天津大学 | Method for rapid preparation of high-strength carbon nanotube macrostructure |
| CN110391399A (en) * | 2018-04-17 | 2019-10-29 | 通用汽车环球科技运作有限责任公司 | The method for preparing lithium anodes |
| CN110465652A (en) * | 2019-07-30 | 2019-11-19 | 华中科技大学 | A kind of platinum iron intermetallic compound of N doping carbon-coating cladding and its preparation and application |
| CN110605131A (en) * | 2019-05-07 | 2019-12-24 | 韦萍洁 | Three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst and preparation method and application thereof |
| CN110783582A (en) * | 2019-11-06 | 2020-02-11 | 浙江理工大学 | Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof |
| CN111346645A (en) * | 2020-03-13 | 2020-06-30 | 苏州大学 | Preparation method and application of high-dispersion alloy nanoparticles |
| CN111416132A (en) * | 2020-04-03 | 2020-07-14 | 北京化工大学 | Carbon-supported ordered platinum-copper-nickel catalyst for fuel cell and preparation method thereof |
-
2020
- 2020-07-23 CN CN202010714990.0A patent/CN112563519B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436722A (en) * | 2003-03-21 | 2003-08-20 | 清华大学 | Vacuum high-temperature process of purifying carbon nanotube |
| CN101395747A (en) * | 2006-01-10 | 2009-03-25 | 卡伯特公司 | Alloy catalyst compositions and processes for making and using same |
| CN101062478A (en) * | 2006-04-26 | 2007-10-31 | 中国科学院大连化学物理研究所 | Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof |
| US20090317289A1 (en) * | 2006-06-30 | 2009-12-24 | N.E. Chemcat Corporation | Process for producing metal nanoparticle and metal nanoparticle produced by the process |
| CN103352189A (en) * | 2013-07-02 | 2013-10-16 | 天津大学 | Method for rapid preparation of high-strength carbon nanotube macrostructure |
| CN110391399A (en) * | 2018-04-17 | 2019-10-29 | 通用汽车环球科技运作有限责任公司 | The method for preparing lithium anodes |
| CN110605131A (en) * | 2019-05-07 | 2019-12-24 | 韦萍洁 | Three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst and preparation method and application thereof |
| CN110465652A (en) * | 2019-07-30 | 2019-11-19 | 华中科技大学 | A kind of platinum iron intermetallic compound of N doping carbon-coating cladding and its preparation and application |
| CN110783582A (en) * | 2019-11-06 | 2020-02-11 | 浙江理工大学 | Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof |
| CN111346645A (en) * | 2020-03-13 | 2020-06-30 | 苏州大学 | Preparation method and application of high-dispersion alloy nanoparticles |
| CN111416132A (en) * | 2020-04-03 | 2020-07-14 | 北京化工大学 | Carbon-supported ordered platinum-copper-nickel catalyst for fuel cell and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZENG SHA ET AL: "PtFe Alloy Nanoparticles Confined on Carbon Nanotube Networks as Air Cathodes for Flexible and Wearable Energy Devices", 《ACS APPLIED NANO MATERIALS》 * |
| 杨勇: "氮掺杂介孔炭的制备及在乙炔氢氯化反应中的应用", 《中国硕士学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151861A (en) * | 2021-04-28 | 2021-07-23 | 中国科学技术大学 | Method for synthesizing carbon-supported monatomic catalyst through thermal shock and carbon-supported monatomic catalyst |
| CN113394410A (en) * | 2021-05-08 | 2021-09-14 | 南京师范大学 | Nitrogen-doped carbon nanosheet composite material anchored with NiPd/Ni and preparation method and application thereof |
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
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