CN115487846A - Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof - Google Patents

Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof Download PDF

Info

Publication number
CN115487846A
CN115487846A CN202211162126.XA CN202211162126A CN115487846A CN 115487846 A CN115487846 A CN 115487846A CN 202211162126 A CN202211162126 A CN 202211162126A CN 115487846 A CN115487846 A CN 115487846A
Authority
CN
China
Prior art keywords
bamboo
carbon nanotube
doped
nanotube structure
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211162126.XA
Other languages
Chinese (zh)
Inventor
马嵩
李帅贞
刘伟
张志东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Priority to CN202211162126.XA priority Critical patent/CN115487846A/en
Publication of CN115487846A publication Critical patent/CN115487846A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

The invention aims to provide packaging Ni 3 The Fe nano-alloy N-doped 1D bamboo-like carbon nano-tube structure is prepared by adopting a one-step synergistic catalytic pyrolysis technology, the carbon nano-tube structure is a three-dimensional conductive network structure formed by mutually interweaving 1D porous hollow carbon nano-tubes with bamboo-like folding characteristics, and N atom doping defects and Ni atoms are contained in the nano-tubes 3 The Fe alloy nano particles are wrapped in the head of the nanotube or the pore of the wall of the nanotube. The invention can prepare a large amount of products by utilizing a simple and harmless one-step synergetic catalytic pyrolysis strategy without any reaction gas, and the doping of N element ensures that the carbon nano-tube becomes disordered and is full of a large number of defects and holes, thereby inducing the bamboo-shaped carbon nano-tube to generate unprecedented new performance, together with Ni 3 The Fe soft magnetic alloy phase forms good electromagnetic matching, so that the Fe soft magnetic alloy phase can be widely applied to various fields of wave absorption, corrosion prevention, adsorption purification and the like.

Description

Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof
Technical Field
The invention belongs to the field of materials, and particularly provides an encapsulated Ni 3 Fe nano-alloy 1D bamboo-like carbon nanotube structure with N-doped defects and preparation method and application thereof.
Background
Nowadays, the society has entered the 5G era and moved forward to the 6G era, and the communication technology using GHz electromagnetic waves as carriers brings high-efficiency information transmission, but due to the high energy density of the electromagnetic waves, serious electromagnetic interference (EMI) and biological radiation problems are brought to sensitive elements and users in various electronic devices. Therefore, there is an urgent need to develop a microwave absorbing material capable of converting electromagnetic energy into thermal energy for solving the problem of electromagnetic radiation (particularly, GHz frequency) of human health, information security and high-precision electronic devices.
Meanwhile, the rapid development of modern electronic countermeasure technology also makes various weapons in future war, such as missile, airplane, tank, naval vessel, and the like face huge threat, so the ability of battlefield survival, penetration and deep strike of weapons is to be continuously improved, and the key is to apply the electromagnetic wave absorbing material to stealth technology, thereby solving some difficult problems in military. The stealth material technology is a stealth means with long-term effectiveness and feasible effectiveness, is particularly important in the stealth technology, and is also the key point of research and development of countries in the world. The technology can effectively inhibit the radar, infrared, laser, electromagnetic signals and other characteristic signals of a target in a specific remote sensing environment by applying various high-tech means, and finally, the weapon is difficult to find, identify and attack in a certain range. Therefore, the research and development and application of the L-Ku (1-18 GHz) full-wave-band wave-absorbing material are particularly important.
In various microwave radiation protection measures, aiming at radiation sources and leakage sources, the core is to adopt wave-absorbing materials to perfectly shield or absorb microwaves for microwave equipment. At present, most wave-absorbing materials are widely applied to severe environments such as acid rain, ocean and the like, so that the wave-absorbing materials are subject to corrosion aging and the problem of pollutant molecule permeation and adhesion in sewage, and the wave-absorbing materials are reduced and even lose the wave-absorbing function, therefore, the development of the three-in-one wave-absorbing device with good microwave absorption performance, corrosion protection performance and adsorption purification performance is imperative.
Ni 3 Fe alloy has better soft magnetic property, ni 3 The Fe active alloy and the nano carbon material are compounded into a feasible strategy, the nano carbon material can effectively improve the conductivity of the wave absorber, provide a larger specific surface area and improve the stability of the wave absorber. Meanwhile, the conductive loss capacity can be changed by regulating the electronic structure of the nearby carbon atoms by doping the heterogeneous atoms into the carbon matrix; and meanwhile, interface polarization and defects are introduced, the number and types of electric dipoles are increased, and the polarization relaxation loss performance is regulated and controlled, so that the electromagnetic matching performance of the wave absorber is effectively improved. Therefore, combining these synergistic advantages to synthesize hetero atom doped carbon matrix supported or encapsulated Ni 3 Fe alloy nanocomposites are an intelligent and interesting strategy. However, the preparation process of such materials usually takes time and lasts long, the preparation process is complicated, the yield is low, subsequent treatment is needed, and the wave-absorbing effect cannot meet the actual complex and variable application requirements, so that no Ni is available at present 3 The Fe alloy and the carbon matrix material are compounded and applied to the relevant reports in the wave absorbing field.
Patent CN113964322A discloses an iron-nickel alloy/carbon nanotube composite material, a preparation method and an application thereof, the method comprises the steps of firstly, fully grinding an iron source, a nickel source and a carbon source according to a certain proportion to obtain a mixture a; then putting the mixture A into a reactor, introducing inert gas, and carrying out heat treatment according to a preset program to obtain a product B; and finally, grinding the product B, putting the product B into a microwave muffle furnace, heating to a preset temperature, and cooling to the normal temperature to obtain the iron-nickel alloy/carbon nano tube composite material. The iron-nickel alloy/carbon nano tube composite material prepared by the method can improve the specific capacity and the storage performance of a battery when being applied to an electrode material, but does not relate to the application in the wave absorbing aspect.
Patent CN105817648A discloses a method for preparing iron-nickel alloy nanocluster-graphene composite material, which comprises adding graphite oxide into a first organic solvent and dispersing, then adding iron acetylacetonate, nickel acetylacetonate and octadecylamine, heating and preserving the mixture and heating up and refluxing, finally adding a second organic solvent to quench, separating the washed product and drying. The iron-nickel alloy nanocluster-graphene composite material obtained by the method takes graphene as a substrate, and iron-nickel alloy nanoparticles are protected and dispersed, so that the iron-nickel alloy nanocluster-graphene composite material has good electromagnetic wave-absorbing performance. But not Ni 3 A composite of Fe alloy phases.
Synthesis of hetero atom doped carbon matrix loaded or encapsulated Ni 3 The application of the Fe alloy in wave-absorbing corrosion prevention and purification has a great application prospect, and development and research are urgently needed.
The invention adopts a one-step synergistic catalytic pyrolysis technology to prepare the packaged Ni in situ 3 The Fe nanometer core has a 1D bamboo-shaped carbon nanometer tube structure with N-doped defects, and because the reaction conditions are flexible, easy to control, safe and reliable, the nanometer composite material which does not need subsequent treatment, has stable environment and special structure and adjustable dielectric and magnetism can be prepared in a large scale and can be used for microwave absorption, corrosion protection and adsorption purification.
Disclosure of Invention
The invention aims to provide packaging Ni 3 An N-doped 1D bamboo-like carbon nano tube structure of Fe nano alloy and application thereof are characterized in that a one-step synergistic catalytic pyrolysis method is adopted, and the 1D bamboo-like carbon nano tube which is induced by N doping is prepared by self-catalytic self-assemblyNi 3 The composite of the Fe alloy core has the advantages that the graphitized carbon tube has high purity and few defects, does not need subsequent treatment, and has excellent performances of synchronous wave absorption, corrosion prevention and adsorption.
The technical scheme of the invention is as follows:
packaging Ni 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized in that: the carbon nanotube structure is a three-dimensional conductive network structure formed by interweaving 1D porous hollow carbon nanotubes with bamboo-like fold characteristics, and N atom doping defects and Ni are arranged in the nanotubes 3 The Fe alloy nanoparticles are wrapped in the nanotube head or wall pores so that the magnetic particles are dispersed with each other.
As a preferred technical scheme:
the percentage content of N-doped atoms in the carbon nanotube structure is 1.0at.% to 10at.%.
The outer diameter of each hollow carbon nanotube in the carbon nanotube structure is 30-300nm; the Ni 3 The diameter of the Fe alloy nano particles is 15-290nm.
The impedance of the carbon nanotube structure in 3.5wt.% NaCl in a neutral saturated salt solution is 18.26K omega cm 2 (ii) a The adsorption equilibrium capacity of the carbon nanotube structure in a pollutant dye solution (such as MG, CR and MO) is 773.6MG g -1 。
The invention also provides the packaging Ni 3 The preparation method of the N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized by comprising the following steps of: the preparation method is characterized in that a complex of melamine (melamine) and chloride salts of metal Ni and Fe is used as a precursor in Ar/H 2 Under the reducing atmosphere, melamine is used as a carbon source, a nitrogen source and a reducing agent, and the precursor is pyrolyzed and carbonized by adopting a one-step synergetic catalytic pyrolysis technology, so that the packaged Ni is prepared 3 An N-doped 1D bamboo-shaped carbon nano tube structure of Fe nano alloy, wherein the chloride (Ni) of Ni and Fe 2+ And Fe 3+ ) Is reduced to transition metal (Ni) 0 And Fe 0 ) Meanwhile, due to the catalytic action of the obtained bimetallic nickel-iron alloy, saturated carbon dissolved in the nickel-iron alloy can be separated out as a graphene coating layer with good crystallizationWhile the structural defects and fracture sites formed in the graphene layer by nitrogen doping may contribute to the formation of new graphene layers, resulting in (encapsulating Ni) 3 Fe nano alloy) 1D bamboo joint-shaped folded hollow carbon tube. The method solves the problems of carbon nanotube and magnetic Ni 3 The preparation technology of Fe alloy composite is difficult, so that the preparation process is simple, the operation is convenient, the cost is low, and the method is safe and reliable.
Wherein:
the ratio of the mass (m 1) of melamine to the total mass (m 2) of the chloride salts of metals Ni and Fe is 3 to 10 (more preferably m1: m2=3 to 5;
the chloride salt of metal Ni and Fe is firstly stirred and mixed in the solvent for 1-10h (preferably 1-5 h), after the melamine is added, the three are continuously stirred and mixed in the solvent for 5-24h (preferably 5-12 h), and the complex melamine-Ni is obtained 2+ /Fe 3+ The complex pyrolysis temperature is 400-1000 ℃, and the heat preservation time is 1-3h; the pyrolysis atmosphere is Ar/Ar + H 2 。
The chloride salts of Ni and Fe are NiCl respectively 2 ·6H 2 O and FeCl 3 ·6H 2 O, and n NiCl2·6H2O: n FeCl3·6H2O 1, = 3; the raw materials of melamine powder and NiCl are used 2 ·6H 2 O、FeCl 3 ·6H 2 O is analytically pure, and no further treatment is carried out; the solvent is preferably absolute ethyl alcohol; magnetic stirring is adopted, and the rotating speed of a magnetic stirrer is 150-500r/min.
The complex melamine-Ni 2+ /Fe 3+ Dispersing in 20-150ml of anhydrous ethanol, evaporating ethanol at 80 deg.C or higher without centrifugal separation, drying, and heating for pyrolysis. And only when the pyrolysis temperature is more than or equal to 600 ℃, the packaged Ni with good crystallization and complete growth can be obtained 3 The Fe nano alloy is provided with a 1D nitrogen-doped bamboo-shaped carbon nano tube.
As a preferable technical scheme: the temperature rise rate of complex pyrolysis is 2-5 ℃/min, the pyrolysis temperature is 700-900 ℃, and the heat preservation time is 2h.
The best scheme is as follows: m1: m2=4, pyrolysis conditions 900 ℃/2h.
Packaging Ni of the invention 3 The N-doped 1D bamboo-shaped carbon nano tube structure of the Fe nano alloy can be applied as a wave-absorbing material with a frequency range of 2 GHz to 18GHz at the temperature of-168 ℃ and room temperature, and the material has more excellent wave-absorbing performance (the maximum bandwidth can reach 6.0GHz at 2 mm) in a high-frequency range (12 GHz to 18 GHz).
Packaging Ni of the invention 3 The N-doped 1D bamboo-shaped carbon nano tube structure of the Fe nano alloy can be used as a wave-absorbing material for corrosion protection and adsorption purification of a frequency band between 2 and 18GHz at room temperature and even at low temperature (the lowest can reach-168 ℃), can be soaked in a neutral salt solution (such as 3.5wt% NaCl) in a severe environment between-168 ℃ and room temperature, and has beneficial corrosion resistance. The material can be soaked in an organic pollutant dye solution at a temperature of-168 ℃ to room temperature, and has outstanding adsorption and purification capacity. The material forms uniformly dispersed spherical Ni due to the doping of N 3 The product is single-phase Ni, and the product is a multi-fold bamboo-shaped and relatively disordered porous nano hollow tubular structure with a Fe nano core 3 Fe is coated on the N-doped carbon nano-tube, the dielectric and magnetism are adjustable, and the one-dimensional structure is obvious and can be clearly observed on XRD, raman, SEM and TEM.
The invention has the beneficial effects that:
the invention has the beneficial effects that:
1. the invention adopts a one-step synergetic catalytic pyrolysis technology to prepare high-quality packaged Ni 3 The Fe nano-alloy 1D bamboo-shaped carbon nano-tube structure with the N-doped defect is simple in equipment, low in production cost, high in production efficiency, green and pollution-free.
2. The scanning electron microscope, the transmission electron microscope and the Raman spectrum show that the product prepared by the method is packaged with Ni 3 The Fe nano-alloy 1D bamboo-shaped carbon nano-tube structure with N-doped defects has the diameter of 30-300nm and high purity; the prepared nano hollow tube is determined to be disordered by ray diffraction (XRD) and Raman (Raman) spectrum, and has N-doped defects.
3. The prepared packaging Ni 3 The 1D bamboo-shaped carbon nanotube structure sample of the Fe nano alloy and having the N-doped defect does not need subsequent treatment.
4. The invention adopts one-step synergistic catalytic pyrolysis technology, the pyrolysis temperature of the tubular furnace can reach 1000 ℃, and the temperature is in Ar/H 2 When the evaporation source melamine (C) is introduced under the continuous flowing atmosphere 3 H 6 N 6 ) Decomposing into C, H, N atoms at 400 deg.C or above, wherein the C, H, and N atoms collide and combine with each other, and re-nucleation into g-C 3 N 4 And NH 3 Meanwhile, the metal chloride is reduced into a metal simple substance and combined into an iron-nickel alloy which is used as a catalyst to catalyze an amorphous C precursor and g-C 3 N 4 Further converting the matrix into head embedded Ni 3 The Fe alloy core has a 1D bamboo-shaped carbon nanotube structure with N-doped defects.
5. In the range of 2-18GHz, the unique microstructure of the product prepared by the method can effectively reduce or avoid magnetic Ni 3 Aggregation, oxidation and corrosion of Fe alloys provide a favorable basis for stable microwave absorption properties. When melamine powder is mixed with NiCl 2 ·6H 2 O and FeCl 3 ·6H 2 When the mass ratio of the total amount of the O powder is 3, 4, 1 and 5, the wave-absorbing property is better (when the ratio of the two is 4. When the mass ratio of the two is 4 3 The Fe nano alloy 1D bamboo-shaped carbon nano tube structure with the N-doped defects has good wave absorbing performance, and the effective bandwidth (the reflection loss is lower than-10 dB (absorption of 90%) and can reach 6.0GHz maximally. The dielectric relaxation is stronger, the cole-cole circle is larger, the number and the types of electric dipoles are more, and the polarization degree is larger.
6. In the range of 2-18GHz, the product prepared by the method has good wave-absorbing effect, the best wave-absorbing effect can reach-57.3 dB (equivalent to more than 99.999 percent of absorption), and the effective bandwidth reaches 6.0GHz when d =2 mm.
7. The product prepared by the method has good preservative effect and the best preservative effect within the range of 0.01-100000HzIn effect, the impedance | Z | can reach 18.26K Ω & cm 2 Corrosion current density I corr A minimum of 10 -7 Orders of magnitude.
8. Within the range of 400-700nm, the product prepared by the method has good adsorption effect, and the best adsorption effect can reach 773.6mg g -1 。
Drawings
FIG. 1. Example 1 encapsulating Ni 3 A transmission electron microscope (morphology) picture of a 1D bamboo-shaped carbon nano tube structure made of Fe nano alloy and having N-doped defects.
FIG. 2. Ni is encapsulated in example 1 3 Scanning electron microscope (21610 times magnified) of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects.
FIG. 3. Specific proportions (8 wt%) of encapsulated Ni 3 The reflection loss of the 1D bamboo-like carbon nano tube structure made of Fe nano alloy and having N-doped defects is in the change relation with the frequency,
FIG. 4. Encapsulation of Ni in example 2 3 And the X-ray diffraction spectrum of the 1D bamboo-shaped carbon nanotube structure made of the Fe nano alloy and having the N-doped defect.
FIG. 5. Encapsulation of Ni in example 2 3 A transmission electron microscope picture of a 1D bamboo-like carbon nanotube structure of Fe nano alloy and with N-doped defects, (a) a morphology picture of an integral composite structure; (b) a core-shell structure morphology graph; and (C) high resolution.
FIG. 6. Ni is encapsulated in example 2 3 Scanning electron microscope (24790 times magnification) of the Fe nano-alloy 1D bamboo-like carbon nanotube structure with N-doped defects.
FIG. 7. Ni is encapsulated in example 2 3 A hysteresis loop of a 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects at normal temperature of 300K.
FIG. 8 specific proportions (8 wt%) of encapsulated Ni 3 The reflection loss of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects is in the change relationship with the frequency (900 ℃ C. +2 h).
FIG. 9 specific proportions (8 wt%) give encapsulation of Ni 3 Fe nano-alloy 1D bamboo with N-doped defectsElectrochemical characterization results of nodal carbon nanotube structures in neutral de-gassing static 3.5wt% aqueous NaCl solution, (a), bode plot, (b), nyquist plot, (c), potentiodynamic polarization plot.
FIG. 10. Encapsulating Ni 3 Fe nano-alloy 1D bamboo-like carbon nanotube structure with N-doped defects in organic dyes MG, CR and MO at maximum absorption wavelength lambda max Adsorption results of (A) sample Ni 3 An absorbance-initial concentration curve of Fe @ NCNT after adsorption on the CR solution, (b) an absorbance-initial concentration curve of commercial Activated Carbon (AC) after adsorption on the CR solution, (c) and adsorption capacity and removal rate curves of a sample in the three dyes.
FIG. 11. Specific proportions (8 wt%) of encapsulated Ni 3 The reflection loss of the 1D bamboo-shaped carbon nanotube structure made of the Fe nano alloy and having N-doped defects is in a frequency variation relationship (700 ℃ C. +2 h).
FIG. 12. Specific proportions (8 wt%) of encapsulated Ni 3 The reflection loss of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects is in the change relationship with the frequency (800 ℃ C. +2 h).
FIG. 13. Ni is encapsulated in example 3 3 A transmission electron microscope picture (overall composite structure morphology picture) of a 1D bamboo-shaped carbon nanotube structure of Fe nano alloy and N-doped defects.
FIG. 14. Ni is encapsulated in example 3 3 Scanning electron microscope (245730 times magnification) of a 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects.
FIG. 15. Specific proportions (8 wt%) of encapsulated Ni 3 The reflection loss of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects is in the change relation with the frequency.
Detailed Description
All examples employ n NiCl2·6H2O :n FeCl3·6H2O Preparation of =3 3 The Fe nano-alloy 1D bamboo-shaped carbon nano-tube structure has N-doped defects.
In the following examples, unless otherwise specified, m1 represents the mass of melamine and m2 represents the total mass of the chloride salts of Ni and Fe, both pure and pureMelamine and NiCl with analytical degree 2 ·6H 2 O and FeCl 3 ·6H 2 O was stirred and mixed in 50ml of absolute ethanol to prepare a precursor (NiCl was kept added) 2 ·6H 2 O and FeCl 3 ·6H 2 The O mass is unchanged and only the melamine addition is changed).
Example 1
Firstly, feCl with a certain mass is added 3 ·6H 2 O(Fe 3+ ) And NiCl 2 ·6H 2 O(Ni 2+ ) After dispersing in 50ml of absolute ethanol for 2 hours with a magnetic stirrer, an appropriate amount of melamine was added with stirring (so that m1: m2=3 = 1), and magnetic stirring was continued for 10 hours until the complex melamine-Ni was formed 2+ /Fe 3+ Stopping stirring, heating the precursor solution at 85 ℃ for 2h to evaporate ethanol and escape to obtain a dry yellow product, namely a complex precursor, grinding the complex precursor until powder is placed in a crucible with a cover and a quartz tube. In a continuous flow of Ar/H 2 Under reducing atmosphere, the precursor is pyrolyzed and carbonized, the heating rate is 2 ℃/min, wherein melamine is used as a carbon source and a nitrogen source to be evaporated into C, N and H atoms at the high temperature of more than 400 ℃, the atoms collide and combine with each other, and meanwhile, nickel salt (Ni) is added 2+ ) And iron salt (Fe) 3+ ) Reduced into nickel-iron alloy as catalytic center to catalyze carbon source to grow into carbon tube, heated to 900 ℃ and insulated for 2h to obtain Ni 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 And the Fe alloy core is completely wrapped by the black sample of the N-doped 1D bamboo-shaped carbon nanotube porous hollow structure network.
FIG. 1 shows Ni encapsulated 3 The transmission electron microscope photo of the 1D bamboo-shaped carbon nanotube structure made of the Fe nano alloy and having the N-doped defect shows that the whole appearance is Ni uniformly dispersed in the mutually-interwoven bamboo-shaped hollow tube network 3 The Fe nano alloy core is distributed in a tubular shape of 30-130nm, and the wall thickness distribution is relatively uniform; the particle size distribution is 15-115nm, the particle size is relatively uniform, and the average particle size is about 80 nm.
FIG. 2 shows Ni encapsulated 3 Fe nano-alloy 1D bamboo-shaped carbon nano with N-doped defectsScanning electron micrographs of the rice-tube structure, at a magnification of 21610, show typical pleated hollow-tube features.
FIG. 3 shows 8wt.% of encapsulated Ni 3 The curve of the change relation curve of the reflection loss of the Fe nano alloy and N-doped defect 1D bamboo-shaped carbon nano tube structure along with the frequency shows that under the condition that the proportion of a nitrogen-containing sample is only 8%, the alloy has better wave-absorbing performance in a high-frequency range (12.7-18 GHz), the reflection loss approaches to-13.5 dB (more than 90% of absorption), and an effective bandwidth of 5.3GHz is provided when D =1.8 mm; in a word, the high frequency band of 12.7-18GHz has excellent thin, light, wide and strong wave-absorbing performance.
Example 2
The difference from example 1 is that m1: m2=4 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 The black sample of the N-doped 1D bamboo-like carbon nanotube porous hollow structure network with the completely coated Fe alloy core (compared with example 1, the proportion of carbon tubes in the product is slightly increased, and the number of magnetic particles is slightly decreased, which is beneficial to the realization of electromagnetic matching).
FIG. 4 shows the resulting encapsulated Ni 3 The X-ray diffraction spectrum (XRD) of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects shows that the X-ray diffraction spectrum has the standard peak of N-doped graphene and Ni 3 Fe single phase standard peak.
FIG. 5 shows Ni encapsulated 3 The transmission electron microscope photograph of the 1D bamboo-shaped carbon nanotube structure made of Fe nano-alloy and having N-doped defects can be seen from FIG. 5 (a), wherein the whole appearance is Ni uniformly wrapped inside (at the head) of the bamboo-shaped carbon tube 3 The Fe alloy balls are distributed in a tubular shape with the diameter of 30-250nm, the diameter distribution is relatively uniform, the particle size distribution is 20-230nm, the particle size is relatively uniform, and the average particle size is about 60 nm; FIG. 5 (b) shows a clear core-shell structure at high magnification; fig. 5 (c) shows a high resolution image, demonstrating that the crystal planes are consistent with the XRD results.
FIG. 6 shows encapsulating Ni 3 Scanning Electron Microscope (SEM) picture of 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defectsIt can be seen that the overall structure is a typical bamboo-like hollow tube structure.
FIG. 7 indicates encapsulating Ni 3 The Fe nano alloy has soft magnetic property at room temperature of a 1D bamboo-shaped carbon nano tube structure with N-doped defects, wherein the saturation magnetization at room temperature is 62.30emu/g, and the coercive force is 100.2Oe.
FIG. 8 gives 8wt.% encapsulated Ni 3 The curve of the change relation curve of the reflection loss of the Fe nano alloy and N-doped defect 1D bamboo-shaped carbon nano tube structure along with the frequency shows that under the condition that the proportion of a nitrogen-containing sample is only 8%, the alloy has better wave-absorbing performance in a high-frequency range (12-18 GHz), the reflection loss is close to-57.3 dB (more than 99.999% of absorption), and the effective bandwidth of 6.0GHz is obtained when D =2.0 mm; in a word, the high frequency band of 12-18GHz has excellent thin, light, wide and strong wave-absorbing performance.
FIG. 9 shows packaging of Ni 3 Electrochemical characterization of 1D bamboo-like carbon nanotube structures of Fe nano-alloy and having N-doping defects in neutral de-gassing static 3.5wt% nacl aqueous solution, wherein graph (a) is bode graph of 0h-720h soaking; FIG. (b) is a Nyquist plot for soaking from 0h to 720 h; plot (c) is a potentiodynamic polarization plot. As can be seen from FIG. (a), the impedance can be reached to 15 k.OMEGA.cm after soaking in 3.5wt% NaCl aqueous solution for one month 2 (ii) a Its plot (b) is almost linear, without any features of capacitive reactance arcs; the polarization diagram in graph (c) shows that the corrosion current density of the material in a neutral 3.5wt.% NaCl aqueous solution can reach a minimum of 10 -7 Magnitude. Thus, it is considered that Ni is encapsulated 3 The Fe nano-alloy 1D bamboo-shaped carbon nano-tube structure with the N-doped defect has good corrosion resistance.
FIG. 10 shows Ni encapsulated 3 Fe nano-alloy 1D bamboo-shaped carbon nano-tube structure with N-doped defects in MG, CR and MO dye aqueous solution (initial concentration is 20-300 mg.L) -1 ) At the wavelength of maximum absorption lambda max The adsorption results of (1). Wherein, taking the adsorption behavior of the sample to the CR dye as an example, the graphs (a) and (b) are respectively the sample Ni 3 Absorbance-initial concentration curves after adsorption of Fe @ NCNT on CR solution and absorbance-initial concentration curves after adsorption of commercial Activated Carbon (AC) on CR solutionThe lines (the inset in panels (a) and (b) correspond to a comparison of the physical photographs of the sample and commercial activated carbon before and after adsorption of CR, respectively); FIG. (c) is a graph of the adsorption capacity and removal rate of the sample among the three dyes. It can be seen that the equilibrium adsorption capacity of all three different dyes increases with increasing initial concentration of the dye and gradually saturates after reaching a certain concentration. Maximum adsorption capacity of MG of 773.6MG g -1 The maximum CR adsorption capacity was 674 mg. G -1 While the maximum adsorption capacity of MO is only 298.6mg g -1 。
Example 3
Different from the example 2 in that the pyrolysis temperature is 700 ℃, and Ni is prepared 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 The Fe alloy core was completely wrapped with the black sample of the N-doped 1D bamboo-like carbon nanotube porous hollow structure network (compared to example 2, the diameter of the carbon tube in the product was reduced, the diameter of the magnetic particle was reduced, and the electromagnetic matching was deteriorated).
FIG. 11 gives 8wt.% encapsulated Ni 3 The curve of the change relation curve of the reflection loss of the Fe nano alloy and N-doped defect 1D bamboo-shaped carbon nano tube structure along with the frequency shows that under the condition that the proportion of a nitrogen-containing sample is only 8%, the alloy has better wave-absorbing performance in a high-frequency range (12.2-18 GHz), the reflection loss approaches to-46.6 dB (more than 99.99% of absorption), and an effective bandwidth of 5.8GHz is obtained when D =2.0 mm; in a word, the high-frequency band of 12.2-18GHz has excellent wave-absorbing performance.
Example 4
The difference from example 2 is that the pyrolysis temperature is 800 ℃, and Ni is prepared 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 The black sample of the N-doped 1D bamboo-like carbon nanotube porous hollow structure network with the completely coated Fe alloy core (compared with example 2, the diameter of the carbon tube in the product is slightly reduced, the diameter of the magnetic particle is slightly reduced, and the electromagnetic matching is slightly worse, but almost comparable to example 2).
FIG. 12 showsOut of 8wt.% of encapsulated Ni 3 The curve of the change relation curve of the reflection loss of the Fe nano alloy and N-doped defect 1D bamboo-shaped carbon nano tube structure along with the frequency shows that under the condition that the proportion of a nitrogen-containing sample is only 8%, the alloy has better wave-absorbing performance in a high-frequency range (12-18 GHz), the reflection loss is close to-53 dB (more than 99.999% of absorption), and the effective bandwidth of 6.0GHz is obtained when D =2.0 mm; in conclusion, the high frequency band of 12-18GHz has excellent wave absorbing performance (only second to example 2). Thus, 900 ℃ is judged as the pyrolysis temperature most favorable for electromagnetic matching.
Example 5
The difference from example 1 is that m1: m2=5 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 And (3) a black sample of the N-doped 1D bamboo-shaped carbon nanotube porous hollow structure network with the completely wrapped Fe alloy core (compared with example 2, the proportion of carbon tubes in the product is further increased, and the quantity of magnetic particles is continuously reduced).
FIG. 13 shows Ni encapsulated 3 The transmission electron microscope photo of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects shows that the whole appearance is Ni uniformly dispersed in a large-area bamboo-shaped hollow tube network which is mutually bent and tangled 3 The Fe nano alloy core is distributed in a tubular shape of 30-200nm, and the wall thickness distribution is relatively uniform; the particle size distribution is 20-180nm, the particle size is relatively uniform, and the average particle size is about 70 nm.
FIG. 14 shows Ni encapsulated 3 The scanning electron microscope photo of the 1D bamboo-shaped carbon nanotube structure made of Fe nano alloy and having N-doped defects is 2450 times of magnification, and typical hollow tube characteristics of bending wrinkles can be seen from the image.
FIG. 15 gives 8wt.% encapsulated Ni 3 The curve of the change relation curve of the reflection loss of the Fe nano alloy and N-doped defect 1D bamboo-shaped carbon nano tube structure along with the frequency shows that under the condition that the proportion of a nitrogen-containing sample is only 8%, the wave absorbing performance is better in a high-frequency range (12.9-17.6 GHz), the reflection loss is close to-14.4 dB (more than 90% of absorption), and 4.7GHz is present when D =1.6mmEffective bandwidth; in a word, the high frequency band of 12.9-17.6GHz has excellent thin, light, wide and strong wave-absorbing performance.
Example 6
The difference from example 1 is that m1: m2=6 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 And the Fe alloy core is completely wrapped by the black sample of the N-doped 1D bamboo-shaped carbon nanotube porous hollow structure network. Compared with the embodiment 2, the proportion of carbon tubes in the product is greatly increased, the number of magnetic particles is obviously reduced, and at the moment, the melamine, namely the carbon source number is obviously increased, the proportion of magnetic components is relatively greatly reduced, the magnetic coupling is weakened, the electromagnetic matching is not good, and the wave absorbing performance is not good.
Example 7
The difference from example 1 is that m1: m2=7 3 Fe is used as a catalytic center to catalyze and promote the self-assembly of amorphous carbon precursors into long, bent and intertwined Ni with good crystallization 3 The Fe alloy core is completely wrapped by the N-doped 1D bamboo-shaped carbon nanotube porous hollow structure network black sample (compared with the example 2, the proportion of the carbon tubes in the product is increased sharply, and the number of the magnetic particles is reduced sharply). At the moment, the conductance loss of the three-dimensional conductive network formed by the carbon tubes is too strong, and the magnetic loss is too small, so that a serious electromagnetic mismatch phenomenon is caused, and the wave-absorbing capability is almost lost.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (12)

1. Packaging Ni 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized in that: the carbon nanotube structure is a 1D porous hollow structure with bamboo-like fold characteristicsThe carbon nanotubes are interlaced to form a three-dimensional conductive network structure, and N atom doping defects and Ni are arranged in the nanotubes 3 The Fe alloy nano particles are wrapped in the head of the nanotube or the pore of the wall of the nanotube.
2. Encapsulating Ni as claimed in claim 1 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized in that: the percentage content of N-doped atoms in the carbon nanotube structure is 1.0at.% to 10at.%.
3. Encapsulating Ni as claimed in claim 1 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized in that: the outer diameter of each hollow carbon nanotube in the carbon nanotube structure is 30-300nm; the Ni 3 The diameter of the Fe alloy nano particles is 15-290nm.
4. Encapsulating Ni as claimed in claim 1 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized in that: the impedance of the carbon nanotube structure in 3.5wt.% NaCl in a neutral saturated salt solution is 18.26K omega cm 2 (ii) a The adsorption equilibrium capacity of the carbon nanotube structure in a pollutant dye solution is 773.6mg g -1 。
5. The packaged Ni of claim 1 3 The preparation method of the N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized by comprising the following steps of: the complex of melamine and chloride salt of metal Ni and Fe is used as a precursor in Ar/H 2 In the reducing atmosphere of (2), melamine is used as a carbon source, a nitrogen source and a reducing agent, and the precursor is pyrolyzed and carbonized by adopting a one-step concerted catalytic pyrolysis technology, so that the packaged Ni is prepared 3 An N-doped 1D bamboo-shaped carbon nanotube structure of Fe nano alloy.
6. Encapsulating Ni as claimed in claim 5 3 The preparation method of the N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized by comprising the following steps of: mass of melamine and total mass of chloride salts of metal Ni and FeThe proportion is 3-10; firstly, the chloride salts of metal Ni and Fe are stirred and mixed in the solvent for 1-10h, after the melamine is added, the three are continuously stirred and mixed in the solvent for 5-24h to obtain the complex melamine-Ni 2+ /Fe 3+ The complex pyrolysis temperature is 400-1000 ℃, and the heat preservation time is 1-3h; the pyrolysis atmosphere is Ar/Ar + H 2 。
7. Encapsulating Ni as claimed in claim 6 3 The preparation method of the N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized by comprising the following steps of: the ratio of the mass of the melamine to the total mass of the metal chloride salts of Ni and Fe is 3-5.
8. Encapsulating Ni as claimed in claim 5 3 The preparation method of the N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is characterized by comprising the following steps of: the heating rate is 2-5 ℃/min, the pyrolysis temperature is 700-900 ℃, and the heat preservation time is 2h.
9. The packaged Ni of claim 1 3 The N-doped 1D bamboo-shaped carbon nanotube structure of the Fe nano alloy is applied as a wave-absorbing material with a frequency band between 2 GHz and 18GHz at the temperature of-168 ℃ to room temperature.
10. Use according to claim 9, characterized in that: the carbon nanotube structure is applied as a wave-absorbing material with a frequency band between 12 GHz and 18GHz at the room temperature of-168 ℃.
11. Use according to claim 9, characterized in that: the carbon nanotube structure is soaked in neutral saturated salt solution at-168-room temperature to be used as a wave-absorbing material.
12. Use according to claim 9, characterized in that: the carbon nanotube structure is soaked in an organic pollutant dye solution at a temperature of-168 ℃ to room temperature to be used as a wave-absorbing material.
CN202211162126.XA 2022-09-23 2022-09-23 Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof Pending CN115487846A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211162126.XA CN115487846A (en) 2022-09-23 2022-09-23 Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211162126.XA CN115487846A (en) 2022-09-23 2022-09-23 Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof

Publications (1)

Publication Number Publication Date
CN115487846A true CN115487846A (en) 2022-12-20

Family

ID=84470688

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211162126.XA Pending CN115487846A (en) 2022-09-23 2022-09-23 Packaging Ni 3 N-doped 1D bamboo-like carbon nanotube structure of Fe nano alloy and application thereof

Country Status (1)

Country Link
CN (1) CN115487846A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045533A (en) * 2007-03-12 2007-10-03 清华大学 Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof
CN104944410A (en) * 2015-06-01 2015-09-30 北京理工大学 Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material
CN108543545A (en) * 2018-04-26 2018-09-18 大连理工大学 A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications
CN113233444A (en) * 2021-04-27 2021-08-10 中国科学院金属研究所 Loaded with Ni3Fe @ C nanocapsule multilayer graphite sheet structure with N-doped defects
CN113964322A (en) * 2021-10-22 2022-01-21 陕西科技大学 Iron-nickel alloy/carbon nanotube composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045533A (en) * 2007-03-12 2007-10-03 清华大学 Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof
CN104944410A (en) * 2015-06-01 2015-09-30 北京理工大学 Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material
CN108543545A (en) * 2018-04-26 2018-09-18 大连理工大学 A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications
CN113233444A (en) * 2021-04-27 2021-08-10 中国科学院金属研究所 Loaded with Ni3Fe @ C nanocapsule multilayer graphite sheet structure with N-doped defects
CN113964322A (en) * 2021-10-22 2022-01-21 陕西科技大学 Iron-nickel alloy/carbon nanotube composite material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAN WANG, ET AL: "Boosting Bifunctional Oxygen Electrolysis for N-Doped Carbon via Bimetal Addition", SMALL, vol. 13, pages 1 - 15 *
XUAN XIE， ET AL: "Rational construction of FeNi3/N doped carbon nanotubes for high-performance and reversible oxygen catalysis reaction for rechargeable Zn-air battery", CHEMICAL ENGINEERING JOURNAL, vol. 452, pages 1 - 11 *
XUEQING XU, ET AL: "In Situ Confined Bimetallic Metal−Organic Framework Derived Nanostructure within 3D Interconnected Bamboo-like Carbon Nanotube Networks for Boosting Electromagnetic Wave Absorbing Performances", ACS APPLIED MATERIALS & INTERFACES, vol. 11, pages 35999 - 36009 *

Similar Documents

Publication Publication Date Title
Xu et al. In situ confined bimetallic metal–organic framework derived nanostructure within 3D interconnected bamboo-like carbon nanotube networks for boosting electromagnetic wave absorbing performances
Yin et al. Magnetically aligned Co–C/MWCNTs composite derived from MWCNT-interconnected zeolitic imidazolate frameworks for a lightweight and highly efficient electromagnetic wave absorber
Wang et al. Honeycomb-like Co/C composites derived from hierarchically nanoporous ZIF-67 as a lightweight and highly efficient microwave absorber
Luo et al. MoS2 spheres decorated on hollow porous ZnO microspheres with strong wideband microwave absorption
Wang et al. Porous carbon polyhedrons coupled with bimetallic CoNi alloys for frequency selective wave absorption at ultralow filler loading
Zhang et al. A facile self-template strategy for synthesizing 1D porous Ni@ C nanorods towards efficient microwave absorption
Li et al. Bifunctional two-dimensional nanocomposite for electromagnetic wave absorption and comprehensive anti-corrosion
Zhao et al. Facile synthesis of novel heterostructure based on SnO2 nanorods grown on submicron Ni walnut with tunable electromagnetic wave absorption capabilities
Jiao et al. Electromagnetic absorption behavior regulation in bimetallic polyphthalocyanine derived CoFe-alloy/C 0D/2D nanocomposites
Li et al. Self-assembly sandwich-like Fe, Co, or Ni nanoparticles/reduced graphene oxide composites with excellent microwave absorption performance
Wang et al. An ultralight nitrogen-doped carbon aerogel anchored by Ni-NiO nanoparticles for enhanced microwave adsorption performance
CN108154984B (en) Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof
Lyu et al. High-performance microwave absorption of MOF‐derived Co3O4@ N-doped carbon anchored on carbon foam
Wang et al. Fe/N-codoped hollow carbonaceous nanospheres anchored on reduced graphene oxide for microwave absorption
Zhang et al. In situ carbon nanotubes encapsulated metal Nickel as high-performance microwave absorber from Ni–Zn Metal–Organic framework derivative
Kou et al. Controlled fabrication of core–shell γ-Fe2O3@ C–Reduced graphene oxide composites with tunable interfacial structure for highly efficient microwave absorption
Peng et al. Progress in graphene-based magnetic hybrids towards highly efficiency for microwave absorption
Wei et al. Bimetallic nanoarrays embedded in three-dimensional carbon foam as lightweight and efficient microwave absorbers
CN115491177B (en) MOF-derived carbon-based magnetic nano composite electromagnetic wave absorbing material and preparation method thereof
Wang et al. Ni-MOF/Ti3C2Tx derived multidimensional hierarchical Ni/TiO2/C nanocomposites with lightweight and efficient microwave absorption
Gu et al. Excellent lightweight carbon-based microwave absorbers derived from metal–organic frameworks with tunable electromagnetic properties
CN112165848A (en) Composite wave-absorbing material with magnetic metal or oxide thereof loaded on graphene and preparation method thereof
Lv et al. Ti3C2Tx/Co-MOF derived TiO2/Co/C composites for broadband and high absorption of electromagnetic wave
CN112409983A (en) Electromagnetic wave absorber based on 2-methylimidazolium cobalt derivative and carbon nanotube composite and preparation method thereof
Jin et al. NiCo@ NPC@ CF nanocomposites derived from NiCo-MOF/cotton for high-performance electromagnetic wave absorption

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination