CN107454815A - Cu2O/MWCNTs composites, preparation method and electro-magnetic wave absorption application - Google Patents

Cu2O/MWCNTs composites, preparation method and electro-magnetic wave absorption application Download PDF

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CN107454815A
CN107454815A CN201710437401.7A CN201710437401A CN107454815A CN 107454815 A CN107454815 A CN 107454815A CN 201710437401 A CN201710437401 A CN 201710437401A CN 107454815 A CN107454815 A CN 107454815A
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mwcnts
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mwcnts composites
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CN107454815B (en
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高圣涛
邢宏龙
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Anhui University of Science and Technology
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Abstract

The invention discloses a kind of Cu2O/MWCNTs composites, preparation method and applications；The present invention has synthesized Cu by simply learning method2O/MWCNTs composites, Cu2O nano-particles are disorderly grown in MWCNTs surfaces and inside.The present invention uses hydro-thermal method, is not added with any surfactant, and the method for avoiding traditional plating or chemical plating, less pollution, preparation method is easy, green, and reaction is easy to control, it is not necessary to expensive equipment, available for industrialized production.

Description

Cu2O/MWCNTs composites, preparation method and electro-magnetic wave absorption application
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of Cu2O/MWCNTs composites and its preparation side Method and application.
Background technology
In recent years, as the fast development of electronics industry, electromagnetic pollution are on the rise, and absorbing material is prevented in electromagnetic pollution Protector for collar domain serves vital effect.Realizing the radar invisible of military equipment simultaneously, weakening electromagnetic interference, guarantee information Field, the absorbing materials such as safety have also played particularly important effect.Absorbing material (microwave absorbing material, electromagnetic wave attenuation material Material or Radar Stealth Materials) reflection of the electromagnetic wave in body surface can be efficiently reduced, while to incide material internal Electromagnetic wave be efficiently damped.Based on above reason, extensive concern of the microwave absorbing material by domestic and international researcher.
Absorbing material can be divided into wave absorbing agent and matrix according to its composition.Matrix primarily serves cohesive in absorbing material Effect, and wave absorbing agent is the main body of absorbing material, plays a part of electromagnetic wave loss.Outstanding wave absorbing agent need to meet lightweight, The demand of absorption intensity is big, absorption band is wide, electromagnetic consumable ability is strong and environmental resistance is strong etc..
Multi-walled carbon nanotube (MWCNTs), there is good chemical stability, excellent heat endurance, high mechanical strength The advantages of with outstanding electric conductivity etc..Light weight simultaneously, has larger potentiality in the wave absorbing agent field for preparing outstanding.
Cuprous oxide be it is a kind of be about 2.0eV to visible light-responded p-type semiconductor material, its energy gap, its lattice In 3d and 4s tracks it is no longer overlapping due to the distance between copper atom, formd in system by a valence band being full of entirely The semiconductor energy gap formed with an empty conduction band, have in information functional material, catalysis, photoelectricity, magnetic material etc. wide General application prospect.
In recent years, also there is many on Cu2The research of O preparation and application.For example, Wang Jiaxing etc. uses electronation Method, the cuprous nano with different shape and particle diameter is prepared by the concentration and pH value that control glucose in solutions Grain, determines cuprous oxide nano particle and rate of release (Wang Jiaxing, Zhang Jianfeng, Zhao Wenjie in the seawater as anti-fouling agent be present Deng；Chinese Surface Engineering；2015,28,2)；Sui etc. utilizes in-situ oxidation etching method, successively adds sodium citrate and glucose two Kind reducing agent, it is prepared for blocking the Cu that octahedra { 110 } crystal face is etched2O nanocages, the wall thickness of the nanocages is 60nm, outside Footpath is 700nm, has geometrical symmetry (Sui Y M, Zeng Y, Zheng W T, the et al.Synthesis of of height polyhedron hollow structure Cu2O and their gas-sensing properties[J] .Sens.Actuators B, 2012,171-172： 135-140.).
But due to Cu2Copper in O is positive monovalence, and long-term use can be unstable, is easily oxidized to cupric； Cu2O powder is easy Aggregation turns into bulky grain, so as to influence the performance of its performance；And Cu2O be a kind of have compared with low energy gap width and conduction band positions compared with High semiconductor, there is the catalytic efficiency caused by light induced electron and hole-recombination is not high the problem of.Therefore current state The inside and outside research on cuprous oxide/carbon composite or copper/carbon composite preparation method is numerous.Such as Application No. CN201310436145.1 Chinese invention patent discloses a kind of ultrasonic wave and prepares carbon graphite alkene load cuprous nano level The method of structure hybridization material, but needed reduced graphene (rGO), pyrene derivatives and cupric salt in this method in organic solvent Middle reaction, operation is more complicated, while organic solvent pollution environment.And for example such as Application No. CN201110459158.1 middle promulgated by the State Council Bright patent discloses a kind of preparation method of copper/carbon nanotube composite superhydrophobic material, and the hydrophobic material obtained by the method has High heat conduction, highly conductive, ultra-hydrophobicity, but processing procedure is more complicated, and need high temperature, condition of high voltage, equipment requirement are higher.
Therefore how it is simple and convenient prepare cuprous oxide/carbon composite, it is compound especially to prepare cuprous oxide/CNT Material and the application in absorbing property, are rarely reported.
The content of the invention
Based on technical problem existing for background technology, it is an object of the present invention to provide a kind of Cu2O/MWCNTs is compound Material.
Second purpose of the invention is to provide a kind of Cu2The preparation method of O/MWCNTs composites.
3rd purpose of the invention is the Cu for providing the preparation of the application preparation method2O/MWCNTs composites are in microwave Application in absorption.
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs tables Face and inside.
Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) pretreatment of multi-walled carbon nanotube：MWCNTs, concentrated nitric acid, question response are sequentially added in 250mL three-necked flasks After end, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO45H2O and PEG, magnetic agitation is to being completely dissolved；Ultrasound is placed in ultrasonic reactor to reaction system mixed liquor Black is changed into from blueness, reacted mixed liquor is titrated to PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace calcining at constant temperature at 300 DEG C, The product obtained after Temperature fall is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.020-0.180g:120-200mL.
Reaction condition in the step 1)：4-8h is reacted at 100-140 DEG C.
MWCNTs, distilled water, CuSO45H in the step 2)2O, PEG mass volume ratio： 0.020-0.320g： 60-100mL：0.150-0.35g：0.100-0.300g.
The concentration of step 2) the sodium hydroxide solution solution is 1-5wt%, rate of titration：5-10S/ drops.
Step 2) the calcination time：2.5-3.5h, heating rate：3℃/min-1。
Cu prepared by the application method2O/MWCNTs composites.
Cu2Application of the O/MWCNTs composites in absorbing material.
XRD is tested：The crystal structure of sample is characterized using LabX XRD-6000 types x-ray diffractometers, wherein X Ray is Cu-K alpha rays, wavelength 0.154nm, 0.02 ° of step-length, tube current 36kV, electric current 30mA, 20-80 ° of scanning angle, is swept Retouch 2 °/min of speed-1。
Sem test：Take a small amount of prepared sample to add in distilled water, ultrasonic disperse, be added drop-wise on conducting resinl, The pattern carry out table to sample using FEI-Sirion200 types field emission scanning electron microscope is bonded at after being dried on sample stage Sign.
Transmissioning electric mirror test：The microstructure of sample is characterized using JEOL-2010 types transmission electron microscope.Take A small amount of sample ultrasonic disperse in distilled water, is added drop-wise on copper mesh, dries, sample introduction, test.
Microwave absorbing property is tested：Using vector network analyzer, VNA, AV3629D, China, the electromagnetism of sample is measured Parameter, test frequency scope are 2-18GHz.It is 3 in mass ratio by sample and paraffin:1 mixing, is poured at 80 DEG C after heating and melting It is 2mm to note and thickness is made in copper ring mould, is tested in the coaxial annulus that external diameter is 7mm and internal diameter is 3mm.
Inhale the ripple mechanism of action：Cu prepared by the application2Cu in O/MWCNTs composites2O nano-particles and MWCNTs it Between form special conductive network structure, add Cu2Conductive path between O nano-particles and MWCNTs.Cu2O nanometers Particle deposition is on MWCNTs and certain chemical interactions between the two be present and causes Cu2O nano-particles are fixed on MWCNTs On, generation for polarization and in Cu2Capacitor arrangement is formed between O nano-particles and MWCNTs interfaces and creates condition, is beneficial to The absorption of wave absorbing agent electromagnetic wave energy.
Compared with prior art, the present invention has the beneficial effect that：
1. the present invention is by being simply chemically synthesized Cu2O/MWCNTs composites, Cu2O nano-particles are disorderly It is grown in MWCNTs surfaces and inside.
2. the present invention uses hydro-thermal method, any surfactant is not added with, the method for avoiding traditional plating or chemical plating, Less pollution, preparation method is easy, green, and reaction is easy to control, it is not necessary to expensive equipment, available for industrialized production.
, can be successfully by Cu using simple chemical method 3. preparation method is simple2It is same that O loads to multi-wall carbon nano-tube pipe surface When, also by Cu2O is loaded to inside nanotube, and the nano composite material being prepared does not need other subsequent treatments, is such as protected Shield atmosphere encloses lower calcining etc..
4. there is excellent absorbing property with the lightweight nano composite material that paraffin is mixed with, ripple neck is inhaled available for high temperature Domain, have it is light and can load it is strong the characteristics of, by the multiple loss characteristic and Cu of multi-walled carbon nanotube (MWCNTs)2O Jie Electrical loss characteristic is combined, the novel wave-absorbing material of preparation, can be met that novel wave-absorbing material is light, wave-sucking performance is strong, be absorbed frequency The requirement such as bandwidth, there is higher theory and practice to be worth, there is good application prospect.
Brief description of the drawings
The XRD spectra of Fig. 1 MWCNTs composites；
Fig. 2 Cu2The amplification SEM photograph of O/MWCNTs composites；
Fig. 3 Cu2O/MWCNTs composites Cu2The TEM photos on O load MWCNTs surfaces；
Fig. 4 Cu2O/MWCNTs composites Cu2O is grown on the TEM photos inside MWCNTs；
Fig. 5 Cu2The full spectrograms of XPS of O/MWCNTs composites；
Fig. 6 Cu2The Cu2p of O/MWCNTs composites XPS spectrum figure；
Fig. 7 Cu2The CuLM2 of O/MWCNTs composites XPS spectrum figure；
Fig. 8 Cu2The O1s of O/MWCNTs composites XPS Subdivision Curves；
Fig. 9 Cu2The reflection loss of O/MWCNTs composites is under Different matching thickness degree with frequency variation curve；
Figure 10 Cu2The cole-cole curves of O/MWCNTs composites；
Figure 11 Cu2The conductive network schematic diagram of O/MWCNTs composites.
Embodiment
The present invention is made with reference to specific embodiment further to explain.
1st, raw material sources：Concentrated nitric acid, analyze pure, Shanghai Ying Yuan Chemical Co., Ltd.s；PEG, 95% Aladdin；Hydroxide Sodium, chemical pure, Xilong Chemical Co., Ltd；CuSO4·5H2O, analyze pure, Tianjin Bo Di Chemical Co., Ltd.s；It is anhydrous Ethanol, analyze pure, Wuxi City Ya Sheng Chemical Co., Ltd.s.
2nd, instrument and equipment：JA2003N electronic balances, Shanghai Precision Scientific Apparatus Co., Ltd；XD-1800D ultrasonic waves are thin Born of the same parents crush instrument, Nanjing Xian Ou instrument manufacturings Co., Ltd.
Embodiment 1
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs Portion and surface.
The preparation method of Cu2O/MWCNTs composites：Method and step is as follows：
1) the pretreatment processing of porous wall carbon nano tube：MWCNTs, concentrated nitric acid are sequentially added in 250mL three-necked flasks, After question response terminates, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO4·5H2O and PEG, magnetic agitation is to being completely dissolved；Be placed in ultrasonic reactor ultrasound to reaction system mixed liquor by Blueness is changed into black, reacted mixed liquor is titrated into PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace in lower calcining at constant temperature, by nature The product obtained after cooling is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.020g:120mL.
Reaction condition in the step 1)：4h is reacted at 100 DEG C.
MWCNTs, distilled water, CuSO in the step 2)4·5H2O, PEG mass volume ratio： 0.020g：60mL： 0.150g：0.100g.
The concentration of step 2) the sodium hydroxide solution solution is 1wt%, rate of titration：10S/ drops.
300 DEG C of the temperature of the step 2) calcining at constant temperature, calcination time：2.5h, heating rate：3℃/min-1。
Refering to Fig. 1-11：
Fig. 1 is Cu prepared by embodiment 12The XRD spectra of O/MWCNTs composites；2 θ=29.73 °, 36.58 °, 42.44 °, 61.45 °, 73.64 ° and 77.45 ° and Cu2(JCPDS Card No.05-0667) (110) of O standards, (111), (200), the position consistency corresponding to (220), (311) and (222) crystal face.Characteristic peak at 2 θ=25.57 ° corresponds to MWCNTs Hexagon graphite-structure (002) crystal face, the intensity at the peak are very weak, it may be possible to due to Cu2O nano-particles are distributed in well Caused by MWCNTs.Other characteristic peaks are had no in figure, illustrate to have prepared pure Cu under this experiment condition2O nano-particles.
Fig. 2-4 is Cu2The SEM photograph and TEM photos of O/MWCNTs composites；Fig. 2-3Cu2O nano-particles are disorderly MWCNTs surfaces are attached to, Fig. 4 shows part Cu2O nano-particles are disorderly grown in inside MWCNTs.It can be seen that in Fig. 3 The Cu2O nano-particles and two MWCNTs to intersect that two phases are adjoined are combined closely, and form polarization and capacitor-like structure, This structure is to Cu2The dielectric properties and electric conductivity of O/MWCNTs composites have a significant impact.
It can be detected with combination of the x-ray photoelectron power spectrum (XPS) to copper atom and oxygen atom, Fig. 5 Cu2O/ The XPS spectrum figure of MWCNTs composites.Fig. 6 detects C, O, Cu element in specimen surface, with Cu2The group of O/MWCNTs compounds It is consistent into element.Fig. 7 is Cu2p spectrograms.933.9eV and 954.5eV is respectively Cu2p3/2 and Cu2p1/2 energy spectral peak, than The Cu2p3/2 and Cu2p1/2 of standard power spectrum peak position increase, and being combined to height can direction movement.Illustrate that the chemical environment of copper changes Become, it may be possible to other atoms there occurs coordination, lose part electronics, the cloud density of valence electron reduces, internally The screen effect of shell electron also reduces, so that the combination of inner-shell electron can increase.Fig. 8 is CuLM2 spectrograms.Power spectrum peak position In 916.5eV, show that copper only exists in the form of monovalence copper in composite.Cu2p3/2 and Cu2p1/2 energy spectral peak it Between do not have other peaks occur further eliminate Cu2+The presence of compound.In Fig. 8, the energy spectral peak with reference to energy 530.7eV is The O1s characteristic peaks of carbonylic oxygen atom, the O1s standards combination than carbonylic oxygen atom can be low, and reason is that carbonylic oxygen atom obtains Cu originals The part electronics of son is so that its combination can reduce.Energy spectral peak with reference to energy 532.2eV and 533.4eV is Cu-O and C-O- respectively C O1s characteristic peaks.It can thus be appreciated that：Cu2Interaction between O and MWCNTs is Cu2Copper atom in O nano-particles with Caused by carbonylic oxygen atom in MWCNTs.
Fig. 9 is Cu2The reflection loss of O/MWCNTs composites is under Different matching thickness degree with frequency variation curve.When When wave absorbing agent thickness only has 1.5mm, -28.8dB is reached in 2-18GHz maximum reflections loss value, when reflection loss value is less than -10dB Absorption maximum width be 2.7GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz maximum reflections Loss value reaches -40.5dB.Experimental data illustrates that by adjusting the thickness for the wave absorbing agent prepared different frequency range microwave can be met Absorption.
Cu2What O/MWCNTs composites had outstanding absorbing property is probably dielectric loss, impedance matching and interface Caused by three factor collective effects of relaxation.Dielectric loss is represented according to Debye theory ε ", is made up of conduction loss and polarization.Debye Dielectric relaxor can help to further understand the dielectric loss mechanism of wave absorbing agent.Figure 10 is Cu2O/MWCNTs composites Cole-cole curves.At least occur 4 semicircles in curve, each semicircle represents a Debye relaxation process, illustrates to inhale ripple The dielectric loss of agent is a complicated directric relaxation process.Cu2O-MWCNTs and Cu2O-Cu2O interface polarization can also cause ε " Value increase.
Cu2The key influence factor of the dielectric properties of O/MWCNTs composites is the electric conductivity of compound.Figure 11 is base In Cu2O and MWCNTs electrology characteristic and Cu2The conductive network schematic diagram that O/MWCNTs composite microstructures feature proposes. Cu2This special construction of O/MWCNTs composites can form a conductive network, increase Cu2O nano-particles and MWCNTs Between conductive path.Cu2O nano-particles, which are deposited on MWCNTs and certain chemical interactions between the two be present, to be caused Cu2O nano-particles are fixed on MWCNTs, generation for polarization and in Cu2Electric capacity is formed between O nano-particles and MWCNTs interfaces Device structure creates condition, is beneficial to the absorption of wave absorbing agent electromagnetic wave energy.
Embodiment 2
Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) the pretreatment processing of porous wall carbon nano tube：MWCNTs, concentrated nitric acid are sequentially added in 250mL three-necked flasks, After question response terminates, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO4·5H2O and PEG, magnetic agitation is to being completely dissolved；Be placed in ultrasonic reactor ultrasound to reaction system mixed liquor by Blueness is changed into black, reacted mixed liquor is titrated into PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace in lower calcining at constant temperature, incite somebody to action from The product so obtained after cooling is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.180g:200mL.
Reaction condition in the step 1)：8h is reacted at 140 DEG C.
MWCNTs, distilled water, CuSO in the step 2)4·5H2O, PEG mass volume ratio：0.020g： 100mL： 0.35g：0.300g.
The concentration of step 2) the sodium hydroxide solution solution is 5wt%, rate of titration：10S/ drops.
300 DEG C of the temperature of the step 2) calcining at constant temperature, calcination time：3.5h, heating rate：3℃/min-1。
When wave absorbing agent thickness only has 1.5mm, -26.8dB is reached in 2-18GHz maximum reflections loss value, reflection loss value is small Absorption maximum width when -10dB is 2.5GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz Maximum reflection loss value reaches -42.5dB.
Embodiment 3
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs Portion.
Claim 1 as described in Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) the pretreatment processing of porous wall carbon nano tube：MWCNTs, concentrated nitric acid are sequentially added in 250mL three-necked flasks, After question response terminates, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO4·5H2O and PEG, magnetic agitation is to being completely dissolved；Be placed in ultrasonic reactor ultrasound to reaction system mixed liquor by Blueness is changed into black, reacted mixed liquor is titrated into PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace in lower calcining at constant temperature, incite somebody to action from The product so obtained after cooling is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.10g:160mL.
Reaction condition in the step 1)：6h is reacted at 120 DEG C.
MWCNTs, distilled water, CuSO in the step 2)4·5H2O, PEG mass volume ratio：0.120g： 80mL： 0.25g：0.15g.
The concentration of step 2) the sodium hydroxide solution solution is 3wt%, rate of titration：8S/ drops.
300 DEG C of the temperature of the step 2) calcining at constant temperature, calcination time：3h, heating rate：3℃/min-1。
When wave absorbing agent thickness only has 1.5mm, -30.1dB is reached in 2-18GHz maximum reflections loss value, reflection loss value is small Absorption maximum width when -10dB is 2.3GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz Maximum reflection loss value reaches -41.2dB.
Embodiment 4
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs tables Face and inside.
Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) pretreatment of multi-walled carbon nanotube：MWCNTs, concentrated nitric acid, question response are sequentially added in 250mL three-necked flasks After end, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO45H2O and PEG, magnetic agitation is to being completely dissolved；Ultrasound is placed in ultrasonic reactor to reaction system mixed liquor Black is changed into from blueness, reacted mixed liquor is titrated to PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace calcining at constant temperature at 300 DEG C, The product obtained after Temperature fall is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.060g:130mL.
Reaction condition in the step 1)：4-8h is reacted at 100-140 DEG C.
MWCNTs, distilled water, CuSO45H in the step 2)2O, PEG mass volume ratio：0.32g： 65mL： 0.18g：0.16g.
The concentration of step 2) the sodium hydroxide solution solution is 2.5wt%, rate of titration：6S/ drops.
Step 2) the calcination time：3.0h, heating rate：3℃/min-1。
Cu prepared by the application method2O/MWCNTs composites.
When wave absorbing agent thickness only has 1.5mm, -28.4dB is reached in 2-18GHz maximum reflections loss value, reflection loss value is small Absorption maximum width when -10dB is 2.9GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz Maximum reflection loss value reaches -43.5dB.
Embodiment 5
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs tables Face and inside.
Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) pretreatment of multi-walled carbon nanotube：MWCNTs, concentrated nitric acid, question response are sequentially added in 250mL three-necked flasks After end, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO45H2O and PEG, magnetic agitation is to being completely dissolved；Ultrasound is placed in ultrasonic reactor to reaction system mixed liquor Black is changed into from blueness, reacted mixed liquor is titrated to PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace calcining at constant temperature at 300 DEG C, The product obtained after Temperature fall is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.035g:160mL.
Reaction condition in the step 1)：5.5h is reacted at 125 DEG C.
MWCNTs, distilled water, CuSO45H in the step 2)2O, PEG mass volume ratio：0.320g：60- 100mL：0.26g：0.175g.
The concentration of step 2) the sodium hydroxide solution solution is 1-5wt%, rate of titration：5-10S/ drops.
Step 2) the calcination time：3.0h, heating rate：3℃/min-1。
Cu prepared by the application method2O/MWCNTs composites.
When wave absorbing agent thickness only has 1.5mm, -24.2dB is reached in 2-18GHz maximum reflections loss value, reflection loss value is small Absorption maximum width when -10dB is 2.5GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz Maximum reflection loss value reaches -39.8dB.
Embodiment 6
A kind of Cu2O/MWCNTs composites, the Cu in the composite wood2O nano-particles are disorderly grown in MWCNTs tables Face and inside.
Cu2The preparation method of O/MWCNTs composites：Method and step is as follows：
1) pretreatment of multi-walled carbon nanotube：MWCNTs, concentrated nitric acid, question response are sequentially added in 250mL three-necked flasks After end, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain through concentrated nitric acid acidification MWCNTs；
2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, distinguished again after ultrasonic disperse 1h Add CuSO45H2O and PEG, magnetic agitation is to being completely dissolved；Ultrasound is placed in ultrasonic reactor to reaction system mixed liquor Black is changed into from blueness, reacted mixed liquor is titrated to PH=11 with sodium hydroxide solution, then use magnetic stirrer 120min；Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, by the solid black of collection Particle, which is put into baking oven at 60 DEG C, dries 12h, then obtained sheet sample is put into tube furnace calcining at constant temperature at 300 DEG C, The product obtained after Temperature fall is milled to obtain Cu2O/MWCNTs composites.
MWCNTs, concentrated nitric acid mass volume ratio in the step 1)：0.160g:190mL.
Reaction condition in the step 1)：4.6h is reacted at 138 DEG C.
MWCNTs, distilled water, CuSO45H in the step 2)2O, PEG mass volume ratio：0.284g： 60- 100mL：0.32g：0.176g.
The concentration of step 2) the sodium hydroxide solution solution is 4.2wt%, rate of titration：9S/ drops.
Step 2) the calcination time：3.0h, heating rate：3℃/min-1。
Cu prepared by the application method2O/MWCNTs composites.
When wave absorbing agent thickness only has 1.5mm, -29.1dB is reached in 2-18GHz maximum reflections loss value, reflection loss value is small Absorption maximum width when -10dB is 2.4GHz (10.7-13.4GHz), when wave absorbing agent thickness is 2.0mm, in 2-18GHz Maximum reflection loss value reaches -38.5dB.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (9)

  1. A kind of 1. Cu2O/MWCNTs composites, it is characterised in that the Cu in the composite wood2O nano-particles disorderly grow In MWCNTs surfaces and inside.
  2. 2. Cu as claimed in claim 12The preparation method of O/MWCNTs composites, it is characterised in that：Method and step is as follows：
    1) pretreatment of multi-walled carbon nanotube：MWCNTs, concentrated nitric acid are sequentially added in 250mL three-necked flasks, question response terminates Afterwards, stand, filter, washing, and spent in 55 DEG C in baking oven and be dried in vacuo 24h, obtain the MWCNTs through concentrated nitric acid acidification；
    2)Cu2The preparation of O/MWCNTs composites：MWCNTs is added in distilled water, is separately added into again after ultrasonic disperse 1h CuSO4·5H2O and PEG, magnetic agitation is to being completely dissolved；Ultrasound is placed in ultrasonic reactor to reaction system mixed liquor by blueness It is changed into black, reacted mixed liquor is titrated to PH=11 with sodium hydroxide solution, then with magnetic stirrer 120min； Reaction adds ethanol after terminating and distillation water washing obtains solid black particle afterwards for several times, and the solid black particle of collection is put into 12h is dried in baking oven at 60 DEG C, then obtained sheet sample is put into tube furnace calcining at constant temperature at 300 DEG C, by natural drop The product obtained after temperature is milled to obtain Cu2O/MWCNTs composites.
  3. A kind of 3. Cu according to claim 22The preparation method of O/MWCNTs composites, it is characterised in that the step 1) MWCNTs, concentrated nitric acid mass volume ratio in：0.020-0.180g:120-200mL.
  4. A kind of 4. Cu according to claim 22The preparation method of O/MWCNTs composites, it is characterised in that the step 1) reaction condition in：4-8h is reacted at 100-140 DEG C.
  5. A kind of 5. Cu according to any one of claim 22The preparation method of O/MWCNTs composites, it is characterised in that institute State MWCNTs in step 2), distilled water, CuSO4·5H2O, PEG mass volume ratio：0.020-0.32g：60-100mL： 0.150-0.35g：0.100-0.300g.
  6. A kind of 6. Cu according to any one of claim 22The preparation method of the preparation method of O/MWCNTs composites, its It is characterised by, the concentration of step 2) the sodium hydroxide solution solution is 1-5wt%, rate of titration：5-10S/ drops.
  7. A kind of 7. Cu according to any one of claim 22The preparation method of O/MWCNTs composites, it is characterised in that institute State step 2) calcination time：2.5-3.5h, heating rate：3℃/min-1。
  8. 8. Cu prepared by any one method of claim 2-72O/MWCNTs composites.
  9. 9. Cu according to claim 82Application of the O/MWCNTs composites in absorbing material.
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