CN104900867B - Preparation method of CNT/Co/MoS2 composite material - Google Patents
Preparation method of CNT/Co/MoS2 composite material Download PDFInfo
- Publication number
- CN104900867B CN104900867B CN201510271300.8A CN201510271300A CN104900867B CN 104900867 B CN104900867 B CN 104900867B CN 201510271300 A CN201510271300 A CN 201510271300A CN 104900867 B CN104900867 B CN 104900867B
- Authority
- CN
- China
- Prior art keywords
- cnt
- mos
- composite
- preparation
- mass fraction
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a CNT/Co/MoS2 composite material, relates to a modification method of MoS2, and aims at solving the problems that according to the existing surface modification method of MoS2, after modification, MoS2 still has hydrophobicity, or serious environment pollution problem is caused as a great deal of organic solvents are used in the existing surface modification method. The preparation method provided by the invention comprises the following steps: 1. performing acid treatment so as to obtain an acidized carbon nano tube; 2. preparing CNT/Co; and 3. loading MoS2 so as to obtain the CNT/Co/MoS2 composite material. The preparation method has the advantage that the surface of carbon nano tube can be uniformly coated by MoS2. The technology is used for preparing the CNT/Co/MoS2 composite material.
Description
Technical field
The present invention relates to a kind of MoS2Method of modifying.
Background technology
China's molybdenite produces aboundresources, molybdenite (MoS2) there are many excellent properties, such as lubrication, catalysis, energy
Amount storage and photoelectric property enjoy the favor of science and industrial circle.Particularly catalytic performance, compared with traditional catalyst, MoS2
Not only there is very high catalytic efficiency, while it can also be prevented effectively from the noble metals such as the Pt sulfur that Jing often occurs in catalytic process
Change hydrogen intoxicating phenomenon.But, in MoS2Major applications during, such as catalysis, energy stores, because molybdenite it is water insoluble,
MoS can directly be limited2Application.At present, solve this problem to rely primarily on：1) resynthesis of molybdate and sulphur source；2) having
Under machine solvent is participated in, surfactant is to MoS2Surface be modified.By molybdate and resynthesis method of the sulphur source to molybdenum sulfide,
Although the higher MoS of catalysis activity can be obtained2, but the higher MoS of the catalysis activity that obtains of the method2Yet suffer from hydrophobicity
Problem；Second surface modifying treatment can cause serious problem of environmental pollution because being related to a large amount of organic solvents, then, together
When be also difficult to produce in batches.
The content of the invention
The invention aims to solve existing MoS2Surface modifying treatment there is modified MoS2Yet suffer from
Hydrophobic problem, or surface modifying treatment causes serious problem of environmental pollution because being related to a large amount of organic solvents, and
A kind of CNT/Co/MoS is provided2The preparation method of composite.
A kind of CNT/Co/MoS2The preparation method of composite, is specifically realized by the following steps：First, acid treatment：Will
CNT is put in acid carries out acid treatment, CNT after being acidified；2nd, CNT/Co is prepared：Will under ultrasonic assistant
CNT is evenly spread in distilled water after acidifying, obtains carbon nano tube dispersion liquid, then by cobalt nitrate under ultrasonic state
In being dissolved in carbon nano tube dispersion liquid, carbon nanotube mixture containing cobalt is obtained, to carbon nanotube mixture containing cobalt under ultrasonic state
Middle Deca sodium borohydride aqueous solution, is then filtered, and solid phase filtrate is rinsed using deionized water, rinses 2～4
It is secondary, solid phase filtrate after being cleaned, then solid phase filtrate after cleaning is vacuum dried, obtain CNT/Co；In step 2
The mass fraction of CNT is 0.1%～1% after being acidified in described carbon nano tube dispersion liquid；Described in step 2 containing cobalt
The mass fraction of cobalt nitrate is 0.3%～3% in carbon nanotube mixture；Sodium borohydride aqueous solution described in step 2 and steaming
The volume ratio of distilled water is (0.8～1.2):In 10, and described sodium borohydride aqueous solution the mass fraction of sodium borohydride be 2%～
30%；3rd, MoS is loaded2：CNT/Co is evenly spread in distilled water under ultrasonic assistant, obtains CNT/Co dispersion liquids, so
Afterwards by MoS under ultrasonic state2Powder body adds CNT/Co dispersion liquids, and continual ultrasonic dispersion 2h～5h, obtains mixture, stands
Layering, takes subnatant and is filtered, and obtains solid formation, and solid formation is rinsed using deionized water, rinses to filtering liquid table
Till face is without metallic luster, solid formation after being cleaned, then solid formation after cleaning is vacuum dried, obtain CNT/Co/
MoS2Composite, the mass fraction of CNT/Co is 0.1%～1% in the CNT/Co dispersion liquids described in step 3, step 3
Described in mixture in MoS2The mass fraction of powder body is 0.2%～3%.
Advantage of the present invention：First, the present invention prepares CNT/Co/MoS2Commercially available MoS is directly used in the method for composite2Powder
Body is preparing raw material, and course of reaction is normal temperature and pressure preparation process, and required consersion unit is also simple, low cost；2nd, this
Bright employing magnetic synthetic method, MoS2It is more uniform in the cladding ratio of carbon nano tube surface；3rd, the present invention prepares CNT/Co/MoS2It is multiple
The method of condensation material is suitable for scale and is combined to；4th, CNT/Co/MoS prepared by the present invention2Composite is in catalyst, the sun
The aspects such as energy battery, lithium ion battery, sensor have a wide range of applications.
Description of the drawings
Fig. 1 is to test the CNT/Co isothermal hysteresis curve figures that a step 2 is obtained；
Fig. 2 is to test a CNT/Co/MoS for obtaining2Composite isothermal hysteresis curve figure；
Fig. 3 is the cyclic voltammetric spectrogram of CNT/Co working electrodes；
Fig. 4 is CNT/Co/MoS2The cyclic voltammetric spectrogram of working electrode；
Fig. 5 is to test the CNT/Co Raman spectrograms that a step 2 is obtained；
Fig. 6 is to test a CNT/Co/MoS for obtaining2Composite Raman spectrogram；
Fig. 7 is CNT/Co/MoS2Working electrode is to H2The I-t response curves of S alkaline solutions；
Fig. 8 is to test the CNT/Co scanning electron microscope (SEM) photographs that two step 2 are obtained；
Fig. 9 is CNT/Co/MoS prepared by this test2Composite scanning electron microscope (SEM) photograph；
Figure 10 is to test the CNT/Co projection electron microscopes that two step 2 are obtained；
Figure 11 is CNT/Co/MoS prepared by this test2Composite projects electron microscope.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of CNT/Co/MoS2The preparation method of composite, specifically presses
What following steps were completed：First, acid treatment：CNT is put in acid carries out acid treatment, CNT after being acidified；2nd,
Prepare CNT/Co：Under ultrasonic assistant by acidifying after CNT evenly spread in distilled water, obtain CNT dispersion
Liquid, is then dissolved in cobalt nitrate in carbon nano tube dispersion liquid under ultrasonic state, carbon nanotube mixture containing cobalt is obtained, in ultrasound
To Deca sodium borohydride aqueous solution in carbon nanotube mixture containing cobalt under state, then filtered, using deionized water to solid
Phase filtrate is rinsed, and rinses 2～4 times, solid phase filtrate after being cleaned, then carries out vacuum to solid phase filtrate after cleaning
It is dried, obtains CNT/Co；The mass fraction of CNT is 0.1% after being acidified in carbon nano tube dispersion liquid described in step 2
～1%；The mass fraction of cobalt nitrate is 0.3%～3% in carbon nanotube mixture containing cobalt described in step 2；In step 2
Described sodium borohydride aqueous solution is (0.8～1.2) with the volume ratio of distilled water:In 10, and described sodium borohydride aqueous solution
The mass fraction of sodium borohydride is 2%～30%；3rd, MoS is loaded2：CNT/Co is evenly spread to into steaming under ultrasonic assistant
In distilled water, CNT/Co dispersion liquids are obtained, then by MoS under ultrasonic state2Powder body adds CNT/Co dispersion liquids, and continual ultrasonic
Dispersion 2h～5h, obtains mixture, and stratification takes subnatant and filtered, and solid formation is obtained, using deionized water to solid phase
Thing is rinsed, and rinses to liquid surface is filtered without metallic luster, solid formation after being cleaned, then solid formation after cleaning is entered
Row vacuum drying, obtains CNT/Co/MoS2Composite, the quality of CNT/Co point in the CNT/Co dispersion liquids described in step 3
Number is 0.1%～1%, MoS in the mixture described in step 32The mass fraction of powder body is 0.2%～3%.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Acid described in step one
For concentrated nitric acid-concentrated sulphuric acid nitration mixture, the volume ratio 1 of described concentrated nitric acid and concentrated sulphuric acid:3, the mass fraction of the concentrated nitric acid is
60%～68%, the mass fraction of the concentrated sulphuric acid is 68%～75%.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment is with the difference of specific embodiment one or one of two：Institute in step one
The acid treatment concrete operations stated are as follows：CNT is put in concentrated nitric acid-concentrated sulphuric acid nitration mixture, in the case where temperature is for 50 DEG C at ultrasound
Reason 6h, that is, complete acid treatment, and the described quality of CNT and the volume ratio of concentrated nitric acid-concentrated sulphuric acid nitration mixture is 1g:40mL.Its
He is identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step 2
The vacuum drying concrete operations stated are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.Other are with specific embodiment one to three-phase
Together.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Institute in step 2
The mass fraction of CNT is 0.1%～0.5% after being acidified in the carbon nano tube dispersion liquid stated.Other and specific embodiment
One to four is identical.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Institute in step 2
The mass fraction of cobalt nitrate is 0.6%～1.5% in the carbon nanotube mixture containing cobalt stated.Other with specific embodiment one to
Five is identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Institute in step 2
The sodium borohydride aqueous solution stated is 1 with the volume ratio of distilled water:The matter of sodium borohydride in 10, and described sodium borohydride aqueous solution
Amount fraction is 2%～10%.Other are identical with specific embodiment one to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Institute in step 3
The vacuum drying concrete operations stated are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.Other and the phase of specific embodiment one to seven
Together.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Institute in step 3
The mass fraction of CNT/Co is 0.1%～0.5% in the CNT/Co dispersion liquids stated.Other and the phase of specific embodiment one to eight
Together.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Institute in step 3
MoS in the mixture stated2The mass fraction of powder body is 0.2%～1%.Other are identical with specific embodiment one to nine.
Using following verification experimental verifications effect of the present invention
Test one：A kind of CNT/Co/MoS2The preparation method of composite, is specifically realized by the following steps：First, acid
Process：CNT is put in acid carries out acid treatment, CNT after being acidified；2nd, CNT/Co is prepared：It is auxiliary in ultrasound wave
Help it is lower CNT after acidifying is evenly spread in distilled water, obtain carbon nano tube dispersion liquid, then under ultrasonic state will
600mg cobalt nitrates are dissolved in 100mL carbon nano tube dispersion liquids, obtain carbon nanotube mixture containing cobalt, to containing under ultrasonic state
Deca 10mL mass fraction is 5% sodium borohydride solution in cobalt carbon nanotube mixture, is then filtered, using deionization
Water is rinsed to solid phase filtrate, rinses 3 times, solid phase filtrate after being cleaned, then solid phase filtrate after cleaning is carried out
Vacuum drying, obtains CNT/Co；The mass fraction of CNT is after being acidified in carbon nano tube dispersion liquid described in step 2
0.1%；3rd, MoS is loaded2：CNT/Co is evenly spread in distilled water under ultrasonic assistant, obtains CNT/Co dispersion liquids,
Then by MoS under ultrasonic state2Powder body adds CNT/Co dispersion liquids, and continual ultrasonic dispersion 2h, obtains mixture, stands and divides
Layer, takes subnatant and is filtered, and obtains solid formation, and solid formation is rinsed using deionized water, rinses to filtering liquid surface
Till without metallic luster, solid formation after being cleaned, then solid formation after cleaning is vacuum dried, obtain CNT/Co/MoS2
Composite, the mass fraction of CNT/Co is 0.1% in the CNT/Co dispersion liquids described in step 3, mixed described in step 3
MoS in compound2The mass fraction of powder body is 0.2%.
Acid described in this test procedure one is concentrated nitric acid-concentrated sulphuric acid nitration mixture, the volume of described concentrated nitric acid and concentrated sulphuric acid
Than 1:3, the mass fraction of the concentrated nitric acid is 65%, and the mass fraction of the concentrated sulphuric acid is 70%.
Acid treatment concrete operations described in this test procedure one are as follows：CNT is put into into concentrated nitric acid-concentrated sulphuric acid to mix
It is supersound process 6h at 50 DEG C in temperature in acid, that is, completes acid treatment, the quality and concentrated nitric acid-dense sulfur of described CNT
The volume ratio of sour nitration mixture is 1g:40mL.
Vacuum drying concrete operations described in this test procedure two are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
Vacuum drying concrete operations described in this test procedure three are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
The CNT/Co/MoS that the CNT/Co and this test obtained to this test procedure two is obtained2Composite carries out magnetic survey
Examination, as depicted in figs. 1 and 2, Fig. 1 is to test the CNT/Co isothermal hysteresis curve figures that a step 2 is obtained to test result；Fig. 2 is examination
Test a CNT/Co/MoS for obtaining2Composite isothermal hysteresis curve figure；This test procedure two can be seen that by Fig. 1 and Fig. 2
The CNT/Co/MoS that the CNT/Co and this test for obtaining is obtained2Composite is ferromagnetic material, and with magnetic saturation phenomenon.
When in CNT/Co outer layers load MoS2When, the magnetic enhancement of material, magnetic moment increase illustrates the CNT/Co/MoS that this test is obtained2It is multiple
MoS in condensation material2With ferromagnetism.
The CNT/Co/MoS that the CNT/Co and this test obtained to this test procedure two is obtained2Composite carries out electrochemistry
Test, concrete grammar is as follows：
The CNT/Co that 2mg this test procedure two is obtained is dispersed in into the Nafion- ethanol solution of 10mL 0.5% (V/W)
In, dispersion liquid is obtained, then dispersant liquid drop is coated in into clean glassy carbon electrode surface, and (glass-carbon electrode is polished successively, cleaning is done
Net glass-carbon electrode), CNT/Co working electrodes are obtained after natural drying.
The CNT/Co/MoS that 2mg this test is obtained2Composite is dispersed in the Nafion- second of 10mL 0.5% (V/W)
In alcoholic solution, dispersion liquid is obtained, then dispersant liquid drop is coated in into clean glassy carbon electrode surface, and (glass-carbon electrode is polished successively, cleaning
Obtain clean glass-carbon electrode), CNT/Co/MoS is obtained after natural drying2Working electrode.
Respectively with CNT/Co working electrodes and CNT/Co/MoS2Working electrode as working electrode, pH=7.0's
NaH2PO4/Na2HPO4Electro-chemical test is carried out in buffer solution, speed is swept：50mV/s, test result as shown in Figure 3 and Figure 4, Fig. 3
It is the cyclic voltammetric spectrogram of CNT/Co working electrodes；Fig. 4 is CNT/Co/MoS2The cyclic voltammetric spectrogram of working electrode；By Fig. 3
Understand with Fig. 4, CNT/Co/MoS2The cyclic voltammetry spectrum feature peak shape of working electrode, position are not in CNT/Co work electricity
The result being superimposed on the basis of the cyclic voltammetric spectrogram of pole, but have skew (0.5V and 1.5V or so) and the new peak (- 1.8V at peak
Left and right) appearance, illustrate MoS2Not only successfully it is supported in CNT/Co substrates, and MoS2Have with CNT/Co substrates and mutually cooperate with
Effect is produced.
The CNT/Co/MoS that the CNT/Co and this test obtained to this test procedure two is obtained2Composite carries out Raman light
Analysis of spectrum, as shown in Figure 5 and Figure 6, Fig. 5 is to test the CNT/Co Raman spectrograms that a step 2 is obtained to test result；Fig. 6 is examination
Test a CNT/Co/MoS for obtaining2Composite Raman spectrogram；By Fig. 5 and Fig. 6 spectrogram interpretations of result：1326cm-1、
1575cm-1It is nearby the feature D peak and G peaks of CNT, 369cm-1、408cm-1The peak of left and right is MoS2E2g 1And A1gFeature
Peak, with MoS2Normalized Raman spectrogram contrast find, E2g 1There is blue shift and A in peak position1gThere is red shift, explanation in characteristic peak positions
In CNT/Co/MoS2MoS in composite2Layer structure change, monolayer or few Rotating fields are changed into from multiple structure, i.e.,
Sheet MoS2It is peeling-off.This kind of MoS2Stripping, cause lamellar MoS2The generation or appearance of edge defect, is that this is tested
The CNT/Co/MoS for arriving2MoS in composite2Produce ferromagnetic basic reason.
Test two：A kind of CNT/Co/MoS2The preparation method of composite, is specifically realized by the following steps：First, acid
Process：CNT is put in acid carries out acid treatment, CNT after being acidified；2nd, CNT/Co is prepared：It is auxiliary in ultrasound wave
Help it is lower CNT after acidifying is evenly spread in distilled water, obtain carbon nano tube dispersion liquid, then under ultrasonic state will
1500mg cobalt nitrates are dissolved in 100mL carbon nano tube dispersion liquids, obtain carbon nanotube mixture containing cobalt, to containing under ultrasonic state
Deca 10mL mass fraction is 5% sodium borohydride solution in cobalt carbon nanotube mixture, is then filtered, using deionization
Water is rinsed to solid phase filtrate, rinses 3 times, solid phase filtrate after being cleaned, then solid phase filtrate after cleaning is carried out
Vacuum drying, obtains CNT/Co；The mass fraction of CNT is after being acidified in carbon nano tube dispersion liquid described in step 2
0.5%；3rd, MoS is loaded2：CNT/Co is evenly spread in distilled water under ultrasonic assistant, obtains CNT/Co dispersion liquids,
Then by MoS under ultrasonic state2Powder body adds CNT/Co dispersion liquids, and continual ultrasonic dispersion 2h, obtains mixture, stands and divides
Layer, takes subnatant and is filtered, and obtains solid formation, and solid formation is rinsed using deionized water, rinses to filtering liquid surface
Till without metallic luster, solid formation after being cleaned, then solid formation after cleaning is vacuum dried, obtain CNT/Co/MoS2
Composite, the mass fraction of CNT/Co is 0.2% in the CNT/Co dispersion liquids described in step 3, mixed described in step 3
MoS in compound2The mass fraction of powder body is 0.5%.
Acid described in this test procedure one is concentrated nitric acid-concentrated sulphuric acid nitration mixture, the volume of described concentrated nitric acid and concentrated sulphuric acid
Than 1:3, the mass fraction of the concentrated nitric acid is 65%, and the mass fraction of the concentrated sulphuric acid is 70%.
Acid treatment concrete operations described in this test procedure one are as follows：CNT is put into into concentrated nitric acid-concentrated sulphuric acid to mix
It is supersound process 6h at 50 DEG C in temperature in acid, that is, completes acid treatment, the quality and concentrated nitric acid-dense sulfur of described CNT
The volume ratio of sour nitration mixture is 1g:40mL.
Vacuum drying concrete operations described in this test procedure two are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
Vacuum drying concrete operations described in this test procedure three are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
Detect CNT/Co/MoS prepared by this test2Composite is to H2The I-t response curves of S alkaline solutions, concrete mistake
Journey is as follows：
The CNT/Co/MoS that 2mg this test is obtained2Composite is dispersed in the Nafion- second of 10mL 0.05% (V/W)
In alcoholic solution, dispersion liquid is obtained, then 15 μ L dispersant liquid drops are coated in into polishing glassy carbon electrode surface (glass-carbon electrode 0.3 μm of Jing successively
α-Al2O3Powder and 0.05 μm of α-Al2O3Powder polishing obtains polishing clean glass-carbon electrode), CNT/ is obtained after natural drying
Co/MoS2Working electrode.
With CNT/Co/MoS2Working electrode as working electrode, by CNT/Co/MoS2Working electrode is put into H2S alkaline solutions
(H2S alkaline solutions are by H2S, NaOH and deionized water are mixed, pH be 7.3) in, be to electrode, calomel electrode with platinum electrode
For auxiliary electrode, current-vs-time test is carried out.After test carries out 50 seconds, every 20 seconds 75 μ LH were added2S alkaline solutions.Test
As a result as shown in fig. 7, Fig. 7 is CNT/Co/MoS2Working electrode is to H2The I-t response curves of S alkaline solutions；Can by Fig. 7
Know, CNT/Co/MoS2Working electrode in applied voltage 0.5V or so, with H2S alkaline solution additions are on the increase, electric current
Increment is continued to increase, and stabling current value also increases therewith, and response time is about 0.2 second, shows CNT/Co/MoS2Working electrode
Show obvious H2S sensitive properties, it was demonstrated that CNT/Co/MoS prepared by this test2Prepared by composite can be in H2S or Na2S is passed
Inductor component aspect is applied.
Fig. 8 is to test the CNT/Co scanning electron microscope (SEM) photographs that two step 2 are obtained；Fig. 9 is CNT/Co/MoS prepared by this test2
Composite scanning electron microscope (SEM) photograph；Figure 10 is to test the CNT/Co transmission electron microscope pictures that two step 2 are obtained；Figure 11 is prepared by this test
CNT/Co/MoS2Composite transmission electron microscope picture；By Fig. 8-11, CNT/Co and this examination that two step 2 are obtained are tested
Test the CNT/Co/MoS of preparation2The TEM figure nanotube walls thickness of composite is uniform, illustrates CNT surface Co and MoS2Distribution is equal
It is even, CNT/Co/MoS2Pipe thickness be about 12nm or so, the pipe thickness of CNT/Co is about 7nm or so, illustrates MoS2Uniformly
It is coated in CNT substrates.
Claims (10)
1. a kind of CNT/Co/MoS2The preparation method of composite, it is characterised in that CNT/Co/MoS2The preparation side of composite
Method is completed according to the following steps：First, acid treatment：CNT is put in acid carries out acid treatment, carbon nanometer after being acidified
Pipe；2nd, CNT/Co is prepared：Under ultrasonic assistant by acidifying after CNT evenly spread in distilled water, obtain carbon nanometer
Pipe dispersion liquid, is then dissolved in cobalt nitrate in carbon nano tube dispersion liquid under ultrasonic state, obtains carbon nanotube mixture containing cobalt,
To Deca sodium borohydride aqueous solution in carbon nanotube mixture containing cobalt under ultrasonic state, then filtered, using deionization
Water is rinsed to solid phase filtrate, rinses 2～4 times, solid phase filtrate after being cleaned, then solid phase filtrate after cleaning is entered
Row vacuum drying, obtains CNT/Co；The mass fraction of CNT after being acidified in carbon nano tube dispersion liquid described in step 2
For 0.1%～1%；The mass fraction of cobalt nitrate is 0.3%～3% in carbon nanotube mixture containing cobalt described in step 2；
Sodium borohydride aqueous solution described in step 2 is (0.8～1.2) with the volume ratio of distilled water:10, and described sodium borohydride
The mass fraction of sodium borohydride is 2%～30% in aqueous solution；3rd, MoS is loaded2：It is under ultrasonic assistant that CNT/Co is uniform
In being distributed to distilled water, CNT/Co dispersion liquids are obtained, then by MoS under ultrasonic state2Powder body adds CNT/Co dispersion liquids, and
Continual ultrasonic disperses 2h～5h, obtains mixture, and stratification takes subnatant and filtered, and solid formation is obtained, using deionization
Water is rinsed to solid formation, rinses to liquid surface is filtered without metallic luster, solid formation after being cleaned, then to cleaning after
Solid formation is vacuum dried, and obtains CNT/Co/MoS2Composite, CNT/Co in the CNT/Co dispersion liquids described in step 3
Mass fraction be 0.1%～1%, MoS in the mixture described in step 32The mass fraction of powder body is 0.2%～3%.
2. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step one
Described acid is concentrated nitric acid-concentrated sulphuric acid nitration mixture, the volume ratio 1 of described concentrated nitric acid and concentrated sulphuric acid:3, the quality of the concentrated nitric acid
Fraction is 60%～68%, and the mass fraction of the concentrated sulphuric acid is 68%～75%.
3. a kind of CNT/Co/MoS according to claim 22The preparation method of composite, it is characterised in that in step one
Described acid treatment concrete operations are as follows：CNT is put in concentrated nitric acid-concentrated sulphuric acid nitration mixture, the ultrasound in the case where temperature is for 50 DEG C
6h is processed, that is, completes acid treatment, the described quality of CNT and the volume ratio of concentrated nitric acid-concentrated sulphuric acid nitration mixture is 1g:40mL.
4. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 2
Described vacuum drying concrete operations are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
5. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 2
The mass fraction of CNT is 0.1%～0.5% after being acidified in described carbon nano tube dispersion liquid.
6. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 2
The mass fraction of cobalt nitrate is 0.6%～1.5% in described carbon nanotube mixture containing cobalt.
7. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 2
Described sodium borohydride aqueous solution is 1 with the volume ratio of distilled water:Sodium borohydride in 10, and described sodium borohydride aqueous solution
Mass fraction is 2%～10%.
8. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 3
Described vacuum drying concrete operations are as follows：6h is vacuum dried in the case where temperature is for 70 DEG C.
9. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 3
The mass fraction of CNT/Co is 0.1%～0.5% in described CNT/Co dispersion liquids.
10. a kind of CNT/Co/MoS according to claim 12The preparation method of composite, it is characterised in that in step 3
MoS in described mixture2The mass fraction of powder body is 0.2%～1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510271300.8A CN104900867B (en) | 2015-05-25 | 2015-05-25 | Preparation method of CNT/Co/MoS2 composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510271300.8A CN104900867B (en) | 2015-05-25 | 2015-05-25 | Preparation method of CNT/Co/MoS2 composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104900867A CN104900867A (en) | 2015-09-09 |
| CN104900867B true CN104900867B (en) | 2017-04-12 |
Family
ID=54033385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510271300.8A Expired - Fee Related CN104900867B (en) | 2015-05-25 | 2015-05-25 | Preparation method of CNT/Co/MoS2 composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104900867B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106611837A (en) * | 2015-10-27 | 2017-05-03 | 上海交通大学 | Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof |
| CN106925303B (en) * | 2017-04-24 | 2019-12-27 | 吉林师范大学 | MoS2/CNTs/C60Composite photocatalyst and preparation method thereof |
| CN107834040A (en) * | 2017-09-28 | 2018-03-23 | 浙江工业大学 | A kind of lithium battery porous carbon negative pole material of bio-based N doping of load molybdenum disulfide and preparation method thereof |
| CN108220828A (en) * | 2018-01-30 | 2018-06-29 | 东莞颠覆产品设计有限公司 | A kind of amorphous alloy composite material and its preparation method and application |
| CN109273726A (en) * | 2018-02-08 | 2019-01-25 | 成都理工大学 | A kind of carbon coated air electrode material and its preparation method and application |
| CN109786673A (en) * | 2019-01-10 | 2019-05-21 | 湘潭大学 | A kind of preparation process of lithium ion battery flexible compound self-supporting electrode |
| CN110380028B (en) * | 2019-07-08 | 2022-09-09 | 武汉理工大学 | CNT/MoS 2 Lithium ion battery cathode material and preparation method thereof |
| CN111250112A (en) * | 2020-03-19 | 2020-06-09 | 武汉理工大学 | High-performance electro-catalytic hydrogen evolution heterogeneous composite catalyst and preparation method thereof |
| CN115155621A (en) * | 2022-05-19 | 2022-10-11 | 福州大学 | Co-MoS 2 /CNT (carbon nano tube) photocatalytic modified film as well as preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613918A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Hydrothermal synthetic method for coating carbon nanometer tube with molybdenum sulphide |
| CN102151575A (en) * | 2011-01-29 | 2011-08-17 | 浙江师范大学 | Method for preparing carbon nanometer tube loaded type catalyst |
| CN102327782A (en) * | 2011-07-06 | 2012-01-25 | 哈尔滨工业大学 | Preparation method of cobalt nanoparticle/carbon nanotube composite material |
| CN103318872A (en) * | 2013-07-03 | 2013-09-25 | 北京理工大学 | Preparation method of carbon nano tubes |
| CN103553134A (en) * | 2013-11-08 | 2014-02-05 | 合肥工业大学 | Composite nanotube composed of molybdenum disulfide-carbon-carbon nanotube and preparation method thereof |
| CN103617893A (en) * | 2013-11-16 | 2014-03-05 | 信阳师范学院 | Supercapacitor electrode material molybdenum sulfide-multiwalled carbon nanotube and preparation method thereof |
| CN104386753A (en) * | 2014-11-21 | 2015-03-04 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotube |
-
2015
- 2015-05-25 CN CN201510271300.8A patent/CN104900867B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613918A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Hydrothermal synthetic method for coating carbon nanometer tube with molybdenum sulphide |
| CN102151575A (en) * | 2011-01-29 | 2011-08-17 | 浙江师范大学 | Method for preparing carbon nanometer tube loaded type catalyst |
| CN102327782A (en) * | 2011-07-06 | 2012-01-25 | 哈尔滨工业大学 | Preparation method of cobalt nanoparticle/carbon nanotube composite material |
| CN103318872A (en) * | 2013-07-03 | 2013-09-25 | 北京理工大学 | Preparation method of carbon nano tubes |
| CN103553134A (en) * | 2013-11-08 | 2014-02-05 | 合肥工业大学 | Composite nanotube composed of molybdenum disulfide-carbon-carbon nanotube and preparation method thereof |
| CN103617893A (en) * | 2013-11-16 | 2014-03-05 | 信阳师范学院 | Supercapacitor electrode material molybdenum sulfide-multiwalled carbon nanotube and preparation method thereof |
| CN104386753A (en) * | 2014-11-21 | 2015-03-04 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotube |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104900867A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104900867B (en) | Preparation method of CNT/Co/MoS2 composite material | |
| Chen et al. | Facile synthesis of self-assembled carbon nanotubes/dye composite films for sensitive electrochemical determination of Cd (II) ions | |
| Zhu et al. | Surface engineering of carbon fiber paper toward exceptionally high-performance and stable electrochemical nitrite sensing | |
| CN106115805B (en) | The preparation method of the sour nickel/mos2 microsphere of nanometer hierarchy cobalt | |
| Liu et al. | In situ synthesis of ceria nanoparticles in the ordered mesoporous carbon as a novel electrochemical sensor for the determination of hydrazine | |
| Cao et al. | Two-dimensional porous micro/nano metal oxides templated by graphene oxide | |
| CN106558423B (en) | Fe2O3Laminar nano array, the Fe with layer structure2O3/ PPy flexible composites and preparation and application | |
| CN102107909B (en) | Method for preparing mesoporous nano manganese dioxide | |
| CN107785181A (en) | A kind of electrode material for super capacitor and preparation method thereof | |
| Wang et al. | NiCo 2 S 4/tryptophan-functionalized graphene quantum dot nanohybrids for high-performance supercapacitors | |
| CN105788882B (en) | The hydrothermal preparing process of cobaltosic oxide nano cube and the application for preparing electrode slice | |
| CN106129407A (en) | MoS2the synthetic method of@graphene composite nano material | |
| Yi et al. | Three-dimensional flower-like nickel oxide/graphene nanostructures for electrochemical detection of environmental nitrite | |
| CN105369248A (en) | Preparation method for super-hydrophobic Co3O4 thin film of micro-nano composite structure | |
| Manikandan et al. | Low-temperature chemical synthesis of three-dimensional hierarchical Ni (OH) 2-coated Ni microflowers for high-performance enzyme-free glucose sensor | |
| Feng et al. | Excellent rate capability supercapacitor electrodes with highly hydroxyl ion adsorption capacity enabled by P-doped MnCo2O4 nanotube arrays | |
| CN110611096A (en) | MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material | |
| Chen et al. | Graphene quantum dots derived from carbon fibers for oxidation of dopamine | |
| Dong et al. | Designed 3D porous core-shell vanadium oxide microspheres for the simultaneous electrochemical sensing of toxic metal ions | |
| CN102849774A (en) | Method for preparing nanometer cerium oxide by hydrothermal method | |
| CN103752815B (en) | A kind of different-shape one-dimensional silver/manganese oxide composite preparation method and application thereof | |
| Shabbir et al. | Facile synthesis of SnO2/graphene and Bi–SnO2/graphene-based nanocomposites as electrode materials for energy storage devices | |
| CN105040069B (en) | A kind of electrochemistry anodic oxidation prepares porous nanometer material Na6Mo7O24·14H2O method | |
| CN109647397A (en) | A method of tungstic acid/Pt nanocomposite is prepared using tungstic acid discoloration | |
| Ma et al. | Fabrication of high photocatalytic activity and easy recovery photocatalysts with ZnFe 2 O 4 supported on ultrathin MoS 2 nanosheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170412 Termination date: 20210525 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |