CN106532040B - A kind of H-MoS2/ NG nanocomposite and preparation method and application - Google Patents
A kind of H-MoS2/ NG nanocomposite and preparation method and application Download PDFInfo
- Publication number
- CN106532040B CN106532040B CN201611036422.XA CN201611036422A CN106532040B CN 106532040 B CN106532040 B CN 106532040B CN 201611036422 A CN201611036422 A CN 201611036422A CN 106532040 B CN106532040 B CN 106532040B
- Authority
- CN
- China
- Prior art keywords
- mos
- parts
- nanocomposite
- preparation
- volume
- 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to Electrocatalytic Activity for Hydrogen Evolution Reaction technical fields, disclose a kind of H-MoS2/ NG nanocomposite and the preparation method and application thereof.Preparation method of the present invention is the following steps are included: by MoS2Growth solution MoS is obtained by hydro-thermal method2Nano particle；Itself and aminopropyl triethoxysilane are mixed in solvent, stirred, the MoS of APS- modification is obtained2Nano particle；Nitrogen-doped graphene precursor solution is placed it in, hydro-thermal method obtains nitrogen-doped graphene cladding MoS2The H-MoS of nano particle2/ NG nanocomposite.Hollow spheres MoS is prepared in the method for the present invention2The composite material of nano particle external sheath nitrogen-doped graphene, its contact area for improving effective electron transfer, increase active site, to enhance electric conductivity, have the characteristics that high mechanical strength, high-specific surface area, high conductivity, low cost, resourceful and catalytic activity of hydrogen evolution is excellent, can be applied to Electrocatalytic Activity for Hydrogen Evolution Reaction field.
Description
Technical field
The invention belongs to Electrocatalytic Activity for Hydrogen Evolution Reaction technical field, in particular to a kind of H-MoS2/ NG nanocomposite and its system
Preparation Method and application.
Background technique
The mankind are undoubtedly the storage and conversion of energy in one of 21 century maximum challenge.Modern society consumes mass storage
Chemical energy in fossil fuel, because the extraction of fossil fuel still maintains relatively low cost with dispatching.However, changing
The burning of stone fuel can pollute air, cause global warming；The extraction of fossil fuel also can cause other environment to be asked with dispatching
Topic；And the protection of fossil fuel is an expense.These social cost can not be ignored again.In global economy, one
The modern society of sustainable development is other than obtaining electric energy from hydroelectric generation and bio-fuel, it is necessary to from solar energy, wind energy
With a large amount of clean electric energy are obtained in the renewable energy such as tide energy.One of them main challenge is exactly these renewable energy
The intermittence of supply, and it is largely dependent upon natural environment.These renewable energy area distributions are uneven to be again
Another big problem.Therefore, it needs to find a kind of alternative clean energy resource and develops a kind of efficient energy storage and conversion
Technology.
As the reproducible energy carrier of cleaning, supplier of the hydrogen as future source of energy, it is desirable that environmental protection, it is economical and efficient
Produce hydrogen.Decompose water prepare hydrogen be it is most reliable at present, most economical effective method has been obtained for its research more and more
Concern.The most effective catalyst of electrochemistry evolving hydrogen reaction should give hydrogen manufacturing the smallest reduction potential, can thus reduce
Overpotential and the efficiency for increasing important electrochemical process.Up to the present, metal platinum is the most effective elctro-catalyst of hydrolytic hydrogen production
One of.It is difficult to meet growing low industrial cost application with expensive price, catalyst made from platonic however, lacking since its is extremely short
Demand, it is an extremely challenging research that using nature, abundant and cost-effective catalyst, which replaces catalyst made from platonic,
Project.
In recent years, researcher proposes many effective Electrocatalytic Activity for Hydrogen Evolution Reaction agent, such as carbide, metal alloy and mistake
Cross metal sulfide.In these elctro-catalysts, two-dimensional MoS2Due to its cheap price, high chemical stability and sudden and violent
The edge of dew is proved to be the very promising catalyst of electrolysis water liberation of hydrogen.However, its person's character for stacking and reuniting is significantly reduced
Active site, moreover, low electric conductivity further limits it in the application of water electrolysis hydrogen production.Maximum exposed edge
Active site and enhancing MoS2Electric conductivity be to improve the key point of its electrocatalysis characteristic, and prepare three-dimensional manometer hollow ball
The MoS of shape2Composite material with carbon material is the effective way for realizing this target.Graphene, the sp of a monatomic thick-layer2
Bonding carbon atom, by its unique advantage, such as big specific surface area, high mechanical strength and high electron conduction,
Caused extensive concern.Currently, experiment and theoretical research all it was demonstrated that adulterate heterogeneous N atom in graphene can be into one
Step improves its electric conductivity, changes the electron density of graphene nanometer sheet, improves the active site of electro-catalysis, become MoS2Growth and
The ideal stent of anchoring.Due to MoS2Match with the layer structure of graphene, the contact surface of effective electron transfer can be increased
Product.Therefore, MoS2Compound with graphene can be by three-dimensional manometer hollow spheres MoS2Electrocatalysis characteristic and nitrogen-doped graphene
High-specific surface area, excellent electric conductivity can integrate, effectively increase active site, further improve the electrocatalysis of electrode
Energy.Method designed by the present invention further applies energy storage field for it and has laid solid theory and practice basis.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of H-MoS2/
NG nanocomposite.
Another object of the present invention is to provide a kind of above-mentioned H-MoS2The preparation method of/NG nanocomposite.The present invention
Method overcomes the problems, such as that the hydrolysis liberation of hydrogen material production of electro-catalysis in the prior art is confined to catalyst made from platonic, provides a kind of extensive
It can be used as electro-catalysis hydrolysis liberation of hydrogen material and the H-MoS with excellent Electrocatalytic Activity for Hydrogen Evolution Reaction2/ NG nanocomposite
Preparation method.
Still a further object of the present invention is to provide above-mentioned H-MoS2/ NG nanocomposite answering in Electrocatalytic Activity for Hydrogen Evolution Reaction field
With.
The purpose of the present invention is realized by following proposal:
A kind of H-MoS2The preparation method of/NG nanocomposite, comprising the following steps:
(1) by MoS2Growth solution MoS is obtained by hydro-thermal method2Nano particle；
(2) by MoS2Nano particle and aminopropyl triethoxysilane (APS) are mixed in solvent, and stirring obtains APS-
The MoS of modification2Nano particle；
(3) MoS for modifying APS-2Nano particle is placed in nitrogen-doped graphene precursor solution, and hydro-thermal method obtains N doping
Graphene coated MoS2Nano particle (H-MoS2/ NG) composite material.
In above-mentioned preparation method, the dosage (bulking value part, mg/mL) of each reactant are as follows: MoS2200~800 weight
Part；0.2~0.8 parts by volume of aminopropyl triethoxysilane (APS)；10~40 parts by volume of graphene oxide；10~30 body of ammonium hydroxide
Product part.
The MoS2Growth solution by being formed including following components: molybdenum trioxide, sodium fluoride, potassium rhodanide, water.
As a kind of embodiment, the MoS2Growth solution by include following bulking value part (mg/mL) component
Composition: 850~880 parts by weight of molybdenum trioxide, 500~520 parts by weight of sodium fluoride, 1800~2000 parts by weight of potassium rhodanide, water
20~40 parts by volume.
Embodiment as one preferred, the MoS2Growth solution by include following bulking value part (mg/
ML) group is grouped as: 870~880 parts by weight of molybdenum trioxide, 510~520 parts by weight of sodium fluoride, 1900~2000 weight of potassium rhodanide
Measure part, 30~40 parts by volume of water.
The nitrogen-doped graphene precursor solution including following components by forming: graphene oxide, ammonium hydroxide and hydroxide
Sodium.
As a kind of embodiment, the nitrogen-doped graphene precursor solution is by including following bulking value part (mg/
ML) group is grouped as: 10~40 parts by volume of graphene oxide, 80~100 parts by weight of 10~30 parts by volume of ammonium hydroxide and sodium hydroxide.
Embodiment as one preferred, the nitrogen-doped graphene precursor solution is by including following bulking value part
(mg/mL) group is grouped as: 20~30 parts by volume of graphene oxide, 90~100 weight of 10~20 parts by volume of ammonium hydroxide and sodium hydroxide
Part.
As a kind of embodiment, in the nitrogen-doped graphene precursor solution concentration of graphene oxide be 0.2~
0.4mg/mL。
Embodiment as one preferred, the concentration of graphene oxide is in the nitrogen-doped graphene precursor solution
0.3~0.4mg/mL.
As a kind of embodiment, hydro-thermal method described in preparation method of the present invention be the hydro-thermal method of this field routine i.e.
It can, it is preferable that the temperature of hydro-thermal method described in step (1) is 200~230 DEG C, and the time is 18~26h.Water described in step (3)
The temperature of thermal method is 120~180 DEG C, and the time is 2~7h.
As a kind of further preferred embodiment, the temperature of hydro-thermal method described in step (1) is 210~220 DEG C, the time
For 20~22h.The temperature of hydro-thermal method described in step (3) is 140~160 DEG C, and the time is 3~5h.
The solvent is organic solvent, is used to provide reaction solution environment, can be toluene.
Graphene oxide used is preferably that Hummers method is prepared.
Preparation method of the present invention passes through hydro-thermal method first and obtains the MoS with hollow spheres2Nano particle recycles APS
It is modified, keeps nano grain surface positively charged, be added Hummers method preparation graphene oxide, using ammonium hydroxide as
Nitrogen source, Direct Hydrothermal method is in MoS2One layer of nitrogen-doped graphene of nano particle external sheath.The composite material being prepared by
The high activity site of hollow molybdenum disulfide nano ball and the superior electrical conductivity energy of nitrogen-doped graphene effectively facilitate hydrolysis analysis
Hydrogen provides very good solution method for current Electrocatalytic Activity for Hydrogen Evolution Reaction problem.Preparation method of the present invention has overpotential low, Ta Feier
The advantages that slope is small, and condition is simple, easy scale.And the method for the present invention can be by setting suitable MoS2Precursor solution component
And ratio, it realizes to the Morphological control of hollow nanospheres, makes its controllable growth；By set suitable hydro-thermal method reaction temperature and
Time obtains suitable three-dimensional MoS2It controls ball in nanometer；NG is set to grow uniform, covering uniformly, and thickness is suitable.
The present invention also provides the H-MoS that the above method is prepared2/ NG nanocomposite, structure are hollow spheres
MoS2Nitrogen-doped graphene (NG) uniformly is coated outside nano material, there is high-specific surface area, high conductivity, low cost, resource
It enriches and there is excellent catalytic activity of hydrogen evolution.
H-MoS of the invention2/ NG nanocomposite can be applied to Electrocatalytic Activity for Hydrogen Evolution Reaction field, especially prepare liberation of hydrogen electricity
Catalysis material.The present invention overcomes the deficiency that noble metal can not be applied on a large scale due to scarcity and valuableness, studies and open
A kind of high-performance, low cost, resourceful and with catalytic activity of hydrogen evolution H-MoS are sent out2/ NG nanocomposite,
Utilize MoS2The contact area of effective electron transfer is improved with the composite material of nitrogen-doped graphene, enhances electric conductivity.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) MoS found at present2Material, shows good electrocatalysis characteristic in terms of water electrolysis hydrogen production, but by
It stacks and reunites in itself being easy, and electric conductivity is poor, so causing its active site relatively low.There to be high ratio in the present invention
Surface area, the NG and MoS of high conductivity2Material progress is compound, by MoS2The big specific surface area of hollow nanosphere, to improve
The specific surface area of electrode material, increases the active site of electrode surface significantly, overcomes the problem of being easy to stack and reuniting,
By high conductivity and high mechanical strength that NG is coated, MoS is greatly improved2Electric conductivity, to increase effectively electrode
The electrocatalysis characteristic of material.
(2) in preparation method of the present invention, by regulating and controlling MoS2The growth of hollow nanosphere and NG material obtains electricity and urges
Change the H-MOS that performance is further promoted2/NG。
Detailed description of the invention
Fig. 1 is MoS2X-ray diffraction (XRD) spectrogram of hollow nanosphere.
Fig. 2 is MoS2Scanning electron microscope (SEM) picture of hollow nanosphere.
Fig. 3 is MoS2Scanning electron microscope (SEM) picture of hollow nanosphere.
Fig. 4 is H-MOS2The SEM picture of/NG composite material.
Fig. 5 is Pt/C, NG, H-MoS2/ NG and H-MoS2Polarization curve.
Fig. 6 is Pt/C, NG, H-MoS2/ NG and H-MoS2Corresponding Tafel curve.
Fig. 7 is H-MoS2/ NG and H-MoS2In 80mA/cm2The time-measuring electric potential of lower long circulating stability is tested.
Fig. 8 is H-MoS2/ NG is in 0.50M H2SO4The polarization that electrolyte is enclosed by the 1st circle of voltage calibration and the 3000th
Curve.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Reagent used in the following example can be obtained from commercial channel.
Embodiment 1
MoS2The hydro-thermal reaction solution composition of hollow nanosphere is 0.87g molybdenum trioxide, 0.52g sodium fluoride, 1.93g sulphur
The deionized water of potassium cyanate and 30mL.
NG hydro-thermal reaction solution composition is graphene oxide 30mL, ammonium hydroxide 15mL and NaOH 100mg.
MoS2Hollow nanosphere is synthesized by what hydro-thermal method was realized.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reaction kettle (reaction solution be generally reaction kettle volume 80%), hydro-thermal reaction is kept for 24 hours at 220 DEG C.Reaction terminates
After be cooled to room temperature, gained sample is spent to be cleaned three times repeatedly from water, and 80 DEG C are dried.
By MoS derived above2Hollow nanosphere (0.5g) is by ultrasonic disperse in toluene solution.After 1h, 0.5mL
APS is added in above-mentioned solution, by the MoS for stirring to get APS- modification for 24 hours2Hollow nanosphere.By APS- obtained above
The MoS of modification2It is 50mL equipped with (reaction solution is generally in the autoclave of NG growth solution that hollow nanosphere, which is placed in volume,
The 80% of reaction kettle volume), hydro-thermal reaction keeps 4h at 150 DEG C.It is cooled to room temperature, is received by centrifuge separation after reaction
Collect black precipitate, remaining NH is washed with HCl solution3, then thoroughly washed six times with deionized water and ethyl alcohol again, and true
In 60 DEG C of dry 12h in empty baking oven, H-MOS is obtained2/ NG composite material.
Performance test, the result is shown in Figure 1~Fig. 8: to the MoS of preparation2Hollow nanosphere has carried out X-ray powder diffraction test
And field emission scanning electron microscope figure, as a result as shown in Fig. 1, Fig. 2 and Fig. 3.X-ray powder diffraction figure shows all
Characteristic peak can belong to characterization hexagonal phase 2H-MoS2Structure (JPCDS 37-1492), to demonstrate prepared production
The purity of object, scanning electron microscope diagram also show three-dimensional MoS2Hollow nanosphere sample has uniform hollow spheres knot
Structure, diameter are about 500 nm.Scanning electron microscope diagram is also had taken to the material after NG has been coated, as seen from Figure 4
NG can be uniformly coated on three-dimensional MoS2Hollow nano ball surface.Finally to prepared H-MoS2/ NG nanocomposite
Electrochemical property test has been carried out, research can be carried out to its electrocatalysis.Using the linear scan volt in electrochemical method
Peace method and time-measuring electric potential test are study its electro-catalysis hydrolytic hydrogen production performance, take-off potential, overpotential, tower including material
Fei Er slope and cyclical stability.By polarization curve as can be seen that it is with lesser take-off potential, overpotential and Ta Feier
Slope.This H-MoS is obtained by test2The take-off potential of/NG nanocomposite is 50mV vs.RHE, and overpotential is
118mV vs.RHE, corresponding Tafel slope are 39mV/dec, and electro-catalysis hydrolysis Hydrogen Evolution Performance is much superior to H-MoS2、
NG.Same time-measuring electric potential curve also shows extraordinary cyclical stability.It is tested by 100,000 seconds time-measuring electric potentials, it is excessively electric
Gesture still maintains 0.17V vs.RHE, under the same conditions than H-MoS2Overpotential it is much lower.Meanwhile passing through
After 3000 circulations, polarization curve is not changed significantly, this has turned out H-MoS2/ NG has good stable circulation
Property.In conclusion H-MoS of the invention2/ NG nanocomposite shows very good electrocatalysis characteristic, in liberation of hydrogen electricity
The application of catalysis has very big prospect.
Embodiment 2
MoS2The hydro-thermal reaction solution composition of hollow nanosphere is 0.85g molybdenum trioxide, 0.50g sodium fluoride, 1.8g sulphur cyanogen
The deionized water of sour potassium and 20mL.
NG hydro-thermal reaction solution composition is graphene oxide 10mL, ammonium hydroxide 15mL and NaOH 80mg.
MoS2Hollow nanosphere is synthesized by what hydro-thermal method was realized.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reaction kettle (reaction solution be generally reaction kettle volume 80%), hydro-thermal reaction keeps 26h at 200 DEG C.Reaction terminates
After be cooled to room temperature, gained sample is spent to be cleaned three times repeatedly from water, and 80 DEG C are dried.
By MoS derived above2Hollow nanosphere (0.2g) is by ultrasonic disperse in toluene solution.After 1h, 0.2mL
APS is added in above-mentioned solution, by the MoS for stirring to get APS- modification for 24 hours2Hollow nanosphere.By APS- obtained above
The MoS of modification2It is 50mL equipped with (reaction solution is generally in the autoclave of NG growth solution that hollow nanosphere, which is placed in volume,
The 80% of reaction kettle volume), hydro-thermal reaction keeps 7h at 120 DEG C.It is cooled to room temperature, is received by centrifuge separation after reaction
Collect black precipitate, remaining NH is washed with HCl solution3, then thoroughly washed six times with deionized water and ethyl alcohol again, and true
In 60 DEG C of dry 12h in empty baking oven, H-MOS is obtained2/ NG composite material.
Embodiment 3
MoS2The hydro-thermal reaction solution composition of hollow nanosphere is 0.88g molybdenum trioxide, 0.51g sodium fluoride, 2g thiocyanic acid
The deionized water of potassium and 40mL.
NG hydro-thermal reaction solution composition is graphene oxide 40mL, ammonium hydroxide 30mL and NaOH 90mg.
MoS2Hollow nanosphere is synthesized by what hydro-thermal method was realized.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reaction kettle (reaction solution be generally reaction kettle volume 80%), hydro-thermal reaction keeps 18h at 230 DEG C.Reaction terminates
After be cooled to room temperature, gained sample is spent to be cleaned three times repeatedly from water, and 80 DEG C are dried.
By MoS derived above2Hollow nanosphere (0.8g) is by ultrasonic disperse in toluene solution.After 1h, 0.8mL
APS is added in above-mentioned solution, by the MoS for stirring to get APS- modification for 24 hours2Hollow nanosphere.By APS- obtained above
The MoS of modification2It is 50mL equipped with (reaction solution is generally in the autoclave of NG growth solution that hollow nanosphere, which is placed in volume,
The 80% of reaction kettle volume), hydro-thermal reaction keeps 2h at 180 DEG C.It is cooled to room temperature, is received by centrifuge separation after reaction
Collect black precipitate, remaining NH is washed with HCl solution3, then thoroughly washed six times with deionized water and ethyl alcohol again, and true
In 60 DEG C of dry 12h in empty baking oven, H-MOS is obtained2/ NG composite material.
Comparative example 1
MoS2The hydro-thermal reaction solution composition of hollow nanosphere is 0.87g molybdenum trioxide, 0.52g sodium fluoride, 1.93g sulphur
The deionized water of potassium cyanate and 30mL.
Three-dimensional MoS2Hollow nanosphere is synthesized by what hydro-thermal method was realized.The MoS for being 50mL by volume2Hollow nano
Ball growth solution is placed in autoclave (reaction solution be generally reaction kettle volume 80%), and hydro-thermal reaction is at 220 DEG C
It keeps for 24 hours.It is cooled to room temperature after reaction, gained sample is spent to be cleaned three times repeatedly from water, and 80 DEG C are dried.
Using in electrochemical method linear sweep voltammetry and time-measuring electric potential test carry out research H-MoS2Electricity
Catalytic performance, obtaining its take-off potential by test is 126mV vs.RHE, and overpotential is 168mV vs.RHE, and corresponding tower is luxuriant and rich with fragrance
Your slope is 57mV/dec, the H-MoS being far longer than in embodiment 12/ NG nanocomposite.This is mainly due to implementing
In example 1, NG has bigger specific surface area, high conductivity and good mechanical strength, greatly improves MoS2Electric conductivity, increase
More active sites, to effectively increase the electrocatalysis characteristic of electrode material.
The present invention is based on the schemes of embodiment 1 to influence H-MoS by regulating and controlling different reaction conditions2The growth of/NG,
Its relationship is as shown in Table 1 and Table 2.
1 MoS of table2The adjusting and controlling growth of hollow nanosphere
The adjusting and controlling growth of 2 NG of table
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of H-MoS2The preparation method of/NG nanocomposite, it is characterised in that the following steps are included:
(1) by MoS2Growth solution MoS is obtained by hydro-thermal method2Nano particle；
(2) by MoS2Nano particle and aminopropyl triethoxysilane are mixed in solvent, and stirring obtains the MoS of APS- modification2
Nano particle；
(3) MoS for modifying APS-2Nano particle is placed in nitrogen-doped graphene precursor solution, and hydro-thermal method obtains nitrogen-doped graphene
Coat MoS2The composite material of nano particle；
The MoS2Growth solution by include following bulking value part group be grouped as: mg/mL, 850~880 weight of molybdenum trioxide
Measure part, 500~520 parts by weight of sodium fluoride, 1800~2000 parts by weight of potassium rhodanide, 20~40 parts by volume of water；
In the preparation method, the dosage of each reactant are as follows: bulking value part, mg/mL, MoS2200~800 parts by weight；Ammonia third
0.2~0.8 parts by volume of ethyl triethoxy silicane alkane；10~40 parts by volume of graphene oxide；10~30 parts by volume of ammonium hydroxide；
The temperature of hydro-thermal method described in step (1) is 200~230 DEG C, and the time is 18~26 h.
2. H-MoS according to claim 12The preparation method of/NG nanocomposite, it is characterised in that: the nitrogen is mixed
Miscellaneous graphene precursor solution including following components by forming: graphene oxide, ammonium hydroxide and sodium hydroxide.
3. H-MoS according to claim 12The preparation method of/NG nanocomposite, it is characterised in that: the nitrogen is mixed
Miscellaneous graphene precursor solution is by including that following bulking value part group is grouped as: mg/mL, 10~40 parts by volume of graphene oxide, ammonia
80~100 parts by weight of 10~30 parts by volume of water and sodium hydroxide.
4. H-MoS according to claim 12The preparation method of/NG nanocomposite, it is characterised in that: the nitrogen is mixed
Miscellaneous graphene precursor solution is by including that following bulking value part group is grouped as: mg/mL, 20~30 parts by volume of graphene oxide, ammonia
90~100 parts by weight of 10~20 parts by volume of water and sodium hydroxide.
5. H-MoS according to claim 12The preparation method of/NG nanocomposite, it is characterised in that: in step (3)
The temperature of the hydro-thermal method is 120~180 DEG C, and the time is 2~7 h.
6. a kind of H-MoS2/ NG nanocomposite, it is characterised in that described in any item preparation methods according to claim 1~5
It obtains.
7. H-MoS as claimed in claim 62Application of/NG the nanocomposite in Electrocatalytic Activity for Hydrogen Evolution Reaction field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611036422.XA CN106532040B (en) | 2016-11-23 | 2016-11-23 | A kind of H-MoS2/ NG nanocomposite and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611036422.XA CN106532040B (en) | 2016-11-23 | 2016-11-23 | A kind of H-MoS2/ NG nanocomposite and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106532040A CN106532040A (en) | 2017-03-22 |
| CN106532040B true CN106532040B (en) | 2019-05-07 |
Family
ID=58356127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611036422.XA Expired - Fee Related CN106532040B (en) | 2016-11-23 | 2016-11-23 | A kind of H-MoS2/ NG nanocomposite and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106532040B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149940B (en) * | 2017-05-05 | 2020-07-28 | 燕山大学 | Preparation method of fluorine and nitrogen co-doped molybdenum disulfide |
| CN110600682B (en) * | 2018-06-12 | 2022-03-01 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN109513454B (en) * | 2018-11-30 | 2021-07-23 | 湘潭大学 | Preparation of MoS by Coulomb interaction2/C3N4Method for preparing composite photocatalyst |
| CN109686954A (en) * | 2018-12-27 | 2019-04-26 | 陕西科技大学 | A kind of C-O-Mo key bridge joint monolithic taper MoS2/ NG sodium ion negative electrode material and preparation method thereof |
| CN110961122B (en) * | 2019-12-23 | 2022-10-14 | 中国石油大学(华东) | MoS for electrocatalytic hydrogen evolution 2 Preparation method of modified three-dimensional porous carbon-based composite material |
| CN111330599A (en) * | 2020-02-10 | 2020-06-26 | 天能电池集团股份有限公司 | Composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and preparation method thereof |
| CN116135311B (en) * | 2023-04-20 | 2023-08-04 | 山西省煤炭地质物探测绘院有限公司 | Nanometer material based on molybdenum disulfide network structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938461A (en) * | 2012-11-19 | 2013-02-20 | 山东大学 | Nano sheet self-assembled MoS2 nano hollow material and preparation and application of MoS2 nano hollow material serving as lithium storage electrode material |
| CN104835654A (en) * | 2015-05-29 | 2015-08-12 | 青岛大学 | 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof |
-
2016
- 2016-11-23 CN CN201611036422.XA patent/CN106532040B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938461A (en) * | 2012-11-19 | 2013-02-20 | 山东大学 | Nano sheet self-assembled MoS2 nano hollow material and preparation and application of MoS2 nano hollow material serving as lithium storage electrode material |
| CN104835654A (en) * | 2015-05-29 | 2015-08-12 | 青岛大学 | 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "A self-Standing and Flexible Electrode of Yolk-Shell CoS2 Spheres Encapsulated with Nitrogen-Doped Graphene for High-Peformance Lithium-Ion Batteries";Wenda Qiu et al.;《Chem.Eur.J》;20151231;第4365-4366页的实验部分，4365页第2栏第2段，图2，图3 |
| "Facile synthesis of Hollow MoS2 microspheres/Amorphous Carbon Composites and Theire Lithium Storage Properties";Wenda Qiu et al.;《Electrochimica Acta》;20131204;第146页第1栏最后1段 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106532040A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106532040B (en) | A kind of H-MoS2/ NG nanocomposite and preparation method and application | |
| Li et al. | Nanoflower-branch LDHs and CoNi alloy derived from electrospun carbon nanofibers for efficient oxygen electrocatalysis in microbial fuel cells | |
| CN110694646B (en) | Bimetallic sulfide composite electrocatalyst and preparation method and application thereof | |
| CN110711596B (en) | Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof | |
| CN108411324A (en) | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN108736031A (en) | A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof | |
| CN106563471B (en) | A kind of core-shell structure copolymer CoS2@NG nanocomposite and its preparation and application | |
| CN107362812B (en) | A kind of compound two-dimensional material of selenium sulfuration rhenium, preparation method and applications | |
| CN109621981B (en) | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| CN105251513A (en) | Electrodeposition preparation method of carbon nanotube/transition metal compound composite material | |
| CN105552393A (en) | Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| CN106669763A (en) | Nitrogen-doped carbon-coated nanoflower-shaped MoSe2 composite material and preparation and application | |
| Chang et al. | Fabrication of bimetallic Co/Zn leaf blade structure template derived Co3O4-ZIF/Zn and its ORR catalytic performance for MFC | |
| CN113862693A (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN113235104A (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN113265674A (en) | Preparation method of MOF-derived CoP hydrogen evolution catalyst | |
| CN105529474A (en) | Graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and preparation method thereof | |
| CN112439430A (en) | Surface doping modification MoS2Preparation method and application of CoS nanowire catalyst | |
| CN111286752B (en) | Nitrogen-doped graphite phase carbon nitride nanosheet/molybdenum disulfide composite material and preparation method thereof | |
| CN107845814B (en) | Efficient electrocatalyst for oxygen reduction reaction in acid-base solution and preparation method thereof | |
| CN112316965B (en) | Preparation method and application of composite material derived by loading molybdenum disulfide nanosheet based on laccase-copper phosphate nanoflowers as substrate | |
| CN112058297B (en) | Nickel-based electro-catalytic material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190507 Termination date: 20211123 |