CN106532040A - H-MoS2/NG nanocomposite material and preparation method and application thereof - Google Patents
H-MoS2/NG nanocomposite material and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
The invention belongs to the technical field of hydrogen evolution electrocatalysis, and discloses an H-MoS2/NG nanocomposite material and a preparation method and application thereof. The preparation method comprises the following steps of obtaining MoS2 nanoparticles from a growth solution of MoS2 through a hydrothermal method; mixing the MoS2 nanoparticles and aminopropyl triethoxy silane into a solvent and stirring to obtain APS-modified MoS2 nanoparticles; and putting the APS-modified MoS2 nanoparticles into a nitrogen-doped graphene precursor solution and obtaining the H-MoS2/NG nanocomposite material of the nitrogen-doped graphene-coated MoS2 nanoparticles through the hydrothermal method. According to the method, the composite material with nitrogen-doped graphene coating outer layers of hollow spherical MoS2 nanoparticles is prepared, the contact area of effective electron transfer is improved and active sites are increased, so that the conductivity is strengthened; and the H-MoS2/NG nanocomposite material has the characteristics of high mechanical strength, high specific surface area, high conductivity, low cost, abundant resources and excellent hydrogen-evolution catalytic performance, and can be used for the field of hydrogen evolution electrocatalysis.
Description
Technical field
The invention belongs to Electrocatalytic Activity for Hydrogen Evolution Reaction technical field, more particularly to a kind of H-MoS2/ NG nano composite materials and its system
Preparation Method and application.
Background technology
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 dispensing.However, changing
The burning meeting contaminated air of stone fuel, causes global warming；The extraction of Fossil fuel can also cause other environment to ask with dispensing
Topic；And the protection of Fossil fuel is an expense.These social cosies cannot be ignored again.In global economy, one
The modern society of sustainable development is except obtaining in addition to electric energy from hydroelectric generation and bio-fuel, it is necessary to from solar energy, wind energy
With the electric energy for obtaining a large amount of cleanings in the regenerative resource such as tide energy.One of them main challenge is exactly these regenerative resources
The intermittence of supply, and it is largely dependent upon natural environment.These regenerative resource area distribution are uneven to be again
Another big problem.Therefore, a kind of alternative clean energy resource of searching and a kind of efficient energy storage of development and conversion are needed badly
Technology.
It is as the reproducible energy carrier of cleaning, supplier of the hydrogen as future source of energy, it is desirable to environmental protection, economical and efficient
Produce hydrogen.It is current most reliable, most economical effective method that decomposition water prepares hydrogen, its research is had been obtained for more and more
Concern.The maximally effective catalyst of electrochemistry evolving hydrogen reaction should give hydrogen manufacturing minimum reduction potential, can thus reduce
The efficiency of overpotential and the important electrochemical process of increase.Up to the present, metal platinum is the maximally effective elctro-catalyst of hydrolytic hydrogen production
One of.However, lacking as which is extremely short and expensive price, catalyst made from platonic is difficult to meet growing low industrial cost's application
Demand, using nature is abundant and cost-effective catalyst to replace catalyst made from platonic be an extremely challenging research
Problem.
In recent years, researcher proposes many effectively Electrocatalytic Activity for Hydrogen Evolution Reaction agent, such as carbide, metal alloy, and mistakes
Cross metal sulfide.In these elctro-catalysts, the MoS of two dimension2Due 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 stacking and the person's character reunited are significantly reduced
Avtive spot, and, low electric conductivity further limit its application in water electrolysis hydrogen production.Exposed edge to greatest extent
Avtive spot and strengthen MoS2Electric conductivity be to improve the key point of its electrocatalysis characteristic, and prepare three-dimensional manometer hollow ball
The MoS of shape2Composite with material with carbon element 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,
Jing causes extensive concern.At present, experiment and theoretical research are all it was demonstrated that can enter one in the heterogeneous N atoms of Graphene doping
Step improves its electric conductivity, changes the electron density of graphene nanometer sheet, improves the avtive spot of electro-catalysis, becomes 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 be integrated, and effectively increase avtive spot, further increase the electrocatalysis characteristic of electrode.
Method designed by of the invention is which further applies energy storage field and has laid solid theory and practice basis.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art and deficiency, the primary and foremost purpose of the present invention is to provide a kind of H-MoS2/
NG nano composite materials.
Another object of the present invention is to provide a kind of above-mentioned H-MoS2The preparation method of/NG nano composite materials.The present invention
During method overcomes prior art, electro-catalysis hydrolysis liberation of hydrogen material produces the problem for being confined to catalyst made from platonic, there is provided a kind of extensive
Batch production can hydrolyze liberation of hydrogen material as electro-catalysis and have the H-MoS of excellent Electrocatalytic Activity for Hydrogen Evolution Reaction2/ NG nano composite materials
Preparation method.
Still a further object of the present invention is to provide above-mentioned H-MoS2/ NG nano composite materials 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 nano composite materials, comprises 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, stirring, obtain APS-
The MoS of modification2Nano-particle；
(3) MoS that APS- is modified2Nano-particle is placed in nitrogen-doped graphene precursor aqueous solution, and hydro-thermal method obtains N doping
Graphene coated MoS2Nano-particle (H-MoS2/ NG) composite.
In above-mentioned preparation method, the consumption (bulking value part, mg/mL) of each reactant is：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 ammonia
Product part.
Described MoS2Growth solution by constituting including following components：Molybdenum trioxide, sodium fluoride, potassium thiocyanate, water.
As a kind of embodiment, described MoS2Growth solution by including following bulking value part (mg/mL) component
Composition：850～880 weight portion of molybdenum trioxide, 500～520 weight portion of sodium fluoride, 1800～2000 weight portion of potassium thiocyanate, water
20～40 parts by volume.
As a kind of preferred embodiment, described MoS2Growth solution by including following bulking value part (mg/
ML) component composition：870～880 weight portion of molybdenum trioxide, 510～520 weight portion of sodium fluoride, 1900～2000 weight of potassium thiocyanate
Amount part, 30～40 parts by volume of water.
Described nitrogen-doped graphene precursor aqueous solution is by constituting including following components：Graphene oxide, ammonia and hydroxide
Sodium.
Used as a kind of embodiment, described nitrogen-doped graphene precursor aqueous solution is by including following bulking value part (mg/
ML) component composition：10～40 parts by volume of graphene oxide, 80～100 weight portion of 10～30 parts by volume of ammonia and sodium hydroxide.
Used as a kind of preferred embodiment, described nitrogen-doped graphene precursor aqueous solution is by including following bulking value part
(mg/mL) component composition：20～30 parts by volume of graphene oxide, 90～100 weight of 10～20 parts by volume of ammonia and sodium hydroxide
Part.
As a kind of embodiment, in the nitrogen-doped graphene precursor aqueous solution concentration of graphene oxide be 0.2～
0.4mg/mL。
Used as a kind of preferred embodiment, in the nitrogen-doped graphene precursor aqueous solution, the concentration of graphene oxide is
0.3～0.4mg/mL.
Used as a kind of embodiment, the hydro-thermal method described in preparation method of the present invention is the conventional hydro-thermal method in this area i.e.
Can, it is preferable that the temperature of hydro-thermal method described in step (1) is 200～230 DEG C, the time is 18～26h.Water described in step (3)
The temperature of full-boiled process is 120～180 DEG C, and the time is 2～7h.
Used as a kind of further preferred embodiment, the temperature of hydro-thermal method described in step (1) is 210～220 DEG C, and the time is
20～22h.The temperature of hydro-thermal method described in step (3) is 140～160 DEG C, and the time is 3～5h.
Described solvent is organic solvent, and which is used for providing reaction solution environment, can be toluene.
Graphene oxide used is preferably what Hummers methods were prepared.
Preparation method of the present invention obtains the MoS with hollow spheres by hydro-thermal method first2Nano-particle, recycles APS
Which is modified, makes nano grain surface positively charged, the graphene oxide for adding Hummers methods to prepare, using ammonia as
Nitrogen source, Direct Hydrothermal method is in MoS2One layer of nitrogen-doped graphene of nano-particle external sheath.The composite for preparing 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 good solution for current Electrocatalytic Activity for Hydrogen Evolution Reaction problem.Preparation method of the present invention has overpotential low, Ta Feier
Slope is little, and condition is simple, the advantages of easy scale.And the inventive method can be by setting suitable MoS2Precursor solution component
And ratio, realize the Morphological control to hollow nanospheres so as to controllable growth；By set suitable hydro-thermal method reaction temperature and
Time, obtain suitable three-dimensional MoS2Control ball in nanometer；Make NG grow homogeneous, covering uniformly, and thickness is suitable.
The present invention also provides the H-MoS that said method is prepared2/ NG nano composite materials, its structure are hollow spheres
MoS2Uniform cladding nitrogen-doped graphene (NG) outside nano material, with high-specific surface area, high conductivity, low cost, resource
Enrich and there is excellent catalytic activity of hydrogen evolution.
The H-MoS of the present invention2/ NG nano composite materials can be applicable to Electrocatalytic Activity for Hydrogen Evolution Reaction field, particularly prepare liberation of hydrogen electricity
Catalysis material.Instant invention overcomes noble metal is unable to the deficiency of large-scale application due to scarcity and costliness, studies and open
A kind of high-performance, low cost, aboundresources and the H-MoS with catalytic activity of hydrogen evolution are sent out2/ NG nano composite materials, its
Using MoS2The contact area of effective electron transfer is improved with the composite of nitrogen-doped graphene, strengthens electric conductivity.
The present invention is had the following advantages and beneficial effect relative to prior art：
(1) MoS for being found at present2Material, shows good electrocatalysis characteristic in terms of water electrolysis hydrogen production, but by
In itself easily stacking and reunion, and electric conductivity is poor, so causing its avtive spot low.Will be with high ratio in the present invention
Surface area, the NG and MoS of high conductivity2Material is combined, by MoS2The big specific surface area of hollow nanosphere, so as to improve
The specific surface area of electrode material, increases the avtive spot of electrode surface significantly, overcomes easily stacking and the problem reunited,
By the high conductivity and high mechanical strength of NG claddings, MoS is greatly improved2Electric conductivity, so as 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 materials, obtains electricity and urges
Change the H-MOS that performance is further lifted2/NG。
Description of the drawings
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 pictures of/NG composites.
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 test of lower long circulating stability.
Fig. 8 is H-MoS2/ NG is in 0.50M H2SO4Electrolyte is bent through the polarization of the 1st circle and the 3000th circle of voltage calibration
Line.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Reagent used in the following example can be obtained from commercial channel.
Embodiment 1
MoS2The hydro-thermal reaction solution composition of hollow nanosphere be 0.87g molybdenum trioxides, 0.52g sodium fluoride, 1.93g sulfur cyanogen
The deionized water of sour potassium and 30mL.
The solution composition of NG hydro-thermal reactions is graphene oxide 30mL, ammonia 15mL and NaOH 100mg.
MoS2Hollow nanosphere be synthesized by hydro-thermal method realization.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reactor (reaction solution is generally the 80% of reactor volume), hydro-thermal reaction keeps 24h at 220 DEG C.Reaction terminates
After be cooled to room temperature, gained sample spends and cleans repeatedly three times 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
During APS adds above-mentioned solution, the MoS of APS- modifications is obtained through the stirring of 24h2Hollow nanosphere.By APS- obtained above
The MoS of modification2Hollow nanosphere is placed in volume for (reaction solution is generally in autoclaves of the 50mL equipped with NG growth solutions
Reactor volume 80%), hydro-thermal reaction keeps 4h at 150 DEG C.Reaction is cooled to room temperature after terminating, and is received by centrifugation
Collection black precipitate, washs the NH of remnants with HCl solution3, then deionized water and ethanol thoroughly washing six times again, and true
12h is dried in 60 DEG C in empty baking oven, H-MOS is obtained2/ NG composites.
Performance test, is as a result shown in Fig. 1～Fig. 8：To the MoS for preparing2Hollow 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 of
Characteristic peak can belong to sign hexagonal phase 2H-MoS2Structure (JPCDS 37-1492), so as to demonstrate prepared product
Purity, scanning electron microscope diagram also show three-dimensional MoS2Hollow nanosphere sample has uniform hollow spheres structure,
Diameter is about 500nm.Also scanning electron microscope diagram is have taken to having coated the material after NG, as seen from Figure 4 NG energy
Three-dimensional MoS is uniformly coated on enough2Hollow nano ball surface.Finally to prepared H-MoS2/ NG nano composite materials are carried out
Electrochemical property test, is studied to its electrocatalysis characteristic.Employ linear sweep voltammetry in electrochemical method and
Time-measuring electric potential is tested to carry out studying its electro-catalysis hydrolytic hydrogen production performance, and take-off potential, overpotential including material, Ta Feier are oblique
Rate and cyclical stability.By polarization curve as can be seen which has less take-off potential, overpotential and Tafel slope.
This H-MoS is obtained by test2The take-off potential of/NG nano composite materials is 50mV vs.RHE, and overpotential is 118mV
Vs.RHE, corresponding Tafel slope be 39mV/dec, electro-catalysis hydrolysis Hydrogen Evolution Performance be much superior to H-MoS2、NG.Equally
Time-measuring electric potential curve also shows extraordinary cyclical stability.Test through the time-measuring electric potentials of 100,000 seconds, its overpotential is still
0.17V vs.RHE are maintained, under the same conditions than H-MoS2Overpotential it is much lower.Meanwhile, circulate through 3000 times
Afterwards, its polarization curve is not changed significantly, and this has turned out H-MoS2/ NG has good cyclical stability.To sum up institute
State, the H-MoS of the present invention2/ NG nano composite materials show very excellent electrocatalysis characteristic, in the application of Electrocatalytic Activity for Hydrogen Evolution Reaction
There is very big prospect.
Embodiment 2
MoS2The hydro-thermal reaction solution composition of hollow nanosphere be 0.85g molybdenum trioxides, 0.50g sodium fluoride, 1.8g sulfur cyanogen
The deionized water of sour potassium and 20mL.
The solution composition of NG hydro-thermal reactions is graphene oxide 10mL, ammonia 15mL and NaOH 80mg.
MoS2Hollow nanosphere be synthesized by hydro-thermal method realization.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reactor (reaction solution is generally the 80% of reactor volume), hydro-thermal reaction keeps 26h at 200 DEG C.Reaction terminates
After be cooled to room temperature, gained sample spends and cleans repeatedly three times 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
During APS adds above-mentioned solution, the MoS of APS- modifications is obtained through the stirring of 24h2Hollow nanosphere.By APS- obtained above
The MoS of modification2Hollow nanosphere is placed in volume for (reaction solution is generally in autoclaves of the 50mL equipped with NG growth solutions
Reactor volume 80%), hydro-thermal reaction keeps 7h at 120 DEG C.Reaction is cooled to room temperature after terminating, and is received by centrifugation
Collection black precipitate, washs the NH of remnants with HCl solution3, then deionized water and ethanol thoroughly washing six times again, and true
12h is dried in 60 DEG C in empty baking oven, H-MOS is obtained2/ NG composites.
Embodiment 3
MoS2The hydro-thermal reaction solution composition of hollow nanosphere be 0.88g molybdenum trioxides, 0.51g sodium fluoride, 2g Hydrogen thiocyanates
The deionized water of potassium and 40mL.
The solution composition of NG hydro-thermal reactions is graphene oxide 40mL, ammonia 30mL and NaOH 90mg.
MoS2Hollow nanosphere be synthesized by hydro-thermal method realization.By MoS2Hollow nanosphere growth solution is placed in height
In pressure reactor (reaction solution is generally the 80% of reactor volume), hydro-thermal reaction keeps 18h at 230 DEG C.Reaction terminates
After be cooled to room temperature, gained sample spends and cleans repeatedly three times 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
During APS adds above-mentioned solution, the MoS of APS- modifications is obtained through the stirring of 24h2Hollow nanosphere.By APS- obtained above
The MoS of modification2Hollow nanosphere is placed in volume for (reaction solution is generally in autoclaves of the 50mL equipped with NG growth solutions
Reactor volume 80%), hydro-thermal reaction keeps 2h at 180 DEG C.Reaction is cooled to room temperature after terminating, and is received by centrifugation
Collection black precipitate, washs the NH of remnants with HCl solution3, then deionized water and ethanol thoroughly washing six times again, and true
12h is dried in 60 DEG C in empty baking oven, H-MOS is obtained2/ NG composites.
Comparative example 1
MoS2The hydro-thermal reaction solution composition of hollow nanosphere be 0.87g molybdenum trioxides, 0.52g sodium fluoride, 1.93g sulfur cyanogen
The deionized water of sour potassium and 30mL.
Three-dimensional MoS2Hollow nanosphere be synthesized by hydro-thermal method realization.By the MoS that volume is 50mL2Hollow nano
Ball growth solution is placed in autoclave (reaction solution is generally the 80% of reactor volume), and hydro-thermal reaction is at 220 DEG C
Keep 24h.Reaction is cooled to room temperature after terminating, and gained sample spends and cleans repeatedly three times from water, and 80 DEG C are dried.
Employ the linear sweep voltammetry in electrochemical method and time-measuring electric potential test to carry out research H-MoS2Electricity
Catalytic performance, it is 126mV vs.RHE to obtain its take-off potential by test, and overpotential is 168mV vs.RHE, corresponding tower phenanthrene
Your slope is 57mV/dec, the H-MoS being far longer than in embodiment 12/ NG nano composite materials.This is mainly due in enforcement
In example 1, NG has the mechanical strength become reconciled than larger specific surface area, high conductivity, greatly improves MoS2Electric conductivity, increase
Many avtive spots, so that effectively increase the electrocatalysis characteristic of electrode material.
Scheme of the present invention based on embodiment 1, by regulating and controlling different reaction conditions, affects H-MoS2The growth of/NG, its
Relation 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
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of H-MoS2The preparation method of/NG nano composite materials, it is characterised in that comprise the following steps：
(1) by MoS2Growth solution MoS is obtained by hydro-thermal method2Nano-particle；
(2) by MoS2Nano-particle and aminopropyl triethoxysilane are mixed in solvent, stirring, obtain the MoS of APS- modifications2
Nano-particle；
(3) MoS that APS- is modified2Nano-particle is placed in nitrogen-doped graphene precursor aqueous solution, and hydro-thermal method obtains nitrogen-doped graphene
Cladding MoS2The composite of nano-particle.
2. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：The preparation side
In method, the consumption of each reactant is：Bulking value part, mg/mL, MoS2200～800 weight portions；Aminopropyl triethoxysilane
0.2～0.8 parts by volume；10～40 parts by volume of graphene oxide；10～30 parts by volume of ammonia.
3. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：Described MoS2
Growth solution by constituting including following components：Molybdenum trioxide, sodium fluoride, potassium thiocyanate, water.
4. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：Described MoS2
Growth solution by constituting including following bulking value part component：Mg/mL, 850～880 weight portion of molybdenum trioxide, sodium fluoride 500
～520 weight portions, 1800～2000 weight portion of potassium thiocyanate, 20～40 parts by volume of water.
5. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：Described nitrogen is mixed
Miscellaneous Graphene precursor aqueous solution is by constituting including following components：Graphene oxide, ammonia and sodium hydroxide.
6. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：Described nitrogen is mixed
Miscellaneous Graphene precursor aqueous solution is by constituting including following bulking value part component：Mg/mL, 10～40 parts by volume of graphene oxide, ammonia
80～100 weight portion of 10～30 parts by volume of water and sodium hydroxide.
7. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：Described nitrogen is mixed
Miscellaneous Graphene precursor aqueous solution is by constituting including following bulking value part component：Mg/mL, 20～30 parts by volume of graphene oxide, ammonia
90～100 weight portion of 10～20 parts by volume of water and sodium hydroxide.
8. H-MoS according to claim 12The preparation method of/NG nano composite materials, it is characterised in that：In step (1)
The temperature of the hydro-thermal method is 200～230 DEG C, and the time is 18～26h；The temperature of hydro-thermal method described in step (3) be 120～
180 DEG C, the time is 2～7h.
9. a kind of H-MoS2/ NG nano composite materials, it is characterised in that the preparation method according to any one of claim 1～7
Obtain.
10. the H-MoS described in claim 92Application of/NG the nano composite materials in Electrocatalytic Activity for Hydrogen Evolution Reaction field.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149940A (en) * | 2017-05-05 | 2017-09-12 | 燕山大学 | A kind of fluorine, nitrogen co-doped method for preparing molybdenum disulfide |
| CN109513454A (en) * | 2018-11-30 | 2019-03-26 | 湘潭大学 | One kind preparing MoS by coulomb interaction2/C3N4The method of composite photo-catalyst |
| 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 |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN110961122A (en) * | 2019-12-23 | 2020-04-07 | 中国石油大学(华东) | MoS for electrocatalytic hydrogen evolution2Preparation 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 |
| CN116135311A (en) * | 2023-04-20 | 2023-05-19 | 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 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149940A (en) * | 2017-05-05 | 2017-09-12 | 燕山大学 | A kind of fluorine, nitrogen co-doped method for preparing molybdenum disulfide |
| CN107149940B (en) * | 2017-05-05 | 2020-07-28 | 燕山大学 | Preparation method of fluorine and nitrogen co-doped molybdenum disulfide |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| 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 |
| CN109513454A (en) * | 2018-11-30 | 2019-03-26 | 湘潭大学 | One kind preparing MoS by coulomb interaction2/C3N4The method of composite photo-catalyst |
| 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 |
| CN110961122A (en) * | 2019-12-23 | 2020-04-07 | 中国石油大学(华东) | MoS for electrocatalytic hydrogen evolution2Preparation method of modified three-dimensional porous carbon-based composite material |
| 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 |
| CN116135311A (en) * | 2023-04-20 | 2023-05-19 | 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 |
| 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 |
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