CN108636427A - A kind of molybdenum disulfide-nitrogen sulfur doping graphite foil composite nano materials and preparation method - Google Patents
A kind of molybdenum disulfide-nitrogen sulfur doping graphite foil composite nano materials and preparation method Download PDFInfo
- Publication number
- CN108636427A CN108636427A CN201810393662.8A CN201810393662A CN108636427A CN 108636427 A CN108636427 A CN 108636427A CN 201810393662 A CN201810393662 A CN 201810393662A CN 108636427 A CN108636427 A CN 108636427A
- Authority
- CN
- China
- Prior art keywords
- foil
- preparation
- nitrogen
- composite nano
- nano materials
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011888 foil Substances 0.000 title claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 42
- 239000010439 graphite Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- TZPQFOBHHGBRNC-UHFFFAOYSA-N [S].[N].[Mo](=S)=S Chemical compound [S].[N].[Mo](=S)=S TZPQFOBHHGBRNC-UHFFFAOYSA-N 0.000 title abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000004108 freeze drying Methods 0.000 claims description 17
- 229910052961 molybdenite Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of preparation method of molybdenum disulfide nitrogen sulfur doping graphite foil composite nano materials, it is with graphite foil, HNO3、H2SO4, four thio ammonium molybdate, thiocarbamide, oxalic acid, ultra-pure water is raw material, pass through respectively nitrogen, the preparation of graphite oxide foil that sulphur atom adulterates, hydrothermal synthesis reaction, clean dry and etc. realization.Raw material of the present invention is simple and easy to get, composite material is obtained by oxidation and water-heat process, whole experiment process process is simple, it is easy to operate, it is easy to realize the large-scale production of product, it can be with 100% recycling during product use, gained molybdenum disulfide nitrogen sulfur doping graphite oxide foil has excellent flexibility, molybdenum disulfide is grown in a manner of epitaxial growth on graphite foil, and product uniformity is good, has good catalytic effect to electrocatalytic hydrogen evolution.In addition, the material is expected to have good application in flexible battery, flexible sensor etc..
Description
Technical field
The invention belongs to inorganic nano material and energy developments and storing technology field, and in particular to a kind of electrocatalytic hydrogen evolution
Composite nano materials and preparation method thereof.
Background technology
With the fast development of the drastically expansion and industry of population, energy problem, which has become, influences human being's production, life
Matter of utmost importance.In order to solve global energy shortage problem, electrochemical decomposition aquatic products hydrogen is more and more paid attention to by people.It is expensive
Metal such as platinum（Pt）And its high electrochemical stability of the alloy due to low potential and in an acidic solution, become most common at present
Hydrogen catalyst is produced in electro-catalysis.However, it has the shortcomings that of high cost and scarcity of resources so that its practical application receives obstruction.
Therefore, the research of the non-precious metal catalyst of high-performance and high performance-price ratio has attracted the concern of vast scientific researcher.
In recent years, the molybdenum disulfide of nanostructure, either theory and experimental study all prove, can be used as HER electricity
Catalyst, large specific surface area, complicated and edge unsaturated bond are more.But its poorly conductive and stability difference are limited and are urged
Change efficiency.In order to combine the excellent properties of some materials, researcher is by MoS2With carbon nanotube（CNTs）It is compound with graphene
So as to improve MoS2As the problem of electrocatalytic hydrogen evolution catalyst poorly conductive and stability difference, make it is compound after composite material at
For the catalyst of efficient HER.Nitrating, sulphur, boron and oxygen doping also have been reported that, because the catalyst after doping is than traditional catalyst
Activity is stronger.Wherein nitrogen and sulfur doping, which can enhance, significantly increases HER activity, this is because atom doped can adjust electron energy level
To improve chemism.Epitaxial growth may insure the bonding of the atomic level between material, effectively facilitates the transfer of charge, carries
Rise the electrocatalysis characteristic of material.
Up to the present, people by prepare diversified molybdenum disulfide nano-composite material to molybdenum disulfide into
Row improved properties, such as carbon fiber-molybdenum disulfide composite material, graphene-molybdenum disulfide composite material etc..Although there are many method,
But still all come with some shortcomings, include mainly that experimentation is complicated, is not easy to form big production；In order to obtain high electrochemistry
Can, the product obtained is typically nano-powder, and leading to sample, the rate of recovery is low in use, it is difficult to meet large area flexible
The demand of electrochemical device；And if by nanomaterial loadings when in the substrates such as nickel foam, although large area may be implemented
Electrode demand, but the flexibility of product is poor, and poor to the catalytic effect of electrocatalytic hydrogen evolution, catalytic process stability is poor, and catalyst holds
It easily falls off from substrate, the molybdenum disulfide composite material obtained at present still waits improving to electrocatalytic hydrogen evolution performance, seeks inexpensive, ring
The friendly and electrocatalysis material with high catalytic activity in border is the key that the development of electro-catalysis technology.
Invention content
First of the present invention is designed to provide a kind of MoS2/ NSGF electrocatalytic hydrogen evolution composite nano materials.
Present invention aims at provide a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials.
The object of the invention is achieved through the following technical solutions：
A kind of MoS2/ NSGF electrocatalytic hydrogen evolution composite nano materials, which is characterized in that it is by following material composition：MoS2/N,
S-Graphene Foil, wherein the MoS2Mass percentage is 5% ~ 15%, the mass percentage of the N is 0.1% ~
The mass percentage of 1%, the S are 0.1% ~ 1%, and the Graphene Foil mass percentages are 84.8% ~ 94.8%.
A kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy are being that it is with graphite
Foil, HNO3、H2SO4, four thio ammonium molybdate, thiocarbamide, oxalic acid, ultra-pure water is raw material, respectively pass through nitrogen, sulphur atom adulterate oxidation
The preparation of graphite foil, hydrothermal synthesis reaction, clean dry and etc. realization.
Further, a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy is being, described
Graphite foil, need to be put into equipped with HNO by the preparation process for the graphite oxide foil that nitrogen, sulphur atom adulterate3And H2SO4Mixed solution
Middle immersion, is then cleaned with deionized water and ethyl alcohol.
Further, a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy is being, described
In the preparation process for the graphite oxide foil that nitrogen, sulphur atom adulterate, after the completion of cleaning, also need to carry out frozen drying.
Further, a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy is being, described
Graphite foil, four thio ammonium molybdate, thiocarbamide, oxalic acid, purified water mass ratio be 0.2:0.35:0.5:0.189:40.
Further, a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy is being, described
Hydrothermal synthesis reaction need to be carried out in the case where being passed through nitrogen.
Specifically, a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, it is special to be, it
It is to include the following steps to be made：
1. the preparation of the graphite oxide foil of nitrogen, sulphur atom doping
Graphite foil is put into equipped with HNO3And H2SO4Mixed solution in impregnate, microwave heating and insulation reaction is used in combination, reaction
After soaked graphite foil sample is taken out, respectively with the deionized water of 100ml or more and washes of absolute alcohol 3-4 times,
After be put into freeze drying box drying, obtain the graphite oxide foil sample of nitrogen, sulfur doping；The HNO3And H2SO4Mixed solution
It is to take mass fraction for 65% ~ 68% HNO3The H that solution and mass fraction are 96% ~ 98%2SO4Solution, by volume 1：3 mixing,
The insulation reaction time is 12 ~ 48 hours；The microwave heating temperature is 80 ~ 85 DEG C, and the microwave power is 300W；It is described
It is -55 ~ -45 DEG C to be freeze-dried temperature setting, and vacuum degree is 10 ~ 50Pa, 24 ~ 48h of drying time；
2. hydrothermal synthesis reaction
Nitrogen described in step 1, oxidized sulfur atom graphite foil sample and four thio ammonium molybdate, thiocarbamide, oxalic acid, ultra-pure water are put into togerther
In reaction kettle, in the case where being passed through nitrogen, hydrothermal synthesis is reacted；The nitrogen pressure is 2 ~ 3MPa, and reaction process also needs
It is stirred, 450 ~ 550 turns/min of speed of agitator, the temperature of the hydrothermal synthesis reaction is 210 ~ 230 DEG C, and the reaction time is
12~48h；
3. clean dry
It after being cooled to 20 ~ 25 DEG C, takes out, cleans, freeze-drying obtains sample；Described clean is gently to press from both sides sample with tweezers
Firmly, it is then washed 3-4 times, will be put into after sample after the completion of cleaning cold respectively with the deionized water of 100ml or more and absolute ethyl alcohol
Freeze drying box drying, cryogenic temperature is set as -55 ~ -45 DEG C, and vacuum degree is 10 ~ 50Pa, 24 ~ 48h of drying time.
The present invention has following advantageous effect：
A kind of MoS of the present invention2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials uses hydro-thermal method for preparation process,
Raw material is simple and easy to get, and composite material is obtained by oxidation and water-heat process, and whole experiment process process is simple, easy to operate,
It is easily achieved the large-scale production of product, it can be with 100% recycling, gained molybdenum disulfide-nitrogen sulfur doping oxygen during product use
There is graphite foil excellent flexibility, molybdenum disulfide to be grown on graphite foil in a manner of epitaxial growth, and product uniformity is good,
There is good catalytic effect to electrocatalytic hydrogen evolution.In addition, the material is expected to have in flexible battery, flexible sensor etc.
Good application.
Description of the drawings
Fig. 1 is the XRD diagram of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1.
Fig. 2 is the SEM figures of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1（Low power）.
Fig. 3 is the SEM figures of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1（High power）.
Fig. 4 is the SEM figures of molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1（Side）.
Fig. 5 is the TEM figures of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1（Front）.
Fig. 6 is the TEM figures of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1（Side）.
Fig. 7 is the selected diffraction figure of epitaxial growth molybdenum disulfide-nitrogen sulfur doping graphite oxide foil prepared by embodiment 1.
Fig. 8 is that embodiment 1 is bent（It is flexible）Performance map.
Fig. 9 is 1 distribution diagram of element of embodiment.
Figure 10 is 1 electro-catalysis H2-producing capacity figure of embodiment（Linear voltammetric scan figure）.
Figure 11 is 1 electro-catalysis of embodiment production stabilized hydrogen performance map（Constant voltage）.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1
With 4 3cm*5cm of ruler clip（Weigh about 0.6g）GF be put into equipped with 15ml65% HNO3With 45mL98% H2SO4 It is mixed
It closes in solution and impregnates 24 h, be used in combination microwave heating to 80 DEG C, microwave power 300W, by soaked graphite oxide foil after reaction
It takes out, respectively with freeze drying box drying is put into after 100ml deionized waters and washes of absolute alcohol 3 times, is freeze-dried temperature -52
DEG C, vacuum degree 10Pa, 36 hours drying times.
0.35g four thio ammonium molybdates are weighed, 0.5g thiocarbamides and 0.189g oxalic acid are dissolved in 40ml deionized waters, stirring
The solution that homogeneous transparent is obtained after 30min pours into the mixed solution in 60ml reaction kettles, 0.2g graphite oxide foils is added, most
Setting reaction kettle mixing speed is 450 revs/min afterwards, is passed through nitrogen protection（Nitrogen pressure is 3MPa）, 210 DEG C of heat preservation 48h.Instead
After answering, reaction kettle is taken out, it is made to naturally cool to 25 DEG C, obtained product is used into 100ml deionized waters and anhydrous respectively
Ethyl alcohol is put into freeze drying box after cleaning 4 times and is dried, -48 DEG C of temperature of freeze-drying, vacuum degree 10Pa, and drying time 36 is small
When, it is dry to terminate to get sample.
The power spectrum attachment of sample spherical aberration transmission electron microscope shows that the Elemental redistribution of sample is highly uniform.Sample can be with
270 degree are bent over, there is good flexibility.
Experiment one：The electrocatalysis characteristic of material is tested
Electro-chemical test uses three-electrode system, is tested by AUTOLAB PGSTAT302N work stations, tests the sample of preparation
It being cut into after 0.5cm*2cm directly as working electrode, immersion electrolyte area is 0.5cm*1cm, and Pt plate electrodes are used as to electrode,
Silver/silver chloride electrode（Ag/AgCl）As reference electrode.Electro-chemical test electrolyte is 0.5M H2SO4Molten before solution testing
Lead to nitrogen 30min in liquid to remove the air in electrolyte, each electrode remains stationary state is accurate to be conducive to obtain when test
Experimental data.The experimental results showed that：The electrocatalytic hydrogen evolution starting voltage of sample is 6 mVvs RHE, electricity when overpotential is 30mV
Current density can reach 10mA/cm2, Ta Feier 66mVdec-1,
Experiment two：Liberation of hydrogen stability test
It continues with three-electrode system to be tested, be measured using constant pressure power mode, 100 are respectively adopted to embodiment 1-3,
200 and 180mV voltages, testing time are 40000 seconds.The experimental results showed that sample carries out 40000 seconds under the constant voltage of 100mV
Stability test, Hydrogen Evolution Performance only reduces by 2 ~ 3%.
Embodiment 2
With 43 cm*5 cm of ruler clip（Weigh about 0.6 g）GF be put into equipped with 15ml68% HNO3With 45mL98% H2SO4
Mixed solution in impregnate 48h, be used in combination microwave heating to 85 DEG C, microwave power 300W, by soaked oxidation stone after reaction
Black foil takes out, respectively with being put into freeze drying box drying, freeze-drying temperature after 100ml deionized waters and washes of absolute alcohol 4 times
- 48 DEG C, vacuum degree 50Pa of degree, 24 hours drying times.
0.35g four thio ammonium molybdates are weighed, 0.5g thiocarbamides and 0.189g oxalic acid are dissolved in 40ml deionized waters, stirring
The solution that homogeneous transparent is obtained after 30min pours into the mixed solution in 60ml reaction kettles, 0.2g graphite oxide foils is added, most
Setting reaction kettle mixing speed is 500 revs/min afterwards, is passed through nitrogen protection（Nitrogen pressure is 2MPa）, 220 DEG C of heat preservation 12h.Instead
After answering, reaction kettle is taken out, it is made to naturally cool to 20 DEG C, obtained product is used into 100ml deionized waters and anhydrous respectively
Ethyl alcohol is put into freeze drying box after cleaning 3 times and is dried, -52 DEG C of temperature of freeze-drying, vacuum degree 50Pa, and drying time 24 is small
When, it is dry to terminate to get sample.
The power spectrum attachment of sample spherical aberration transmission electron microscope shows that the Elemental redistribution of sample is highly uniform.Sample can be with
270 degree are bent over, there is good flexibility.The electrocatalytic hydrogen evolution starting voltage of sample is 10mVvs RHE, and overpotential is
Current density can reach 10mA/cm when 39mV2, Ta Feier 69mVdec-1.Sample carries out under the constant voltage of 100mV
40000 seconds stability tests, Hydrogen Evolution Performance reduce by 3 ~ 4%.
Embodiment 3
With 43 cm*5 cm of ruler clip（Weigh about 0.6 g）GF be put into equipped with 15ml65% HNO3With 45mL98% H2SO4
Mixed solution in impregnate 36 h, be used in combination microwave heating to 82 DEG C, microwave power 300W, by soaked oxidation stone after reaction
Black foil takes out, respectively with being put into freeze drying box drying, freeze-drying temperature after 100ml deionized waters and washes of absolute alcohol 4 times
- 50 DEG C, vacuum degree 30Pa of degree, 36 hours drying times.
0.35g four thio ammonium molybdates are weighed, 0.5g thiocarbamides and 0.189g oxalic acid are dissolved in 40ml deionized waters, stirring
The solution that homogeneous transparent is obtained after 30min pours into the mixed solution in 60ml reaction kettles, 0.2g graphite oxide foils is added, most
Setting reaction kettle mixing speed is 500 revs/min afterwards, is passed through nitrogen protection（Nitrogen pressure is 3MPa）, 230 DEG C of heat preservation 36h.Instead
After answering, reaction kettle is taken out, it is made to naturally cool to 25 DEG C, obtained product is used into 100ml deionized waters and anhydrous respectively
Ethyl alcohol is put into freeze drying box after cleaning 4 times and is dried, -50 DEG C of temperature of freeze-drying, vacuum degree 30Pa, and drying time 36 is small
When, it is dry to terminate to get sample.
The power spectrum attachment of sample spherical aberration transmission electron microscope shows that the Elemental redistribution of sample is highly uniform.Sample can be with
270 degree are bent over, there is good flexibility.The electrocatalytic hydrogen evolution starting voltage of sample is 19mVvs RHE, and overpotential is
Current density can reach 10mA/cm when 48mV2, Ta Feier 72mVdec-1,.Sample carries out under the constant voltage of 100mV
40000 seconds stability tests, Hydrogen Evolution Performance reduce by 4 ~ 5%.
Claims (7)
1. a kind of MoS2/ NSGF electrocatalytic hydrogen evolution composite nano materials, it is characterised in that：It is by following material composition：Wherein institute
State MoS2Mass percentage is 5% ~ 15%, and the mass percentage of the N is 0.1% ~ 1%, and the mass percentage of the S is
0.1% ~ 1%, the Graphene Foil mass percentages are 84.8% ~ 94.8%.
2. a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy are being：It is with graphite foil,
HNO3、H2SO4, four thio ammonium molybdate, thiocarbamide, oxalic acid, ultra-pure water is raw material, respectively pass through nitrogen, sulphur atom adulterate graphite oxide
The preparation of foil, hydrothermal synthesis reaction, clean dry and etc. realization.
3. a kind of MoS as claimed in claim 22The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, it is special
In：Graphite foil, need to be put into equipped with HNO by the preparation process for the graphite oxide foil that the nitrogen, sulphur atom adulterate3And H2SO4Mixing
It impregnates in solution, is then cleaned with deionized water and ethyl alcohol.
4. a kind of MoS as claimed in claim 32The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, it is special
In：In the preparation process for the graphite oxide foil that the nitrogen, sulphur atom adulterate, after the completion of cleaning, also need to carry out frozen drying.
5. a kind of MoS as claimed in claim 42The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, it is special
In：The graphite foil, four thio ammonium molybdate, thiocarbamide, oxalic acid, purified water mass ratio be 0.2:0.35:0.5:0.189:40.
6. a kind of MoS as claimed in claim 52The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, it is special
In：The hydrothermal synthesis reaction need to be carried out in the case where being passed through nitrogen.
7. a kind of MoS2The preparation method of/NSGF electrocatalytic hydrogen evolution composite nano materials, spy are being：It is include following step
It is rapid to be made：
（1）The preparation for the graphite oxide foil that nitrogen, sulphur atom adulterate
Graphite foil is put into equipped with HNO3And H2SO4Mixed solution in impregnate, microwave heating and insulation reaction is used in combination, reaction
After soaked graphite foil sample is taken out, respectively with the deionized water of 100ml or more and washes of absolute alcohol 3-4 times,
After be put into freeze drying box drying, obtain the graphite oxide foil sample of nitrogen, sulfur doping；The HNO3And H2SO4Mixed solution
It is to take mass fraction for 65% ~ 68% HNO3The H that solution and mass fraction are 96% ~ 98%2SO4Solution, by volume 1：3 mixing,
The insulation reaction time is 12 ~ 48 hours；The microwave heating temperature is 80 ~ 85 DEG C, and the microwave power is 300W；It is described
It is -55 ~ -45 DEG C to be freeze-dried temperature setting, and vacuum degree is 10 ~ 50Pa, 24 ~ 48h of drying time；
（2）Hydrothermal synthesis reaction
By step（1）The nitrogen, oxidized sulfur atom graphite foil sample and four thio ammonium molybdate, thiocarbamide, oxalic acid, ultra-pure water are put together
Enter in reaction kettle, in the case where being passed through nitrogen, hydrothermal synthesis is reacted；The nitrogen pressure is 2 ~ 3MPa, and reaction process is also
It need to be stirred, 450 ~ 550 turns/min of speed of agitator, the temperature of the hydrothermal synthesis reaction is 210 ~ 230 DEG C, the reaction time
For 12 ~ 48h；
（3）Clean dry
It after being cooled to 20 ~ 25 DEG C, takes out, cleans, freeze-drying obtains sample；Described clean is gently to press from both sides sample with tweezers
Firmly, it is then washed 3-4 times, will be put into after sample after the completion of cleaning cold respectively with the deionized water of 100ml or more and absolute ethyl alcohol
Freeze drying box drying, cryogenic temperature is set as -55 ~ -45 DEG C, and vacuum degree is 10 ~ 50Pa, 24 ~ 48h of drying time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810393662.8A CN108636427B (en) | 2018-04-27 | 2018-04-27 | Molybdenum disulfide-nitrogen sulfur doped graphite foil composite nanomaterial and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810393662.8A CN108636427B (en) | 2018-04-27 | 2018-04-27 | Molybdenum disulfide-nitrogen sulfur doped graphite foil composite nanomaterial and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108636427A true CN108636427A (en) | 2018-10-12 |
| CN108636427B CN108636427B (en) | 2021-02-02 |
Family
ID=63747975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810393662.8A Expired - Fee Related CN108636427B (en) | 2018-04-27 | 2018-04-27 | Molybdenum disulfide-nitrogen sulfur doped graphite foil composite nanomaterial and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108636427B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN104773720A (en) * | 2015-03-31 | 2015-07-15 | 东华大学 | Method for preparing single-layer molybdenum disulfide flake doped graphene composite film |
| CN105529448A (en) * | 2016-01-22 | 2016-04-27 | 西北工业大学 | Preparation method for flexible lithium ion battery cathode material |
| CN106803462A (en) * | 2016-11-30 | 2017-06-06 | 同济大学 | A kind of flexible extensible ultracapacitor and its preparation based on graphene composite film |
| CN107221635A (en) * | 2017-06-29 | 2017-09-29 | 三峡大学 | A kind of wire structure carbon fiber/MoS2/MoO2Flexible electrode material and preparation method thereof |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107747106A (en) * | 2017-09-22 | 2018-03-02 | 天津大学 | Nitrogen, the three-dimensional carbon nanometer network load molybdenum disulfide nano material of sulfur doping and preparation |
-
2018
- 2018-04-27 CN CN201810393662.8A patent/CN108636427B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN104773720A (en) * | 2015-03-31 | 2015-07-15 | 东华大学 | Method for preparing single-layer molybdenum disulfide flake doped graphene composite film |
| CN105529448A (en) * | 2016-01-22 | 2016-04-27 | 西北工业大学 | Preparation method for flexible lithium ion battery cathode material |
| CN106803462A (en) * | 2016-11-30 | 2017-06-06 | 同济大学 | A kind of flexible extensible ultracapacitor and its preparation based on graphene composite film |
| CN107221635A (en) * | 2017-06-29 | 2017-09-29 | 三峡大学 | A kind of wire structure carbon fiber/MoS2/MoO2Flexible electrode material and preparation method thereof |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107747106A (en) * | 2017-09-22 | 2018-03-02 | 天津大学 | Nitrogen, the three-dimensional carbon nanometer network load molybdenum disulfide nano material of sulfur doping and preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108636427B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105688958B (en) | Polyhedron shape phosphatization cobalt/graphitic carbon hybrid material and its preparation method and application | |
| CN108543543B (en) | A kind of preparation method of nickel phosphide-N doping graphite oxide foil composite nano materials | |
| Yue et al. | Interwoven CoSe2/CNTs hybrid as a highly efficient and stable electrocatalyst for hydrogen evolution reaction | |
| CN110354905A (en) | A kind of electrolysis water liberation of hydrogen catalyst n iCoP/NF@PANI composite material and preparation method | |
| CN105460921A (en) | Molybdenum selenide nanosheets/graphene nanoribbons composite material and preparation method thereof | |
| CN107188230B (en) | A kind of compound bouquet of molybdenum disulfide-carbon and its preparation method and application | |
| CN105280900A (en) | Tungsten disulfide/graphene nanobelt composite material and preparation method thereof | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN106449175A (en) | Method for preparing nickel tungstate/polyaniline super-capacitor electrode material by taking foamed nickel as substrate | |
| Chen et al. | Pt NPs-loaded siloxene nanosheets for hydrogen co-evolutions from Zn-H2O fuel cells-powered water-splitting | |
| CN107768600B (en) | A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof | |
| CN111871421A (en) | Nickel-iron-molybdenum hydrotalcite nanowire bifunctional electrocatalyst and preparation method thereof | |
| CN108796551A (en) | It is supported on sea urchin shape vulcanization Co catalysts in nickel foam and preparation method thereof, as the application of electrolysis water oxygen-separating catalyst | |
| CN106952737A (en) | A kind of preparation method of tungsten disulfide flake nano material | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN105413729A (en) | Preparation method of nitrogen-doped carbon nanofiber aerogel with inlaid molybdenum carbide particles | |
| CN108695500A (en) | The preparation method of carbon pipe modified molybdenum disulfide lithium ion battery negative material | |
| CN105932302A (en) | Carbon nanotube array electrode loaded with MnO<2> nanosheets on surface, and preparation method and application therefor | |
| CN108722453A (en) | A kind of phosphating sludge/carbon composite nano-material for alkaline electrocatalytic hydrogen evolution | |
| CN109786742B (en) | Se-doped MXene battery negative electrode material and preparation method and application thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN109201083A (en) | A kind of nano flower-like vanadium disulfide/difunctional composite electrocatalyst of hydroxyl vanadium oxide and preparation method thereof | |
| Fang et al. | Hexagonal CoSe2 nanosheets stabilized by nitrogen-doped reduced graphene oxide for efficient hydrogen evolution reaction | |
| CN107069054A (en) | The fuel cell catalyst materials preparation method of efficient stable | |
| Hou et al. | Preparation of flexible composite electrode with bacterial cellulose (BC)-derived carbon aerogel supported low loaded NiS for methanol electrocatalytic oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210202 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |