CN106881116A - Molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material and its preparation method and application - Google Patents
Molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material and its preparation method and application Download PDFInfo
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- CN106881116A CN106881116A CN201710088450.4A CN201710088450A CN106881116A CN 106881116 A CN106881116 A CN 106881116A CN 201710088450 A CN201710088450 A CN 201710088450A CN 106881116 A CN106881116 A CN 106881116A
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- walled carbon
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 102
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 5
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 34
- 238000004073 vulcanization Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910003185 MoSx Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material and its preparation method and application, belong to the synthesis technical field of industrial liberation of hydrogen material.Technical scheme main points are：The preparation method of the molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material, multi-walled carbon nano-tubes and four thio ammonium molybdate are scattered in N, in the mixed solution of N dimethylformamides and deionized water, above-mentioned solution is transferred in reactor again reacts 12h in 180 220 DEG C, product is cleaned with ethanol and deionized water successively after being centrifuged, and the solid after washing is obtained into target product in 100 DEG C of vacuum drying 12h has the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of core shell structure.Molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material prepared by the present invention can be used preferably as liberation of hydrogen catalyst, and show excellent hydrogen evolution activity and stability.
Description
Technical field
The invention belongs to the synthesis technical field of industrial liberation of hydrogen material, and in particular to a kind of vulcanization with core shell structure
Molybdenum/multi-walled carbon nano-tubes hybrid material and its preparation method and application.
Background technology
Hydrogen is a kind of important renewable and clean energy resource and the raw material of industry, is widely used, and demand is big.The preparation of hydrogen
Method has：Water-gas method, cracking petrol gas method, ammonolysis craft method, metal replacement method and electrolysis liberation of hydrogen method etc., wherein electrolysis liberation of hydrogen method
Because possessing the advantages such as low cost, liberation of hydrogen be efficient and environment-friendly, by the extensive concern of researcher.
The technological core for being electrolysed liberation of hydrogen method is liberation of hydrogen material, and the liberation of hydrogen material of most rationality is metal platinum, but platinum is because of ground
Shell storage is rare and expensive, influences its extensive use in liberation of hydrogen industry, by other metals or compound modified,
Obtain that performance is suitable, lower-cost material substitution platinum or platinum alloy, be always the Main way of liberation of hydrogen material development.
The activity of liberation of hydrogen material depends on material electric conductivity in itself, chemical property, material morphology and material surface area etc.
Factor, material typically transient metal sulfide or selenides that the comparing done instantly is popular, such as：WS2、CoSe2、NiSe2、
MoSe2、MoS2Deng wherein molybdenum bisuphide closest to platinum or platinum in steady chemical structure, relative low price and catalysis activity because closing
Gold, has therefore suffered from extensive research.
The liberation of hydrogen of molybdenum bisuphide material derives from its edge active point, by the various nano level molybdenum sulfide of controlledly synthesis
Such as, the structure such as nano wire, nanotube, nanometer sheet, its main purpose is to improve edge active dot density to material.Instantly prepare
The more classical method of nanometer class molybdenum disulfide liberation of hydrogen material has：Oxidation-reduction method, solvothermal method and electrodeposition process etc..It is logical
Crossing solvothermal method can form the outstanding sulfide linkage of a large amount of high activities of production on amorphous molybdenum sulfide, and its operating process is relative
Simply, thus be generally used.The lifting of molybdenum sulfide electric conductivity is mainly and is doped using molybdenum sulfide and carbon nanomaterial
Arrive, conventional material has CNT, Graphene and NACF, but during doping, inevitably to liberation of hydrogen
The pattern of material causes certain destruction, is easily reduced its specific surface area and reduces hydrogen evolution activity point；The uneven situation of doping
Under, its liberation of hydrogen efficiency also can be impacted.For a long time, how electric conductivity obtained by suitable doping way and hydrogen evolution activity is equal
Preferably liberation of hydrogen material, is always the difficult point and focus during liberation of hydrogen material development.
The content of the invention
Present invention solves the technical problem that there is provided a kind of molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hydridization
Material and preparation method thereof, by solvent thermal reaction method by ultra-thin molybdenum sulfide（MoSx）Nanometer sheet is uniformly deposited on many wall carbon
On nanotube, this molybdenum sulfide nanometer sheet defect concentration is high, and goffering is more, while surface is rich in undersaturated outstanding sulfide linkage, because
And evolving hydrogen reaction is active（HER）It is relatively strong, while one-dimensional nucleocapsid structure in obtained molybdenum sulfide/multi-walled carbon nano-tubes hybrid material
The transmission of the transfer and electric charge beneficial to electronics is configured with, therefore Hydrogen Evolution Performance is superior, therefore the vulcanization with core shell structure for preparing
Molybdenum/multi-walled carbon nano-tubes hybrid material can be used preferably as liberation of hydrogen catalyst, and show excellent hydrogen evolution activity and
Stability.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, the molybdenum sulfide with core shell structure/many wall carbon
The preparation method of nanotube hybrid material, it is characterised in that concretely comprise the following steps：By multi-walled carbon nano-tubes and four thio ammonium molybdate point
Dissipate in the mixed solution of DMF and deionized water, then above-mentioned solution is transferred in reactor in 180-
220 DEG C of reaction 12h, product is cleaned with ethanol and deionized water successively after being centrifuged, by the solid after washing in 100
DEG C vacuum drying 12h obtains target product and has the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of core shell structure.
Further preferably, the purity of described multi-walled carbon nano-tubes reaches more than 95%, and its external diameter is 10-20nm, and length is
25-35μm。
Further preferably, the amount ratio of described multi-walled carbon nano-tubes, four thio ammonium molybdate and DMF
Example is 15mg:25-100mg:N in the mixed solution of 10-25mL, DMF and deionized water, N- dimethyl methyl
Acid amides is 1 with the volume ratio of deionized water:2.
Molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material of the present invention, it is characterised in that be by
What the above method was prepared, wherein molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes is 1:1.
Molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material of the present invention exists as liberation of hydrogen catalyst
Application in electrode, it is characterised in that detailed process is：Molybdenum sulfide/multi-walled carbon nano-tubes hybrid material is supported on glass-carbon electrode
Go up and coat the films of nafion@117 and electrode is obtained.
The present invention has the advantages that compared with prior art：The present invention is synthesized by easy solvent heat sedimentation
Carbon multi-wall nano tube loaded ultra-thin molybdenum sulfide nanometer sheet hybrid material, molybdenum sulfide nanometer sheet uniform load is in more in the hybrid material
To form core shell structure on wall carbon nano tube, the liberation of hydrogen of prepared caterpillar shape molybdenum sulfide/multi-walled carbon nano-tubes hybrid material
Overpotential（η）It is 102mV, in current density（J）It is 10mAcm-2When, its Tafel slope of curve（b）It is 35mVdec-1,
Polarized 5h under 150mV and SHE current potentials, and its hydrogen evolution activity is not decayed significantly, and its excellent Hydrogen Evolution Performance is not less than
The Hydrogen Evolution Performance of other the liberation of hydrogen materials even above reported at present.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of molybdenum sulfide/multi-walled carbon nano-tubes hybrid material under different enlargement ratios, wherein molybdenum sulfide
It is 1 with the mass ratio of multi-walled carbon nano-tubes:1；
Fig. 2 is the scanning electron microscope (SEM) photograph and transmission electron microscope picture of the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of different quality ratio, its
Molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 1 in middle A and B:The mass ratio of molybdenum sulfide and multi-walled carbon nano-tubes in 2, C and D
It is 1:Molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 2 in 1, E and F:1；
Fig. 3 is the powder diagram of pure vulcanization molybdenum powder and molybdenum sulfide/multi-walled carbon nano-tubes hybrid material, sulphur in hybrid material
It is 1 to change molybdenum with the mass ratio of multi-walled carbon nano-tubes:1；
Fig. 4 is the Raman spectrogram of pure vulcanization molybdenum powder and molybdenum sulfide/multi-walled carbon nano-tubes hybrid material, sulphur in hybrid material
It is 1 to change molybdenum with the mass ratio of multi-walled carbon nano-tubes:1；
Fig. 5 is the x-ray photoelectron spectroscopy figure of molybdenum element in pure vulcanization molybdenum powder and molybdenum sulfide/multi-walled carbon nano-tubes hybrid material,
Molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 1 in hybrid material:1；
Fig. 6 is the x-ray photoelectron spectroscopy figure of the element sulphur of pure vulcanization molybdenum powder and molybdenum sulfide/multi-walled carbon nano-tubes hybrid material,
Molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 1 in hybrid material:1；
Fig. 7 is that the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material corrected by solution ohmmic drop is 0.5mol/L in molar concentration
Sulfuric acid solution in linear volt-ampere curve, sweep speed is 5mVs-1；
Fig. 8 is that molybdenum sulfide is 10mAcm in current density with multi-walled carbon nano-tubes hybrid material-2When corresponding Tafel curves；
Fig. 9 be molybdenum sulfide with multi-walled carbon nano-tubes hybrid material when current potential is 0.2V the difference of oxidation current and reduction current with
Sweep speed linear relationship chart；
Figure 10 is impedance spectra of the molybdenum sulfide with multi-walled carbon nano-tubes hybrid material when overpotential is 100mV；
Figure 11 is molybdenum sulfide and multi-walled carbon nano-tubes hybrid material the 5h timing Ampere currents figures when electrode potential is 150mV, interior
Illustration is magnified partial view in the timing Ampere currents curve of molybdenum sulfide/multi-walled carbon nano-tubes hybrid material；
Figure 12 is that the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material corrected by solution ohmmic drop is 0.5mol/L in molar concentration
Before stability test in sulfuric acid solution（Dotted line）After stability test（Solid line）Linear volt-ampere curve, interior illustration is corresponding for its
Tafel curves.
Specific real-time mode
The above of the invention is described in further details by the following examples, but this should not be interpreted as the present invention
The scope of above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to of the invention
Scope.
Embodiment 1
The preparation of pure vulcanization molybdenum powder
50mg four thio ammonium molybdates are scattered in the mixed solution of 15mL DMFs and 30mL deionized waters,
Above-mentioned solution is transferred in reactor again 12h is reacted in 200 DEG C, product be centrifuged after successively with ethanol and go from
Sub- water cleaning, is vacuum dried the solid constituent after washing 12h and obtains the pure vulcanization molybdenum powder of target product in 100 DEG C.
Embodiment 2
Mass ratio is 1:The preparation of 2 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material
By 15mg multi-walled carbon nano-tubes and 25mg four thio ammonium molybdates be scattered in 10mL N,N-dimethylformamides and 20mL go from
In the mixed solution of sub- water, then above-mentioned solution is transferred in reactor reacts 12h in 200 DEG C, product is centrifuged
Cleaned with ethanol and deionized water successively afterwards, the solid constituent after washing is vacuum dried into 12h in 100 DEG C obtains target product tool
The mass ratio for having core shell structure is 1:2 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material.
Embodiment 3
Mass ratio is 1:The preparation of 1 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material
By 15mg multi-walled carbon nano-tubes and 50mg four thio ammonium molybdates be scattered in 20mL N,N-dimethylformamides and 40mL go from
In the mixed solution of sub- water, then above-mentioned solution is transferred in reactor reacts 12h in 200 DEG C, product is centrifuged
Cleaned with ethanol and deionized water successively afterwards, the solid constituent after washing is vacuum dried into 12h in 100 DEG C obtains target product tool
The mass ratio for having core shell structure is 1:1 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material.
Embodiment 4
Mass ratio is 2:The preparation of 1 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material
15mg multi-walled carbon nano-tubes and 100mg four thio ammonium molybdates are scattered in 25mL N,N-dimethylformamides and 50mL goes
In the mixed solution of ionized water, then above-mentioned solution is transferred in reactor reacts 12h in 200 DEG C, product is through centrifugation point
Cleaned with ethanol and deionized water successively after, the solid constituent after washing is vacuum dried into 12h in 100 DEG C obtains target product
Mass ratio with core shell structure is 2:1 molybdenum sulfide/multi-walled carbon nano-tubes hybrid material.
Fig. 1 is molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（Mass ratio is 1:1）Transmission retouch electron microscope, wherein vulcanizing
The average chi footpath of molybdenum nanometer sheet is equably supported on multi-wall carbon nano-tube pipe surface and forms thick close connected ripple in 10nm or so
Line shape fold., similar to caterpillar shape, edge is more, is a kind of two-dimentional molybdenum sulfide nano material for whole hybrid material.High-resolution is saturating
Electron microscope display molybdenum sulfide nanometer sheet edge thickness is penetrated no more than 2nm, its side view shows some molybdenum sulfide sandwich constructions, layer
Between distance be 0.65nm, it is believed that be two-dimentional molybdenum sulfide（002）Face.SEAD figure is shown as typical cyclic structure,
Indicate its undefined structure.In order to compare, pure vulcanization molybdenum powder is also prepared for, it is made up of nanometer plate, chi footpath size is 20-
100nm。
Fig. 2 is the scanning electron microscope (SEM) photograph and transmission electron microscope of the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of different quality ratio
Figure, molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 1 in wherein A and B:The matter of molybdenum sulfide and multi-walled carbon nano-tubes in 2, C and D
Amount is than being 1:Molybdenum sulfide and the mass ratio of multi-walled carbon nano-tubes are 2 in 1, E and F:1, from scanning electron microscope (SEM) photograph as can be seen that molybdenum sulfide
On multi-walled carbon nanotubes, its thickness is 10-20nm to nanometer sheet uniform load, even if the quality of molybdenum sulfide and multi-walled carbon nano-tubes
Ratio increases to 2 from 0.5, and the thickness of molybdenum sulfide does not have significant change, but the density of molybdenum sulfide nanometer sheet load substantially increases.
Fig. 3 be the angle of diffraction be 14.2 °, 33.2 ° and 59.0 ° correspond to molybdenum sulfide（002）、（100）With（110）Crystal face,
And it is consistent with the iris of molybdenum sulfide.Compared with pure vulcanization molybdenum powder, diffraction maximum is all born and moves on to the relatively low angle of diffraction, and
The weakened of diffraction maximum, illustrates that multi-walled carbon nano-tubes can suppress the accumulation of molybdenum sulfide.In addition, in molybdenum sulfide/many walls
On the diffraction pattern of carbon nano-tube hybridization material, occurs a stronger diffraction maximum in 26.2 ° of angles of diffraction, it should be attributed to many walls
CNT（002）Face.
Fig. 4 is in 382cm-1And 407cm-1There are two absworption peaks, correspond respectively to vulcanize the E of molybdenum powder1 2gAnd A1gShake
Movable model, compared with pure vulcanization molybdenum powder, the A of molybdenum sulfide/multi-walled carbon nano-tubes hybrid material1gRaman signal is shown as red
Move, after illustrating to introduce multi-walled carbon nano-tubes, the number of plies of molybdenum sulfide is reduced, and this is consistent with the result of powder diffraction.On the other hand,
E1 2gAnd A1gThe difference of vibration signal may be at the quantity of crystal end molybdenum sulfide, compared with pure vulcanization molybdenum powder, vulcanization
Molybdenum/relatively weak the E of multi-walled carbon nano-tubes hybrid material1 2gThere is the end sulphur of higher density in signal instruction molybdenum sulfide nanometer sheet
Change molybdenum.And this end molybdenum sulfide has unsaturated sulphur atom higher, they are often the activated centre of liberation of hydrogen catalysis.
As shown in figure 5, the matched curve of molybdenum 3d spectrum shows two kinds of valence states of molybdenum：Mo4+And Mo6+, further deconvolute point
Mo in analysis display molybdenum sulfide4+Electronics is to having two kinds of different phase 2H and 1T phases, wherein the 2H phases of molybdenum sulfide, its Mo4+ 3d
Electronics is pointed to 228.6eV（3d 5/2）And 231.5eV（3d 3/2）.The 1T phases of molybdenum sulfide, its Mo4+3d electronics is pointed to
229.5eV（3d 5/2）And 232.1eV（3d 3/2）.For Mo6+, its electronics is to appearing in 232.8eV（3d 5/2）With
234.9eV（3d 3/2）, indicate that the oxide of molybdenum is present（Molybdenum oxide）.In addition, the 2s electronic signals of sulphion are appeared in
226.0eV, and with the 3d electronics overlap of peaks of molybdenum.
Fig. 6 be sulphur 2p spectrum electronics matched curves molybdenum sulfide/multi-walled carbon nano-tubes hybrid material in sulphur atom show
Two kinds of valence states：S2-And S2 2-It is similar, S2-2p electronics is to there is also two-phase, wherein appearing in 161.5eV（2p 3/2）With
162.8eV（2p 1/2）A pair of peaks correspond to molybdenum sulfide 2H phases, appear in 162.2eV（2p 3/2）And 163.4eV（2p
1/2）A pair of peaks correspond to molybdenum sulfide 1T phases.From Mo4+3d and S2-The X-ray electronic signal peak intensity of 2p electronics pair can be with
Find out, in molybdenum sulfide/carbon nano-tube hybridization material, 2H phase molybdenum sulfides are dominant.And S2 2-2p electronics peak-to-peak signals appear in S2-2p believes
In number background, its 2p electronics is to appearing in 164.2eV（2p 3/2）And 165.5eV（2p 1/2）.The S of these bridgings2 2-Or angle
S on top2-It is beneficial to carry out evolving hydrogen reaction by traditional vulcanization dehydrogenation reaction course.
Fig. 7 be deduct solution resistance after molar concentration be 0.5mol/L sulfuric acid solutions in catalytic hydrogen evolution reaction it is linear
Voltammogram, pure multi-walled carbon nano-tubes does not have obvious liberation of hydrogen electric current occur in the current potential studied, and molybdenum sulfide/many wall carbon
Nanotube hybrid material shows hydrogen evolution activity higher, and this can be 10mAcm from current density-2When overpotential find out.Should
The hydrogen evolution activity of hybrid material is relevant with the load capacity of the molybdenum sulfide on multi-walled carbon nano-tubes, when molybdenum sulfide and multi-walled carbon nano-tubes
Mass ratio be 1:When 1, the overpotential of the hybrid material is minimum, is 102mV, and the overpotential is far below pure vulcanization molybdenum powder
356mV, the also slightly above 66mV of platinum/carbon electrode.
Molybdenum sulfide/multi-walled carbon nano-tubes hybrid material hydrogen evolution activity higher can also be demonstrate,proved from the relatively low Tafel slopes of curve
It is real, as shown in figure 8, in molybdenum sulfide/multi-walled carbon nano-tubes hybrid material, molybdenum sulfide is 1 with the mass ratio of multi-walled carbon nano-tubes:
When 1, current density is 10mAcm-2, its Tafel slope of curve is being 35mVdec-1, much smaller than pure vulcanization molybdenum powder
156mV·dec-1, close to the 31mVdec of platinum/C catalyst-1.In acid medium, evolving hydrogen reaction is related to three main steps
Suddenly, there is main discharge step first, also known as Volmer reactions：H3O+ + e− → Hads + H2O, is followed by electrochemical desorption
Step, i.e. Heyrovsky are reacted：Hads+ H3O+ + e− → H2 + H2O, followed by conjunction with step, i.e. Tafel reactions：
Hads + Hads → H2.The electrochemical kinetics model indicates, if liberation of hydrogen rate-limiting step be Volmer, Heyrovsky or
If Tafel reactions, its corresponding Tafel slope of a curve is about 120mVdec-1、40mV·dec-1Or 30mV
dec-1.For molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（Mass ratio is 1:1）, Tafel slope of a curves are 35mVdec-1, illustrate that the evolving hydrogen reaction experienced a quick Volmer reaction first, then it is probably that the rate (Tafel) of speed limit is tied again
Close step.For pure vulcanization molybdenum powder, its larger Tafel slope of curve may come from its poor electric conductivity.Molybdenum sulfide/
The hydrogen evolution activity of multi-walled carbon nano-tubes hybrid material is derived from its huge electrochemistry specific surface area.But direct measurement electrochemistry compares table
Area comparison is difficult, and reason is capacitance behavior unknown on multi-walled carbon nano-tubes and molybdenum sulfide.But it is with respect to specific surface area
Can be by measuring its double layer capacity（Cdll）And obtain, the latter is considered as being proportional to its electrochemistry specific surface area.In current potential model
It is -0.05-0.55V to enclose, and the current-responsive produced on its cyclic voltammogram mostlys come from double layer capacity change.And double layer capacity
Can be calculated from cyclic voltammogram, i.e., by calculating oxidation current and reduction current difference and scanning speed in 0.20V
Spend the slope of linearity curve.
As shown in figure 9, molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（Mass ratio is 1:1）Show maximum double layer capacity
The μ Fcm of value 50.2-2, it is 20 times of pure vulcanization molybdenum powder（2.3μF·cm-2）.Obviously, the electrochemistry of liberation of hydrogen material compares table
Area is relevant with introduced CNT.Although molybdenum sulfide nanometer sheet has huge specific surface area, its poorly conductive, thus
Its electrochemistry specific surface area is not high.As shown in Electronic Speculum, molybdenum sulfide/multi-walled carbon nano-tubes hybrid material has nucleocapsid knot
Structure.Its internal multi-walled carbon nano-tubes can serve as nanometer current-collector to accelerate the electron transmission of molybdenum sulfide matrix, and this can be solved
The hydrogen evolution activity for releasing molybdenum sulfide/multi-walled carbon nano-tubes hybrid material is higher than pure vulcanization molybdenum powder.And molybdenum sulfide/many wall carbon are received
Mitron hybrid material forms caterpillar pattern, and this one-dimensional configuration is more beneficial for diffusion of the Hydrogen Proton in electrode surface, and this is sulphur
The reason for changing molybdenum/multi-walled carbon nano-tubes hybrid material with electrochemistry specific surface area higher.
Molybdenum sulfide/excellent Hydrogen Evolution Performance of multi-walled carbon nano-tubes hybrid material can be carried out from its liberation of hydrogen kinetic mechanism
Explain, as shown in Figure 10, when overpotential is 100mV, its electrochemical impedance spectroscopy is a semicircle, and it corresponds to solution electrode circle
The faraday's reaction in face produces reaction impedance.Molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（Mass ratio is 1:1）Reaction impedance is most
It is small, it is 11 Ω, much smaller than 450 Ω, illustrate that the evolving hydrogen reaction on molybdenum sulfide/multi-walled carbon nano-tubes hybrid material is a fast electric
Sub- transfer process.This hydrogen evolution activity high is relevant with the core shell structure of its one-dimensional configuration, and it is conducive on electrode interface
Electron transmission and electric charge are transmitted.
Molybdenum sulfide/multi-walled carbon nano-tubes hybrid material operation stability can be entered by linear volt-ampere and timing ampere technology
Row assessment.Even if Figure 11 is the typical zigzag ampere curve of molybdenum sulfide/multi-walled carbon nano-tubes hybrid material, this is that hydrogen is produced
Raw, aggregation and release result alternately.Although, by (presence) above-mentioned fluctuation, in general, this is miscellaneous for timing ampere curve
Change material in 150mV current potential steady-state polarization 5h, decline without there is obvious electric current.On the other hand, molybdenum sulfide/multi-wall carbon nano-tube
The frequency that pipe hybrid material Hydrogen Evolution Performance higher can occur from timing ampere curve current density higher and current fluctuation
On embody.
Figure 12 is the linear volt-ampere before molybdenum sulfide/multi-walled carbon nano-tubes hybrid material electrochemical stability is tested and after test
Figure, for molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（Mass ratio is 1:1）, its cathode-current density do not decay significantly,
And the molybdenum sulfide of other mass ratioes/multi-walled carbon nano-tubes hybrid material, its linear volt-ampere shows the decline of obvious hydrogen evolution activity,
This corresponding Tafel slopes of curve can also find out from interior illustration.
In sum, the present invention is received by the easy carbon nanotube loaded ultra-fine molybdenum sulfide of solvent heat sedimentation synthesizing multi-wall
Rice piece, in the hybrid material molybdenum sulfide nanometer sheet uniform load on multi-walled carbon nano-tubes to form core shell structure, it is prepared
The overpotential of hydrogen evolution of caterpillar shape molybdenum sulfide/multi-walled carbon nano-tubes hybrid material（η）It is 102mV, in current density（J）For
10mA·cm-2When, its Tafel slope of curve（b）It is 35mVdec-1, polarized 5h under 150mV and SHE current potentials, and its liberation of hydrogen is lived
Property does not decay significantly, and its excellent Hydrogen Evolution Performance is not less than the analysis of other liberation of hydrogen materials of even above current report
Hydrogen performance.
Embodiment above describes general principle of the invention, principal character and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, simply original of the invention is illustrated described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (7)
1. there is the preparation method of the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of core shell structure, it is characterised in that specific steps
For：Multi-walled carbon nano-tubes and four thio ammonium molybdate are scattered in the mixed solution of DMF and deionized water,
Above-mentioned solution is transferred in reactor again 12h is reacted in 180-220 DEG C, product be centrifuged after successively with ethanol and
Deionized water is cleaned, and the solid after washing is obtained into target product in 100 DEG C of vacuum drying 12h has the vulcanization of core shell structure
Molybdenum/multi-walled carbon nano-tubes hybrid material.
2. the preparation method of the molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material according to claim 1,
It is characterized in that：The purity of described multi-walled carbon nano-tubes reaches more than 95%, and its external diameter is 10-20nm, and length is 25-35 μm.
3. the preparation method of the molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material according to claim 1,
It is characterized in that：The usage ratio of described multi-walled carbon nano-tubes, four thio ammonium molybdate and N,N-dimethylformamide is 15mg:
25-100mg:In the mixed solution of 10-25mL, DMF and deionized water DMF with go from
The volume ratio of sub- water is 1:2.
4. there is the molybdenum sulfide/multi-walled carbon nano-tubes hybrid material of core shell structure, it is characterised in that appointed by claim 1-3
What the method described in meaning one was prepared.
5. the molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material according to claim 4, its feature exists
In：Described molybdenum sulfide is 1 with the mass ratio of multi-walled carbon nano-tubes:1.
6. the molybdenum sulfide with the core shell structure/multi-walled carbon nano-tubes hybrid material described in claim 4 is used as liberation of hydrogen catalyst
Application in the electrodes.
7. the molybdenum sulfide with core shell structure/multi-walled carbon nano-tubes hybrid material according to claim 6 is urged as liberation of hydrogen
Agent application in the electrodes, it is characterised in that detailed process is：Molybdenum sulfide/multi-walled carbon nano-tubes hybrid material is supported on glass
On carbon electrode and coat the films of nafion@117 i.e. be obtained electrode.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745391A (en) * | 2018-05-24 | 2018-11-06 | 杭州电子科技大学 | A kind of New Two Dimensional black phosphorus nanometer sheet-MoS2Composite solar hydrogen manufacturing material and its preparation method and application |
| CN109097790A (en) * | 2018-06-19 | 2018-12-28 | 重庆大学 | The preparation method and water electrolysis hydrogen production reactor of body phase hydrogen-precipitating electrode |
| CN111450853A (en) * | 2020-04-01 | 2020-07-28 | 南通大学 | Silkworm cocoon-like structure electrocatalyst and preparation method thereof |
| CN114204017A (en) * | 2021-11-12 | 2022-03-18 | 闽都创新实验室 | Multi-component hollow array structure transition metal selenide electrode material and preparation method thereof |
| CN115155621A (en) * | 2022-05-19 | 2022-10-11 | 福州大学 | Co-MoS 2 /CNT (carbon nano tube) photocatalytic modified film as well as preparation method and application thereof |
| CN116099551A (en) * | 2023-02-07 | 2023-05-12 | 昆明理工大学 | Preparation method and application of carbon nano tube composite material |
| CN116586077A (en) * | 2023-06-19 | 2023-08-15 | 福大紫金氢能科技股份有限公司 | Monolithic catalyst and preparation method and application thereof |
| US11932966B2 (en) * | 2020-04-16 | 2024-03-19 | The Florida International University Board Of Trustees | Metal sulfide filled carbon nanotubes and synthesis methods thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047927A (en) * | 2015-08-21 | 2015-11-11 | 复旦大学 | Aligned carbon nano tube/molybdenum disulfide composite fiber and preparation method and application thereof |
-
2017
- 2017-02-20 CN CN201710088450.4A patent/CN106881116A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047927A (en) * | 2015-08-21 | 2015-11-11 | 复旦大学 | Aligned carbon nano tube/molybdenum disulfide composite fiber and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LILI GONG ET AL.: "Photocurrent Response in Multiwalled Carbon Nanotube Core–Molybdenum Disulfide Shell Heterostructures", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| YA YAN ET AL.: "Facile synthesis of low crystalline MoS2 nanosheet-coated CNTs for enhanced hydrogen evolution reaction", 《NANOSCALE》 * |
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| CN109097790A (en) * | 2018-06-19 | 2018-12-28 | 重庆大学 | The preparation method and water electrolysis hydrogen production reactor of body phase hydrogen-precipitating electrode |
| CN109097790B (en) * | 2018-06-19 | 2020-04-21 | 重庆大学 | Preparation method of bulk phase hydrogen evolution electrode and water electrolysis hydrogen production reactor |
| CN111450853A (en) * | 2020-04-01 | 2020-07-28 | 南通大学 | Silkworm cocoon-like structure electrocatalyst and preparation method thereof |
| US11932966B2 (en) * | 2020-04-16 | 2024-03-19 | The Florida International University Board Of Trustees | Metal sulfide filled carbon nanotubes and synthesis methods thereof |
| CN114204017A (en) * | 2021-11-12 | 2022-03-18 | 闽都创新实验室 | Multi-component hollow array structure transition metal selenide electrode material and preparation method thereof |
| CN114204017B (en) * | 2021-11-12 | 2023-09-15 | 闽都创新实验室 | Multi-component hollow array structure transition metal selenide electrode material and preparation method thereof |
| CN115155621A (en) * | 2022-05-19 | 2022-10-11 | 福州大学 | Co-MoS 2 /CNT (carbon nano tube) photocatalytic modified film as well as preparation method and application thereof |
| CN116099551A (en) * | 2023-02-07 | 2023-05-12 | 昆明理工大学 | Preparation method and application of carbon nano tube composite material |
| CN116586077A (en) * | 2023-06-19 | 2023-08-15 | 福大紫金氢能科技股份有限公司 | Monolithic catalyst and preparation method and application thereof |
| CN116586077B (en) * | 2023-06-19 | 2023-11-17 | 福大紫金氢能科技股份有限公司 | Monolithic catalyst and preparation method and application thereof |
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