CN107774282A - Three-dimensional grapheme network structure loads the preparation and application of molybdenum disulfide nano material - Google Patents
Three-dimensional grapheme network structure loads the preparation and application of molybdenum disulfide nano material Download PDFInfo
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- CN107774282A CN107774282A CN201710791716.1A CN201710791716A CN107774282A CN 107774282 A CN107774282 A CN 107774282A CN 201710791716 A CN201710791716 A CN 201710791716A CN 107774282 A CN107774282 A CN 107774282A
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- molybdenum disulfide
- dimensional grapheme
- molybdenum
- network structure
- disulfide nano
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 47
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 239000007832 Na2SO4 Substances 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 9
- 241000446313 Lamella Species 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000002803 fossil fuel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005255 carburizing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QXDDUAGHAWNZHJ-UHFFFAOYSA-N [C].[Mo](=S)=S Chemical compound [C].[Mo](=S)=S QXDDUAGHAWNZHJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000009466 transformation Effects 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
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- B01J35/33—Electric or magnetic properties
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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- 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
- B01J35/396—Distribution of the active metal ingredient
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The present invention relates to a kind of three-dimensional grapheme network structure load molybdenum disulfide nano material and its preparation and application, the material is molybdenum disulfide nano sheet uniform load on three-dimensional grapheme network, wherein molybdenum disulfide nano sheet is in 50 200nm, three-dimensional grapheme thickness is 1 10nm, three-dimensional grapheme network radius mass percent of molybdenum disulfide and total carbon in 5 50 μm, the material is：(0.4‑0.8):(0.6‑0.2).
Description
Technical field
The present invention relates to a kind of three-dimensional grapheme network structure load molybdenum disulfide nano material and preparation and application, belong to
Electrocatalytic hydrogen evolution reacts field.
Background technology
Energy and environment problem is the serious problems of facing mankind.With a large amount of uses of fossil fuel, energy and environment
Problem becomes to become increasingly conspicuous, such as air pollution, global warming.Meanwhile the undue dependence to fossil fuel also causes our warp
Ji is easier to be influenceed by these fossil fuels.Therefore, we are badly in need of developing a kind of cleaning, reproducible fossil fuel replacement
Product.Hydrogen (H2) due to having the advantages that extensive source, combustion heat value are high and environmentally friendly, and be considered as 21 century most develop it is latent
The clean energy resource of power.
Although protium is element most abundant on the earth, it is not with H2Form exist, therefore we need
Will a kind of efficient, sustainable production hydrogen technology.At present, industrially the mode of production hydrogen mainly has three kinds：Methane gas is reformed, coal gas
Change and water electrolysis, wherein first two account for 95%, water electrolysis only accounts for 4%.Because SMR and CG are strongly dependent upon fossil fuel and produce
Raw substantial amounts of CO2, all optimal production hydrogen modes or water electrolysis.
Molybdenum disulfide is a kind of higher electrocatalytic hydrogen evolution reaction (HER) catalyst of activity, and research is most hot at present
Material.Molybdenum disulfide is a kind of class grapheme material of the stratiform accumulation of hexagon, and interlamellar spacing is aboutBetween layers
Active force is Van der Waals force.Crystal structure has the 1T phases of metal phase and the 2H phases of semiconductor phase, and the electric conductivity of 1T phases is better than 2H.
For thermodynamic (al) angle, the growth of molybdenum disulfide lamella is more likely in in-plane, however, its avtive spot but position
In on the unsaturated S atom of edge.Therefore increase MoS2Edge site be advantageous to improve catalytic activity.
The factor for influenceing HER catalytic activity has：The assertive evidence catalytic activity of catalytic site, the number of avtive spot and catalyst
Electric conductivity.Therefore, can be lived by following three approach to improve molybdenum disulfide material HER：(1) by increasing molybdenum disulfide
The avtive spot of the method increase material of the molybdenum disulfide of the defects of material or preparation nanostructured；(2) molybdenum disulfide is passed through
The transformation (2H → 1T) of phase structure or (3) molybdenum disulfide increase the electric conductivity of material with C-material and metal composite.
The content of the invention
It is an object of the invention to provide a kind of three-dimensional grapheme network structure load molybdenum disulfide carbon composite nano-material
Preparation method and applications.The material is made up of molybdenum disulfide lamella particle uniform load to three-dimensional grapheme network, and it is made
Preparation Method process is simple, can volume production, the material as electrocatalytic hydrogen evolution reaction elctro-catalyst there is good performance, application prospect
It is wide.Technical scheme realized by following steps,
A kind of three-dimensional grapheme network structure loads molybdenum disulfide nano material, it is characterised in that the material is curing
Molybdenum nanometer sheet uniform load is on three-dimensional grapheme network, and wherein molybdenum disulfide nano sheet is thick in 50-200nm, three-dimensional grapheme
Spend for 1-10nm, three-dimensional grapheme network radius is at 5-50 μm, and the mass percent of molybdenum disulfide and total carbon is in the material：
(0.4-0.8):(0.6-0.2)。
The preparation method of above-mentioned three-dimensional grapheme network structure load molybdenum disulfide nano material, it is characterised in that including
Following steps：
(1) is mixed into carbon source, Yi Sishui with the one or more in sucrose, glucose, citric acid, ammonium citrate, starch
Conjunction ammonium paramolybdate is molybdenum source, with sodium sulphate (Na2SO4) be template, using the molybdenum mol ratio in the carbon and molybdenum source in carbon source as (10~
100):1, with the molybdenum and Na in molybdenum source2SO4Mass ratio be 1：(10~100) count, by carbon source, molybdenum source and Na2SO4Addition go from
Dissolved in sub- water, stir wiring solution-forming, then after ultrasonic mixing is uniform；It is spray-dried to obtain presoma, vapo(u)rizing temperature is 105
DEG C~220 DEG C；
(2) presoma grind into powder made from step (1) is laid in Noah's ark, is placed in tube furnace flat-temperature zone and is forged by
Burn：With N2Or Ar one kind or mixing are used as inert gas source, are first passed through inert gas 30- by 200~400ml/min of flow
60 minutes to exclude air；Again using Ar as carrier gas, carrier gas flux is fixed as 50~200ml/min, with 1~10 DEG C/min's
Programming rate heats up tube furnace to 650~800 DEG C, and insulation 1-8h is carbonized, and reaction is cooled to room temperature after terminating, and is calcined
Product；
(3) calcined product made from collection steps (2), finely ground, being washed in calcined product does not have Na2SO4Untill, in temperature
Spend to dry at 60~120 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material.
The three-dimensional grapheme network structure loads molybdenum disulfide nano materials application and reacted in electrocatalytic hydrogen evolution.
The present invention has advantages below：The present invention prepares the load of three-dimensional grapheme network structure using raw material cheap and easy to get
Molybdenum disulfide nano material, cost is cheap, and course of reaction is simple, controllability is strong, and molybdenum disulfide dispersiveness is preferably.The material simultaneously
Structure is homogeneous, and pattern is excellent, excellent performance, has good performance for electrocatalytic hydrogen evolution reaction.
Brief description of the drawings
Fig. 1 is the SEM photographs that the three-dimensional grapheme network structure that the embodiment of the present invention 1 obtains loads molybdenum disulfide nano material
Piece.From this view it is apparent that three-dimensional grapheme network morphology.
Fig. 2 is the SEM photographs that the three-dimensional grapheme network structure that the embodiment of the present invention 1 obtains loads molybdenum disulfide nano material
Piece.From this view it is apparent that three-dimensional grapheme piece thickness.
Fig. 3 is the TEM photographs that the three-dimensional grapheme network structure that the embodiment of the present invention 1 obtains loads molybdenum disulfide nano material
Piece.From this view it is apparent that molybdenum disulfide nano sheet is dispersed on carbon base body.
Fig. 4 is that the three-dimensional grapheme network structure that the embodiment of the present invention 1 obtains loads carbon molybdenum disulfide nano material
HRTEM photos.From this view it is apparent that the number of plies of molybdenum disulfide.
Fig. 5 is the XRD that the three-dimensional grapheme network structure that the embodiment of the present invention 1 obtains loads molybdenum disulfide nano material
Spectrum.
Fig. 6 is that the three-dimensional grapheme network structure obtained using the embodiment of the present invention 1 loads molybdenum disulfide nano material work
For the performance map of electrocatalytic hydrogen evolution catalysts.
Embodiment
The particular content of the present invention is described as follows with reference to specific embodiment：
Embodiment 1：
Weigh 3.8g citric acids, 0.25g tetra- is hydrated ammonium paramolybdate and 2.8g Na2SO4, by mixture be dissolved in 50ml go from
In sub- water, with mixing speed 300r/min magnetic stirring apparatus, stirring and dissolving wiring solution-forming, then again using power as the super of 400W
Sound device ultrasound 15min, it is well mixed.It is spray-dried to obtain presoma, vapo(u)rizing temperature is at 125 DEG C.Milled mixtures, take
10g mixed-powder is placed in Noah's ark, and Noah's ark is put into tube furnace, and the Ar inert gases 30min for being passed through 200ml/min is excluded
Air, then the H with 200ml/min2750 DEG C of temperature is warming up to for carrier gas and with 10 DEG C/min programming rate, insulation 2h is carried out
Carburizing reagent, reaction are cooled to room temperature under Ar atmosphere protections after terminating, obtain calcined product.Collect calcined product, finely ground, water
Being washed till in product does not have Na2SO4Untill, dried at 80 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material
Material, its three-dimensional grapheme thickness are<5nm, molybdenum disulfide lamella size are 200~300nm.
Obtained material 5mg is taken to be scattered in the mixed solution of 5% μ L of Nafion solution 50, the μ L of isopropanol 950 composition
In, with 0.5M H2SO4As electrolyte, using graphite rod as negative pole, Ag/AgCl electrodes are as reference electrode, and it is in 5mV/s
Sweep -400mV swept to by 0mV under speed, as shown in fig. 6, in 10mA/cm2Current density under overpotential be 420mV.
Embodiment 2：
Weigh 3.8g citric acids, 0.25g tetra- is hydrated ammonium paramolybdate and 2.8g Na2SO4, by mixture be dissolved in 50ml go from
In sub- water, with mixing speed 300r/min magnetic stirring apparatus, stirring and dissolving wiring solution-forming, then again using power as the super of 400W
Sound device ultrasound 15min, it is well mixed.It is spray-dried to obtain presoma, vapo(u)rizing temperature is at 125 DEG C.Milled mixtures, take
10g mixed-powder is placed in Noah's ark, and Noah's ark is put into tube furnace, and the Ar inert gases 30min for being passed through 200ml/min is excluded
Air, then the H with 200ml/min2700 DEG C of temperature is warming up to for carrier gas and with 10 DEG C/min programming rate, insulation 6h is carried out
Carburizing reagent, reaction are cooled to room temperature under Ar atmosphere protections after terminating, obtain calcined product.Collect calcined product, finely ground, water
Being washed till in product does not have Na2SO4Untill, dried at 80 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material
Material, its three-dimensional grapheme thickness are<5nm, molybdenum disulfide lamella size are 200~300nm.
Embodiment 3：
Weigh 3.8g citric acids, 0.25g tetra- is hydrated ammonium paramolybdate and 2.8g Na2SO4, by mixture be dissolved in 50ml go from
In sub- water, with mixing speed 300r/min magnetic stirring apparatus, stirring and dissolving wiring solution-forming, then again using power as the super of 400W
Sound device ultrasound 15min, it is well mixed.It is spray-dried to obtain presoma, vapo(u)rizing temperature is at 125 DEG C.Milled mixtures, take
10g mixed-powder is placed in Noah's ark, and Noah's ark is put into tube furnace, and the Ar inert gases 30min for being passed through 200ml/min is excluded
Air, then the H with 200ml/min2800 DEG C of temperature is warming up to for carrier gas and with 10 DEG C/min programming rate, insulation 6h is carried out
Carburizing reagent, reaction are cooled to room temperature under Ar atmosphere protections after terminating, obtain calcined product.Collect calcined product, finely ground, water
Being washed till in product does not have Na2SO4Untill, dried at 80 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material
Material, its three-dimensional grapheme thickness are<5nm, molybdenum disulfide lamella size are 200~300nm.
Embodiment 4：
Weigh 3.8g citric acids, 0.5g tetra- is hydrated ammonium paramolybdate and 2.8g Na2SO4, by mixture be dissolved in 50ml go from
In sub- water, with mixing speed 300r/min magnetic stirring apparatus, stirring and dissolving wiring solution-forming, then again using power as the super of 400W
Sound device ultrasound 15min, it is well mixed.It is spray-dried to obtain presoma, vapo(u)rizing temperature is at 125 DEG C.Milled mixtures, take
10g mixed-powder is placed in Noah's ark, and Noah's ark is put into tube furnace, and the Ar inert gases 30min for being passed through 200ml/min is excluded
Air, then the H with 200ml/min2750 DEG C of temperature is warming up to for carrier gas and with 10 DEG C/min programming rate, insulation 6h is carried out
Carburizing reagent, reaction are cooled to room temperature under Ar atmosphere protections after terminating, obtain calcined product.Collect calcined product, finely ground, water
Being washed till in product does not have Na2SO4Untill, dried at 80 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material
Material, its three-dimensional grapheme thickness are<5nm, molybdenum disulfide lamella size are 200~300nm.
Claims (3)
1. a kind of three-dimensional grapheme network structure loads molybdenum disulfide nano material, it is characterised in that the material is molybdenum disulfide
Nanometer sheet uniform load is on three-dimensional grapheme network, and wherein molybdenum disulfide nano sheet is in 50-200nm, three-dimensional grapheme thickness
For 1-10nm, three-dimensional grapheme network radius is at 5-50 μm, and the mass percent of molybdenum disulfide and total carbon is in the material：
(0.4-0.8):(0.6-0.2)。
2. the preparation method of the three-dimensional grapheme network structure load molybdenum disulfide nano material described in claim 1, its feature
It is to comprise the following steps：
(1) is mixed into carbon source with the one or more in sucrose, glucose, citric acid, ammonium citrate, starch, secondary with four hydrations
Ammonium molybdate is molybdenum source, with sodium sulphate (Na2SO4) it is template, using the molybdenum mol ratio in the carbon and molybdenum source in carbon source as (10~100):
1, with the molybdenum and Na in molybdenum source2SO4Mass ratio be 1：(10~100) count, by carbon source, molybdenum source and Na2SO4Add deionized water
Middle dissolving, wiring solution-forming is stirred, then after ultrasonic mixing is uniform；Be spray-dried to obtain presoma, vapo(u)rizing temperature 105 DEG C~
220℃；
(2) presoma grind into powder made from step (1) is laid in Noah's ark, is placed in tube furnace flat-temperature zone and is calcined by：
With N2Or Ar one kind or mixing are used as inert gas source, are first passed through inert gas 30-60 by 200~400ml/min of flow
Minute to exclude air；Again using Ar as carrier gas, carrier gas flux is fixed as 50~200ml/min, with 1~10 DEG C/min liter
Warm speed heats up tube furnace to 650~800 DEG C, and insulation 1-8h is carbonized, and reaction is cooled to room temperature after terminating, and obtains calcining production
Thing；
(3) calcined product made from collection steps (2), finely ground, being washed in calcined product does not have Na2SO4Untill, it is in temperature
Dried at 60~120 DEG C, obtain three-dimensional grapheme network structure load molybdenum disulfide nano material.
3. the three-dimensional grapheme network structure load molybdenum disulfide nano materials application described in claim 1 is anti-in electrocatalytic hydrogen evolution
Should.
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