CN106622297B - A kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material method - Google Patents
A kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material method Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 206
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 94
- 239000011733 molybdenum Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 71
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 44
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 230000009467 reduction Effects 0.000 title claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 125
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000000843 powder Substances 0.000 claims abstract description 106
- 238000009830 intercalation Methods 0.000 claims abstract description 83
- 230000002687 intercalation Effects 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000006722 reduction reaction Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 33
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 235000010344 sodium nitrate Nutrition 0.000 claims description 20
- 239000004317 sodium nitrate Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 19
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 14
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 12
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 12
- 239000004473 Threonine Substances 0.000 claims description 12
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 12
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000001493 tyrosinyl group Chemical group [H]OC1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- 125000000341 threoninyl group Chemical group [H]OC([H])(C([H])([H])[H])C([H])(N([H])[H])C(*)=O 0.000 claims description 2
- 125000000430 tryptophan group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C2=C([H])C([H])=C([H])C([H])=C12 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
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- 239000000463 material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 27
- 238000010792 warming Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000002023 wood Substances 0.000 description 18
- 238000012512 characterization method Methods 0.000 description 15
- 239000008236 heating water Substances 0.000 description 15
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- 238000012216 screening Methods 0.000 description 14
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 239000010408 film Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 graphene alkene Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
Abstract
The present invention provides a kind of protein matters to restore preparation class graphene molybdenum disulfide-graphene composite material method, and molybdenum disulfide powder is added in intercalation solution and carries out intercalation, filters, dries after the reaction was completed, obtains intercalation molybdenum disulfide powder；Intercalation molybdenum disulfide powder made from step 1 and protein matter and water are mixed and stirred for uniformly, dry, grinding obtains precursor powder；Precursor powder carries out reduction reaction under a shielding gas, cooling after fully reacting, takes out reaction product, and class graphene molybdenum disulfide-graphene composite material is obtained after grinding.The present invention combines intercalation reduction synthesis class graphene molybdenum disulfide and graphene synthesis, only completes the removing of intercalation molybdenum disulfide and the generation of graphene with a step, is successfully prepared class graphene molybdenum disulfide-graphene composite material.
Description
Technical field
The invention belongs to New Two Dimensional Material Fields, are related to class graphene molybdenum disulfide composite material, and in particular to a kind of
Protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material method.
Background technique
The class graphene molybdenum disulfide (Graphene-like molybdenum disulfide) being made of few layer of molybdenum disulfide is that one kind has
New Two Dimensional (2D) lamellar compound of similar graphene-structured and performance.In recent years with its unique physics, chemical property and
As emerging research hotspot.Class graphene molybdenum disulfide has " Sanming City by what the multilayer molybdenum disulfide of hexagonal crystal system formed
Control sandwich " the two dimensional crystal material of layer structure, single layer molybdenum disulfide is made of three layers of atomic layer, and intermediate one layer is molybdenum atom
Layer, upper layer and lower layer are sulphur atom layer, and molybdenum atom layer forms class " sandwich " structure folded by two layers of sulphur atom layer, and molybdenum is former
Son and sulphur atom are with Covalent bonding together formation two-dimensional atomic crystal；Multilayer molybdenum disulfide is made of several single layer molybdenum disulfide, and one
As be no more than five layers, for interlayer there are weak Van der Waals force, interlamellar spacing is about 0.65nm.
As a kind of important two-dimensional layer nano material, few layer molybdenum disulfide is being lubricated with its unique layer structure
The various fields such as agent, catalysis, energy stores, photoelectric material, semiconductor devices, composite material are widely used.Compared to graphene
Zero band gap, there are regulatable band gaps for class graphene molybdenum disulfide, and brighter prospect is possessed in field of photoelectric devices；
Compared to the three-dimensional bulk structure of silicon materials, class graphene molybdenum disulfide has the two-dimensional layered structure of nanoscale, can by with
Semiconductor or specification be smaller, the higher electronic chip of efficiency manufacturing, and will obtain in fields such as follow-on nano-electric devices
It is widely applied.
Experiments have shown that molybdenum disulfide has the ability of electrocatalytic hydrogen evolution reaction, at the edge of molybdenum disulfide, there are many liberation of hydrogen is anti-
The active point (Science.2007,317 (5834): 100-102) answered.According to this experimental evidence, in conjunction with molybdenum disulfide sheet
It is anti-for photocatalysis production oxygen can to speculate that molybdenum disulfide can be used as photochemical catalyst for the characteristic of semiconductor and optical absorption characteristics of body
It answers.But since molybdenum disulfide itself belongs to narrow-band semiconductor, it is very by force, to be individually used for light that this, which has just been doomed its oxidability not,
When catalyst therefore its catalytic activity may be restricted and influence.Research shows that molybdenum disulfide is deposited on the synthesis of the surface CdS
Efficient visible light produces hydrogen photochemical catalyst, and highest photocatalysis produces 36 times of (Journal of that oxygen activity is CdS
American Chemical Society.2008,130(23):7176-7177).This demonstrate that molybdenum disulfide is good light
Catalysis produces the co-catalyst of hydrogen reaction, and hews out the road Liao Yitiaoxin for Photocatalyzed Hydrogen Production for molybdenum disulfide.Meanwhile curing
The controllable band gap of molybdenum makes it possess potentiality in electrode material and energy storage field, but its carrier mobility is not high constrains it yet
Development on electricity device.
For graphene, high electron mobility makes it have the light induced electron and hole for improving photocatalytic system
The potentiality of separative efficiency；Secondly, good optical transparence makes while graphite is dilute to have compound with other photochemical catalysts but not
Influence the ability of the light absorption of photochemical catalyst；Finally, two-dimensional layered structure and bigger serface have graphene as light
A possibility that ideal carrier of catalyst.But graphite is dilute to be limited to its zero band gap, prevent graphene directly as light from urging
Agent uses.
The molybdenum disulfide of stratiform is used in combination with other organic or inorganic particles, is to mention using their synergistic effect
Rise one of molybdenum disulfide photocatalysis performance and the method for electric property.Class graphene molybdenum disulfide possesses large number of edge and urges
Change site and outstanding co-catalysis ability, performance may be implemented after the graphene synthetic composite material with high electron mobility
Be complementary to one another with light-catalysed synergistic effect, produce hydrogen photochemical catalyst field and such as electrode material and energy storage material research and development are efficient
The electricity devices fields such as material possess huge potentiality.
Chinese invention patent CN201210303392 disclose a kind of tubular graphene alkene-molybdenum disulfide nano-composite material and
Soluble molybdenum hydrochlorate is prepared into using second alcohol and water as the mixed solution of solvent by preparation method；Sodium sulfocyanate and chlorination is added
Sodium is added stannic oxide/graphene nano piece ultrasonic disperse to uniform, reaction mixture is transferred to stainless steel cauldron one after stirring
Determine to react at temperature；Room temperature is cooling after reaction, centrifuge separation, washing, drying；In N2-H2Mixing atmosphere in 800-900 DEG C of heat
2h is handled, tubular graphene alkene/molybdenum disulfide nano-composite material is obtained.
Chinese patent CN201210326035.5 discloses a kind of graphene-molybdenum disulfide nano-composite material preparation side
Method, the specific steps are that: 1) using graphite as raw material, graphite oxide is prepared by aoxidizing graft process；2) by the graphite oxide of preparation
With deionized water dissolving, ultrasound removing obtains graphene oxide solution, DMF, molybdate is then added, is eventually adding reducing agent,
It is uniformly dispersed, obtains mixed solution；3) mixed solution is transferred in reaction kettle, under the conditions of being more than or equal to 180 DEG C of temperature
5~10h is kept the temperature, product centrifugation, washing remove DMF, and it is dry, obtain Graphene/molybdenum disulfide composite electrode material product.
Chinese patent CN201510149438.0 discloses a kind of graphene-molybdenum disulfide nano-composite material preparation side
Method, step include the following steps: preparing single layer molybdenum disulfide by lithium ion graft process, prepared and aoxidized using hummer ' s method
Graphene mixes the molybdenum disulfide thin slice of synthesis and graphene by certain proportion, and ultrasonic disperse is at homogeneous mixture solotion, so
The graphene composite thin film of doping single layer curing molybdenum sheet is obtained by filtering afterwards, is then restored and is adulterated with hydroiodic acid
The graphene composite film of single layer curing molybdenum sheet, the laminated film after reduction successively use dehydrated alcohol and deionized water to rinse,
It is dried in vacuo the graphene composite film for obtaining doping single layer curing molybdenum sheet again.
Although molybdenum disulfide-graphene composite material has been made using chemical synthesis in mean disclosed above, these
The big multipaths of preparation method is more, the high requirements on the equipment and complicated for operation, some are even easy to produce pollution, do not meet environmentally friendly production
Idea of development.Therefore, a kind of simple and environmentally friendly class graphene molybdenum disulfide-graphene nanocomposite material of process is explored
Simple preparation method is very necessary.
Summary of the invention
Based on problems of the prior art, the invention proposes a kind of protein matters to restore preparation class graphene two
Molybdenum sulfide-graphene composite material method obtains the class graphene molybdenum disulfide-graphite with nanoscale, superior performance
Alkene composite material solves existing class graphene molybdenum disulfide-graphene composite material preparation flow complexity, is also easy to produce pollution
The technical issues of.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved:
A kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material method, this method packet
Include following steps:
Molybdenum disulfide powder is added in intercalation solution and carries out intercalation by step 1, filters, dries after the reaction was completed
It is dry, obtain intercalation molybdenum disulfide powder；
The intercalation solution is the mixed solution of potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide composition；
The molybdenum disulfide powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and mass concentration 30%
Hydrogen peroxide between proportion relation be 1g:(1~4) g:(0.5~2) g:(9~40) mL:(4~20) mL；
Intercalation molybdenum disulfide powder made from step 1 and protein matter and water are mixed and stirred for uniformly by step 2,
Dry, grinding, obtains precursor powder；
Proportion relation between the intercalation molybdenum disulfide powder and protein matter and water is 2g:(2~7) g:(20
~70) g；
Step 3, precursor powder carry out reduction reaction under a shielding gas, cooling after fully reacting, take out reaction and produce
Object obtains class graphene molybdenum disulfide-graphene composite material after grinding.
The present invention also has following distinguishing feature:
Specifically, the protein matter is tyrosine, tryptophan, phenylalanine or threonine.
Preferably, the molybdenum disulfide powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and quality are dense
Proportion relation between the hydrogen peroxide of degree 30% is 1g:2g:1g:23mL:7mL.
Preferably, the proportion relation between the intercalation molybdenum disulfide powder and protein matter and water is 2g:2.2g:
22g。
Specifically, in step 1, the process of the intercalation are as follows: molybdenum disulfide powder is added in mixed solution,
10~30 DEG C of 1~3h of reaction are heated to, then at 30~70 DEG C and stir 20~50min, it is stirred to react 10 at 75~100 DEG C~
Then 30min filters, is dry, obtaining intercalation molybdenum disulfide powder.
Specifically, after intercalation molybdenum disulfide powder, protein matter and the water is mixed evenly, in drying box
50~100 DEG C at a temperature of by 6~dry for 24 hours, grind, obtain precursor powder.
Specifically, in step 3, the process of the reduction reaction are as follows: be packed into precursor powder obtained in step 2
Boat is burnt, is put into tube furnace, is continually fed into protective atmosphere and is reacted, takes out reduction after cooling to room temperature with the furnace after the reaction was completed
Product to get arrive class graphene molybdenum disulfide-graphene composite material；
When the protein matter is tyrosine, the temperature of reduction reaction is 280~400 DEG C, soaking time is 120~
150min；When the protein matter is tryptophan, the temperature of reduction reaction is 240~320 DEG C, soaking time is 90~
150min；When the protein matter is phenylalanine, the temperature of reduction reaction is 250~320 DEG C, soaking time is 60~
90min；When the protein matter is threonine, the temperature of reduction reaction is 200~300 DEG C, soaking time is 70~
100min。
Preferably, the protective atmosphere is nitrogen or argon gas.
Compared with prior art, the present invention beneficial has the technical effect that
(I) present invention is mixed to form presoma using protide organic carbon source and molybdenum disulfide, so that organic carbon source is inserted into
Molybdenum disulfide powder interlayer increases its interfloor distance, weakens molybdenum disulfide interlayer van der Waals interaction, makes egg in conjunction with pyroreaction
The reduction and removing of molybdenum disulfide are realized in white class carbonization.
(II) present invention combines intercalation reduction synthesis class graphene molybdenum disulfide and graphene synthesis, only with a step, that is, complete
At the removing of intercalation molybdenum disulfide and the generation of graphene, it is successfully prepared class graphene molybdenum disulfide-graphene composite wood
Material.
(III) product prepared by the present invention is the class with high carrier mobility and high rim active catalyst sites quantity
Graphene molybdenum disulfide and the compound nano material of graphene, and class graphene molybdenum disulfide is grown on graphene sheet layer, is made
The photocatalysis performance of graphene is improved for outstanding co-catalyst；Meanwhile the two synergistic effect so that composite material in electricity
Pole material and energy storage material field have immeasurable great potential, greatly expand the application range of molybdenum disulfide.
(IV) present invention preparation class graphene molybdenum disulfide-graphene composite material, it is easy to operate, it does not need complicated and numerous
Trivial preparation facilities, preparation efficiency is high, and yield is big, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is class graphene molybdenum disulfide-graphene composite material Raman map in embodiment 1.
Fig. 2 is class graphene molybdenum disulfide-graphene composite material SEM figure in embodiment 1.
Fig. 3 is molybdenum disulfide-graphene composite material Raman map in comparative example 1.
Fig. 4 is molybdenum disulfide-graphene composite material SEM figure in comparative example 1.
Fig. 5 is class graphene molybdenum disulfide-graphene composite material Raman map in comparative example 6.
Fig. 6 is class graphene molybdenum disulfide-graphene composite material SEM figure in comparative example 6.
Particular content of the invention is described in more detail with reference to embodiments.
Specific embodiment
It should be noted that heretofore described class graphene molybdenum disulfide is the molybdenum disulfide of few layer structure, it is described
The structure that few layer structure is 1~5 layer.
In compliance with the above technical solution, specific embodiments of the present invention are given below, it should be noted that the present invention not office
It is limited to following specific embodiments, all equivalent transformations made on the basis of the technical solutions of the present application each falls within protection model of the invention
It encloses.The present invention is described in further details below with reference to embodiment.
Embodiment 1:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 20g, the concentrated sulfuric acid of sodium nitrate 10g, mass concentration 98% is 230mL
Hydrogen peroxide with mass concentration 30% is 70mL；
Then heating water bath at 30 DEG C and stirs 30min, carries out intercalation, be then heated to 75 to 15 DEG C of reaction 2h
DEG C it is stirred to react 30min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 2.2g tyrosine to be added in 22g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tyrosine
Vulcanize molybdenum powder, stirs evenly, it is dry by 8h at a temperature of 60 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 350 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 130min with the furnace
Material.
The Raman map of class graphene molybdenum disulfide-graphene composite material manufactured in the present embodiment is as shown in Figure 1, height
Resolution ratio SEM figure is as shown in Figure 2.
E in Raman map in Fig. 12g 1With Ag 1Value is respectively 381.1 and 405.5, displacement difference 24.4, referring to Raman spectral difference
Related article (Li H, Zhang Q, Yap C C R, the et al.From Bulk to of relationship between value and the molybdenum disulfide number of plies
Monolayer MoS2:Evolution of Raman Scattering[J].Advanced Functional
Materials, 2012,22 (7): 1385-1390.) it is found that displacement difference is less than 25, the number of plies of the product is 1~5 layer, is belonged to few
Layer structure molybdenum disulfide, the peak characteristic peak D and G peak value of graphene distinguish D=1325.9, G=1588.9, that is, show the present embodiment
Prepared sample is class graphene molybdenum disulfide-graphene composite material.Fig. 2 middle high-resolution SEM figure is shown as the class of few layer
Graphene molybdenum disulfide-graphene composite material.Comprehensive attached drawing is it can be concluded that sample prepared by the present embodiment is class graphene
Molybdenum disulfide-graphene composite material.
Embodiment 2:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 40g, the concentrated sulfuric acid of sodium nitrate 5g, mass concentration 98% be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 10 DEG C and stirs 30min, carries out intercalation, be then heated to 95 to 10 DEG C of reaction 2h
DEG C it is stirred to react 25min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 6.0g tyrosine to be added in 60g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tyrosine
Vulcanize molybdenum powder, stirs evenly, it is dry by 7.5h at a temperature of 70 in drying box DEG C, it is ground to the sieving of 200 mesh, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 280 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 150min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 3:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 10g, the concentrated sulfuric acid of sodium nitrate 8g, mass concentration 98% be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 45 DEG C and stirs 50min, carries out intercalation, be then heated to 98 to 30 DEG C of reaction 1h
DEG C it is stirred to react 15min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 4.0g tyrosine to be added in 40g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tyrosine
Vulcanize molybdenum powder, stirs evenly, it is dry by 8h at a temperature of 50 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 400 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 120min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 4:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 15g, the concentrated sulfuric acid of sodium nitrate 20g, mass concentration 98% is 210mL
Hydrogen peroxide with mass concentration 30% is 100mL.
Then heating water bath at 35 DEG C and stirs 20min, carries out intercalation, be then heated to 12 DEG C of reaction 2.5h
80 DEG C are stirred to react 30min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation two
Vulcanize molybdenum powder.
Step 2 takes 5.4g tyrosine to be added in 54g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tyrosine
Vulcanize molybdenum powder, stirs evenly, it is dry by 7h at a temperature of 90 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through nitrogen, is warming up to 320 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 140min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 5:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 35g, the concentrated sulfuric acid of sodium nitrate 18g, mass concentration 98% be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 50 DEG C and stirs 20min, carries out intercalation, be then heated to 100 to 25 DEG C of reaction 3h
DEG C it is stirred to react 10min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 3.4g tryptophan to be added in 34g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tryptophan
Vulcanize molybdenum powder, stirs evenly, it is dry by 18h at a temperature of 100 in drying box DEG C, it is ground to the sieving of 200 mesh, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 240 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 150min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 6:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 25g, the concentrated sulfuric acid of sodium nitrate 15g, mass concentration 98% is 150mL
Hydrogen peroxide with mass concentration 30% is 120mL.
Then heating water bath at 32 DEG C and stirs 25min, carries out intercalation, be then heated to 18 DEG C of reaction 2.5h
78 DEG C are stirred to react 20min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation two
Vulcanize molybdenum powder.
Step 2 takes 2.2g tryptophan to be added in 22g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tryptophan
Vulcanize molybdenum powder, stir evenly, by drying for 24 hours at a temperature of 80 in drying box DEG C, the sieving of 200 mesh is ground to, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 320 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 120min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 7:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 30g, the concentrated sulfuric acid of sodium nitrate 12g, mass concentration 98% is 255mL
Hydrogen peroxide with mass concentration 30% is 65mL.
Then heating water bath at 42 DEG C and stirs 45min, carries out intercalation, be then heated to 20 DEG C of reaction 1.5h
88 DEG C are stirred to react 12min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation two
Vulcanize molybdenum powder.
Step 2 takes 6.0g tryptophan to be added in 60g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tryptophan
Vulcanize molybdenum powder, stirs evenly, it is dry by 20h at a temperature of 75 in drying box DEG C, it is ground to the sieving of 200 mesh, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 280 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 130min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 8:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 20g, the concentrated sulfuric acid of sodium nitrate 10g, mass concentration 98% is 225mL
Hydrogen peroxide with mass concentration 30% is 75mL.
Then heating water bath at 35 DEG C and stirs 20min, carries out intercalation, be then heated to 15 DEG C of reaction 2.5h
83 DEG C are stirred to react 18min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation two
Vulcanize molybdenum powder.
Step 2 takes 4.3g tryptophan to be added in 43g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tryptophan
Vulcanize molybdenum powder, stirs evenly, it is dry by 16h at a temperature of 80 in drying box DEG C, it is ground to the sieving of 200 mesh, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through nitrogen, is warming up to 300 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 90min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 9:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 40g, the concentrated sulfuric acid of sodium nitrate 5g, mass concentration 98% be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 38 DEG C and stirs 25min, carries out intercalation, be then heated to 86 to 12 DEG C of reaction 2h
DEG C it is stirred to react 11min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 4.0g phenylalanine to be added in 40g deionized water, is stirring evenly and then adding into 2.0g to phenylalanine and inserts
Layer molybdenum disulfide powder, stirs evenly, dry by 13h at a temperature of 85 in drying box DEG C, is ground to the sieving of 200 mesh, obtains
To precursor powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 320 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 60min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 10:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 10g, the concentrated sulfuric acid of sodium nitrate 8g, mass concentration 98% be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 70 DEG C and stirs 30min, carries out intercalation, be then heated to 25 DEG C of reaction 1.5h
90 DEG C are stirred to react 22min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation two
Vulcanize molybdenum powder.
Step 2 takes 3.7g phenylalanine to be added in 37g deionized water, is stirring evenly and then adding into 2.0g to phenylalanine and inserts
Layer molybdenum disulfide powder, stirs evenly, dry by 10h at a temperature of 55 in drying box DEG C, is ground to the sieving of 200 mesh, obtains
To precursor powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 250 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 90min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 11:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 15g, the concentrated sulfuric acid of sodium nitrate 20g, mass concentration 98% is 200mL
Hydrogen peroxide with mass concentration 30% is 100mL.
Then heating water bath at 60 DEG C and stirs 36min, carries out intercalation, be then heated to 96 to 20 DEG C of reaction 2h
DEG C it is stirred to react 10min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 4.3g phenylalanine to be added in 43g deionized water, is stirring evenly and then adding into 2.0g to phenylalanine and inserts
Layer molybdenum disulfide powder, stirs evenly, dry by 9h at a temperature of 75 in drying box DEG C, is ground to the sieving of 200 mesh, obtains
Precursor powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 280 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 80min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 12:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution become potassium chlorate be 35g, the concentrated sulfuric acid of sodium nitrate 18g, mass concentration 98% be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 52 DEG C and stirs 42min, carries out intercalation, be then heated to 10 DEG C of reaction 2.5h
100 DEG C are stirred to react 10min, and acquired solution after reaction is filtered and dries filter cake, are ground to the sieving of 200 mesh, obtain intercalation
Molybdenum disulfide powder.
Step 2 takes 7.0g phenylalanine to be added in 70g deionized water, is stirring evenly and then adding into 2.0g to phenylalanine and inserts
Layer molybdenum disulfide powder, stirs evenly, dry by 8h at a temperature of 60 in drying box DEG C, is ground to the sieving of 200 mesh, obtains
Precursor powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through nitrogen, is warming up to 300 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 75min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 13:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 takes 4.4g threonine to be added in 44g deionized water, is stirring evenly and then adding into 2.0g intercalation two to threonine
Vulcanize molybdenum powder, stirs evenly, it is dry by 18h at a temperature of 75 in drying box DEG C, it is ground to the sieving of 200 mesh, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 300 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 70min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 14:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 takes 3.9g threonine to be added in 39g deionized water, is stirring evenly and then adding into 2.0g intercalation two to threonine
Vulcanize molybdenum powder, stir evenly, by drying for 24 hours at a temperature of 60 in drying box DEG C, the sieving of 200 mesh is ground to, before obtaining
Drive body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 200 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 100min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 15:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 takes 6.8g threonine to be added in 68g deionized water, is stirring evenly and then adding into 2.0g intercalation two to threonine
Vulcanize molybdenum powder, stirs evenly, it is dry by 9h at a temperature of 80 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 250 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 85min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Embodiment 16:
The present embodiment provides a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material side
Method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 takes 2.0g threonine to be added in 20g deionized water, is stirring evenly and then adding into 2.0g intercalation two to threonine
Vulcanize molybdenum powder, stirs evenly, it is dry by 9h at a temperature of 80 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 280 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide-graphene composite wood is arrived after cooling to room temperature after 75min with the furnace
Material.
The present embodiment products therefrom class graphene molybdenum disulfide-graphene composite material characterization result and 1 base of embodiment
This is identical.
Comparative example 1:
This comparative example provide it is a kind of prepare molybdenum disulfide-graphene composite material method, method includes the following steps:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder, be added by step 1
Mass concentration is in the 10%, ethanol solution containing 100g polyphenylene sulfide, and heating water bath is to 30 DEG C and stirs 12h, is mixed
Liquid.5gKMnO is added in above-mentioned mixed liquor4Powder, heating water bath is to 50 DEG C and stirs 18h, filters and dries filter cake, grinds
It is milled to the sieving of 200 mesh, obtains intercalation molybdenum disulfide powder.
Step 2 is identical as the step of embodiment 1 two.
Step 3 is identical as the step of embodiment 1 three.
Raman spectrum analysis and sem analysis have been carried out to molybdenum disulfide made from this comparative example.Raman map such as Fig. 3
Shown, high-resolution SEM figure is as shown in Figure 4.Its characteristic peak E in Fig. 32g 1With Ag 1Value is respectively 381.1 and 409.1, and displacement difference is
28.0, displacement difference is greater than 25, belongs to block structure molybdenum disulfide.The form of molybdenum disulfide shows this product molybdenum disulfide in Fig. 4
Block accumulation, is presented multilayered structure, is not belonging to few layer molybdenum disulfide.
Comparative example 2:
This comparative example provide it is a kind of prepare molybdenum disulfide-graphene composite material method, method includes the following steps:
Step 1, identical as processes other in the step of embodiment 1 one, difference is only in that: the composition of intercalation solution
The concentrated sulfuric acid for potassium permanganate 20g, sodium nitrate 10g, mass concentration 98% is 230mL.
Step 2 is identical as the step of embodiment 1 two.
Step 3 is identical as the step of embodiment 1 three.
There is the accumulation of molybdenum disulfide block as comparative example 1 in molybdenum disulfide made from this comparative example, is not belonging to class graphite
Alkene molybdenum disulfide-graphene composite material.
Comparative example 3:
This comparative example provide it is a kind of prepare molybdenum disulfide-graphene composite material method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 is identical as the step of embodiment 1 two.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 350 DEG C, reaction by step 3
Taking-up product is ground to get molybdenum disulfide-graphene composite material is arrived after cooling to room temperature after 10min with the furnace.
There is molybdenum disulfide block heap as comparative example 1 in molybdenum disulfide-graphene composite material made from this comparative example
Product, and the appearance without finding graphene-structured, are not belonging to class graphene molybdenum disulfide nano-composite material.
Comparative example 4:
This comparative example provide it is a kind of prepare molybdenum disulfide-graphene composite material method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 is identical as the step of embodiment 1 two.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 200 DEG C, reaction by step 3
Taking-up product is ground to get molybdenum disulfide-graphene composite material is arrived after cooling to room temperature after 120min with the furnace.
There is molybdenum disulfide block heap as comparative example 1 in molybdenum disulfide-graphene composite material made from this comparative example
Product, and the appearance without finding graphene-structured, are not belonging to class graphene molybdenum disulfide nano-composite material.
Comparative example 5:
This comparative example provide it is a kind of prepare molybdenum disulfide-graphene composite material method, method includes the following steps:
Step 1 is identical as the step of embodiment 1 one.
Step 2 is identical as the step of embodiment 1 two.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 800 DEG C, reaction by step 3
Taking-up product is ground to get molybdenum disulfide-graphene composite material is arrived after cooling to room temperature after 15min with the furnace.
There is molybdenum disulfide block heap as comparative example 1 in molybdenum disulfide-graphene composite material made from this comparative example
Product, and the appearance without finding graphene-structured, are not belonging to class graphene molybdenum disulfide nano-composite material.
Comparative example 6:
The method that this comparative example provides a kind of carbohydrate organic carbon reduction preparation class graphene molybdenum disulfide, this method include with
Lower step:
Molybdenum disulfide powder is ground to the sieving of 200 mesh, takes 10g screenings molybdenum disulfide powder to be added to slotting by step 1
In layer solution, the group of intercalation solution becomes that potassium chlorate is 20g, the concentrated sulfuric acid of sodium nitrate 10g, mass concentration 98% is 230mL
Hydrogen peroxide with mass concentration 30% is 70mL；
Then heating water bath at 30 DEG C and stirs 30min, carries out intercalation, be then heated to 75 to 15 DEG C of reaction 2h
DEG C it is stirred to react 30min, acquired solution after reaction is filtered and dries filter cake, is ground to the sieving of 200 mesh, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2 takes 0.5g tyrosine to be added in 15g deionized water, is stirring evenly and then adding into 2.0g intercalation two to tyrosine
Vulcanize molybdenum powder, stirs evenly, it is dry by 8h at a temperature of 60 in drying box DEG C, it is ground to the sieving of 200 mesh, obtains forerunner
Body powder.
Precursor powder is fitted into burning boat and is placed in tube furnace, be passed through argon gas, is warming up to 330 DEG C, reaction by step 3
Taking-up product is ground to get class graphene molybdenum disulfide is arrived after cooling to room temperature after 30min with the furnace.
The Raman map of the class graphene molybdenum disulfide of this comparative example preparation is as shown in figure 5, high-resolution SEM figure such as Fig. 6
It is shown.
E in Raman map in Fig. 52g 1With Ag 1Value is respectively 382.2 and 405.1, displacement difference 22.9, referring to Raman spectral difference
Related article (Li H, Zhang Q, Yap C C R, the et al.From Bulk to of relationship between value and the molybdenum disulfide number of plies
Monolayer MoS2:Evolution of Raman Scattering[J].Advanced Functional
Materials, 2012,22 (7): 1385-1390.) it is found that displacement difference is less than 25, the number of plies of the product is 1~5 layer, is belonged to few
Layer structure molybdenum disulfide shows that sample prepared by the present embodiment is class graphene molybdenum disulfide.Fig. 6 middle high-resolution SEM figure
It is shown as the class graphene molybdenum disulfide of few layer.Comprehensive attached drawing is it can be concluded that sample prepared by the present embodiment is class graphene two
Molybdenum sulfide.
From the comparison of comparative example 6 and embodiment 1 as can be seen that the proportion of intercalation molybdenum disulfide powder and protein matter is closed
System is to whether can to generate class graphene molybdenum disulfide-graphene composite material most important.When protein matter is largely excessive
When, then cooperate reaction condition appropriate, composite material can be just generated, and when protein matter is appropriate or a small amount of, then with suitable
When reaction condition, then can be only generated class graphene molybdenum disulfide.
Claims (6)
1. a kind of protein matter reduction preparation class graphene molybdenum disulfide-graphene composite material method, which is characterized in that
Method includes the following steps:
Molybdenum disulfide powder is added in intercalation solution and carries out intercalation by step 1, filters, dries after the reaction was completed, obtains
To intercalation molybdenum disulfide powder；
The intercalation solution is the mixed solution of potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide composition；
Pair of the molybdenum disulfide powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and mass concentration 30%
Proportion relation between oxygen water is 1g:(1~4) g:(0.5~2) g:(9~40) mL:(4~20) mL；
Intercalation molybdenum disulfide powder made from step 1 and protein matter and water are mixed and stirred for uniformly by step 2, dry,
Grinding, obtains precursor powder；
Proportion relation between the intercalation molybdenum disulfide powder and protein matter and water is 2g:(2~7) g:(20~70)
g；
Step 3, precursor powder carry out reduction reaction under a shielding gas, cooling after fully reacting, take out reaction product, grind
Class graphene molybdenum disulfide-graphene composite material is obtained after mill；
The protein matter is tyrosine, tryptophan, phenylalanine or threonine；
In step 3, the process of the reduction reaction are as follows: precursor powder obtained in step 2 is packed into and burns boat, is put into pipe
It in formula furnace, is continually fed into protective atmosphere and is reacted, take out reduzate after cooling to room temperature with the furnace after the reaction was completed to get arriving
Class graphene molybdenum disulfide-graphene composite material；
When the protein matter is tyrosine, the temperature of reduction reaction is 280~400 DEG C, soaking time is 120~
150min；When the protein matter is tryptophan, the temperature of reduction reaction is 240~320 DEG C, soaking time is 90~
150min；When the protein matter is phenylalanine, the temperature of reduction reaction is 250~320 DEG C, soaking time is 60~
90min；When the protein matter is threonine, the temperature of reduction reaction is 200~300 DEG C, soaking time is 70~
100min。
2. the method as described in claim 1, which is characterized in that the molybdenum disulfide powder and potassium chlorate, sodium nitrate, quality
Proportion relation between the concentrated sulfuric acid of concentration 98% and the hydrogen peroxide of mass concentration 30% is 1g:2g:1g:23mL:7mL.
3. the method as described in claim 1, which is characterized in that the intercalation molybdenum disulfide powder and protein matter and water
Between proportion relation be 2g:2.2g:22g.
4. the method as described in claim 1, which is characterized in that in step 1, the process of the intercalation are as follows: by two sulphur
Change molybdenum powder be added mixed solution in, be heated to 10~30 DEG C of 1~3h of reaction, then at 30~70 DEG C and stirring 20~50min,
It is stirred to react 10~30min at 75~100 DEG C, then filters, is dry, obtaining intercalation molybdenum disulfide powder.
5. the method as described in claim 1, which is characterized in that in step 2, the intercalation molybdenum disulfide powder, protide
After substance and water are mixed evenly, at a temperature of 50~100 DEG C in drying box by 6~dry for 24 hours, grind, before obtaining
Drive body powder.
6. method according to any one of claims 1 to 5, which is characterized in that the protective atmosphere be nitrogen or
Argon gas.
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| CN101857195A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Efficient mechanical method for peeling layered compounds |
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| CN105789595A (en) * | 2016-04-25 | 2016-07-20 | 绍兴文理学院 | Preparation method of graphene/molybdenum disulfide composite material |
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| CN104495935A (en) * | 2014-12-03 | 2015-04-08 | 安徽百特新材料科技有限公司 | Preparation method of molybdenum disulfide nanosheet in stripping manner |
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