CN106622297A - A method of preparing a graphene-like molybdenum disulfide-graphene composite material through protein substance reduction - Google Patents
A method of preparing a graphene-like molybdenum disulfide-graphene composite material through protein substance reduction Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 198
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 147
- 239000011733 molybdenum Substances 0.000 title claims abstract description 145
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 75
- 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
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000843 powder Substances 0.000 claims abstract description 106
- 238000009830 intercalation Methods 0.000 claims abstract description 80
- 230000002687 intercalation Effects 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 70
- 238000003756 stirring Methods 0.000 claims abstract description 69
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006722 reduction reaction Methods 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 46
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 40
- 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
- 239000000463 material Substances 0.000 claims description 32
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004473 Threonine Substances 0.000 claims description 8
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 7
- COLNVLDHVKWLRT-QMMMGPOBSA-N phenylalanine group Chemical group N[C@@H](CC1=CC=CC=C1)C(=O)O COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 7
- 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 6
- 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 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical group OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 48
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 45
- 235000018102 proteins Nutrition 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- 238000010792 warming Methods 0.000 description 20
- 238000005987 sulfurization reaction Methods 0.000 description 18
- 239000002023 wood Substances 0.000 description 18
- 239000003643 water by type Substances 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 15
- 239000008236 heating water Substances 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 14
- 238000012216 screening Methods 0.000 description 14
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- 235000008729 phenylalanine Nutrition 0.000 description 10
- 235000008521 threonine Nutrition 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000002360 preparation method Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002994 phenylalanines Chemical class 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 150000003588 threonines Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019441 ethanol Nutrition 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
- 239000002356 single layer Substances 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
- 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
- 238000009825 accumulation 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 graphene alkene Chemical class 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
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005461 lubrication 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
- 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
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing 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
A method of preparing a graphene-like molybdenum disulfide-graphene composite material through protein substance reduction is provided. The method includes adding molybdenum disulfide powder into an intercalation solution to perform an intercalation reaction, and performing filtration and drying after the reaction is finished to obtain intercalated molybdenum disulfide powder; mixing the prepared intercalated molybdenum disulfide powder with a protein substance and water, fully stirring the mixture, drying the mixture and grinding the mixture to obtain precursor powder; and subjecting the precursor powder to a reduction reaction under protection by a protective gas, cooling the reaction product after the reaction is finished, taking the reaction product out, and grinding the product to obtain the composite material. According to the method, intercalation, reduction and synthesis of the graphene-like molybdenum disulfide and graphene synthesis are combined, intercalated molybdenum disulfide stripping and grapheme generation are completed only by one step, and the composite material is prepared successfully.
Description
Technical field
The invention belongs to New Two Dimensional Material Field, is related to class Graphene molybdenum bisuphide composite, and in particular to a kind of
The method that protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material.
Background technology
The class Graphene molybdenum bisuphide (Graphene-like molybdenum bisuphide) being made up of few layer of molybdenum bisuphide 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
Become emerging study hotspot.Class Graphene molybdenum bisuphide by the multilayer molybdenum bisuphide of hexagonal crystal system constitute with " Sanming City
Control sandwich " the two dimensional crystal material of layer structure, individual layer molybdenum bisuphide is made up of three layers of atomic layer, and middle one layer is molybdenum atom
Layer, upper and lower two-layer is sulphur atom layer, and molybdenum atom layer forms class " sandwich " structure folded by two-layer sulphur atom layer, and molybdenum is former
Son forms two-dimensional atomic crystal with sulphur atom with Covalent bonding together；Multilayer molybdenum bisuphide is made up of some individual layer molybdenum bisuphide, and one
As be less than five layers, there is weak Van der Waals force in interlayer, interlamellar spacing is about 0.65nm.
Used as the important two-dimensional layer nano material of a class, few layer molybdenum bisuphide is with its unique layer structure in lubrication
The various fields such as agent, catalysis, energy stores, photoelectric material, semiconductor devices, composite are widely used.Compared to Graphene
Zero band gap, there is regulatable band gap, in field of photoelectric devices brighter prospect possessed in class Graphene molybdenum bisuphide；
Compared to the three-dimensional bulk structure of silicon materials, class Graphene molybdenum bisuphide has the two-dimensional layered structure of nanoscale, can by with
To manufacture, semiconductor or specification are less, the electronic chip that efficiency is higher, will obtain in fields such as follow-on nano-electric devices
Extensively application.
Experiment proves the ability that there is molybdenum bisuphide electrocatalytic hydrogen evolution to react, and has many liberations of hydrogen anti-at the edge of molybdenum bisuphide
Active site position (the Science.2007,317 (5834) for answering:100-102).According to this experimental evidence, with reference to molybdenum bisuphide sheet
The characteristic of semiconductor and optical absorption characteristics of body, can speculate that molybdenum bisuphide can be used for photocatalysis product oxygen as photochemical catalyst anti-
Should.But because molybdenum bisuphide belongs in itself narrow-band semiconductor, it is not very strong that this has just been doomed its oxidability, is individually used for light
Its catalysis activity may be therefore suffered from limiting and affected during catalyst.Research shows that molybdenum bisuphide is deposited on the synthesis of CdS surfaces
Efficient visible ray produces hydrogen photochemical catalyst, and 36 times of (Journal of that oxygen activity is CdS are produced in its highest photocatalysis
American Chemical Society.2008,130(23):7176-7177).This demonstrate that molybdenum bisuphide is good light
The co-catalyst of hydrogen reaction is produced in catalysis, and hews out Liao Yitiaoxin roads for Photocatalyzed Hydrogen Production for molybdenum bisuphide.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 possess the light induced electron and hole for improving photocatalytic system
The potentiality of separative efficiency；Secondly, while good optical transparence makes that graphite is dilute to possess compound with other photochemical catalysts but not
Affect the ability of the light absorbs of photochemical catalyst；Finally, two-dimensional layered structure and bigger serface make Graphene possess as light
The possibility of the ideal carrier of catalyst.But, graphite is dilute to be limited to its zero band gap so that Graphene can not be urged directly as light
Agent is used.
It is to carry using their cooperative effect by the molybdenum bisuphide of stratiform with other organic or inorganic particulate compound uses
Rise one of method of molybdenum bisuphide photocatalysis performance and electric property.Class Graphene molybdenum bisuphide possesses large number of edge and urges
Change site and outstanding co-catalysis ability, after the Graphene synthetic composite material with high electron mobility performance can be realized
It is complementary to one another and light-catalysed synergy, in the efficient product hydrogen photochemical catalyst field of research and development and such as electrode material and energy storage material
The electricity device fields such as material possess huge potentiality.
Chinese invention patent CN201210303392 disclose a kind of tubular graphene alkene-molybdenum disulfide nano-composite material and
Its preparation method, by soluble molybdenum hydrochlorate the mixed solution with second alcohol and water as solvent is prepared into；Add sodium sulfocyanate and chlorination
Sodium, adds stannic oxide/graphene nano piece ultrasonic disperse to uniform after stirring, reaction mixture is proceeded to into stainless steel cauldron one
Determine to be reacted at temperature；Room temperature cooling after reaction, centrifugation is washed, is dried；In N2-H2Mixing atmosphere in 800-900 DEG C of heat
2h is processed, 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, it is concretely comprised the following steps：1) with graphite as raw material, by aoxidizing graft process graphite oxide is prepared；2) graphite oxide that will be prepared
Deionized water dissolves, and ultrasound is peeled off and obtains graphene oxide solution, is subsequently adding DMF, molybdate, is eventually adding reducing agent,
It is uniformly dispersed, obtains mixed solution；3) mixed solution is transferred in reactor, under the temperature conditionss more than or equal to 180 DEG C
5～10h of insulation, product centrifugation, washing remove DMF, are dried, and 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, its step includes the following steps：Individual layer molybdenum bisuphide is prepared by lithium ion graft process, is prepared using hummer ' s methods and is aoxidized
Graphene, the molybdenum bisuphide thin slice and Graphene of synthesis is mixed by certain proportion, ultrasonic disperse uniformly mixed solution, so
Obtain the graphene composite thin film of doping individual layer curing molybdenum sheet by suction filtration afterwards, then adulterated with hydroiodic acid reduction
The graphene composite film of individual layer curing molybdenum sheet, the laminated film priority absolute ethyl alcohol and deionized water rinsing after reduction,
The graphene composite film for obtaining doping individual layer curing molybdenum sheet is vacuum dried again.
Although mean disclosed above has been obtained molybdenum bisuphide-graphene composite material using chemical synthesis, these
The big multipaths of preparation method is more, and complex operation high to equipment requirement, and some even easily produce pollution, do not meet environmentally friendly production
Idea of development.Therefore, a kind of simple and environmentally friendly class Graphene molybdenum bisuphide-graphene nanocomposite material of flow process is explored
Simple method for preparing is very necessary.
The content of the invention
Based on problems of the prior art, the present invention proposes a kind of protein matter reduction and prepares class Graphene two
The method of molybdenum sulfide-graphene composite material, obtains and has nanoscale, the class Graphene molybdenum bisuphide-graphite of superior performance
Alkene composite, solves existing class Graphene molybdenum bisuphide-graphene composite material preparation flow complexity, is also easy to produce pollution
Technical problem.
In order to solve above-mentioned technical problem, the application is adopted the following technical scheme that and is achieved：
A kind of method that protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material, the method bag
Include following steps：
Step one, molybdenum disulfide powder is added in intercalation solution carries out intercalation, filters after the completion of reaction, dries
It is dry, obtain intercalation molybdenum disulfide powder；
Described intercalation solution is the mixed solution of potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide composition；
Described 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；
Step 2, intercalation molybdenum disulfide powder obtained in step one and protein matter and water are mixed and stirred for uniformly,
It is dried, grinds, obtains precursor powder；
Described intercalation molybdenum disulfide powder and the proportion relation between protein matter and water are 2g：(2～7) g：(20
～70) g；
Step 3, precursor powder carries out under a shielding gas reduction reaction, cooling after reaction completely, takes out reaction and produces
Thing, obtains class Graphene molybdenum bisuphide-graphene composite material after grinding.
The present invention also has following distinguishing feature：
Specifically, described protein matter is TYR, tryptophan, phenylalanine or threonine.
Preferably, described molybdenum disulfide powder is dense with potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and quality
Proportion relation between the hydrogen peroxide of degree 30% is 1g：2g：1g：23mL：7mL.
Preferably, described intercalation molybdenum disulfide powder and the proportion relation between protein matter and water are 2g：2.2g：
22g。
Specifically, in step one, the process of described intercalation is：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 20～50min is stirred, stirring reaction 10 at 75～100 DEG C～
30min, then suction filtration, drying, obtains intercalation molybdenum disulfide powder.
Specifically, after described intercalation molybdenum disulfide powder, protein matter and water mixing and stirring, in drying box
50～100 DEG C at a temperature of through 6～24h be dried, grinding, obtain precursor powder.
Specifically, in step 3, the process of described reduction reaction is：The precursor powder of gained in step 2 is loaded
Boat is burnt, in being put into tube furnace, protective atmosphere is continually fed into and is reacted, cooled to the furnace after the completion of reaction and take out after room temperature reduction
Product, that is, obtain class Graphene molybdenum bisuphide-graphene composite material；
When described protein matter is TYR, the temperature of reduction reaction is 280～400 DEG C, temperature retention time is 120～
150min；When described protein matter is tryptophan, the temperature of reduction reaction is 240～320 DEG C, temperature retention time is 90～
150min；When described protein matter is phenylalanine, the temperature of reduction reaction is 250～320 DEG C, temperature retention time is 60～
90min；When described protein matter is threonine, the temperature of reduction reaction is 200～300 DEG C, temperature retention time is 70～
100min。
Preferably, described protective atmosphere is nitrogen or argon gas.
Compared with prior art, beneficial has the technical effect that the present invention：
(I) present invention is mixed to form presoma using protide organic carbon source and molybdenum bisuphide so that organic carbon source is inserted
Molybdenum disulfide powder interlayer increases its interfloor distance, weakens molybdenum bisuphide interlayer van der Waals interaction, and with reference to pyroreaction egg is made
White class carbonization is realized the reduction of molybdenum bisuphide and is peeled off.
(II) present invention combines intercalation reduction synthesis class Graphene molybdenum bisuphide and Graphene synthesis, has only been with a step
Into the stripping and the generation of Graphene of intercalation molybdenum bisuphide, class Graphene molybdenum bisuphide-Graphene composite wood is successfully prepared
Material.
(III) product prepared by the present invention is the class with high carrier mobility and high rim active catalyst sites quantity
The nano material that Graphene molybdenum bisuphide and Graphene are combined, and class Graphene molybdenum bisuphide is grown on graphene sheet layer, is made
For the photocatalysis performance that outstanding co-catalyst improves Graphene；Meanwhile, the synergy of the two causes composite in electricity
Pole material and energy storage material field have immeasurable great potential, greatly expand the range of application of molybdenum bisuphide.
(IV) present invention prepares class Graphene molybdenum bisuphide-graphene composite material, simple to operate, it is not necessary to complicated and numerous
Trivial preparation facilities, preparation efficiency is high, and yield is big, is adapted to industrialized production.
Description of the drawings
Fig. 1 is the Raman collection of illustrative plates of the class Graphene molybdenum bisuphide-graphene composite material in embodiment 1.
Fig. 2 is the SEM figures of the class Graphene molybdenum bisuphide-graphene composite material in embodiment 1.
Fig. 3 is the Raman collection of illustrative plates of the molybdenum bisuphide-graphene composite material in comparative example 1.
Fig. 4 is the SEM figures of the molybdenum bisuphide-graphene composite material in comparative example 1.
Fig. 5 is the Raman collection of illustrative plates of the class Graphene molybdenum bisuphide-graphene composite material in comparative example 6.
Fig. 6 is the SEM figures of the class Graphene molybdenum bisuphide-graphene composite material in comparative example 6.
The particular content of the present invention is described in more detail with reference to embodiments.
Specific embodiment
It should be noted that heretofore described class Graphene molybdenum bisuphide is the molybdenum bisuphide of few Rotating fields, it is described
Few Rotating fields are 1～5 layer of structure.
Defer to above-mentioned technical proposal, the specific embodiment of the present invention given below, it should be noted that the present invention not office
It is limited to specific examples below, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.The present invention is described in further details with reference to embodiment.
Embodiment 1：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 20g, sodium nitrate be 10g, mass concentration 98% the concentrated sulfuric acid be 230mL
It is 70mL with the hydrogen peroxide of mass concentration 30%；
Then heating water bath at 30 DEG C and stirs 30min to 15 DEG C of reaction 2h, carries out intercalation, is subsequently heated to 75
DEG C stirring reaction 30min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 2.2g TYRs and adds in 22g deionized waters, treats that TYR is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 8h at a temperature of 60 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 350 DEG C, reaction
Cool to taking-up product after room temperature after 130min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The Raman collection of illustrative plates of class Graphene molybdenum bisuphide-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 collection of illustrative plates in Fig. 12g 1With Ag 1Value is respectively 381.1 and 405.5, and displacement difference is 24.4, with reference to Raman spectral difference
Related article (Li H, Zhang Q, Yap C C R, the et al.From Bulk to of relation between value and the molybdenum bisuphide number of plies
Monolayer MoS2:Evolution of Raman Scattering[J].Advanced Functional
Materials,2012,22(7):1385-1390.) understand, displacement difference is less than 25, and the number of plies of the product is 1～5 layer, belongs to few
Rotating fields molybdenum bisuphide, the characteristic peak D peaks of Graphene and G peak values difference D=1325.9, G=1588.9, that is, show the present embodiment
Prepared sample is class Graphene molybdenum bisuphide-graphene composite material.Fig. 2 middle high-resolution SEM figures are shown as few layer of class
Graphene molybdenum bisuphide-graphene composite material.Comprehensive accompanying drawing can show that the sample prepared by the present embodiment is class Graphene
Molybdenum bisuphide-graphene composite material.
Embodiment 2：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 40g, sodium nitrate be 5g, mass concentration 98% the concentrated sulfuric acid be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 10 DEG C and stirs 30min to 10 DEG C of reaction 2h, carries out intercalation, is subsequently heated to 95
DEG C stirring reaction 25min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 6.0g TYRs and adds in 60g deionized waters, treats that TYR is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 7.5h at a temperature of 70 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 280 DEG C, reaction
Cool to taking-up product after room temperature after 150min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 3：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 10g, sodium nitrate be 8g, mass concentration 98% the concentrated sulfuric acid be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 45 DEG C and stirs 50min to 30 DEG C of reaction 1h, carries out intercalation, is subsequently heated to 98
DEG C stirring reaction 15min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 4.0g TYRs and adds in 40g deionized waters, treats that TYR is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 8h at a temperature of 50 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 400 DEG C, reaction
Cool to taking-up product after room temperature after 120min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 4：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 15g, sodium nitrate be 20g, mass concentration 98% the concentrated sulfuric acid be 210mL
It is 100mL with the hydrogen peroxide of mass concentration 30%.
Then heating water bath at 35 DEG C and stirs 20min to 12 DEG C of reaction 2.5h, carries out intercalation, be subsequently heated to
80 DEG C of stirring reactions 30min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation two
Sulfuration molybdenum powder.
Step 2, takes 5.4g TYRs and adds in 54g deionized waters, treats that TYR is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 7h at a temperature of 90 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through nitrogen, is warming up to 320 DEG C, reaction
Cool to taking-up product after room temperature after 140min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 5：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 35g, sodium nitrate be 18g, mass concentration 98% the concentrated sulfuric acid be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 50 DEG C and stirs 20min to 25 DEG C of reaction 3h, carries out intercalation, is subsequently heated to 100
DEG C stirring reaction 10min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 3.4g tryptophans and adds in 34g deionized waters, treats that tryptophan is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 18h at a temperature of 100 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 240 DEG C, reaction
Cool to taking-up product after room temperature after 150min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 6：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 25g, sodium nitrate be 15g, mass concentration 98% the concentrated sulfuric acid be 150mL
It is 120mL with the hydrogen peroxide of mass concentration 30%.
Then heating water bath at 32 DEG C and stirs 25min to 18 DEG C of reaction 2.5h, carries out intercalation, be subsequently heated to
78 DEG C of stirring reactions 20min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation two
Sulfuration molybdenum powder.
Step 2, takes 2.2g tryptophans and adds in 22g deionized waters, treats that tryptophan is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 24h at a temperature of 80 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 320 DEG C, reaction
Cool to taking-up product after room temperature after 120min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 7：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 30g, sodium nitrate be 12g, mass concentration 98% the concentrated sulfuric acid be 255mL
It is 65mL with the hydrogen peroxide of mass concentration 30%.
Then heating water bath at 42 DEG C and stirs 45min to 20 DEG C of reaction 1.5h, carries out intercalation, be subsequently heated to
88 DEG C of stirring reactions 12min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation two
Sulfuration molybdenum powder.
Step 2, takes 6.0g tryptophans and adds in 60g deionized waters, treats that tryptophan is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 20h at a temperature of 75 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 280 DEG C, reaction
Cool to taking-up product after room temperature after 130min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 8：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 20g, sodium nitrate be 10g, mass concentration 98% the concentrated sulfuric acid be 225mL
It is 75mL with the hydrogen peroxide of mass concentration 30%.
Then heating water bath at 35 DEG C and stirs 20min to 15 DEG C of reaction 2.5h, carries out intercalation, be subsequently heated to
83 DEG C of stirring reactions 18min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation two
Sulfuration molybdenum powder.
Step 2, takes 4.3g tryptophans and adds in 43g deionized waters, treats that tryptophan is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 16h at a temperature of 80 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through nitrogen, is warming up to 300 DEG C, reaction
Cool to taking-up product after room temperature after 90min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 9：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 40g, sodium nitrate be 5g, mass concentration 98% the concentrated sulfuric acid be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 38 DEG C and stirs 25min to 12 DEG C of reaction 2h, carries out intercalation, is subsequently heated to 86
DEG C stirring reaction 11min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 4.0g phenylalanines and adds in 40g deionized waters, treats that phenylalanine is stirring evenly and then adding into 2.0g and inserts
Layer molybdenum disulfide powder, stirs, and is dried through 13h at a temperature of 85 in drying box DEG C, is ground to 200 mesh and sieves, and obtains
To precursor powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 320 DEG C, reaction
Cool to taking-up product after room temperature after 60min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 10：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 10g, sodium nitrate be 8g, mass concentration 98% the concentrated sulfuric acid be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 70 DEG C and stirs 30min to 25 DEG C of reaction 1.5h, carries out intercalation, be subsequently heated to
90 DEG C of stirring reactions 22min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation two
Sulfuration molybdenum powder.
Step 2, takes 3.7g phenylalanines and adds in 37g deionized waters, treats that phenylalanine is stirring evenly and then adding into 2.0g and inserts
Layer molybdenum disulfide powder, stirs, and is dried through 10h at a temperature of 55 in drying box DEG C, is ground to 200 mesh and sieves, and obtains
To precursor powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 250 DEG C, reaction
Cool to taking-up product after room temperature after 90min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 11：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 15g, sodium nitrate be 20g, mass concentration 98% the concentrated sulfuric acid be 200mL
It is 100mL with the hydrogen peroxide of mass concentration 30%.
Then heating water bath at 60 DEG C and stirs 36min to 20 DEG C of reaction 2h, carries out intercalation, is subsequently heated to 96
DEG C stirring reaction 10min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 4.3g phenylalanines and adds in 43g deionized waters, treats that phenylalanine is stirring evenly and then adding into 2.0g and inserts
Layer molybdenum disulfide powder, stirs, and is dried through 9h at a temperature of 75 in drying box DEG C, is ground to 200 mesh and sieves, and obtains
Precursor powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 280 DEG C, reaction
Cool to taking-up product after room temperature after 80min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 12：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 35g, sodium nitrate be 18g, mass concentration 98% the concentrated sulfuric acid be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 52 DEG C and stirs 42min to 10 DEG C of reaction 2.5h, carries out intercalation, be subsequently heated to
100 DEG C of stirring reactions 10min, resulting solution after reaction are filtered and dry filter cake, are ground to 200 mesh and are sieved, and obtain intercalation
Molybdenum disulfide powder.
Step 2, takes 7.0g phenylalanines and adds in 70g deionized waters, treats that phenylalanine is stirring evenly and then adding into 2.0g and inserts
Layer molybdenum disulfide powder, stirs, and is dried through 8h at a temperature of 60 in drying box DEG C, is ground to 200 mesh and sieves, and obtains
Precursor powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through nitrogen, is warming up to 300 DEG C, reaction
Cool to taking-up product after room temperature after 75min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 13：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2, takes 4.4g threonines and adds in 44g deionized waters, treats that threonine is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 18h at a temperature of 75 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 300 DEG C, reaction
Cool to taking-up product after room temperature after 70min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 14：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2, takes 3.9g threonines and adds in 39g deionized waters, treats that threonine is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 24h at a temperature of 60 in drying box DEG C, is ground to 200 mesh and sieves, before obtaining
Drive body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 200 DEG C, reaction
Cool to taking-up product after room temperature after 100min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 15：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2, takes 6.8g threonines and adds in 68g deionized waters, treats that threonine is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 9h at a temperature of 80 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 250 DEG C, reaction
Cool to taking-up product after room temperature after 85min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Embodiment 16：
The present embodiment provides the side that a kind of protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material
Method, the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2, takes 2.0g threonines and adds in 20g deionized waters, treats that threonine is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 9h at a temperature of 80 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 280 DEG C, reaction
Cool to taking-up product after room temperature after 75min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide-Graphene composite wood
Material.
The characterization result of the present embodiment products therefrom class Graphene molybdenum bisuphide-graphene composite material and the base of embodiment 1
This is identical.
Comparative example 1：
This comparative example provides a kind of method for preparing molybdenum bisuphide-graphene composite material, and the method is comprised the following steps：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, takes 10g screenings molybdenum disulfide powders, is added into
Mass concentration is that in the 10%, ethanol solution containing 100g polyphenylene sulfides, 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 200 mesh to sieve, obtains intercalation molybdenum disulfide powder.
Step 2 is identical with the step of embodiment 1 two.
Step 3 is identical with the step of embodiment 1 three.
Raman spectrum analyses and sem analysis have been carried out to molybdenum bisuphide obtained in this comparative example.Raman collection of illustrative plates 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 more than 25, belongs to block structure molybdenum bisuphide.The form of molybdenum bisuphide shows this product molybdenum bisuphide in Fig. 4
Block is piled up, and sandwich construction is presented, and is not belonging to few layer of molybdenum bisuphide.
Comparative example 2：
This comparative example provides a kind of method for preparing molybdenum bisuphide-graphene composite material, and the method is comprised the following steps：
Step one, it is identical with other processes in the step of embodiment 1 one, differ only in：The composition of intercalation solution
For potassium permanganate 20g, sodium nitrate be 10g, mass concentration 98% the concentrated sulfuric acid be 230mL.
Step 2 is identical with the step of embodiment 1 two.
Step 3 is identical with the step of embodiment 1 three.
There is the accumulation of molybdenum bisuphide block as comparative example 1 in molybdenum bisuphide obtained in this comparative example, is not belonging to class graphite
Alkene molybdenum bisuphide-graphene composite material.
Comparative example 3：
This comparative example provides a kind of method for preparing molybdenum bisuphide-graphene composite material, and the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2 is identical with the step of embodiment 1 two.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 350 DEG C, reaction
Cool to taking-up product after room temperature after 10min with the furnace to be ground, that is, obtain molybdenum bisuphide-graphene composite material.
There is molybdenum bisuphide block heap as comparative example 1 in molybdenum bisuphide-graphene composite material obtained in this comparative example
Product, and the appearance of graphene-structured is not found, it is not belonging to class Graphene molybdenum disulfide nano-composite material.
Comparative example 4：
This comparative example provides a kind of method for preparing molybdenum bisuphide-graphene composite material, and the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2 is identical with the step of embodiment 1 two.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 200 DEG C, reaction
Cool to taking-up product after room temperature after 120min with the furnace to be ground, that is, obtain molybdenum bisuphide-graphene composite material.
There is molybdenum bisuphide block heap as comparative example 1 in molybdenum bisuphide-graphene composite material obtained in this comparative example
Product, and the appearance of graphene-structured is not found, it is not belonging to class Graphene molybdenum disulfide nano-composite material.
Comparative example 5：
This comparative example provides a kind of method for preparing molybdenum bisuphide-graphene composite material, and the method is comprised the following steps：
Step one is identical with the step of embodiment 1 one.
Step 2 is identical with the step of embodiment 1 two.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 800 DEG C, reaction
Cool to taking-up product after room temperature after 15min with the furnace to be ground, that is, obtain molybdenum bisuphide-graphene composite material.
There is molybdenum bisuphide block heap as comparative example 1 in molybdenum bisuphide-graphene composite material obtained in this comparative example
Product, and the appearance of graphene-structured is not found, it is not belonging to class Graphene molybdenum disulfide nano-composite material.
Comparative example 6：
This comparative example provides the method that a kind of reduction of carbohydrate organic carbon prepares class Graphene molybdenum bisuphide, the method include with
Lower step：
Step one, is ground to molybdenum disulfide powder 200 mesh and sieves, take 10g screenings molybdenum disulfide powders be added to it is slotting
Layer solution in, intercalation solution consist of potassium chlorate for 20g, sodium nitrate be 10g, mass concentration 98% the concentrated sulfuric acid be 230mL
It is 70mL with the hydrogen peroxide of mass concentration 30%；
Then heating water bath at 30 DEG C and stirs 30min to 15 DEG C of reaction 2h, carries out intercalation, is subsequently heated to 75
DEG C stirring reaction 30min, resulting solution after reaction is filtered and dries filter cake, is ground to 200 mesh and is sieved, and obtains the sulphur of intercalation two
Change molybdenum powder.
Step 2, takes 0.5g TYRs and adds in 15g deionized waters, treats that TYR is stirring evenly and then adding into 2.0g intercalations two
Sulfuration molybdenum powder, stirs, and is dried through 8h at a temperature of 60 in drying box DEG C, is ground to 200 mesh and sieves, and obtains forerunner
Body powder.
Step 3, is fitted into precursor powder burning boat and is placed in tube furnace, is passed through argon gas, is warming up to 330 DEG C, reaction
Cool to taking-up product after room temperature after 30min with the furnace to be ground, that is, obtain class Graphene molybdenum bisuphide.
The Raman collection of illustrative plates of class Graphene molybdenum bisuphide prepared by this comparative example is as shown in figure 5, high-resolution SEM figure such as Fig. 6
It is shown.
E in Raman collection of illustrative plates in Fig. 52g 1With Ag 1Value is respectively 382.2 and 405.1, and displacement difference is 22.9, with reference to Raman spectral difference
Related article (Li H, Zhang Q, Yap C C R, the et al.From Bulk to of relation between value and the molybdenum bisuphide number of plies
Monolayer MoS2:Evolution of Raman Scattering[J].Advanced Functional
Materials,2012,22(7):1385-1390.) understand, displacement difference is less than 25, and the number of plies of the product is 1～5 layer, belongs to few
Rotating fields molybdenum bisuphide, that is, show that sample prepared by the present embodiment is class Graphene molybdenum bisuphide.Fig. 6 middle high-resolutions SEM schemes
It is shown as few layer of class Graphene molybdenum bisuphide.Comprehensive accompanying drawing can show that the sample prepared by the present embodiment is class Graphene two
Molybdenum sulfide.
From the contrast of comparative example 6 and embodiment 1 as can be seen that intercalation molybdenum disulfide powder is closed with the proportioning of protein matter
System is most important to whether generating class Graphene molybdenum bisuphide-graphene composite material.When protein matter it is excessive in a large number
When, then coordinate appropriate reaction condition, composite 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 bisuphide.
Claims (8)
1. a kind of method that protein matter reduction prepares class Graphene molybdenum bisuphide-graphene composite material, it is characterised in that
The method is comprised the following steps：
Step one, molybdenum disulfide powder is added in intercalation solution carries out intercalation, filters after the completion of reaction, dries, and obtains
To intercalation molybdenum disulfide powder；
Described intercalation solution is the mixed solution of potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide composition；
Described molybdenum disulfide powder is double with 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；
Step 2, intercalation molybdenum disulfide powder obtained in step one and protein matter and water are mixed and stirred for uniformly, dry,
Grinding, obtains precursor powder；
Described intercalation molybdenum disulfide powder and the proportion relation between protein matter and water are 2g：(2～7) g：(20～70)
g；
Step 3, precursor powder carries out under a shielding gas reduction reaction, cooling after reaction completely, takes out product, grinds
Class Graphene molybdenum bisuphide-graphene composite material is obtained after mill.
2. the method for claim 1, it is characterised in that described protein matter is TYR, tryptophan, phenylpropyl alcohol ammonia
Acid or threonine.
3. the method for claim 1, it is characterised in that described 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.
4. the method for claim 1, it is characterised in that described intercalation molybdenum disulfide powder and protein matter and water
Between proportion relation be 2g：2.2g：22g.
5. the method for claim 1, it is characterised in that in step one, the process of described intercalation is：By two sulphur
Change molybdenum powder to add in mixed solution, be heated to 10～30 DEG C of 1～3h of reaction, then at 30～70 DEG C and stir 20～50min,
10～30min of stirring reaction at 75～100 DEG C, then suction filtration, drying, obtains intercalation molybdenum disulfide powder.
6. the method for claim 1, it is characterised in that in step 2, described intercalation molybdenum disulfide powder, protide
After material and water mixing and stirring, it is dried through 6～24h at a temperature of 50～100 DEG C in drying box, grinding, before obtaining
Drive body powder.
7. method as claimed in claim 2, it is characterised in that in step 3, the process of described reduction reaction is：By step
The precursor powder of gained loads burning boat in two, in being put into tube furnace, is continually fed into protective atmosphere and is reacted, after the completion of reaction
Cool to the furnace and take out after room temperature reduzate, that is, obtain class Graphene molybdenum bisuphide-graphene composite material；
When described protein matter is TYR, the temperature of reduction reaction is 280～400 DEG C, temperature retention time is 120～
150min；When described protein matter is tryptophan, the temperature of reduction reaction is 240～320 DEG C, temperature retention time is 90～
150min；When described protein matter is phenylalanine, the temperature of reduction reaction is 250～320 DEG C, temperature retention time is 60～
90min；When described protein matter is threonine, the temperature of reduction reaction is 200～300 DEG C, temperature retention time is 70～
100min。
8. the method as described in claim 1 to 7 any claim, it is characterised in that described protective atmosphere be nitrogen or
Argon gas.
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