CN106315548B - A kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@and preparation method thereof - Google Patents
A kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@and preparation method thereof Download PDFInfo
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011733 molybdenum Substances 0.000 title claims abstract description 55
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 50
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012159 carrier gas Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000011669 selenium Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000010276 construction Methods 0.000 claims abstract description 6
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 6
- 235000016768 molybdenum Nutrition 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract 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 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical group 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910016001 MoSe Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 transition metal selenides Chemical class 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018113 Se—Mo—Se Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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—
-
- B01J35/40—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The present invention relates to a kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@and preparation method thereof, belong to technical field of material.The kernel of composite construction proposed by the present invention, which is carbon fiber, shell, is into two selenizing molybdenum nanometer sheets of array-like.The present invention uses thermal evaporation techniques directly to evaporate selenium powder as selenium source, under carrier gas effect, fumigates impregnated MoO at high temperature in vacuum tube furnace3The pre-oxidized acrylonitrile polymer fiber of suspension synthesizes while realizing carbon fiber and two selenizing molybdenum nanometer sheets, and bis- selenizing molybdenum nanometer sheet core-shell structures of the carbon fiber@are prepared in energy high productivity.The product yield of this method is big, density is high, purity is high, morphology controllable, without post-processing；And this method have many advantages, such as equipment and it is simple for process, synthesis growth conditions is stringent controllable, product yield is high, of low cost, production process clean environment firendly.Obtained material is excellent visible light catalyst, elctro-catalyst, sodium/lithium-ion anode material and luminescent crystal tube material.
Description
Technical field
The present invention relates to a kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@and preparation method thereof, belong to material
Preparing technical field.
Background technology
In recent years, two-dimension nano materials are drawn due to its unique structure and performance and in the application of micro-nano person in electronics
The extensive concern of people is played.Representative two-dimension nano materials are graphenes, it has strong toughness, good conduction
The performances such as property, high electron mobility, have extensive potential application in fields such as nanoelectronics, photonic propulsion, sensors.With
Graphene compares, and the forbidden band of transition metal dichalcogenide is slightly wide, as the band gap of tungsten disulfide is about 1.8eV, the band of molybdenum disulfide
Gap is about 1.2eV, and scene effect transistor and low power electronic device etc. play effect more outstanding.The mistake of single layer
Crossing metal disulfides has very strong Quantum geometrical phase and inverting symmetrically destructive, this is also fully consistent with spintronics and exists
Application aspect is to semiconductor requirement.Selenium is as Group VIA element, in atomic structure, compound structure and physicochemical properties etc.
Aspect is closely similar with sulphur, and therefore, two-dimentional transition metal selenides all has become the heat studied now as its sulphur compound
Point.
There are many specific physical properties for transient metal sulfide and selenides, such as semiconductive, metallicity, superconductivity, magnetic
Property etc..Wherein, two selenizing molybdenum (MoSe2) be grey black covalent compound, belong to hexagonal crystal system, have similar to sandwich
It is laminar structured, it is loose by faint Van der Waals force between layers with strong Covalent bonding together between Se and Mo atoms in layer
Ground is combined together.Due to two selenizing molybdenums it is laminar structured in it is so loose that combine by faint Van der Waals force between layers
Together, two adjacent molecular layers can be slided mutually, therefore two selenizing molybdenums have lower friction coefficient, be commonly used for solid profit
Lubrication prescription reduces the abrasion between secondary to mill, reduces the running resistance of mechanical equipment, reduce energy consumption, prolong the service life；Meanwhile
Since its chemical property is stablized, two selenizing molybdenums can be used for high temperature and pressure lubricant.In addition, two selenizing molybdenums also have special physics
And chemical property.It is in triangular prism column, Mo-Se faceted pebbles if each molybdenum atom is surrounded by six selenium atoms in two selenizing molybdenum materials
Quite a lot of, large specific surface area, high surface activity has excellent catalytic activity, is widely used as adding hydrogen, taking off for PETROLEUM PROCESSING industry
Sulfur catalyst and wastewater treatment catalyst.Since it is with larger interlamellar spacing, some ions such as Li+And Na+It can hold very much
It changes places and is inserted into the interlayer of two selenizing molybdenums, form intercalation compound, in material modification, prepare new function material (such as battery electricity
Pole material) etc. have greatly application and development.In recent years, it has been found that two selenizing molybdenums rely on the layer of Se-Mo-Se structures
Number can be changed into direct band-gap semicondictor from indirect band-gap semiconductor, when by the thickness limit of two selenizing molybdenums be monolayer
When, the semiconductor of indirect energy gap can be converted into the semiconductor of direct band gap, and in the best of solar energy conversion
There is properties, the intensity of luminescence generated by light such as high absorption coefficient to significantly improve sunlight in region, two selenizing molybdenums it is this
Semiconductive has a wide range of applications in opto-electronic conversion and opto-electronic device etc..Such as on photodetector, two selenium
Change the excellent properties that molybdenum is shown in all various aspects and causes domestic and international scientist's great interest (QiShu Yan etc., the conjunction of two selenizing molybdenums
At the progress with application, Harbin University of Science and Technology's journal, 2016, Vol.21, n1, pp.22-26).
Due to the compound property potentiality with huge improvement material between material, two selenizing molybdenum-base composite materials are also
The hot spot of current research.Such as use plasma enhanced chemical vapor deposition method and chemical vapour deposition technique former on graphite plate matrix
Position growth MoSe2The MoSe of nanometer sheet synthesis2/ graphene composite material has high catalytic activity and excellent stability,
There is important application foreground in Visible Light Induced Photocatalytic organic pollution, photocatalytic water, electro-catalysis etc..However, although about two selenizings
There are many intercalation compound of molybdenum, compound doped and compound loaded research, ground about two selenizing molybdenums and the compound of carbon material
Study carefully seldom.Moreover, because the carbon materials non-refractory such as graphene, the preparation method of traditional two selenizing molybdenums/carbon composite is more
For liquid phase method, such as sol-gel method, hydro-thermal method, coprecipitation.But the chemical reaction of these liquid phase methods is complicated, is difficult to control
System, and need the processes such as complicated subsequent purification removal of impurities.In contrast, the physical vapour deposition (PVD)s such as thermal evaporation have it is at low cost,
Preparation process is simple, technological parameter controllability is strong, the features such as industrial mass production can be achieved.
The characteristics of present invention is just pyrolyzed into carbon at high temperature using preoxidised polyacrylonitrile (PAN) fiber, in electron tubes type
In stove, uses thermal evaporation techniques directly to evaporate selenium powder as selenium source, under carrier gas effect, fumigate impregnated MoO at high temperature3It is outstanding
The pre-oxidized acrylonitrile polymer fiber of turbid synthesizes while realizing carbon fiber and two selenizing molybdenum nanometer sheets, has been prepared one
The special bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@of kind, two selenizings molybdenum nanometer sheet therein are grown at array-like
Carbon fiber surface.Moreover, sandwich yield that this method is prepared is big, density is high, purity is high, morphology controllable, nothing
It needs to post-process, and preparation method is economic and environment-friendly.
Invention content
It is this multiple it is an object of the present invention to proposing a kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@
The kernel for closing structure is carbon fiber, and shell is into two selenizing molybdenum nanometer sheets of array-like.This sandwich is urged for light
When change, the feature that two selenizing molybdenum nanometer sheet band gap can be made full use of smaller improves the absorptivity of visible light, moreover it is possible to utilize carbon fiber
The good electric conductivity of dimension promotes the separation of the light induced electron and hole that are generated in photocatalytic process, improves photocatalysis efficiency；
Therefore, this sandwich can significantly improve degradation efficiency of the visible light to harmful organic contaminants, improve visible light light
The efficiency of water hydrogen manufacturing is solved, and improves the efficiency etc. of solar energy electrotransformation.Due in this sandwich by array-like
Two selenizing molybdenum nanometer sheets and high conductivity carbon fiber constitute, use it for being conducive to when sodium ion, Anode of lithium cell material
The insertion and deintercalation of ion improve battery capacity；Conduction for being conducive to electronics when electro-catalysis hydrolytic hydrogen production improves hydrogen manufacturing effect
Rate.In addition, this sandwich is also expected have important application in fields such as lighting transistors.
The second object of the present invention is that provide bis- selenizing molybdenum nanometer sheet core-shell structures of this carbon fiber@makes accordingly
Preparation Method.Sandwich yield that this method is prepared is big, density is high, purity is high, morphology controllable, without post-processing；
And this method have equipment and it is simple for process, synthesis growth conditions is stringent controllable, product yield is high, it is of low cost, produced
The advantages that journey clean environment firendly.
In order to reach above-mentioned target, bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@proposed by the present invention, feature
It is, the kernel of the composite construction is carbon fiber, and shell is into two selenizing molybdenum nanometer sheets of array-like.This carbon fiber@bis-
Selenizing molybdenum nanometer sheet core-shell structure, product purity is high, density is big, and carbon fiber is fully wrapped up by two selenizing molybdenum nanometer sheets and is in
Existing nucleocapsid, 3-8 μm of kernel carbon fiber diameter, two selenizing molybdenum nanometer sheet of shell are arranged in array, nanometer sheet thickness 30-
80nm, nanoscale are orderly.
The preparation method of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@provided by the invention, which is characterized in that should
The characteristics of method is just pyrolyzed into carbon at high temperature using pre-oxidized acrylonitrile polymer fiber, in vacuum tube furnace, with thermal evaporation skill
Art directly evaporates selenium powder as selenium source, under carrier gas effect, fumigates impregnated MoO at high temperature3The pre-oxidation of suspension is poly-
Dralon synthesizes while realizing carbon fiber and two selenizing molybdenum nanometer sheets, and the carbon fiber@is prepared in energy high productivity
Two selenizing molybdenum nanometer sheet core-shell structures.
The preparation method of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@proposed by the present invention, includes the following steps
And content：
(1) in vacuum tube furnace, the alumina ceramic crucible equipped with selenium powder is placed on above air-flow apart from stove center
At heating region 25-45cm, MoO was impregnated by filling3The quartz substrate of the pre-oxidized acrylonitrile polymer fiber of suspension is placed on
Stove center heating region.
(2) before heating, 0.01Pa first is evacuated to whole system hereinafter, being then passed through height into system with vacuum pump
Pure inert carrier gas, and be repeated as many times, with the air in removal system.Then 300-500 is warming up to the rate of 10-20 DEG C/min
DEG C, and 5-20 minutes are kept the temperature, then it is warming up to 1050-1150 DEG C with the rate of 20-30 DEG C/min, and keep the temperature 0.5-6 hours.Adding
In thermal process, it is 100-300 standard cubes li to be passed through carrier gas under the premise of vacuum system continue working and keep carrier gas flux
Rice is per minute, and entire heating process is completed under inert carrier gas protection, last Temperature fall to room temperature, you can on substrate
To a large amount of high-purities, bis- selenizing molybdenum nanometer sheet core-shell structures of highdensity carbon fiber@.
In the above preparation method, the evaporation source selenium powder in the step (1) is ommercially available AR.
In the above preparation method, the MoO in the step (1)3Suspension is the commercially available pure MoO of analysis3Powder is in absolute ethyl alcohol
In disperse, wherein MoO3The proportioning of powder and ethyl alcohol is (5-80g):(50-100mL).
In the above preparation method, the pre-oxidized acrylonitrile polymer fiber in the step (1) is commercially available chemically pure reagent.
In the above preparation method, the pre-oxidized acrylonitrile polymer fiber in the step (1) is in MoO3It is impregnated in suspension
Then 10-60min dries for use.
In the above preparation method, the evaporation source selenium powder in the step (1) is 25- at a distance from the heating region of stove center
45cm。
In the above preparation method, high-purity inert carrier gas is argon gas, one kind among nitrogen in the step (2).
In the above preparation method, the inert carrier gas in the step (2) is high-purity gas, and purity is in 99.99vol.%
More than.
In the above preparation method, the inert carrier gas flow in the step (2) is every point of 100-300 standard cubic centimeters
Clock.
In the above preparation method, the heating process in the step (2) is first to be warming up to the rate of 10-20 DEG C/min
300-500 DEG C, and 5-20 minutes are kept the temperature, then it is warming up to 1050-1150 DEG C with the rate of 20-30 DEG C/min, and it is small to keep the temperature 0.5-6
When.
In the above preparation method, the temperature-fall period in the step (2) is Temperature fall to room temperature.
Bis- selenizing molybdenum nanometer sheet core-shell structures of the carbon fiber@are prepared using this technology, there is equipment and technique letter
The features such as single, synthesis growth conditions is stringent controllable, product yield is high, of low cost, production process clean environment firendly；The carbon obtained
Bis- selenizing molybdenum nanometer sheet core-shell structure density of fiber@is high, purity is high, and nanoscale is orderly, diameter and thickness is uniform, pattern
Controllably, it is not necessarily to post-processing.
Description of the drawings
Fig. 1 is that the X-ray of the bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@obtained by the embodiment of the present invention 1 is spread out
Penetrate style and its analysis result
Fig. 2 is sweeping for the surface of the bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@obtained by the embodiment of the present invention 1
Retouch electromicroscopic photograph
Fig. 3 is at the section of the bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@obtained by the embodiment of the present invention 1
Scanning electron microscope surface picture
Specific implementation mode
Technical scheme of the present invention is described further with reference to embodiment.
The present invention proposes a kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@, which is characterized in that the composite junction
The kernel of structure is carbon fiber, and shell is into two selenizing molybdenum nanometer sheets of array-like.Bis- selenizing molybdenum nanometer sheet nucleocapsids of this carbon fiber@
Composite construction, product purity is high, density is big, and carbon fiber is fully wrapped up by two selenizing molybdenum nanometer sheets and nucleocapsid is presented, kernel
3-8 μm of carbon fiber diameter, two selenizing molybdenum nanometer sheet of shell are arranged in array, nanometer sheet thickness 30-80nm, and nanoscale is orderly.
The present invention also provides the preparation methods of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@, which is characterized in that
The characteristics of this method is just pyrolyzed into carbon at high temperature using pre-oxidized acrylonitrile polymer fiber, in vacuum tube furnace, uses thermal evaporation
Technology directly evaporates selenium powder as selenium source, under carrier gas effect, fumigates impregnated MoO at high temperature3The pre-oxidation of suspension
Polyacrylonitrile fibre synthesizes while realizing carbon fiber and two selenizing molybdenum nanometer sheets, and the carbon fiber is prepared in energy high productivity
Tie up bis- selenizing molybdenum nanometer sheet core-shell structures of@.
The preparation method of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@proposed by the present invention, includes the following steps
And content：
(1) using commercially available analysis pure selenium powder, MoO3Powder and the pure pre-oxidized acrylonitrile polymer fiber of chemistry are raw material.
(2) by MoO3Powder is with absolute ethyl alcohol according to (5-80g):The proportioning of (50-100mL) mixes, and is sufficiently stirred and is made
Even suspension；Then 10-60min is impregnated into pre-oxidized acrylonitrile polymer fiber placement wherein；Then it dries, for use.
(3) in vacuum tube furnace, the alumina ceramic crucible equipped with selenium powder is placed on above air-flow apart from stove center
At heating region 25-45cm, MoO was impregnated by filling3The quartz substrate of the pre-oxidized acrylonitrile polymer fiber of suspension is placed on
Stove center heating region.
(4) before heating, 0.01Pa first is evacuated to whole system hereinafter, being then passed through height into system with vacuum pump
Pure inert carrier gas, and be repeated as many times, with the air in removal system.Then 300-500 is warming up to the rate of 10-20 DEG C/min
DEG C, and 5-20 minutes are kept the temperature, then it is warming up to 1050-1150 DEG C with the rate of 20-30 DEG C/min, and keep the temperature 0.5-6 hours.Adding
In thermal process, it is 100-300 standard cubes li to be passed through carrier gas under the premise of vacuum system continue working and keep carrier gas flux
Rice is per minute, and entire heating process is completed under inert carrier gas protection, last Temperature fall to room temperature, you can on substrate
To a large amount of high-purities, bis- selenizing molybdenum nanometer sheet core-shell structures of highdensity carbon fiber@.
(5) high-purity inert carrier gas used in is one kind among argon gas, nitrogen, and purity is and whole in 99.99vol.% or more
A experiment heating process is completed under carrier gas protection.
Bis- selenizing molybdenum nanometer sheet core-shell structures of obtained carbon fiber@are light green color fibrous material in appearance.
Under a scanning electron microscope, it may be observed that a large amount of fiber, and core-shell structure, X-ray diffraction point is presented in fiber
Analysis shows that this material is the C/MoSe of high-purity2Composite material.Its kernel is the carbon fiber of 3-8 μm or so of diameter, and shell is
A large amount of two selenizing molybdenum nanometer sheets arranged into an array, nanometer sheet thickness 30-80nm.
In short, it is compound to obtain high-purity, bis- selenizing molybdenum nanometer sheet nucleocapsids of highdensity carbon fiber@with this technology energy high yield
Structure.
Embodiment 1：In vacuum tube furnace, the alumina ceramic crucible equipped with 3g selenium powders is placed on distance above air-flow
At the heating region 37cm of stove center, it will fill through a concentration of 1g MoO3The suspension immersion treatment that powder and 5mL absolute ethyl alcohols are prepared
And the quartz substrate for the pre-oxidized acrylonitrile polymer fiber dried is placed on stove center heating region.
Before heating, 0.01Pa first is evacuated to whole system hereinafter, being then passed through into system with vacuum pump
The high-purity argon gas of 99.99vol.% or more, and be repeated 3 times, with the air in removal system.Then it is heated up with 20 DEG C/min rates
To 400 DEG C, 10 minutes are kept the temperature, then 1110 DEG C are warming up to 20 DEG C/min rates, and keeps the temperature 3 hours.During heating, true
It is 200 sccms to be passed through argon gas under the premise of empty set system continue working and keep carrier gas flux, and is entirely added
Thermal process is completed under protection of argon gas, last Temperature fall to room temperature, you can a large amount of high-purities, highdensity are obtained on substrate
Bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@.
Obtained light green color fibrous material is the C/MoSe of high-purity2Composite material (see Fig. 1), this material are carbon
Bis- selenizing molybdenum nanometer sheet core-shell structures (see Fig. 2) of fiber@, kernel are the high density that carbon fiber, shell are into array-like
Two selenizing molybdenum nanometer sheets (see Fig. 3), resulting materials yield is big, nanometer sheet diameter, thickness uniformly (see Fig. 2).
Claims (3)
1. a kind of preparation method of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@, which is characterized in that the composite construction
Kernel be carbon fiber, shell is into two selenizing molybdenum nanometer sheets of array-like；Carbon fiber is by two selenizing molybdenums in the composite construction
Nanometer sheet fully wraps up and nucleocapsid is presented；The preparation method of the composite construction is in vacuum tube furnace, with thermal evaporation skill
Art directly evaporates selenium powder as selenium source, under carrier gas effect, fumigates impregnated MoO at high temperature3The pre-oxidation of suspension is poly-
Dralon synthesizes while realizing carbon fiber and two selenizing molybdenum nanometer sheets, and the carbon fiber@is prepared in energy high productivity
Two selenizing molybdenum nanometer sheet core-shell structures；Include the following steps：
(1) in vacuum tube furnace, the alumina ceramic crucible equipped with selenium powder is placed on above air-flow and is heated apart from stove center
At the 25-45cm of region, MoO was impregnated by filling3The quartz substrate of the pre-oxidized acrylonitrile polymer fiber of suspension is placed in stove
Entreat heating region；
(2) before heating, 0.01Pa first is evacuated to whole system hereinafter, being then passed through into system high-purity lazy with vacuum pump
Property carrier gas, and be repeated as many times, with the air in removal system；Then it is warming up to 300-500 DEG C with the rate of 10-20 DEG C/min,
And 5-20 minutes are kept the temperature, then it is warming up to 1050-1150 DEG C with the rate of 20-30 DEG C/min, and keep the temperature 0.5-6 hours；It is heating
In the process, it is 100-300 standard cubic centimeters to be passed through carrier gas under the premise of vacuum system continue working and keep carrier gas flux
It is per minute, and entire heating process is completed under inert carrier gas protection, last Temperature fall to room temperature, you can obtained on substrate
A large amount of high-purity, bis- selenizing molybdenum nanometer sheet core-shell structures of highdensity carbon fiber@.
2. preparation method described in accordance with the claim 1, which is characterized in that selenium powder and MoO in the step (1)3Powder is commercially available
Analytical reagents, pre-oxidized acrylonitrile polymer fiber are commercially available chemically pure reagent；The MoO3Suspension is MoO3Powder is in absolute ethyl alcohol
In disperse, wherein MoO3The proportioning of powder and ethyl alcohol is (5-80g):(50-100mL)；The pre-oxidized acrylonitrile polymer fiber
In MoO3Soaking time in suspension is 10-60min, is then dried for use；The evaporation selenium powder and stove center heating region
Distance be 25-45cm.
3. preparation method described in accordance with the claim 1, which is characterized in that high-purity inert carrier gas in the step (2) is argon
One kind among gas, nitrogen, for purity in 99.99vol.% or more, flow is 100-300 sccms；It is described
Heating process keeps the temperature 5-20 minutes to be first warming up to 300-500 DEG C with the rate of 10-20 DEG C/min, then with 20-30 DEG C/min
Rate be warming up to 1050-1150 DEG C, and keep the temperature 0.5-6 hours.
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