CN109879274A - Molte-salt synthesis prepares spiral carbon nano pipe and its preparation method and application - Google Patents
Molte-salt synthesis prepares spiral carbon nano pipe and its preparation method and application Download PDFInfo
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- CN109879274A CN109879274A CN201910341626.1A CN201910341626A CN109879274A CN 109879274 A CN109879274 A CN 109879274A CN 201910341626 A CN201910341626 A CN 201910341626A CN 109879274 A CN109879274 A CN 109879274A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 41
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000002696 manganese Chemical class 0.000 claims abstract description 24
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 21
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 7
- -1 bio-separation Substances 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000002887 superconductor Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 238000004781 supercooling Methods 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 70
- 238000012360 testing method Methods 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229910052845 zircon Inorganic materials 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- VNFVKWMKVDOSKT-LREBCSMRSA-N (2r,3r)-2,3-dihydroxybutanedioic acid;piperazine Chemical compound C1CNCCN1.OC(=O)[C@H](O)[C@@H](O)C(O)=O VNFVKWMKVDOSKT-LREBCSMRSA-N 0.000 description 1
- 102100024109 Cyclin-T1 Human genes 0.000 description 1
- 101000910488 Homo sapiens Cyclin-T1 Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018648 Mn—N Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012900 molecular simulation Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Spiral carbon nano pipe and its method are prepared with molte-salt synthesis the present invention provides a kind of, the calcination process specifically by soluble fuse salt, applied to manganese salt and melamine.It is increased with temperature, melamine is carbonized to form graphitic nitralloy carbon, and higher temperature causes the carbon atom of carbonitride thermal decomposition, nitrogen-atoms to gather in manganese salt nano particle, and then precipitating forms new graphite synusia, and graphite synusia curls into carbon nanotube.Spiral carbon nano pipe prepared by the present invention, because having chirality, can not only show metal and semiconductor behavior, additionally it is possible to show semimetal behavior, can be used as superconductor compared to straight carbon nanotube.The spiral carbon nano pipe performance is stablized, and can be used for the fields such as electro-magnetic wave absorption material, bio-separation, water process, water body detection, food safety detection, complete solution water, sensor fuel.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of side that spiral carbon nano pipe is prepared using molte-salt synthesis
Method.
Background technique
1993, Dunlap and Ihara etc. predicted the helical form being made of completely carbon atom by theoretical calculation first
Structure.And this helical structure being made of light dydrocarbon, carbon six and seven ring of carbon is demonstrate,proved by means such as molecular simulations be thermodynamically
Stable.The research and development of spiral carbon nano pipe provide it is a kind of with new construction, performance and the material of application, from micro-nano
Device has many promising applications to macroscopic materials fields such as compound enhancings.
At present preparation carbon nanotube method: graphite acr method, floating catalyst system, laser steaming process, pyrolyzed-polymer method,
Chemical vapor deposition.In addition to chemical vapor deposition method, in these methods, energy input is higher, and carbon atom arrangement is tended to
Form more stable six ring structure of carbon, the generation of rare helix tube.The most commonly used method for preparing spiral carbon nano pipe is
Chemical vapor deposition, but degree of graphitization is low, requirement big to catalyst is high, and the device is complicated, and gas atmosphere requires harshness, simultaneously
Limits throughput.Importantly, in terms of the Morphological control of spiral carbon nano pipe there is also larger difficulty, while each preparation
The yield of spiral carbon nano pipe is generally little in the process, and both of these problems affect spiral carbon nano pipe as a kind of green wood
Material widely application.Therefore, how preparing the spiral carbon nano pipe of single pattern and agglomerate structure-controllable will be this field
One of important goal in research.
Molte-salt synthesis is the friendly process developed in recent years for preparing controllable nano material.Carbon prepared by this method
Material shape is uniform, loosely organized, pore structure is abundant, greatly improves catalytic performance or capacitor activity.And needed for this method
Raw material is cheap and easy to get, preparation process is simple, cost is relatively low, for spiral carbon nano pipe batch preparation and structure regulating provide and
One can efficacious prescriptions method.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of spiral carbon nano pipe, solve existing helical form carbon nanometer
The problem of tube preparation method is complicated, and temperature is high, and time-consuming, and product purity is low.It is that soluble fuse salt is applied to transition metal
The calcination process of halide salts and melamine.It is increased with temperature, melamine is carbonized to form graphitic nitralloy carbon, higher temperature
Carbon atom, the nitrogen-atoms for causing carbonitride to thermally decompose gather in manganese salt nano particle, and then precipitating forms new graphite synusia,
Graphite synusia curls into carbon nanotube.Since the interplanar anisotropy of manganese salt nano particle and carbon atom are in different crystal faces
On deposition rate it is different and cause carbon nanotube helix-coil, and anisotropic degree is bigger, and carbon nanometer spiral degree is also
It is bigger.
To achieve the goals above, the preparation method of a kind of spiral carbon nano pipe of the present invention, including following step
It is rapid:
(1) manganese salt and melamine are put into ethyl alcohol, are uniformly mixed, are subsequently placed in Rotary Evaporators in certain temperature
Lower revolving a period of time, by ethanol evaporation, obtain solid powder；
(2) solid powder that step (1) obtains is mixed with solubility melting salt powder, is subsequently placed in tube furnace,
In melamine higb pressure atmosphere, 700~900 DEG C are warming up to the rate of 1~5 DEG C/min and carries out 2~4h of calcining, finally through being subcooled
But, pickling, washing, drying obtain fillable carbon nanotube；Fuse salt is CaCl2、KCl、ZnCl2、MgCl2One of or it is more
Kind.
Preferably, the forming method of the melamine higb pressure atmosphere is to be passed through from tube furnace air inlet into tube furnace
Balloon is fixed on the gas outlet of tube furnace after air is discharged, seals gas outlet by inert gas, then carries out high temperature and forges
It burns.It is continually fed into inert gas with calcination process, reaction is carried out under the protection of inert gas and is compared, in melamine high pressure atmosphere
It is reacted in enclosing, the type of product can be controlled, the manganese salt in raw material is substantially all and is converted into simple substance manganese, it will not
There is oxide the case where mixing of simple substance manganese, manganese, improves the utilization rate of manganese salt, and then improve the production of spiral carbon nano pipe
Rate.
Preferably, the calcination temperature in the step (2) is 800 DEG C, and heating rate is 2.5 DEG C of min-1, calcination time is
3h。
Preferably, solid powder is mixed with melting salt powder using ball mill in step (2), powder after mixing
Particle size range is preferably 50~70nm.
Preferably, the dosage of transition metal halide salt and soluble fuse salt is that two kinds of substances are minimum in two-phase phasor
The corresponding amount of fusing point, the molar ratio of manganese ion and melamine in the manganese salt are 1:1.25, and the manganese salt is four hydrations two
Manganese chloride or manganese nitrate, two kinds of manganese salts can obtain the spiral carbon nano pipe of function admirable.
Preferably, the acid cleaning process uses nitric acid or hydrochloric acid, preferably nitric acid.
Carbon nanotube prepared by spiral carbon nano pipe preparation method of the present invention.
Spiral carbon nano pipe prepared by the present invention serves as carrier, is applied to field of compound material；With chirality, not only may be used
Show metal and semiconductor behavior, additionally it is possible to show semimetal behavior, be applied to superconductor field；It can will be electric with high frequency waves resonance
Thermal energy can be transformed into, be applied to electromagnetic wave absorbent material field；Because having magnetism, it is applied to bio-separation, water process, water body inspection
It surveys, field of detection of food safety；Catalytic oxidation-reduction reacts in a fuel cell, is applied to fuel cell；Catalysis hydration hydrazine reaction,
As sensor material.The liberation of hydrogen analysis oxygen of material is had excellent performance, and is used for complete solution water.The large specific surface area of material can be used for lithium sulphur
Battery.In addition, its magnetic field that can produce nanometer range when passing through electric current, it is expected to make high-performance hard disk magnetic head, it is excellent because having
Good energy absorption capability, when it is used for high polymer enhancing, the composite material of formation has good mechanical strength.
Compared with prior art, the invention has the following advantages: the addition of (1) manganese salt makes it possible to melamine
As the use of carbon source preparation carbon nanotube, especially manganese nitrate, strong corrosive can be modified carbon material surface, and
It can make carbon nano tube-doped more nitrogen-atoms, form more Mn-N active sites, and then improve performance；(2) in high temperature
In reaction system, the addition of fuse salt can reduce the fusing point of manganese salt, in addition, fuse salt calcium chloride play the role of dura mater version and
The effect of pore-creating not only increases the mesoporous performance of carbon nanotube and increases surface area, and promotes spiral carbon nano pipe
Generation；(3) ball milling is carried out under certain condition, so that the partial size of raw material is less than 100nm, promotes the life of spiral carbon nano pipe
At increasing the active site and defect level on its surface, and improve yield；(4) it is carried out in melamine higb pressure atmosphere anti-
It answers, the type of product can be controlled, the manganese salt in raw material is substantially all and is converted into simple substance manganese, be not in simple substance
Oxide the case where mixing of manganese, manganese, the utilization rate of manganese salt is improved, and then improve the yield of spiral carbon nano pipe；(5) last
Obtained spiral carbon nano pipe has many concave and convex surfaces, increases specific surface area, and can make surface-active after spiral
Site is increased, and surface defect is more, promotes its application in terms of electrochemistry.
Detailed description of the invention
The SEM figure that Fig. 1 is Mn@N-CNT-1 prepared by the embodiment of the present invention 1.
The SEM figure that Fig. 2 is Mn@N-CNT-2 prepared by the embodiment of the present invention 2.
The SEM figure that Fig. 3 is Mn@N-CNT-3 prepared by the embodiment of the present invention 3.
The SEM figure that Fig. 4 is Mn@N-CNT-4 prepared by the embodiment of the present invention 4.
The SEM figure that Fig. 5 is Mn@N-CNT-5 prepared by the embodiment of the present invention 5.
The SEM figure that Fig. 6 is Mn@N-CNT-6 prepared by the embodiment of the present invention 6.
The SEM figure that Fig. 7 is Mn@N-CNT-7 prepared by the embodiment of the present invention 7.
The SEM figure that Fig. 8 is Mn@N-CNT-8 prepared by the embodiment of the present invention 8.
Fig. 9 is the droplet measurement figure of Mn@N-CNT-2 prepared by the embodiment of the present invention 2.
Figure 10 is the droplet measurement figure of Mn@N-CNT-3 prepared by the embodiment of the present invention 3.
Figure 11 is the droplet measurement figure of Mn@N-CNT-4 prepared by the embodiment of the present invention 4.
Figure 12 is the droplet measurement figure of Mn@N-CNT-5 prepared by the embodiment of the present invention 5.
Figure 13 is the BET test chart of N-CNT-2~5 Mn@prepared by the embodiment of the present invention 2~5.
Figure 14 is the Mn@graph of pore diameter distribution of N-CNT-2~5 prepared by the embodiment of the present invention 2~5.
Figure 15 is Mn@N-CNT-4 Raman spectrogram prepared by the embodiment of the present invention 2~5.
The spiral carbon nano pipe photo that Figure 16 is the embodiment of the present invention 4 (right side) and prepared by embodiment 9 (left side).
Figure 17 is the magnetic detection figure of Mn@N-CNT-4 spiral carbon nano pipe prepared by embodiment 4.
Figure 18 is the Mn N-CNT-4 of the preparation of embodiment 4 in no hydrazine hydrate (1mol L-1KOH) and there is a hydrazine hydrate (1mol L-1KOH+0.1mol L-1N2H4) in the case of cyclic voltammetry.
Figure 19 is cyclical stability of the Mn@N-CNT-4 of the preparation of the embodiment of the present invention 4 in hydrazine hydrate solution, is respectively
Initially, 3000 circle of 1000 circle of circulation, 2000 circle of circulation and circulation.
Figure 20 is N-CNT-2~5 Mn@of the preparation of the embodiment of the present invention 2~5 in 0.1mol L-1KOH solution in
ORR test chart.
Figure 21 is Mn@N-CNT-4 catalyst prepared by the present invention in 1mol L-1KOH solution in OER test.
Figure 22 is Mn@N-CNT-4 catalyst prepared by the present invention in 1mol L-1KOH solution in HER test.
Figure 23 is the complete solution water test chart of Mn@N-CNT-4 prepared by the present invention.
Figure 24 is charge-discharge test figure of the Mn@N-CNT-4 prepared by the present invention in lithium-sulfur cell.
Specific embodiment
The preparation and catalysis work that spiral carbon nano pipe of the invention is further detailed below by embodiment
Property is described further.
The preparation (no fuse salt) of embodiment 1:Mn@N-CN-1
The preparation of Mn@N-CNT-1: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h is rotated at 45 DEG C, ethanol evaporation obtains solid envelope evil spirit.Obtained solid powder is packed into ceramic crucible
In, it is subsequently placed in tube furnace, is passed through nitrogen into tube furnace from tube furnace air inlet, after air is discharged, balloon is fixed on
On the gas outlet of tube furnace, gas outlet is sealed.Temperature is risen to 800 DEG C with the rate of heat addition of 2.5 DEG C/min, and in the temperature
It is lower to be kept for 180 minutes.Then, with 5 DEG C of min-1Cooling rate temperature is cooled to 30 DEG C.Products therefrom is in 1M HNO3Solution
It is middle to handle for 24 hours, to remove unreacted manganese salt.After acid processing, pH is washed to as neutrality, and 12 hours dry at 60 DEG C, obtained
To product Mn@N-CNT-1.
The preparation (no ball milling) of embodiment 2:Mn@N-CN-2
The preparation of Mn@N-CNT-2: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h, ethanol evaporation are rotated at 45 DEG C.Obtained solid powder and 0.3163g calcium chloride are simply mixed, it is former
Expect particle diameter distribution in 90-200nm.It is then charged into ceramic crucible, is subsequently placed in tube furnace, from tube furnace air inlet to tubular type
It is passed through nitrogen in furnace, after air is discharged, balloon is fixed on the gas outlet of tube furnace, gas outlet is sealed.With 2.5 DEG C/min
The rate of heat addition temperature is risen to 800 DEG C, and at such a temperature keep 180 minutes.Then, with 5 DEG C of min-1Cooling rate will
Temperature is cooled to 30 DEG C.Products therefrom is in 1M HNO3It is handled in solution for 24 hours, to remove unreacted manganese salt.After acid processing, water
PH is washed till as neutrality, and 12 hours dry at 60 DEG C, obtains product Mn@N-CNT-2, yield 42.3%.
The preparation (ball milling 6 hours) of embodiment 3:Mn@N-CNT-3
The preparation of Mn@N-CNT-3: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h, ethanol evaporation are rotated at 45 DEG C.By obtained solid powder and 0.3163g calcium chloride in zircon sand pot
With 6000rpm ball milling 6 hours, raw material particle size was in 200-400nm after ball milling.Later, it fills this blend into ceramic crucible, then
It is placed in tube furnace, is passed through nitrogen into tube furnace from tube furnace air inlet, after air is discharged, balloon is fixed in tube furnace
Gas outlet on, seal gas outlet.Temperature is risen to 800 DEG C with the rate of heat addition of 2.5 DEG C/min, and is kept at such a temperature
180 minutes.Then, with 5 DEG C of min-1Cooling rate temperature is cooled to 30 DEG C.Products therefrom is in 1M HNO3It is handled in solution
For 24 hours, to remove unreacted manganese salt.After acid processing, pH is washed to as neutrality, and 12 hours dry at 60 DEG C, obtains product
Mn@N-CNT-3, yield 49.1%.
The preparation (ball milling 12 hours) of embodiment 4:Mn@N-CNT-4
The preparation of Mn@N-CNT-4: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h, ethanol evaporation are rotated at 45 DEG C.By obtained solid powder and 0.3163g calcium chloride in zircon sand pot
With 6000rpm ball milling 12 hours, raw material particle size was in 50-70nm after ball milling.Later, it fills this blend into ceramic crucible, then
It is placed in tube furnace, is passed through nitrogen into tube furnace from tube furnace air inlet, after air is discharged, balloon is fixed in tube furnace
Gas outlet on, seal gas outlet.Temperature is risen to 800 DEG C with the rate of heat addition of 2.5 DEG C/min, and is kept at such a temperature
180 minutes.Then, with 5 DEG C of min-1Cooling rate temperature is cooled to 30 DEG C.Products therefrom is in 1M HNO3It is handled in solution
For 24 hours, to remove unreacted manganese salt.After acid processing, pH is washed to as neutrality, and 12 hours dry at 60 DEG C, obtains product
[email protected] measured, left or right helical structure is presented in the tubular state of present invention gained Mn@N-CCNT, also occurs about center
The symmetrical " V " shape CCNTs structure of Mn catalyst granules, yield 55.6%.
The preparation (ball milling 18 hours) of embodiment 5:Mn@N-CNT-5
The preparation of Mn@N-CNT-5: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h, ethanol evaporation are rotated at 45 DEG C.By obtained solid powder and 0.3163g calcium chloride in zircon sand pot
With 6000rpm ball milling 18 hours, raw material particle size was in 150-250nm or so after ball milling.Later, ceramic crucible is filled this blend into
In, it is subsequently placed in tube furnace, is passed through nitrogen into tube furnace from tube furnace air inlet, after air is discharged, balloon is fixed on
On the gas outlet of tube furnace, gas outlet is sealed.Temperature is risen to 800 DEG C with the rate of heat addition of 2.5 DEG C/min, and in the temperature
It is lower to be kept for 180 minutes.Then, with 5 DEG C of min-1Cooling rate temperature is cooled to 30 DEG C.Products therefrom is in 1M HNO3Solution
It is middle to handle for 24 hours, to remove unreacted manganese salt.After acid processing, pH is washed to as neutrality, and 12 hours dry at 60 DEG C, obtained
To product Mn@N-CNT-5, yield 47.2%.
The preparation of embodiment 6:Mn@N-CNT-6
Temperature is risen to 700 DEG C divided by the rate of heat addition of 2.5 DEG C/min by the present embodiment, and keeps 240 points at such a temperature
Clock, other are identical as 4 step of embodiment, obtain product and obtain product Mn@N-CNT-6.
The preparation of embodiment 7:Mn@N-CNT-7
Temperature is risen to 900 DEG C divided by the rate of heat addition of 2.5 DEG C/min by the present embodiment, and keeps 180 points at such a temperature
Clock, other are identical as 4 step of embodiment, obtain product and obtain product Mn@N-CNT-7.
The preparation of embodiment 8:Mn@N-CNT-8
Temperature is risen to 800 DEG C divided by the rate of heat addition of 10 DEG C/min by the present embodiment, and keeps 180 points at such a temperature
Clock, other are identical as 4 step of embodiment, obtain product and obtain product Mn@N-CNT-8.
The preparation of embodiment 9:Mn@N-CNT-9
The preparation of Mn@N-CNT-4: 0.2g manganese nitrate and 1.562g melamine are dissolved in 40mL ethyl alcohol, ultrasound is stirred
After mixing 30 minutes, 1h, ethanol evaporation are rotated at 45 DEG C.By obtained solid powder and 0.3163g calcium chloride in zircon sand pot
With 6000rpm ball milling 12 hours, raw material particle size was in 50-70nm after ball milling.Later, it fills this blend into ceramic crucible, then
It is placed in inert gas tubular type furnace (i.e. in calcination process lasting be passed through nitrogen).With the rate of heat addition of 2.5 DEG C/min by temperature
800 DEG C are risen to, and is kept for 180 minutes at such a temperature.Then, with 5 DEG C of min-1Cooling rate temperature is cooled to 30 DEG C.Institute
Product is obtained in 1M HNO3It is handled in solution for 24 hours, to remove unreacted manganese salt.After acid processing, pH is washed to as neutrality, and
It is 12 hours dry at 60 DEG C, obtain product Mn@N-CNT-9, yield 25.2%.
Fig. 1~8 are the SEM of the carbon nanotube of Examples 1 to 8 preparation.It can be seen from the figure that embodiment 4 prepares Mn@N-
CNT-4 performance is best, and diameter is distributed in 500~1000nm, and spiral shell diameter is distributed in 80~400nm, and screw pitch is distributed in 20~300nm,
It is relatively large in diameter the transmission conducive to electrolyte and the conduction of ion.Fig. 9~12 are the spiral carbon nano pipe of embodiment 2-5 preparation
Droplet measurement figure.Figure 13~14 are the BET test of spiral carbon nanotubes prepared by embodiment 2~5, wherein Mn@N-CNT-2 ratio
Surface area is 150.089m2/ g, Mn@N-CNT-3 specific surface area are 134.586m2/ g, Mn@N-CNT-4 specific surface area is
424.59m2/ g, Mn@N-CNT-5 specific surface area are 223.17m2/g.Figure 14 is the hole of carbon nanotube prepared by embodiment 2-5
Diameter distribution, it can be seen that the pore-size distribution of spiral carbon nano pipe mainly based on mesoporous (0-50nm is mesoporous), shows its work
Property site is more, and defect center is more.Figure 15 is spiral carbon nanotubes Raman spectrogram prepared by embodiment 2~5, wherein the peak D is vertical to be sat
Product defect level is marked-represents, the peak G ordinate-represents product crystallinity, and the half-peak breadth at the peak D represents the purity of product, ID/IG
Ratio it is bigger, show that defect level is higher, active site is more, and the half-peak breadth at the peak D is narrower to show that purity is higher.Figure 16 is this
The spiral carbon nano pipe photo of inventive embodiments 4 (right side) and embodiment 9 (left side) preparation, it can be seen that under inert gas protection
The reaction of progress, manganese salt is largely converted into manganese monoxide (in green), rather than exists in the form of manganese simple substance, and this portion
Divide manganese monoxide to be exposed to outside, is just difficult to fix carbon material, more spiral carbon nanotubes can not be formed.
Figure 17 is Mn@N-CNT-4 magnetic detection figure prepared by embodiment 4, it can be seen that it has magnetism.Figure 18 is Mn@
N-CNT-4 is in no hydrazine hydrate (1mol L-1KOH) and there is a hydrazine hydrate (1mol L-1KOH+0.1mol L-1N2H4) in the case of circulation
Volt-ampere test.From take-off potential and the peak point current of Figure 18 curve, it can be concluded that, Mn N-CNT-4 has oxidation catalysis to hydrazine hydrate
Effect.Figure 19 is cyclical stability of the Mn@N-CNT-4 in hydrazine hydrate solution.Circulation 3000 circle after, peak point current only under
Drop 40% or so, illustrates that Mn@N-CNT-4 Compounds with Hydrazine Hydrate Catalyzed has good stability.Figure 20 is Mn@N-CNT prepared by embodiment 2~5
As catalyst and existing Pt/C as catalyst in 0.1mol L-1KOH solution in ORR test.It can be observed from fig. 20 that
Mn@N-CNT catalyst prepared by the present invention compares Pt/C catalyst, take-off potential and half-wave point be respectively 0.90V and
0.73V shows good hydrogen reduction performance.Figure 21 is Mn@N-CNT-4 catalyst prepared by the present invention in 1mol L-1KOH
OER test in solution.As shown in Figure 21, Mn@N-CNT-4 is in 2mA cm-2~10mA cm-2Current density under overpotential
Respectively less than standard material RuO2Overpotential, it is known that the analysis oxygen of Mn@N-CNT-4 is had excellent performance.
Figure 22 is Mn@N-CNT-4 catalyst prepared by the present invention in 1mol L-1KOH solution in HER test.Figure 23
For the complete solution water test chart of Mn@N-CNT-4 prepared by the present invention.As shown in Figure 22, Mn@N-CNT-4 is in 20mA cm-2Electric current is close
The lower overpotential of degree is and the overpotential difference about 0.15V of standard material Pt/C, the Mn@N- in the Hydrogen Evolution Performance similar to carbon material
The analysis oxygen performance level of CNT-4 is in medium on the upper side.
Figure 23 is the complete solution water test chart of Mn@N-CNT-4 catalyst prepared by the present invention, and explanation can carry out complete solution water.
Figure 24 be charge-discharge test figure of the Mn@N-CNT-4 prepared by the present invention as negative electrode material in lithium-sulfur cell, by
The charge-discharge test of 1st circle and the 100th circle illustrates good cycling stability.
Claims (9)
1. a kind of preparation method of spiral carbon nano pipe, which comprises the following steps:
(1) manganese salt and melamine are put into ethyl alcohol, are uniformly mixed, are subsequently placed in Rotary Evaporators in certain temperature backspin
A period of time is steamed, by ethanol evaporation, obtains solid powder；
(2) solid powder that step (1) obtains is mixed with solubility melting salt powder, is subsequently placed in tube furnace, in inertia
Under the protection of gas or in melamine higb pressure atmosphere, 700~900 DEG C are warming up to the rate of 1~5 DEG C/min and carries out calcining 2
~4h finally obtains fillable carbon nanotube through supercooling, pickling, washing, drying；Fuse salt is CaCl2、KCl、ZnCl2、
MgCl2One of or it is a variety of.
2. the preparation method of spiral carbon nano pipe according to claim 1, which is characterized in that the melamine high pressure
The forming method of atmosphere is to be passed through inert gas into tube furnace from tube furnace air inlet, after air is discharged, balloon is fixed on
On the gas outlet of tube furnace, gas outlet is sealed.
3. the preparation method of spiral carbon nano pipe according to claim 1, which is characterized in that in the step (2)
Calcination temperature is 800 DEG C, and heating rate is 2.5 DEG C of min-1, calcination time 3h.
4. the preparation method of spiral carbon nano pipe according to claim 1, which is characterized in that use ball in step (2)
Grinding machine mixes solid powder with melting salt powder, and the particle size range of powder is 50~70nm after mixing.
5. the preparation method of spiral carbon nano pipe according to claim 1, which is characterized in that transition metal halide salt
It is the corresponding amount of two kinds of substances minimum fusing point in two-phase phasor with the dosage of soluble fuse salt, the manganese ion in the manganese salt
Molar ratio with melamine is 1:1.25, and the manganese salt is four hydration manganous chloride or manganese nitrate.
6. the preparation method of spiral carbon nano pipe according to claim 1, which is characterized in that the acid cleaning process uses
Nitric acid or hydrochloric acid.
7. the preparation method of spiral carbon nano pipe according to claim 6, which is characterized in that the acid cleaning process uses
Nitric acid.
8. carbon nanotube prepared by a kind of preparation method of spiral carbon nano pipe described in claim 1-7.
9. spiral carbon nano pipe according to any one of claims 8 composite material, superconductor, electromagnetic wave absorbent material, bio-separation,
Water process, water body detection, food safety detection, fuel cell, sensor material, complete solution water, the application in cell negative electrode material.
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