CN106829924A - A kind of preparation method of one-dimensional porous CNT - Google Patents
A kind of preparation method of one-dimensional porous CNT Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of one-dimensional porous CNT, the one-dimensional porous CNT is the one-dimensional porous CNT of N doping or the one-dimensional porous CNT of nitrogen cobalt codope；With ZnO nano-wire as core, the ZnO@ZIF 8 and ZnO@Zn/Co ZIF presomas of monometallic class zeolite imidazole ester framework compound ZIF 8 or bimetallic hydridization class zeolite imidazole ester framework compound Zn/Co ZIF as shell；Then by ZnO ZIF 8 or ZnO Zn/Co ZIF high-temperature calcinations in an inert atmosphere, one-dimensional porous CNT is obtained.Synthetic method of the present invention is simple, is not required to remove stratum nucleare template with pickling, is capable of achieving environment-friendly preparation technology；Obtained specific surface area of carbon nanotube is high, and active site enriches, and has very big application potential in fields such as electrochemical energy storage, catalysis and metal-air batteries.
Description
Technical field
The invention belongs to carbon material technical field, more particularly to a kind of preparation method of one-dimensional porous CNT.
Background technology
In the advanced energy conversion such as fuel cell and metal-air battery and memory device, oxygen reduction reaction
(ORR) it is an extremely important reaction.At present, platinum (Pt) base catalyst is the maximally efficient electrode catalysts of ORR.However,
Because platinum is expensive, scarcity of resources, and easily it is poisoned by potential fuel, the large-scale commercial for limiting platinum catalyst should
With.Therefore, it is fuel cell and metal-air battery large-scale commercial applications to develop non-precious metal catalyst cheap, efficiently, stable
The only way which must be passed of change.Up to the present, researcher has developed a large amount of without platinum catalyst, including carbon-supported catalysts, transition
Metal oxide, sulfide and carbide etc..Wherein carbon-supported catalysts, such as CNT has high conductivity and specific surface area,
Better crystallinity degree, the CNT of advantage, the particularly functional modification such as heat endurance, chemical stability be high, introduces new urging
Change avtive spot, show excellent ORR catalytic performances, become preferable electrode material has huge in energy device
Application prospect.
At present, the preparation method of CNT mainly have arc process, laser evaporization method, electron beam or ion beam evaporation methods,
Solar energy induction evaporation, catalyst pyrolytic hydrocarbon method, high pressure CO disproportionation cracking process, amorphous carbon hydrothermal growth process
Deng.The wherein most commonly seen preparation method of CNT is mainly arc process, laser ablation method and chemical vapour deposition technique.With
Continue to develop and the innovation of carbon nanotube preparation technology, these preparation methods have been provided with easily controllable, simple system and can
Realize the advantages such as the continuous production of industrialization.However, single CNT lacks abundant active site.Research shows,
The carbon-based material of the doping such as hetero atom such as N, O, P, B, Co, Fe has ORR catalysis activities higher, high stability, anti-Poisoning
The advantages of, it is most promising base metal ORR catalyst.Hard template method is to prepare another way of CNT
Footpath, while Heteroatom doping can be realized.Therefore, develop and expand template prepare Heteroatom doping CNT have it is non-
Often important research and application value.
In recent years, metal-organic framework materials (Metal-Oragnic Frameworks, MOFs) are due to can be in molecular water
Its chemical composition and chemical property are accurately controlled on flat, it is considered to be before glucose, organic polymer etc. preferably carbon
Drive body.Carbon material (MOFs derived carbons, MDCs) inherits the part-structure feature of MOFs, example as obtained in MOFs
Such as uniform Heteroatom doping, big specific surface area etc..However, MDCs there is also many deficiencies.In MDCs preparation process, high temperature
Pyrolysis step controllability is poor, and carbon skeleton can occur partly to cave under high temperature, and MDCs nano particles are easily polymerized, so as to reduce
The accessible surface product of MDCs.Additionally, there is substantial amounts of micropore in MDCs after pyrolysis.These micropores be unfavorable for reactant/
The transmission of electrolyte, and electrochemical double layer (electrochemical double layer, EDL) may be induced to overlap, lead
The quality of catalyst is caused to waste.
Compared with 0 wiener rice grain, monodimension nanometer material, such as CNT have good bridging property, can strengthen electricity
Son transmission, reduction ion diffusion length, so as to substantially improve the electrochemical kinetics of material, make it have ORR catalysis higher
Activity.Therefore, one-dimensional MDCs has faster ORR electrochemical kinetics than the MDCs nano particles of 0 dimension, is more suitable for gold
Applied in category air cell.In recent years, one-dimensional MDCs reports.
In document " Nanowire-Directed Templating Synthesis of Metal-Organic
Framework Nanofibers and Their Derived Porous Doped Carbon Nanofibers for
In Enhanced Electrocatalysis.J.Am.Chem.Soc.136 (2014) 14385-14388 ", Shu-Hong Yu classes
Topic group is reported and uses tellurium nano-wire to prepare Te@ZIF-8 presomas as template, then is carbonized and obtains one-dimensional MDCs, and nitrogen is mixed
Miscellaneous CNT (NCNT).But NCNT pipe diameters obtained in the method are too small (~10nm), and only realize nitrogen list
Doping.
In document " 1D Co-and N-Doped Hierarchically Porous Carbon Nanotubes
Derived from Bimetallic Metal Organic Framework for Efficient Oxygen and Tri-
iodide Reduction Reactions.Adv.Energy Mater.DOI:In 10.1002/aenm.201601979 ",
Arumugam Manthiram seminars report and use tellurium nanotube to prepare Te@Zn/Co-ZIF presomas as template, then will
Its carbonization obtains one-dimensional MDCs, nitrogen cobalt codope CNT (CoN-pCNT).CoN-pCNT obtained in the method overcomes pipe
The small shortcoming of road diameter, while realizing nitrogen cobalt codope.But it has the disadvantage strictly to control Zn and Co's in preparation process
Mol ratio is higher than 10:1, due to caving in for carbon skeleton, Co contents higher can reduce mesoporous quantity.Furthermore, it is contemplated that the poison of Te
Property and the Co-N that causes of limitation Co saltxThe loss of avtive spot, should develop a kind of alternative and obtain has abundant Co-NxIt is living
The one-dimensional MDCs of grading-hole in property site.
Based on problem above, to overcome the deficiencies in the prior art, a kind of easily operated, environment-friendly and easy formation is probed into
The preparation method of the CNT of the one-dimensional Heteroatom doping of pore system is classified, is that there is weight with the performance advantage for playing CNT
Want meaning.
The content of the invention
It is an object of the invention to provide a kind of preparation method of one-dimensional porous CNT, overcome and prepare in the prior art
Porous CNT template there is toxicity, Co-NxThe shortcomings of avtive spot is few.
The technology of the present invention thinking is as follows：The present invention is preparing core shell structure ZnO@ZIF-8, ZnO@Zn/Co-ZIF nano wires
During presoma, with ZnO nano-wire as template and Zn sources, a certain amount of cobalt ions is added to form monometallic or bimetallic
Hydridization class zeolite imidazole ester framework compound (ZIF-8 or Zn/Co-ZIF) shell, then by ZnO@ZIF-8, ZnO@Zn/Co-ZIF
Presoma carries out high temperature carbonization treatment, prepare the porous CNT of N doping (N-doped carbonnanotube, NCNT) and
The porous CNT of nitrogen cobalt codope (Co/NCNT), nothing removes template step.
The invention provides a kind of preparation method of one-dimensional porous CNT, the one-dimensional porous CNT is with ZnO
Nano wire is that template and Zn sources are prepared from, and the one-dimensional porous CNT is the one-dimensional porous CNT of N doping or nitrogen cobalt
The one-dimensional porous CNT of codope；
The one-dimensional porous preparation method of carbon nano-tube of N doping is comprised the following steps：
1) preparation of presoma：
ZnO nano-wire is added in mixed solutions of the DMF with water composition, at room temperature ultrasound fully diffusion；Add 2-
, be transferred to solution in water heating kettle after being well mixed by methylimidazole, reactor is placed in 3-5h is reacted in constant temperature oven, reaction knot
Shu Hou, is centrifuged, washs, drying, and obtains ZnO ZIF-8 presomas；
2) carburising step：
ZnO@ZIF-8 presomas are placed in tube furnace, heat up carbonization in the atmosphere of inert gas, then natural cooling
To room temperature, the one-dimensional porous CNT of single dispersing N doping is obtained, the one-dimensional porous specific surface area of carbon nanotube of N doping is
400-600m2g-1；
The preparation method of the one-dimensional porous CNT of nitrogen cobalt codope is comprised the following steps：
1) preparation of presoma：
ZnO nano-wire is added in mixed solutions of the DMF with water composition, at room temperature ultrasound fully diffusion；Add 2-
Methylimidazole, cobalt salt is added after being well mixed, and finally solution is transferred in water heating kettle, and reactor is placed in constant temperature oven instead
After answering 3-5h, reaction to terminate, it is centrifuged, washs, drying, obtains ZnO@Zn/Co-ZIF presomas；
2) carburising step：
ZnO@Zn/Co-ZIF presomas are placed in tube furnace, heat up carbonization in the atmosphere of inert gas, then natural
Room temperature is cooled to, the one-dimensional porous CNT of nitrogen cobalt codope is obtained, the one-dimensional porous CNT of nitrogen cobalt codope compares table
Area is 400-600m2g-1。
Preferably, the one-dimensional porous CNT of nitrogen cobalt codope and the one-dimensional porous CNT preparation process 1 of N doping) in
2-methylimidazole is 4-32 with the mol ratio of ZnO nano-wire:1.
Preferably, the one-dimensional porous CNT of nitrogen cobalt codope and the one-dimensional porous CNT preparation process 1 of N doping) in
DMF is 1-3 with the volume ratio of water:1.
Preferably, the one-dimensional porous CNT of nitrogen cobalt codope and the one-dimensional porous CNT preparation process 1 of N doping) in
Oven temperature is 40-70 DEG C.
Preferably, the one-dimensional porous CNT preparation process 2 of nitrogen cobalt codope) in the mol ratio of ZnO and cobalt salt be 14-
35:1。
Preferably, the one-dimensional porous CNT preparation process 2 of nitrogen cobalt codope) described in cobalt salt be cobalt nitrate, cobalt acetate
Or cobalt chloride.
Preferably, the one-dimensional porous CNT of nitrogen cobalt codope and the one-dimensional porous CNT preparation process 2 of N doping) in
The flow of inert gas is 50-150mL/min, and carburizing temperature is 800-900 DEG C, and carbonization time is 1-3h.
Preferably, the one-dimensional porous CNT of nitrogen cobalt codope and the one-dimensional porous CNT preparation process 2 of N doping) in
Inert gas is nitrogen or argon gas.
Compared with prior art, the invention has the advantages that：
1) present invention is by adjusting the mol ratio of ZnO and Co salt, prepares the core shell structure ZnO@ZIF-8 of different Co contents with
ZnO@Zn/Co-ZIF nanowire composites；
2) present invention with ZnO@ZIF-8 and ZnO@Zn/Co-ZIF as presoma, directly carbonize, during ZnO with generate
Carbon obtains macropore hollow duct after reacting completely, obtain tubular nanowire, i.e. CNT；
3) one-dimensional porous length of carbon nanotube prepared by the present invention is 3-50 μm；Caliber is 100-200nm；Pipe thickness is
10-30nm；Pipe diameter is 40-120nm；
4) one-dimensional porous CNT prepared by the present invention can realize that the uniform N doping of shell carbon material and nitrogen cobalt are co-doped with
It is miscellaneous；
5) one-dimensional porous CNT prepared by the present invention has good monodispersity and specific surface area (400- higher
600m2g-1)
6) synthetic method of the present invention is simple, is not required to remove stratum nucleare template with pickling, is capable of achieving environment-friendly preparation technology.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) photo of the ZnO@Zn/Co-ZIF nanowire precursors of preparation in embodiment 1
(under 500nm scales).
Fig. 2 is ESEM (SEM) photo of the one-dimensional porous CNT of nitrogen cobalt codope of preparation in embodiment 1
(under 200nm scales).
Fig. 3 is X-ray diffraction (XRD) spectrogram of the one-dimensional porous CNT of nitrogen cobalt codope of preparation in embodiment 1.
Fig. 4 is the nitrogen adsorption curve map (77K) of the one-dimensional porous CNT of nitrogen cobalt codope of preparation in embodiment 1.
Specific embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, with reference to specific embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
ZnO nano-wire used of the invention is purchased from Nanjing Xian Feng Nono-material Science ＆ Technology Ltd., ZnO nano-wire (No. CAS
7440-66-6, diameter 20-60nm, 5-50 μm of length).
Embodiment 1
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 3:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 0.41g 2-methylimidazoles, after ultrasonic 2-3min, adds cobalt salt
After 18.0mg is well mixed, the solution in conical flask is poured into water heating kettle, be placed in 50 DEG C of baking ovens and react 4h, reaction terminates
Afterwards, through being centrifuged, washing, dry, ZnO@Zn/Co-ZIF presomas are obtained.
(2) by step 1) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature process furnances, with 5 in nitrogen atmosphere
DEG C/speed of min is warming up to 800 DEG C, inert gas flow velocity is 50mL/min.After carbonizing 3h at 900 DEG C, room is naturally cooled to
Temperature, obtains the one-dimensional porous CNT (Co/NCNT) of nitrogen cobalt codope of the present invention.
It will be seen from figure 1 that ZnO@Zn/Co-ZIF nano wires prepared by step (1) have a core shell structure, ZnO cores it is straight
Footpath is 30 ± 10nm, and shell ZIF-8 thickness is 30 ± 10nm.As shown in Fig. 2 the CNT obtained after carbonization, caliber is 150
± 10nm, carbon wall thickness is 25 ± 5nm, and pipe diameter is 80 ± 10nm.White particle is to be received by the cobalt that graphitic carbon is wrapped up in figure
Rice corpuscles.Fig. 3 is the XRD spectra of the gained one-dimensional porous CNT of nitrogen cobalt codope, and diffraction maximum position is about right in 2 θ=26 °
Answer (002) crystal face of graphite-structure, 2 θ=44 °, (111), (200) of 51 ° of face-centered cubic cobalt crystal corresponding with 71 ° and
(220) crystal face.Fig. 4 is the nitrogen adsorption curve map (77K) of the gained one-dimensional porous CNT of nitrogen cobalt codope, is calculated it
Specific surface area (BET surface area) is 422m2g-1。
Embodiment 2
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 2:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 1.6g 2-methylimidazoles, after ultrasonic 2-3min, adds cobalt salt
After 12.0mg is well mixed, the solution in conical flask is poured into water heating kettle, be placed in 60 DEG C of baking ovens and react 3h, reaction terminates
Afterwards, through being centrifuged, washing, dry, ZnO@Zn/Co-ZIF presomas are obtained.
(2) by step 1) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature process furnances, with 5 in nitrogen atmosphere
DEG C/speed of min is warming up to 800 DEG C, inert gas flow velocity is 50mL/min.After carbonizing 3h at 800 DEG C, room is naturally cooled to
Temperature, obtains the one-dimensional porous CNT (Co/NCNT) of nitrogen cobalt codope of the present invention.
Embodiment 3
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 3:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 3.2g 2-methylimidazoles, after ultrasonic 2-3min, adds cobalt salt
After 8.0mg is well mixed, the solution in conical flask is poured into water heating kettle, be placed in and 2h is reacted in 70 DEG C of baking ovens, after reaction terminates,
Through centrifugation, washing, dry, obtain ZnO@Zn/Co-ZIF presomas.
(2) by step 1) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature process furnances, with 5 in nitrogen atmosphere
DEG C/speed of min is warming up to 900 DEG C, inert gas flow velocity is 50mL/min.After carbonizing 2h at 900 DEG C, room is naturally cooled to
Temperature, obtains the one-dimensional porous CNT (Co/NCNT) of nitrogen cobalt codope of the present invention.
Embodiment 4
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 3:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 0.82g 2-methylimidazoles, after ultrasonic 2-3min, by conical flask
In solution pour into water heating kettle, be placed in and 4h reacted in 50 DEG C of baking ovens, reaction terminate after, through centrifugation, washing, dry, obtain
ZnO@ZIF-8 presomas.
(2) by step 1) the ZnO@ZIF-8 presomas that obtain are placed in high temperature process furnances, in nitrogen atmosphere with 5 DEG C/
The speed of min is warming up to 900 DEG C, and inert gas flow velocity is 50mL/min.After carbonizing 3h at 900 DEG C, room temperature is naturally cooled to,
Obtain the porous CNT of N doping of the present invention (NCNT).
Embodiment 5
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 2:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 1.6g 2-methylimidazoles, after ultrasonic 2-3min, by conical flask
In solution pour into water heating kettle, be placed in and 3h reacted in 60 DEG C of baking ovens, reaction terminate after, through centrifugation, washing, dry, obtain
ZnO@ZIF-8 presomas.
(2) by step 1) the ZnO@ZIF-8 presomas that obtain are placed in high temperature process furnances, in nitrogen atmosphere with 5 DEG C/
The speed of min is warming up to 800 DEG C, and inert gas flow velocity is 50mL/min.After carbonizing 3h at 800 DEG C, room temperature is naturally cooled to,
Obtain the porous CNT of N doping of the present invention (NCNT).
Embodiment 6
(1) take ZnO nano-wire 80.0mg and be added to and fill DMF and water mixed solvent (64mL, volume ratio 3:1) conical flask
In, ultrasound 20min makes it fully spread at room temperature, is subsequently added into 3.2g 2-methylimidazoles, after ultrasonic 2-3min, by conical flask
In solution pour into water heating kettle, be placed in and 1h reacted in 70 DEG C of baking ovens, reaction terminate after, through centrifugation, washing, dry, obtain
ZnO@ZIF-8 presomas.
(2) by step 1) the ZnO@ZIF-8 presomas that obtain are placed in high temperature process furnances, in nitrogen atmosphere with 5 DEG C/
The speed of min is warming up to 900 DEG C, and inert gas flow velocity is 50mL/min.After carbonizing 2h at 900 DEG C, room temperature is naturally cooled to,
Obtain the porous CNT of N doping of the present invention (NCNT).
Claims (8)
1. a kind of preparation method of one-dimensional porous CNT, the one-dimensional porous CNT with ZnO nano-wire as template and
Zn sources are prepared from, and the one-dimensional porous CNT is that the one-dimensional porous CNT of N doping or nitrogen cobalt codope are one-dimensional porous
CNT, it is characterised in that：
The one-dimensional porous preparation method of carbon nano-tube of N doping is comprised the following steps：
1) preparation of presoma：
ZnO nano-wire is added in mixed solutions of the DMF with water composition, at room temperature ultrasound fully diffusion；Add 2- methyl
, be transferred to solution in water heating kettle after being well mixed by imidazoles, reactor is placed in 3-5h is reacted in constant temperature oven, and reaction terminates
Afterwards, it is centrifuged, washs, drying, obtains ZnO@ZIF-8 presomas；
2) carburising step：
ZnO@ZIF-8 presomas are placed in tube furnace, heat up carbonization in the atmosphere of inert gas, then naturally cools to room
Temperature, obtains the one-dimensional porous CNT of single dispersing N doping, the one-dimensional porous specific surface area of carbon nanotube of single dispersing N doping
It is 400-600m2g-1；
The preparation method of the one-dimensional porous CNT of nitrogen cobalt codope is comprised the following steps：
1) preparation of presoma：
ZnO nano-wire is added in mixed solutions of the DMF with water composition, at room temperature ultrasound fully diffusion；Add 2- methyl
Imidazoles, cobalt salt is added after being well mixed, and finally solution is transferred in water heating kettle, reactor is placed in 3- is reacted in constant temperature oven
5h, after reaction terminates, is centrifuged, washs, drying, and obtains ZnO@Zn/Co-ZIF presomas；
2) carburising step：
ZnO@Zn/Co-ZIF presomas are placed in tube furnace, heat up carbonization in the atmosphere of inert gas, then natural cooling
To room temperature, the one-dimensional porous CNT of nitrogen cobalt codope, the one-dimensional porous specific surface area of carbon nanotube of nitrogen cobalt codope are obtained
It is 400-600m2g-1。
2. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope and nitrogen are mixed
Miscellaneous one-dimensional porous CNT preparation process 1) in the mol ratio of 2-methylimidazole and ZnO nano-wire be 4-32:1.
3. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope and nitrogen are mixed
Miscellaneous one-dimensional porous CNT preparation process 1) in the volume ratio of DMF and water be 1-3:1.
4. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope and nitrogen are mixed
Miscellaneous one-dimensional porous CNT preparation process 1) in oven temperature be 40-70 DEG C.
5. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope prepares step
It is rapid 2) in the mol ratio of ZnO nano-wire and cobalt salt be 14-35:1.
6. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope prepares step
It is rapid 2) described in cobalt salt be cobalt nitrate, cobalt acetate or cobalt chloride.
7. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope and nitrogen are mixed
Miscellaneous one-dimensional porous CNT preparation process 2) in inert gas flow be 50-150mL/min, carburizing temperature is 800-900
DEG C, carbonization time is 1-3h.
8. preparation method according to claim 1, it is characterised in that：The one-dimensional porous CNT of nitrogen cobalt codope and nitrogen are mixed
Miscellaneous one-dimensional porous CNT preparation process 2) in inert gas be nitrogen or argon gas.
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| CN114976069A (en) * | 2022-06-23 | 2022-08-30 | 香港科技大学深圳研究院 | Preparation method and application of zeolite-like imidazole ester framework/graphene catalyst |
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