CN106564875A - Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles - Google Patents
Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles Download PDFInfo
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Abstract
The invention relates to a preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles. The method comprises the following steps: adding cobalt ions in ZnO nanosphere template and Zn source to form a double-metal hybrid zeolite imidazate skeleton compound shell, namely the ZnO@Zn/Co-ZIF precursor; and then performing high-temperature carbonization on the ZnO@Zn/Co-ZIF precursor to directly obtain the cobalt-nitrogen co-doped hollow carbon nano-particles with the specific surface area as 400-600m<2>g-1. By use of the preparation method disclosed by the invention, the synthesis method is simple, the operation of removing a nuclear layer template by use of acid-pickling is unnecessary, and the environment-friendly preparation process can be realized.
Description
Technical field
The invention belongs to technical field of nano material, the nitrogen co-doped hollow carbon nano-particle of more particularly to a kind of single dispersing cobalt
Preparation method.
Background technology
In recent years, the porous carbon nanomaterial that hetero atom (such as nitrogen, boron, phosphorus, sulfur, cobalt etc.) adulterates, particularly with special
The hollow structure carbon nanomaterial of pore structure, because which has larger specific surface area and a pore volume, relatively low density, and well
Physics and the advantages of chemical stability, in catalysis, adsorbent, the field such as electrode material and battery have a wide range of applications.One
Aspect, after hetero atom is introduced into carbon structure, because which is different from carbon atom bond distance, valency electron and atomic size, adjacent carbon atom is attached
There is defect in peri position point, and CHARGE DISTRIBUTION is uneven, and the electric neutrality of material with carbon element is damaged, and the catalysis for being more beneficial for constructing material with carbon element is lived
Property center.On the other hand, the material with carbon element of hollow structure has unique macropore hollow and porous carbon shell, can substantially improve electronics
Migration and diffusion, so as to improve the catalysis activity of material with carbon element.Therefore, prepare Heteroatom doping hollow material with carbon element have it is important
Research Significance.
At present, the preparation method for preparing hollow carbon nano-particle has：Template, vapour deposition process, arc discharge method, laser
Evaporation etc..Wherein template is using a kind of widest method for preparing hollow carbon granule.Template can be divided into hard template
Method and soft template method.Hard template method mostly with monodispersed silicon ball, polymer drops etc. as template, then in its superficial growth carbon source
Compound, obtains composite material of core-shell structure, selects suitable method to go removing template to obtain hollow carbon granule after carbonization.Although
Hollow carbon particle size prepared by hard template method is homogeneous, and with higher monodispersity, but during template is gone, template
Removal can not thoroughly cause its purity not high, or even easily cause the broken of carbon granule or subside.
Vapour deposition process is one of hollow carbon granule common method of synthesis.Its principle is the organic gas under flowing atmosphere
As carbon source, it is pyrolyzed under the high temperature conditions, makes the process of catalyst surface deposition growing solid carbon.Due to vapour deposition process it is general
Make catalyst with metal-oxide, but it is very few to the study on mechanism of catalyst, therefore in building-up process, have by-product to give birth to
Into.Therefore, obtained in the method, hollow carbon particle purity is not also high.
Arc discharge method is also a kind of method for preparing hollow carbon granule, according to Chinese patent CN1454839, its concrete reality
The mode of applying is to lead to noble gases in the electric arc reaction room containing graphite anode and negative electrode, applies a voltage to the two poles of the earth with pulse current
Between, so as to produce arc discharge reaction, collection be deposited on negative electrode product be hollow carbon granule, the carbon granule purity compared with
Height, but cost is also very high.
In recent years, with metal-organic framework materials, particularly class zeolitic imidazolate framework material ZIF-67 is used as forerunner
Body, high temperature cabonization can directly obtain the nitrogen co-doped porous carbon materials of cobalt.In document " Well-defined
carbonpolyhedrons prepared from nano metal-organic frameworks for oxygen
Reduction.J.Mater.Chem.A, 2 (2014) 11606-11613 " in, Ruqiang Zou etc. report size tunable
The nitrogen co-doped porous carbon nano-particle of cobalt, its shortcoming are obtained material with carbon element specific surface area (100-400m2g-1) relatively small.
In document " FromBimetallic Metal-Organic Framework to Porous Carbon:High Surface
Area and Multicomponent Active Dopants for Excellent
Electrocatalysis.Adv.Mater., in 27 (2015) 5010-5016 ", Hai-Long Jiang etc. are reported based on double
The porous carbon nanomaterial of metal hybrid metal-organic framework (Zn/Co-ZIF) presoma.By regulating and controlling Zn/Co in reactant
Different mol ratios (0,0.2,5,10,20,40,100), can substantially improve material with carbon element specific surface area (270,362,550,
1090、1225、1480、2184m2g-1), and abundant CoN is introduced in material with carbon elementxActive catalyst sites.Wherein work as Zn/Co
When mol ratio is 20, the material with carbon element for obtaining shows optimal electrocatalysis characteristic.Document above reports that the material with carbon element for obtaining all is
Monodispersed solid porous carbon nano-particle, not with hollow structure.
To overcome the deficiencies in the prior art, probe into a kind of simple to operate, low cost prepares Heteroatom doping hollow carbon
Grain method, has great importance to play its performance advantage.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt, overcomes
The porous carbon nano-particle prepared in prior art does not have the shortcomings that hollow structure, specific surface area are low.
The present invention adds cobalt ion to form bimetallic hydridization class zeolite imidazole ester bone with ZnO nano ball template and Zn sources
Frame compound (Zn/Co-ZIF) shell, i.e. ZnO@Zn/Co-ZIF presomas；Then ZnO@Zn/Co-ZIF presomas are carried out into high temperature
Carbonization, directly obtains the nitrogen co-doped hollow carbon nano-particle of cobalt, and nothing removes template step.
The invention provides a kind of preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt, including following step
Suddenly：
1) preparation of ZnO nano ball：
After by the zinc acetate aqueous solution of 0.1mol/L and 0.1mol/L triethanolamine aqueous solution stirring and evenly mixings, ultrasound in water-bath
Reaction；Then stand 10h；It is centrifuged, washs, is dried to obtain the ZnO nano ball that particle size range is 150-250nm；
2) preparation of ZnO@Zn/Co-ZIF presomas：
By cobalt salt and step 1) in gained ZnO nano ball be added to the mixing of N,N-dimethylformamide (DMF)/water composition
In solution, ultrasound fully spreads at room temperature；2-methylimidazole mix homogeneously is subsequently adding, solution is transferred to into hydro-thermal after mixing
In kettle, water heating kettle is placed in 50-70 DEG C of baking oven and reacts 3-5h, after reaction terminates, be centrifuged, wash, being dried, obtaining
ZnO@Zn/Co-ZIF presomas；
3) carburising step：
By step 2) in gained ZnO@Zn/Co-ZIF presomas be placed in tube furnace, in the atmosphere of noble gases heat up
Carbonization, then naturally cools to room temperature, obtains the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt；
Above-mentioned steps 1) in zinc acetate aqueous solution and triethanolamine aqueous solution volume ratio be 1:5, bath temperature is 20-50
DEG C, the ultrasonic reaction time is 20-40min；
Above-mentioned steps 2) in the mol ratio of 2-methylimidazole and ZnO nano ball be 4-32:1；
Above-mentioned steps 2) in the mol ratio of ZnO and cobalt salt be 14-35:1；
Above-mentioned steps 2) described in cobalt salt be cobalt nitrate, cobaltous acetate or cobaltous chloride；
Above-mentioned steps 2) in the volume ratio of DMF and water be 1-3:1；
Above-mentioned steps 3) in noble gases flow be 50-150mL/min, carburizing temperature be 800-900 DEG C, carbonization time
For 1-3h；
Above-mentioned steps 3) in noble gases be nitrogen or argon；
Compared with prior art, the invention has the advantages that：
1) mol ratio of the present invention by regulation ZnO and Co salt, prepares the nucleocapsid structure ZnO@Zn/Co- of difference Co contents
ZIF nanometer polyhedral composites；
2) present invention controls carbon by the particle diameter (150-250nm) of control ZnO with ZnO@Zn/Co-ZIF as presoma
Consumption of the ZnO to carbon during change, obtains macropore hollow carbon nano-particle after ZnO is reacted completely；
3) the uniform cobalt of the achievable shell material with carbon element of hollow carbon nano-particle prepared by the present invention is nitrogen co-doped, and keeps many
Face bodily form looks；
4) hollow carbon nano-particle prepared by the present invention has good monodispersity and higher specific surface area (400-
600m2g-1)
5) synthetic method of the present invention is simple, is not required to remove stratum nucleare template with pickling, is capable of achieving eco-friendly preparation technology.
Description of the drawings
Scanning electron microscope (SEM) photo (under 500nm scales) of ZnO nano balls of the Fig. 1 to prepare in embodiment 1.
Transmission electron microscope (TEM) photo (the 100nm scales of ZnO@Zn/Co-ZIF presomas of the Fig. 2 to prepare in embodiment 1
Under).
Transmission electron microscope (TEM) photo (100nm of cobalt nitrogen co-doped hollow carbon nano-particles of the Fig. 3 to prepare in embodiment 1
Under scale).
X-ray diffraction (XRD) spectrogram of cobalt nitrogen co-doped hollow carbon nano-particles of the Fig. 4 to prepare in embodiment 1.
The nitrogen adsorption curve chart (77K) of cobalt nitrogen co-doped hollow carbon nano-particles of the Fig. 5 to prepare 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 simply exemplary, and it is not intended to limit the scope of the present invention.
Embodiment 1
(1) in a conical flask 40mL concentration is added to be 0.1mol/L zinc acetate aqueous solutions, 200mL concentration is 0.1mol/L
30min is stirred under triethanolamine aqueous solution, room temperature, which after ultrasonic irradiation 20min, is stood into 10h in 30 DEG C of water-bath then.
Jing is centrifuged, washs, is dried, and obtains ZnO nano ball.
(2) by step 1) obtain 80.0mg ZnO nanos ball and 20.0mg cobalt nitrates are added to and fill DMF and water mixing is molten
Agent (64mL, volume ratio 3:1), in conical flask, under room temperature, ultrasound 20min makes which fully spread, and is subsequently added into 0.660g 2- first
Base imidazoles, after ultrasonic 5min, transfers them in hydro-thermal water heating kettle, is placed in 50 DEG C of baking ovens and reacts 5h, reaction terminate after, Jing from
The heart, washing, drying, obtain ZnO@Zn/Co-ZIF presomas.
(3) by step 2) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature furnace, in nitrogen atmosphere with 5 DEG C/
To 800 DEG C, inert gas flow velocity is 50mL/min to the ramp of min.It is carbonized at 800 DEG C after 3h, naturally cools to room temperature,
Obtain the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt of the present invention.
Scanning electron microscope (SEM) photos of the Fig. 1 for ZnO nano ball (under 500nm scales)；Fig. 2 is nucleocapsid structure ZnO@Zn/
Transmission electron microscope (TEM) photo (under 100nm scales) of Co-ZIF presomas；Fig. 3 is the nitrogen co-doped hollow carbon nano-particle of cobalt
Transmission electron microscope (TEM) photo (under 100nm scales)；Fig. 4 is the XRD spectra of the nitrogen co-doped hollow carbon nano-particle of gained cobalt；Fig. 4
For the nitrogen adsorption curve chart (77K) of the nitrogen co-doped hollow carbon nano-particle of gained cobalt.
It will be seen from figure 1 that ZnO nano ball prepared by step (1) has uniform particle diameter (200 ± 20nm).Can from Fig. 2
To be clear that nucleocapsid structure ZnO@Zn/Co-ZIF nano-particle, its pattern is polyhedron, the particle diameter of ZnO cores is 150 ±
20nm, shell ZIF-8 thickness is 70 ± 10nm.As shown in figure 3, the hollow carbon obtained after carbonization maintains original polyhedron shape
Looks, a diameter of 150 ± 20nm of hollow core, carbon wall thickness are 15 ± 5nm, and in figure, in white circle, black particle is by graphitic carbon bag
The cobalt nanometer particle wrapped up in.Fig. 4 is the XRD spectra of the nitrogen co-doped hollow carbon nano-particle of gained cobalt, and diffraction maximum position is about in 2 θ
(002) crystal face of=26 ° of correspondence graphite-structures, in 2 θ=44 °, (111) and (200) of face-centered cubic cobalt crystal corresponding with 51 ° are brilliant
Face.Fig. 5 is the nitrogen adsorption curve chart (77K) of the nitrogen co-doped hollow carbon nano-particle of gained cobalt, is calculated its specific surface area
(BET surface area) is 420m2g-1。
Embodiment 2
(1) in a conical flask 40mL concentration is added to be 0.1mol/L zinc acetate aqueous solutions, 200mL concentration is 0.1mol/L
30min is stirred under triethanolamine aqueous solution, room temperature, which after ultrasonic irradiation 20min, is stood into 10h in 30 DEG C of water-bath then.
Jing is centrifuged, washs, is dried, and obtains ZnO nano ball.
(2) by step 1) obtain 80.0mg ZnO nanos ball and 12.0mg cobalt nitrates are added to and fill DMF and water mixing is molten
Agent (64mL, volume ratio 2:1), in conical flask, under room temperature, ultrasound 20min makes which fully spread, and is subsequently added into 0.660g 2- first
Base imidazoles, after ultrasonic 5min, transfers them in hydro-thermal water heating kettle, is placed in 60 DEG C of baking ovens and reacts 4h, reaction terminate after, Jing from
The heart, washing, drying, obtain ZnO@Zn/Co-ZIF presomas.
(3) by step 2) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature furnace, in nitrogen atmosphere with 5 DEG C/
To 900 DEG C, inert gas flow velocity is 50mL/min to the ramp of min.It is carbonized at 900 DEG C after 3h, naturally cools to room temperature,
Obtain the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt of the present invention.
Embodiment 3
(1) in a conical flask 40mL concentration is added to be 0.1mol/L zinc acetate aqueous solutions, 200mL concentration is 0.1mol/L
30min is stirred under triethanolamine aqueous solution, room temperature, which after ultrasonic irradiation 20min, is stood into 10h in 30 DEG C of water-bath then.
Jing is centrifuged, washs, is dried, and obtains ZnO nano ball.
(2) by step 1) obtain 80.0mg ZnO nanos ball and 8.0mg cobalt nitrates are added to and fill DMF and water mixed solvent
(64mL, volume ratio 1:1) in conical flask, under room temperature, ultrasound 20min makes which fully spread, and is subsequently added into 1.32g 2- methyl miaows
Azoles, after ultrasonic 5min, the solution in conical flask is poured in water heating kettle, is placed in 70 DEG C of baking ovens and is reacted 3h, after reaction terminates, Jing
It is centrifuged, washs, is dried, obtains ZnO@Zn/Co-ZIF presomas.
(3) by step 2) the ZnO@Zn/Co-ZIF presomas that obtain are placed in high temperature furnace, in nitrogen atmosphere with 5 DEG C/
To 900 DEG C, inert gas flow velocity is 50mL/min to the ramp of min.It is carbonized at 900 DEG C after 3h, naturally cools to room temperature,
Obtain the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt of the present invention.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, embodiments of the present invention can be made with various changes, replace and change.
Claims (8)
1. a kind of preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt, comprises the steps：
1) preparation of ZnO nano ball：
After by the zinc acetate aqueous solution of 0.1mol/L and 0.1mol/L triethanolamine aqueous solution stirring and evenly mixings, in water-bath, ultrasound is anti-
Should；Then stand 10h；It is centrifuged, washs, is dried to obtain the ZnO nano ball that particle size range is 150-250nm；
2) preparation of ZnO@Zn/Co-ZIF presomas：
By cobalt salt and step 1) in gained ZnO nano ball be added to DMF/ water composition mixed solution in, ultrasound is filled at room temperature
Divide diffusion；2-methylimidazole mix homogeneously is subsequently adding, solution is transferred in water heating kettle after mixing, water heating kettle is placed in into 50-
3-5h is reacted in 70 DEG C of baking ovens, after reaction terminates, is centrifuged, washed, being dried, obtaining ZnO@Zn/Co-ZIF presomas；
3) carburising step：
By step 2) in gained ZnO@Zn/Co-ZIF presomas be placed in tube furnace, in the atmosphere of noble gases heat up carbonization,
Then room temperature is naturally cooled to, the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt is obtained, the single dispersing cobalt is nitrogen co-doped hollow
Carbon nano-particle specific surface area is 400-600m2g-1。
2. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 1) in zinc acetate aqueous solution and triethanolamine aqueous solution volume ratio be 1:5, bath temperature is 20-50 DEG C, during ultrasonic reaction
Between be 20-40min.
3. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 2) in the mol ratio of 2-methylimidazole and ZnO nano ball be 4-32:1.
4. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 2) in the mol ratio of ZnO and cobalt salt be 14-35:1.
5. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 2) described in cobalt salt be cobalt nitrate, cobaltous acetate or cobaltous chloride.
6. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 2) in the volume ratio of DMF and water be 1-3:1.
7. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 3) in noble gases flow be 50-150mL/min, carburizing temperature be 800-900 DEG C, carbonization time is 1-3h.
8. the preparation method of the nitrogen co-doped hollow carbon nano-particle of single dispersing cobalt according to claim 1, it is characterised in that：
Step 3) in noble gases be nitrogen or argon.
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| CN108682872A (en) * | 2018-05-22 | 2018-10-19 | 江苏理工学院 | A kind of preparation method of the nitrogen co-doped grading-hole carbon nanosheet oxygen reduction catalyst of iron cobalt |
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