CN107352527B - A kind of carbon nano-tube material preparation process that phosphorus is nitrogen co-doped - Google Patents
A kind of carbon nano-tube material preparation process that phosphorus is nitrogen co-doped Download PDFInfo
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Abstract
The invention discloses a kind of carbon nano-tube material preparation methods that phosphorus is nitrogen co-doped, with aqueous solvent, it is used as phosphorus source and carbon source to dissolve mix by a certain percentage with nitrogen source and catalysis carbon-forming agent simultaneously organic phosphoric acid, it is ground after Rotary Evaporators remove water, high temperature cabonization is carried out at different temperatures, then pickling removes the carbon forming agent porous carbon material nitrogen co-doped to get phosphorus.Material phosphorus with higher, nitrogen content and the biggish specific surface area that preparation method through the invention obtains.It is demonstrated experimentally that the material is used for electro-catalysis redox reactions excellent effect under acid condition, can be recycled repeatedly, catalyst stability is high.Simultaneously as phosphorous, nitrogen-containing group presence, so that carbon nano-tube material of the invention is expected for being catalyzed, gas storage, the carrier of clean energy resource, supercapacitor etc..
Description
Technical field
The present invention relates to technical field of chemistry more particularly to a kind of carbon nano-tube material preparation processes that phosphorus is nitrogen co-doped.
Background technique
Porous carbon material is a series of because having the characteristics that chemical stability height, acid and alkali-resistance, high temperature resistant, conduction, thermally conductive etc., extensively
Applied to electrode material (such as fuel cell, supercapacitor), adsorbent material, energy storage material and catalyst carrier etc..It is porous
Carbon Materials include active carbon (AC), activated carbon fibre (ACF), mesoporous carbon (MC) and carbon nanotube (CNTs) etc..
Theoretical and experimental study show the heteroatomic crystal structure for adulterating changeable Carbon Materials and electronic structure to
Improve its chemical property and catalytic performance.It is nitrogen co-doped to Carbon Materials progress phosphorus, the structure of material can be made to become unordered, with
Change its mechanical property.Heteroatomic introducing can change the local charge density of material, make to generate more active sites, simultaneously
The defect caused by adulterating can further increase the activity of material.With high activity site and the nitrogen co-doped Carbon Materials of defect phosphorus
It can participate in reacting directly as catalyst, can also be used as the carrier of metallic catalyst, it can form strong key with metallic
It takes over control only its reunion and falls off.
The Carbon Materials of N doping obtain express delivery development in recent years, and preparation process can be divided mainly into two major classes: fabricated in situ
Method and post treatment method.According to the processing mode containing nitrogen precursor, in-situ synthesis can be divided into liquid phase template, gas phase template,
Hydro-thermal method, direct pyrolysis method and chemical reaction method.Post treatment method can be divided into two kinds of dry and wet again.
And nitrogen co-doped its preparation process of porous carbon material of phosphorus is always the heat studied, main preparation process is former
Position synthetic method, such as document (Jintao Zhang, Zhenghang Zhao, Zhenhai Xia, Liming Dai. A
metal-free bifunctional electrocatalyst for oxygen reduction and oxygen
Evolution reactions. Nature Nanotech. 2015,10,444-452) it reports and is with phytic acid
Phosphorus source, aniline are prepared for the nitrogen co-doped porous carbon material of phosphorus by polymerizeing pyrolysismethod for nitrogen source.The phosphorus of in-situ synthesis preparation
In the skeleton that phosphorus, nitrogen are mainly present in Carbon Materials in the form of structure phosphorus, nitrogen in nitrogen co-doped porous carbon material, and phosphorus,
Nitrogen content is generally higher, and operation is simple and phosphorus, nitrogen-atoms are distributed more uniformly in the material of synthesis.
It there is no the report coexisted in a kind of raw material based on phosphorus source and carbon source in the prior art.Based on reported conjunction in situ
It is prepared in the Carbon Materials of Heteroatom doping at method, stresses the investigation of materials of N doping, and the material nitrogen co-doped for phosphorus is ground
Study carefully less.Currently, it is nitrogen co-doped to prepare phosphorus by pyrolysismethod as phosphorus source and carbon source using the organic phospho acid for containing phenyl ring
The research of carbon nano-tube material is a blank.
Summary of the invention
The object of the invention is that providing a kind of carbon nano-tube material that phosphorus is nitrogen co-doped to solve the above-mentioned problems
Preparation process.
The present invention through the following technical solutions to achieve the above objectives:
The present invention adds nitrogen source and catalysis carbon-forming agent, using high temperature pyrolysis using organic phospho acid simultaneously as phosphorus source and carbon source
The nitrogen co-doped carbon nano-tube material of phosphorus is prepared in method；The nitrogen co-doped carbon nano-tube material of the phosphorus uses following steps system
It is standby: phosphorus source, nitrogen source and catalysis carbon-forming agent being added in deionized water, removed after uniform solution is prepared under water-bath through Rotary Evaporators
Moisture is removed, is calcined in nitrogen atmosphere after obtained solid is ground；By products therefrom pickling remove carbon forming agent, ethanol washing, very
The nitrogen co-doped carbon nano-tube material of phosphorus is obtained after sky is dry.
The organic phospho acid is phenyl-phosphonic acid, phenyl phosphinic acid, diphenyl phosphonic acid, methylphenylphosphinic acid, ethyl
One or more kinds of mixtures of phenyl phosphinic acid, 2- carboxyethyl phenyl hypophosphorous acid.
The nitrogen source is one of cyanamide, dicyandiamide, melamine, urea；The catalysis carbon-forming agent is chlorine
Change the mixture of one or both of cobalt, frerrous chloride.
The mass ratio of the phosphorus source, nitrogen source and carbon forming agent is 0.1 ~ 0.5:1: ~ 2.5, preferably 0.2 ~ 0.4:1: ~ 2.5.
The bath temperature is 60 ~ 90 oC, and calcination process uses from room temperature degree and is warming up to calcination temperature, described
Calcining heating rate is 2.0 ~ 5.0 oC/min, and calcination temperature is 600 ~ 900 oC, and calcination time is 2 ~ 4h.
The acid is concentrated hydrochloric acid enriching nitric acid, volume ratio 3:1.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
The nitrogen co-doped carbon nano-tube material of the phosphorus is used for electrocatalytic oxidation reduction reaction.
The beneficial effects of the present invention are:
The present invention is a kind of carbon nano-tube material preparation process that phosphorus is nitrogen co-doped, and compared with prior art, the present invention exists
By phosphorus source and carbon source together as one in preparation process, i.e., contains phenyl ring in used phosphorus source, catalysis carbon-forming agent is added and prepares
The carbon nano-tube material of phosphorus with higher, N doping amount has preferable performance in electrochemical catalysis, is mainly shown as and connects
Near noble metal catalyst Pt/C take-off potential, and the stability of material is good.
The advantages of preparation process of the nitrogen co-doped carbon nano-tube material of phosphorus of the present invention is: raw material are simple and easy to get,
Preparation condition is controllable, can large-scale application in industrial production etc..
Material phosphorus with higher, nitrogen content and the biggish specific surface area that preparation process through the invention obtains.
It is demonstrated experimentally that the material is used for electro-catalysis redox reactions excellent effect under acid condition, repeatedly catalysis can be recycled
Agent stability is high.Simultaneously as phosphorous, nitrogen-containing group presence so that carbon nano-tube material of the invention be expected for being catalyzed,
Gas storage, the carrier of clean energy resource, supercapacitor etc..
Detailed description of the invention
Fig. 1 is the BET and pore size distribution figure of the nitrogen co-doped carbon nano-tube material of the obtained phosphorus of embodiment 1；
(a) is BET distribution map in Fig. 1；It (b) is pore size distribution figure；
Fig. 2 is SEM and the TEM figure of the nitrogen co-doped carbon nano-tube material of the obtained phosphorus of embodiment 1；
(a) is SEM figure in Fig. 2；(b) scheme for TEM；
Fig. 3 is that the full spectrogram of XPS of the nitrogen co-doped carbon nano-tube material of the obtained phosphorus of embodiment 1, the XPS swarming of N1s are quasi-
Close the XPS swarming fitted figure of figure, P2p；
The full spectrogram of (a) XPS in Fig. 3；(b) the XPS swarming fitted figure of N1s；(c) the XPS swarming fitted figure of P2p；
Fig. 4 is the polarization curves of oxygen reduction of the nitrogen co-doped carbon nano-tube material of the obtained phosphorus of embodiment 7.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
Embodiment 1
Phenyl-phosphonic acid (a) 0.50g, dicyandiamide 5.0g, CoCL2 6H2O 5.0g are taken, is added in 100ml water, 60 o are heated
C stirs 30min, is mixed into uniform solution.Moisture is removed with Rotary Evaporators, blue solid is obtained, is put into quartz boat after grinding
In, it is placed in tube furnace, 600oC polymerization 4h is warming up to 2.5oC/min in nitrogen atmosphere, is removed after being cooled to room temperature with chloroazotic acid
After going cobalt granule, washing dry, black solid powder, the as nitrogen co-doped carbon nano-tube material PNC-a-600 of phosphorus are obtained, than
Surface area is 353m2/ g, Kong Rongwei 0.52cm3/ g, aperture 5.1nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 2
Phenyl phosphinic acid (b) 0.50g, melamine 5.0g, four water frerrous chloride 5.0g are taken, is added in 100ml water, adds
80 oC of heat stir 30min, are mixed into uniform solution.Moisture is removed with Rotary Evaporators, light green solid is obtained, is put after grinding
Enter in quartz boat, be placed in tube furnace, 700oC polymerization 4h is warming up to 3.0oC/min in nitrogen atmosphere, after being cooled to room temperature
Iron particle, which is removed, after washing is dry with chloroazotic acid obtains black solid powder, the as nitrogen co-doped carbon nano-tube material PNC- of phosphorus
B-700, specific surface area 468m2/ g, Kong Rongwei 0.56cm3/ g, aperture 6.2nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 3
Diphenyl phosphonic acid (c) 1.0g, cyanamide 5.0g, CoCL2 6H2O 5.0g are taken, is added in 100ml water, is heated
60 oC stir 30min, are mixed into uniform solution.Moisture is removed with Rotary Evaporators, blue solid is obtained, is put into stone after grinding
Ying Zhouzhong is placed in tube furnace, is warming up to 800oC polyase 13 h in nitrogen atmosphere with 3.0oC/min, is used king after being cooled to room temperature
Water removes iron particle and obtains black solid powder, the as nitrogen co-doped carbon nano-tube material PNC-c- of phosphorus after washing is dry
800, specific surface area 509m2/ g, Kong Rongwei 0.63cm3/ g, aperture 6.8nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 4
Methylphenylphosphinic acid (d) 1.0g, urea 5.0g, CoCL2 6H2O 5.0g are taken, is added in 100ml water, is heated
60 oC stir 30min, are mixed into uniform solution.Moisture is removed with Rotary Evaporators, blue solid is obtained, is put into stone after grinding
Ying Zhouzhong is placed in tube furnace, is warming up to 900oC polymerization 2h in nitrogen atmosphere with 3.0oC/min, is used king after being cooled to room temperature
Water removes iron particle and obtains black solid powder, the as nitrogen co-doped carbon nano-tube material PNC-d- of phosphorus after washing is dry
900, specific surface area 623m2/ g, Kong Rongwei 0.69cm3/ g, aperture 7.2nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 5
Ethylphenyl phosphinic acids (e) 1.0g, dicyandiamide 5.0g, four water frerrous chloride 5.0g are taken, are added in 100ml water,
60 oC stirring 30min is heated, uniform solution is mixed into.Moisture is removed with Rotary Evaporators, light green solid is obtained, after grinding
It is put into quartz boat, is placed in tube furnace, 900oC polymerization 2h is warming up to 4.0oC/min in nitrogen atmosphere, is cooled to room temperature
Iron particle, which is removed, after washing is dry with chloroazotic acid afterwards obtains black solid powder, the as nitrogen co-doped carbon nano-tube material of phosphorus
PNC-e-900, specific surface area 732m2/ g, Kong Rongwei 0.78cm3/ g, aperture 9.5nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 6
2- carboxyethyl phenyl phosphinic acid (f) 0.50g, melamine 5.0g, CoCL2 6H2O 5.0g are taken, 100ml is added to
In water, 90 oC of heating stir 30min, are mixed into uniform solution.Moisture is removed with Rotary Evaporators, obtains blue solid, is ground
After be put into quartz boat, be placed in tube furnace, in nitrogen atmosphere with 5.0oC/min be warming up to 900oC polymerization 2h, be cooled to room
Wen Houyong chloroazotic acid removes iron particle and obtains black solid powder, the as nitrogen co-doped carbon nano-tube material of phosphorus after washing is dry
PNC-f-900, specific surface area 806m2/ g, Kong Rongwei 0.92cm3/ g, aperture 9.6nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
Embodiment 7
Phenyl phosphinic acid (f) 0.50g, dicyandiamide 5.0g, four water frerrous chloride 2.5g, CoCL2 6H2O 2.5g are taken, are added
Into 100ml water, 70 oC of heating stir 30min, are mixed into uniform solution.Moisture is removed with Rotary Evaporators, it is solid to obtain blue
Body is put into quartz boat after grinding, is placed in tube furnace, is warming up to 900oC polymerization 2h in nitrogen atmosphere with 5.0oC/min,
It is cooled to after room temperature and removes iron particle with chloroazotic acid, after washing drying, obtain black solid powder, the as nitrogen co-doped carbon of phosphorus is received
Nanotube material PNC-a-900, specific surface area 531m2/ g, Kong Rongwei 0.56cm3/ g, aperture 5.4nm.
The existence form of the nitrogen co-doped carbon nano-tube material phosphorus of the phosphorus includes metal phosphide, phosphorous oxides, phosphorus charcoal
Compound, the content of phosphorus are 1 ~ 10 wt%.
The existence form of the nitrogen co-doped carbon nano-tube material nitrogen of the phosphorus includes pyridine nitrogen, graphite mould nitrogen and oxidized form
Nitrogen, the content of nitrogen are 3 ~ 13 wt %.
The nitrogen co-doped carbon nano-tube material of resulting phosphorus is used for electrocatalytic oxidation reduction reaction.Electrochemistry experiment is in three electricity
It is carried out in polar body system；Test carries out on AtuoLab electrochemical workstation；O2It is saturated 0.1 M HClO4Solution sweeps speed 10
mV·s-1, 0.03 ~ 1.1 V of scanning range.Choose dynamics Controlling section or mix 0.9 V(RHE of control interval) when electric current
Carry out power current calculating.As seen from Figure 4, the take-off potential of the hydrogen reduction of the nitrogen co-doped carbon nano-tube catalyst of phosphorus is big
In Pt/C, show the overpotential of the hydrogen reduction on the nitrogen co-doped carbon nanotube electrode of phosphorus lower than Pt/C electrode.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of carbon nano-tube material preparation process that phosphorus is nitrogen co-doped, it is characterised in that: using organic phospho acid simultaneously as phosphorus source
And carbon source, nitrogen source and catalysis carbon-forming agent are added, the nitrogen co-doped carbon nano-tube material of phosphorus is prepared using high temperature pyrolytic cracking (HTP)；Institute
It states the nitrogen co-doped carbon nano-tube material of phosphorus to prepare using following steps: deionization is added in phosphorus source, nitrogen source and catalysis carbon-forming agent
It is prepared in water, under water-bath and removes moisture through Rotary Evaporators after uniform solution, after obtained solid is ground in nitrogen atmosphere
Calcining；Products therefrom pickling is removed into catalysis carbon-forming agent, ethanol washing obtains the nitrogen co-doped carbon nanotube of phosphorus after vacuum drying
Material；
The organic phospho acid is phenyl-phosphonic acid, phenyl phosphinic acid, diphenyl phosphonic acid, methylphenylphosphinic acid, ethylphenyl
One or more kinds of mixtures of phosphinic acids, 2- carboxyethyl phenyl hypophosphorous acid；
The nitrogen source is one of cyanamide, dicyandiamide, melamine, urea；The catalysis carbon-forming agent be cobalt chloride,
The mixture of one or both of frerrous chloride.
2. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 1, it is characterised in that: the phosphorus
The mass ratio in source, nitrogen source and carbon forming agent is 0.1~0.5:1 :~2.5.
3. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 1, it is characterised in that: the water
Bath temperature is 60~90 DEG C, and calcination process uses from room temperature degree and is warming up to calcination temperature, and the calcining heating rate is 2.0
~5.0 DEG C/min, calcination temperature is 600~900 DEG C, and calcination time is 2~4h.
4. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 1, it is characterised in that: the acid
For concentrated hydrochloric acid enriching nitric acid, volume ratio 3:1.
5. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 1, it is characterised in that: the phosphorus nitrogen
The existence form of the carbon nano-tube material phosphorus of codope includes metal phosphide, phosphorous oxides, phosphorus carbide, and the content of phosphorus is 1
~10wt%.
6. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 1, it is characterised in that: the phosphorus nitrogen
The existence form of the carbon nano-tube material nitrogen of codope includes pyridine nitrogen, graphite mould nitrogen and oxidized form nitrogen, and the content of nitrogen is 3~
13wt%.
7. the nitrogen co-doped carbon nano-tube material preparation process of phosphorus according to claim 5 or 6, it is characterised in that: described
The nitrogen co-doped carbon nano-tube material of phosphorus be used for electrocatalytic oxidation reduction reaction.
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| CN109728246B (en) * | 2018-12-13 | 2021-08-06 | 太原理工大学 | Nitrogen-phosphorus co-doped ordered mesoporous carbon material and preparation method and application thereof |
| CN109573983B (en) * | 2019-01-25 | 2022-03-11 | 青岛科技大学 | Transition metal filled carbon nanotube, preparation method and application |
| CN110683530A (en) * | 2019-08-26 | 2020-01-14 | 广西大学 | Method for in-situ synthesis of cobalt-nitrogen co-doped carbon nano tube |
| CN110518238B (en) * | 2019-08-27 | 2022-04-26 | 江苏大学 | Synthesis of sodium ion battery anode material Na based on organic phosphonic acid3V2(PO4)3Nitrogen-doped carbon and preparation method thereof |
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| CN103183330B (en) * | 2013-04-02 | 2015-02-25 | 中国矿业大学 | Controllable synthesis method for nitrogen and phosphorus co-doped graphitized carbon ball with hollow structure |
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