CN108002378A - A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle - Google Patents
A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle Download PDFInfo
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- CN108002378A CN108002378A CN201711234794.8A CN201711234794A CN108002378A CN 108002378 A CN108002378 A CN 108002378A CN 201711234794 A CN201711234794 A CN 201711234794A CN 108002378 A CN108002378 A CN 108002378A
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Abstract
The present invention relates to field of inorganic materials, it is desirable to provide a kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle.It is in organic solvent, to make phosphinate that polymerization crosslinking reaction occur with the metal organic frame with surface-active hydroxyl；Reaction product removes metallic atom after carbonization treatment, then through pickling；Then by graphitization processing, the nitrogen-phosphor codoping carbon tube bundle of mechanical performance enhancing is obtained.After the present invention uses phosphinate modified metal organic frame, nitrogen-phosphor codoping carbon material can be obtained.The mechanical performance enhancing of carbon material after graphitization, phenomena such as effectively prevent reunion, structure collapses.Product after phosphinate is modified, its electrocatalysis characteristic are significantly improved, and splendid catalytic activity are not only shown in terms of oxygen reduction reaction, while preferable performance is also shown on oxygen evolution reaction.
Description
Technical field
The invention belongs to the field of inorganic material, and in particular to a kind of preparation of porous nitrogen-phosphor codoping carbon tube bundle and should
With.
Background technology
Metal-air battery (such as zinc and air cell) have energy conversion efficiency height, clean environment firendly, energy density greatly it is excellent
Point, is a kind of cleaning, efficient power generator.Develop the redox reactions on efficient catalytic metal-air battery cathode
(Oxygen Reduction Reaction, ORR) and oxygen evolution reaction (Oxygen Evolution Reaction, OER) are these
The key of battery technology development.Platinum is the effective catalyst for being catalyzed ORR at present, but its OER catalytic activity is poor, ruthenium and iridium
It is the effective catalyst for being catalyzed OER reactions, but its ORR activity is very low.Therefore develop and a kind of possess while be catalyzed ORR and OER
Bifunctional catalyst is of great significance.Using metal organic frame as predecessor, the porous carbon that is obtained after high temperature cabonization
Material has the advantages that specific surface area is big, avtive spot is more, is a kind of potential electrocatalysis material for substituting noble metal.Especially have
The porous carbon materials of three-dimensional intercommunication hollow structure, are more advantageous to the conveying of material, therefore the electro catalytic activity with higher.But
Most of porous carbon materials phenomena such as easy recurring structure caves in, reunites under the high temperature conditions, so as to destroy the material of porous carbon
Transmission channel influences catalytic activity.And the porous carbon materials of hollow structure lack support due to inside, it is easier to cave in existing
As.
Using ZnO as hard template and zinc source, there is provided zinc ion is reacted with 2-methylimidazole, can be in ZnO surfaces homoepitaxial
ZIF-8 (ZIF-8, zeolite imidazole ester frame structure material), forms ZnO@ZIF-8 core shell structures, then by high temperature cabonization, pickling
Remove ZnO, most can obtain the N doping porous carbon pipe of hollow structure through graphitization processing afterwards.Using ZnO clusters as template, you can obtain
The nitrogen-doped carbon tube bundle of hollow structure.But in high temperature graphitization processing procedure, nitrogen-doped carbon tube bundle can recurring structure cave in,
Shrinkage phenomenon, so as to influence electrocatalysis characteristic.Therefore exploitation one kind can strengthen porous carbon materials structure and can significantly improve carbon materials
The method of material electrocatalysis characteristic has important practical significance.The present invention carries out surface chemistry to metal organic frame before carbonization
Modification, so as to strengthen the mechanical performance of carbon material, makes it keep good structure and morphology in high-temperature process, while obtain nitrogen phosphorus
Codope product, significantly increases its electrocatalysis characteristic, and this method has no document report.
The content of the invention
The technical problem to be solved in the present invention is, overcome in the prior art carbon pipe with cave in shrink phenomena such as not
A kind of foot, there is provided preparation method structure-reinforced, that there is the nitrogen-phosphor codoping carbon tube bundle of efficient catalytic ORR and OER at the same time.This hair
It is bright by metal organic frame carry out surface modification, make to form covalent bond between its surface hydroxyl and phosphinate, so as to reach
To the purpose for strengthening carbon material mechanical strength in carbonisation.
To solve technical problem, solution of the invention is：
A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle is provided, is in organic solvent, to make hypophosphorous acid
With the metal organic frame with surface-active hydroxyl polymerization crosslinking reaction occurs for ester；Reaction product is after carbonization treatment, then passes through
Pickling removes metallic atom；Then by graphitization processing, the nitrogen-phosphor codoping carbon tube bundle of mechanical performance enhancing is obtained；
The preparation method of the metal organic frame with surface-active hydroxyl is：ZnO clusters are added to 2- methyl miaows
In the methanol solution of azoles, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, are done after then being washed successively with alcohol, water
It is dry spare.
In the present invention, shown in the structural formula such as formula (I) of the phosphinate：
In formula, R1, R2, the alkyl for each standing alone as C1~C4.
In the present invention, the organic solvent is any one in acetone, butanone, tetrahydrofuran or toluene.
In the present invention, the phosphinate and the mass ratio of metal organic frame that are added when polymerization crosslinking is reacted and started
For 1: 2.5-25；It is 80-150 DEG C to control the temperature that polymerization crosslinking reacts, when the reaction time is 5-48 small.
In the present invention, the mass concentration of the phosphinate solution added is 0.1%~1%.
In the present invention, the carburizing temperature is 450-550 DEG C.
In the present invention, the graphitization temperature is 700-1100 DEG C, time during graphitization processing for 2-4 it is small when.
In the present invention, when preparing metal organic frame, the ratio of the methanol solution of ZnO clusters and 2-methylimidazole is 1g:
20-50ml, and the concentration of the methanol solution of 2-methylimidazole is 0.1M/L.
Inventive principle describes：
The present invention utilizes activity hydroxy existing for metal organic frame surface, by with the P-H of high activity in phosphinate,
P-O key reactive polymerics, form the phosphorous polymer to interweave on surface, are then carbonized again after high temperature, in molecular level to porous carbon
The mechanical performance of material is strengthened, so that porous carbon materials effectively prevent structure collapses and reunite existing under the high temperature conditions
As (attached drawing 4,5).In addition phosphorous polymer provides phosphorus source, and the 2-methylimidazole in ZIF-8 provides abundant nitrogen source, so that
Nitrogen-phosphor codoping porous carbon materials (attached drawing 7,8) have been obtained at high temperature.Above-mentioned two aspects factor result in nitrogen phosphorus and is co-doped with jointly
Miscellaneous carbon tube bundle has the ORR catalytic performance (attached drawing 9) more prominent than platinum carbon, its limiting current density (5.3mA/cm2) ratio is not
Product (the 4.1mA/cm modified through phosphinate2) significantly increase, it has been even more than platinum carbon；Initial reduction current potential (0.92) with not
The product (0.83) of modification is compared and has shuffled 90mV.In terms of OER, the nitrogen-phosphor codoping product after modification has lower catalysis
The current density of overpotential and bigger, shows obvious OER catalytic activity.
Compared with the prior art, the beneficial effects of the invention are as follows：
1st, relative in the prior art without modification direct graphitization after product compared with, the present invention use phosphinate
After modified metal organic frame, nitrogen-phosphor codoping carbon material can be obtained.The mechanical performance enhancing of carbon material after graphitization, effectively
Phenomena such as avoiding reunion, structure collapses (Fig. 4).The carbon carbon tube bundle of same quality, the bulk product bigger after modification is (after modification
Almost it is twice than modification front volume), illustrate to shrink and obtained obvious improvement phenomena such as caving in.
2nd, the product after phosphinate is modified, its electrocatalysis characteristic is significantly improved, not only anti-in hydrogen reduction
Answer aspect to show splendid catalytic activity, while preferable performance is also shown on oxygen evolution reaction.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of ZnO clusters；
Fig. 2 is the scanning electron microscope (SEM) photograph of ZnO@ZIF-8 clusters；
Fig. 3 is the scanning electron microscope (SEM) photograph without the nitrogen-doped carbon tube bundle of phosphinate modification；
Fig. 4 is the nitrogen-phosphor codoping carbon tube bundle scanning electron microscope (SEM) photograph being prepared after phosphinate is modified；
Fig. 5 is the nitrogen-phosphor codoping carbon tube bundle hollow structure figure being prepared after phosphinate is modified；
Fig. 6 is transmission electron microscope (TEM) figure of nitrogen-phosphor codoping carbon tube bundle hollow structure；
Fig. 7 is nitrogen-phosphor codoping carbon tube bundle x-ray photoelectron spectroscopy (XPS) wide range figure；
Fig. 8 is x-ray photoelectron spectroscopy (XPS) figure of the P element of nitrogen-phosphor codoping carbon tube bundle；
Fig. 9 is the nitrogen-phosphor codoping carbon that the nitrogen-doped carbon tube bundle being prepared without phosphinate modification is prepared with the present invention
The electro catalytic activity of tube bundle compares figure.(a) is oxygen reduction reaction linear scan curve map in figure, and (b) linearly sweeps for oxygen evolution reaction
Curve map is retouched, all catalyst loadings are 0.1mg/cm2。
Embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment 1
The methanol solution of 0.5g ZnO clusters (attached drawing 1), the 2-methylimidazole of 30mL 0.1M/L is added to tetra- poly- fluorine of 50mL
In reaction kettle, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, it is dry after being washed successively with alcohol, water.
By obtained ZnO@ZIF-8 clusters (0.5g, attached drawing 2), the hypophosphorous acid mono-n-butylester of 0.1% mass concentration of 20g third
Ketone solution is added in four poly- fluorine reaction kettles, when confined reaction 24 is small under the conditions of 110 DEG C, obtains chemically modified ZnO
ZIF-8 clusters, then by the ZnO ZIF-8 clusters after modification in nitrogen atmosphere, when carbonization 3 is small under the conditions of 550 DEG C, obtain ZnO
C, then ZnO templates and other materials containing Zn in ZnO@C are removed with the hydrochloric acid solution pickling of 1M/L, then frozen dried, obtain nothing
Metal nitrogen-phosphor codoping carbon tube bundle.Finally by nitrogen-phosphor codoping carbon tube bundle is placed in 850 DEG C, graphitization processing 3 is small under inert atmosphere
When, obtain the nitrogen-phosphor codoping carbon tube bundle of high electrocatalytic active.
As seen from Figure 4, after phosphinate is modified again high temperature graphitization processing porous carbon tube bundle, its pattern completely with
ZnO clusters are consistent, and obvious structure collapses and agglomeration do not occur, and attached drawing 5,6 illustrates the nitrogen-phosphor codoping obtained after modification
Carbon tube bundle has complete hollow structure, its carbon thickness of pipe wall is about 5nm.Attached drawing 7 illustrates after phosphinate is modified, graphitization
Nitrogen-phosphor codoping product has been obtained after processing, P is can see on XPS wide ranges2sPeak, Fig. 8 can be seen that P element doping after form
P-C keys and P-O keys.
Embodiment 2
The methanol solution of 0.5g ZnO clusters, the 2-methylimidazole of 30mL 0.1M/L is added to the poly- fluorine reaction kettles of 50mL tetra-
In, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, it is dry after being washed successively with alcohol, water.
The tetrahydrofuran of product ZnO@ZIF-8 clusters (0.5g), the hypophosphorous acid isobutyl ester of 0.2% mass concentration of 20g is molten
Liquid, under the conditions of 110 DEG C, when confined reaction 24 is small in four poly- fluorine reaction kettles, obtains chemically modified ZnO ZIF-8 clusters,
Then by the ZnO ZIF-8 clusters after modification under the conditions of 550 DEG C, when carbonization 3 is small in nitrogen atmosphere, ZnO C are obtained, then use
The hydrochloric acid solution pickling of 1M/L removes ZnO templates and other materials containing Zn in ZnO@C, then frozen dried, obtains no metal nitrogen
Phosphor codoping carbon tube bundle.Finally by when nitrogen-phosphor codoping carbon tube bundle is placed in 1100 DEG C, graphitization processing 4 is small under inert atmosphere, obtain
To the nitrogen-phosphor codoping carbon tube bundle of high electrocatalytic active.
Embodiment 3
The methanol solution of 0.5g ZnO clusters, the 2-methylimidazole of 20mL 0.1M/L is added to the poly- fluorine reaction kettles of 50mL tetra-
In, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, it is dry after being washed successively with alcohol, water.
By product ZnO@ZIF-8 clusters (0.5g), the butanone solution of the hypophosphorous acid methyl esters of 0.5% mass concentration of 20g, 80
Under the conditions of DEG C, when confined reaction 48 is small in four poly- fluorine reaction kettles, chemically modified ZnO ZIF-8 clusters are obtained, then will be repaiied
ZnO ZIF-8 clusters after decorations when carbonization 3 is small in nitrogen atmosphere, obtain ZnO C, then the hydrochloric acid with 1M/L under the conditions of 500 DEG C
Solution acid removes the ZnO templates and other materials containing Zn gone in ZnO C, then frozen dried, obtains no metal nitrogen-phosphor codoping carbon
Tube bundle.Finally by when nitrogen-phosphor codoping carbon tube bundle is placed in 950 DEG C, graphitization processing 2 is small under inert atmosphere, obtain high electro-catalysis and live
The nitrogen-phosphor codoping carbon tube bundle of property.
Embodiment 4
The methanol solution of 0.5g ZnO clusters, the 2-methylimidazole of 50mL 0.1M/L is added to the poly- fluorine reaction kettles of 100mL tetra-
In, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, it is dry after being washed successively with alcohol, water.
By product ZnO@ZIF-8 clusters (0.5g), the toluene solution of the hypophosphorous acid ethyl ester of 1% mass concentration of 20g, 150
Under the conditions of DEG C, when confined reaction 5 is small in four poly- fluorine reaction kettles, chemically modified ZnO ZIF-8 clusters are obtained, then will modification
ZnO ZIF-8 clusters afterwards when carbonization 3 is small in nitrogen atmosphere, obtain ZnO C under the conditions of 450 DEG C, then molten with the hydrochloric acid of 1M/L
Liquid pickling removes ZnO templates and other materials containing Zn in ZnO C, then frozen dried, obtains no metal nitrogen-phosphor codoping carbon pipe
Cluster.Finally by when nitrogen-phosphor codoping carbon tube bundle is placed in 700 DEG C, graphitization processing 3 is small under inert atmosphere, high electrocatalytic active is obtained
Nitrogen-phosphor codoping carbon tube bundle.
Comparative example
The 2-methylimidazole methanol solution of 0.5g ZnO clusters, 30mL 0.1M/L is added in the poly- fluorine reaction kettles of 50mL tetra-,
When reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, it is dry after being washed successively with alcohol, water.
By obtained ZnO ZIF-8 clusters in nitrogen atmosphere, when carbonization 3 is small under the conditions of 550 DEG C, ZnO C are obtained, then use
The hydrochloric acid solution pickling of 1M/L removes ZnO templates and other materials containing Zn in ZnO@C, then frozen dried, obtains nitrogen-doped carbon
Tube bundle.Finally by when nitrogen-doped carbon tube bundle is placed in 850 DEG C, graphitization processing 3 is small under inert atmosphere, nitrogen-doped carbon tube bundle is obtained.
Can be seen that by attached drawing 3, the porous carbon tube bundle modified without phosphinate, hence it is evident that recurring structure caves in phenomenon,
Its pattern differs larger with ZnO clusters, and under identical quality, its volume is much smaller than the product modified through phosphinate (repaiies
Almost it is twice than modification front volume after decorations), further explanation is shunk and problem of caving in；It can be seen that by attached drawing 9, with nitrogen phosphorus
Codope product is compared, the product modified without phosphinate, its ORR limiting current density is minimum, initial reduction current potential
Overpotential it is maximum, its OER catalytic performance is similarly poorer than nitrogen-phosphor codoping product.
Claims (8)
1. a kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle, it is characterised in that be in organic solvent, to make secondary
With the metal organic frame with surface-active hydroxyl polymerization crosslinking reaction occurs for phosphate；Reaction product after carbonization treatment,
Again metallic atom is removed through pickling；Then by graphitization processing, the nitrogen-phosphor codoping carbon tube bundle of mechanical performance enhancing is obtained；
The preparation method of the metal organic frame with surface-active hydroxyl is：ZnO clusters are added to 2-methylimidazole
In methanol solution, when reaction 3 is small under the conditions of 80 DEG C, ZnO ZIF-8 clusters are obtained, drying is standby after then being washed successively with alcohol, water
With.
2. according to the method described in claim 1, it is characterized in that, shown in the structural formula of the phosphinate such as formula (I)：
In formula, R1, R2, the alkyl for each standing alone as C1~C4.
3. according to the method described in claim 1, it is characterized in that, the organic solvent is acetone, butanone, tetrahydrofuran or first
Any one in benzene.
4. the according to the method described in claim 1, it is characterized in that, phosphinate added when polymerization crosslinking is reacted and started
Mass ratio with metal organic frame is 1: 2.5-25；It is 80-150 DEG C to control the temperature that polymerization crosslinking reacts, the reaction time
For 5-48 it is small when.
5. according to the method described in claim 1, it is characterized in that, the mass concentration of the phosphinate solution added is
0.1%~1%.
6. according to the method described in claim 1, it is characterized in that, the carburizing temperature is 450-550 DEG C.
7. according to the method described in claim 1, it is characterized in that, the graphitization temperature be 700-1100 DEG C, graphitization
When time during processing is 2-4 small.
8. according to the method described in claim 1, it is characterized in that, when preparing metal organic frame, ZnO clusters and 2- methyl miaows
The ratio of the methanol solution of azoles is 1g: 40-100ml, and the concentration of the methanol solution of 2-methylimidazole is 0.1M/L.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120238021A1 (en) * | 2011-03-18 | 2012-09-20 | William Marsh Rice University | Methods of synthesizing three-dimensional heteroatom-doped carbon nanotube macro materials and compositions thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
| US20140347785A1 (en) * | 2013-05-21 | 2014-11-27 | National Tsing Hua University | Supercapacitor and method for manufacturing electrode thereof |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105752960A (en) * | 2016-03-08 | 2016-07-13 | 兰州理工大学 | Sulfur and phosphorus co-doped mesoporous carbon material and preparation method thereof |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106475122A (en) * | 2016-10-14 | 2017-03-08 | 中国石油大学(华东) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst |
| CN106629671A (en) * | 2017-01-04 | 2017-05-10 | 苏州金泉新材料股份有限公司 | Preparation method of multifunctional nanocluster |
| CN106992076A (en) * | 2017-03-08 | 2017-07-28 | 北京化工大学 | A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material |
| CN107346825A (en) * | 2017-06-30 | 2017-11-14 | 北京化工大学 | Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof |
-
2017
- 2017-11-30 CN CN201711234794.8A patent/CN108002378B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120238021A1 (en) * | 2011-03-18 | 2012-09-20 | William Marsh Rice University | Methods of synthesizing three-dimensional heteroatom-doped carbon nanotube macro materials and compositions thereof |
| US20140347785A1 (en) * | 2013-05-21 | 2014-11-27 | National Tsing Hua University | Supercapacitor and method for manufacturing electrode thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105752960A (en) * | 2016-03-08 | 2016-07-13 | 兰州理工大学 | Sulfur and phosphorus co-doped mesoporous carbon material and preparation method thereof |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106475122A (en) * | 2016-10-14 | 2017-03-08 | 中国石油大学(华东) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst |
| CN106629671A (en) * | 2017-01-04 | 2017-05-10 | 苏州金泉新材料股份有限公司 | Preparation method of multifunctional nanocluster |
| CN106992076A (en) * | 2017-03-08 | 2017-07-28 | 北京化工大学 | A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material |
| CN107346825A (en) * | 2017-06-30 | 2017-11-14 | 北京化工大学 | Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YIMING LI ETAL: "Interlocked multi-armed carbon for stable oxygen", 《CHEM. COMMUN》 * |
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