CN108298518A - A kind of preparation method of the carbon material of single atomic dispersion - Google Patents
A kind of preparation method of the carbon material of single atomic dispersion Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the carbon material of single atomic dispersion, belong to technical field of new material preparation.The preparation method of the material is obtained from calcining the hybrid precursor of the porphyrin organic backbone for being coordinated transition metal in porphyrin ring and the porphyrin organic backbone for being coordinated transition metal in carbon material or porphyrin ring with polymer formation under certain temperature and atmospheric condition.Its mesoporphyrin organic backbone is that porphyrin and derivatives of porphyrin structural unit are formed by connecting by covalent bond；Porphyrin organic backbone forms hybrid with polymer with carbon material or porphyrin organic backbone by intermolecular force；Resulting materials are transition metal single atomic dispersion in carbon material skeleton.The preparation method has higher monatomic density and stability using the porphyrin organic backbone precursor for suitably forming monatomic site, resulting materials, and synthetic method is simple, and yield is high, is suitable for a variety of transition metal, can largely prepare the carbon material of single atomic dispersion.
Description
Technical field
The invention belongs to technical field of new material preparation, and in particular to a kind of preparation side of the carbon material of single atomic dispersion
Method.
Background technology
One of the critical issue that control accurate is material science is carried out to material on an atomic scale.The material of single atomic dispersion
Expect due to specific chemical constitution, ultra high density atom positions and fully exposed active sites, in catalysis, the energy, electricity
Son, sensing and the fields such as biology show wide application prospect.Wherein, monodispersed transition metal atoms are carried on carbon skeleton
Not only the high density with monatomic material, height expose monatomic active site to material, while it is highly conductive also to show carbon material
Property, the advantages such as high-specific surface area and abundant pore structure, there is higher diversity in chemical composition and shape characteristic, therefore
It has received widespread attention.
However, the means that are effectively synthesized of monatomic material do not obtain also adequately developing and studying at present.For monodisperse
Transition metal atoms are carried on carbon skeleton material system, and current main synthesis strategy is that pyrolysis contains transition metal and carbon skeleton
Precursor to prepare the carbon material of single atomic dispersion.Yuanjun Chen et al. report a kind of based on the organic bone of pyrogenic metal
Frame material prepares the material that monatomic iron is carried on graphene, shows higher hydrogen reduction electro-chemical activity (Yuanjun
Chen et al.,Angewandte Chemie International Edition,2017,56,1).Ruiguo Cao et al.
It reports and a kind of higher energy storage is shown based on the pyrolysis iron standby monatomic iron of the peptide cyanines material that is carried on carbon nanotube live
Property with stability (Ruiguo Cao et al., Nature Communications, 2013,4,2076).
Although the carbon material of single transition metal atoms dispersion is prepared in some researchs, it is easy, effective with it is big
Carbon material of the synthesis with the monatomic site density of higher transition metal of scale is still very difficult.In high temperature pyrolysis process
In, transition metal atoms tend to self-assemble or form carbide with carbon skeleton, greatly reduce single atomic dispersion state
Transition metal sites.Simultaneously as under high temperature carbon precursor unstability, transition metal it is monatomic around chemical composition
It is uncontrollable with structure.These factors all greatly constrain effectively constructing and apply for monatomic material.For high temperature pyrolysis body
System, the regulation and control to its precursor are the key factors that orientation constructs product after pyrolysis.Therefore, selection is single former with suitable construction
Sub- material precursor constructs monatomic and surrounding chemical structural points in advance, is the efficient preparation monatomic site material of high density
Effective means.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of the carbon material of single atomic dispersion, and the technical solution taken is such as
Under：
A kind of preparation method of the carbon material of single atomic dispersion, which is characterized in that this method contains following steps：
1) transition will be coordinated in the porphyrin organic backbone for being coordinated transition metal in porphyrin ring and carbon material or porphyrin ring
The hybrid that the porphyrin organic backbone of metal is formed with polymer is positioned over as precursor in reactor, in the load of inert gas
It is heated to 400-1100 DEG C under gas atmosphere；Wherein transition metal is coordinated in the form of single atomic dispersion in porphyrin organic backbone
Precursor is used as in hybrid；
2) constant temperature is calcined for 1-48 hours after reactor reaches above-mentioned temperature, calcining at constant temperature processing after stop heating and
It is cooled to room temperature under controlled atmosphere；
3) product after above-mentioned calcining is taken out, acid solution is added thereto to remove impurity, fully by product after reaction
Filtration washing obtains the carbon material of transition metal single atomic dispersion.
The carbon material of the single atomic dispersion is transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag
With one or more of Au is above is scattered in carbon material skeleton with monoatomic existence form.
The hybrid that the porphyrin organic backbone is formed with carbon material or porphyrin organic backbone with polymer is by porphyrin
Organic backbone is formed with polymer by intermolecular force with carbon material or porphyrin organic backbone；Its mesoporphyrin organic backbone is
The organic backbone that porphyrin and derivatives of porphyrin are connected by covalent bond；The mass ratio of carbon material and porphyrin organic backbone is 1:
0.1-1:10；The mass ratio 1 of polymer and porphyrin organic backbone:0.1-1:10.
The interior ring hetero atom of the porphyrin and derivatives of porphyrin is the one or more of N, O and S；Inner ring coordination atom
For one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au, match to coordination atom single atomic dispersion
Position is in porphyrin inner ring；The porphyrin organic backbone is two dimension or three-dimensional structure.
Preferably, the carbon material is graphite, graphene, carbon nanotube, carbon fiber or carbon black；The polymer is poly- second
Alkene, polypropylene, polystyrene, polyaniline, Kynoar or polytetrafluoroethylene (PTFE).
The monatomic coordination with porphyrin organic backbone precursor of transition metal in the carbon material of the single atomic dispersion
Transition metal atoms type is identical.
Preferably, the inert gas is one kind in nitrogen, argon gas or helium, and the flow of inert gas is 100-
500mL min-1.The acid is the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid, a concentration of 1-10mol L-1。
The temperature of the acid processing procedure is 25-100 DEG C, and the reaction time is 1-24 hours.
The present invention has the following advantages the technique effect of high-lighting：The carbon material of the single atomic dispersion, due to it
The complex for the single atomic dispersion that porphyrin organic backbone precursor mesoporphyrin is formed with transition metal, has effectively constructed monatomic position
Point structure so that monatomic carbon material derived from it has higher monatomic site density and stability.The conjunction of the material
It is simple and effective at method, it is suitable for a variety of transition metal, can be largely prepared and be scattered in carbon with single transition metal atoms
The material system of skeleton provides higher application prospect for it in catalysis, the energy, sensing, biology and the fields such as electronics.
Specific implementation mode
The present invention provides a kind of preparation methods of the carbon material of single atomic dispersion, specifically comprise the following steps：
1) transition will be coordinated in the porphyrin organic backbone for being coordinated transition metal in porphyrin ring and carbon material or porphyrin ring
The hybrid that the porphyrin organic backbone of metal is formed with polymer is positioned over as precursor in reactor, in the load of inert gas
It is heated to 400-1100 DEG C under gas atmosphere；Wherein transition metal is coordinated in the form of single atomic dispersion in porphyrin organic backbone
Precursor is used as in hybrid；The carbon material of the single atomic dispersion be transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
One or more in Zn, Pd, Pt, Ag and Au are scattered in monoatomic existence form in carbon material skeleton；Described
The hybrid that porphyrin organic backbone is formed with carbon material or porphyrin organic backbone with polymer is by porphyrin organic backbone and carbon materials
Material or porphyrin organic backbone are formed with polymer by intermolecular force；Its mesoporphyrin organic backbone is that porphyrin and porphyrin derive
The organic backbone that object is connected by covalent bond；The mass ratio of carbon material and porphyrin organic backbone is 1:0.1-1:10；Polymer
With the mass ratio 1 of porphyrin organic backbone:0.1-1:10；The interior ring hetero atom of the porphyrin and derivatives of porphyrin is the one of N, O and S
Kind or more than one；Inner ring coordination atom is one kind or several in Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au
Kind, it is coordinated in porphyrin inner ring to coordination atom single atomic dispersion；The porphyrin organic backbone is two dimension or three-dimensional structure；It is described
Carbon material is graphite, graphene, carbon nanotube, carbon fiber or carbon black；The polymer be polyethylene, polypropylene, polystyrene,
Polyaniline, Kynoar or polytetrafluoroethylene (PTFE)；Transition metal in the carbon material of the single atomic dispersion is monatomic and porphyrin
Complexed transition metal atomic species in organic backbone precursor is identical；The inert gas is in nitrogen, argon gas or helium
One kind, the flow of inert gas is 100-500mL min-1；
2) constant temperature is calcined for 1-48 hours after reactor reaches above-mentioned temperature, calcining at constant temperature processing after stop heating and
It is cooled to room temperature under controlled atmosphere；
3) product after above-mentioned calcining is taken out, acid solution is added thereto to remove impurity, fully by product after reaction
Filtration washing obtains the carbon material of transition metal single atomic dispersion；The acid is hydrochloric acid, sulfuric acid, nitric acid, acetic acid and hydrofluoric acid
In a kind of aqueous solution, a concentration of 1-10mol L-1；The temperature of the acid processing procedure is 25-100 DEG C, and the reaction time is
1-24 hours.
The present invention is described further with reference to embodiment, so that those skilled in the art further understand
The present invention.
Embodiment 1
N porphyrins organic backbone and graphene hybrid that 10.0g Co are coordinated are placed in reactor, in 100mL min-1
800 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 12 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 150mL is added
1mol L-1Hydrochloric acid solution and be transferred in 500mL flasks, 12 hours are reacted under the conditions of 50 DEG C to go out decontamination.Fully reaction
Afterwards, product is filtered, three times with ethyl alcohol washing, dries at 60 DEG C 24 hours and spread out to get the N porphyrin organic backbones being coordinated to Co
The carbon material of raw monatomic Co dispersions.Test shows that the content of monatomic Co is 3.1%.
Embodiment 2
O porphyrins organic backbone and Kynoar hybrid that 15.0g Pd are coordinated are placed in reactor, in 200mL
min-1650 DEG C are warming up under the argon gas atmosphere of flow, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature
48 hours.Stop heating after constant temperature processing, is cooled to room temperature under protection of argon gas.Then calcined product is taken out, is added
250mL5mol L-1Salpeter solution and be transferred in 500mL flasks, 24 hours are reacted under the conditions of 25 DEG C to go out decontamination.Fully
After reaction, product is filtered, three times with ethyl alcohol washing, 24 hours are dried at 80 DEG C to get the organic bone of O porphyrins being coordinated to Pd
The carbon material of monatomic Pd dispersions derived from frame.Test shows that the content of monatomic Pd is 4.2%.
Embodiment 3
S porphyrins organic backbone and carbon fiber hybrid that 15.0g Cu are coordinated are placed in reactor, in 500mL min-1
1100 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 20 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 6 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 250mL is added
3mol L-1Sulfuric acid solution and be transferred in 500mL flasks, 1 hour is reacted under the conditions of 65 DEG C to go out decontamination.Fully reaction
Afterwards, product is filtered, three times with ethyl alcohol washing, dries at 60 DEG C 24 hours and spread out to get the S porphyrin organic backbones being coordinated to Cu
The carbon material of raw monatomic Cu dispersions.Test shows that the content of monatomic Cu is 2.9%.
Embodiment 4
N porphyrins organic backbone that 20.0g Mn are coordinated and polyaniline hybridized object are placed in reactor, in 250mL min-1
400 DEG C are warming up under the helium atmosphere of flow, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 1 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under helium protection.Then calcined product is taken out, 150mL is added
10mol L-1Acetic acid solution and be transferred in 500mL flasks, 2 hours are reacted under the conditions of 100 DEG C to go out decontamination.Fully reaction
Afterwards, product is filtered, three times with ethyl alcohol washing, dries at 60 DEG C 24 hours and spread out to get the N porphyrin organic backbones being coordinated to Mn
The carbon material of raw monatomic Mn dispersions.Test shows that the content of monatomic Mn is 4.3%.
Embodiment 5
S porphyrins organic backbone and graphite hybrid that 10.0g Cr are coordinated are placed in reactor, in 500mL min-1Stream
600 DEG C are warming up under the nitrogen atmosphere of amount, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 20 hours.
Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 250mL 6mol are added
L-1Hydrofluoric acid solution and be transferred in 500mL flasks, 12 hours are reacted under the conditions of 30 DEG C to go out decontamination.Fully after reaction,
Product is filtered, three times with ethyl alcohol washing, dries at 60 DEG C 24 hours and derives to get the S porphyrin organic backbones being coordinated to Cr
Monatomic Cr dispersion carbon material.Test shows that the content of monatomic Cr is 3.2%.
Embodiment 6
N porphyrins organic backbone and carbon nano-tube hybridization object that 15.0g Ti are coordinated are placed in reactor, in 300mL
min-1800 DEG C are warming up under the argon gas atmosphere of flow, heating rate is 25 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature
3 hours.Stop heating after constant temperature processing, is cooled to room temperature under protection of argon gas.Then calcined product is taken out, is added
150mL2mol L-1Hydrochloric acid solution and be transferred in 500mL flasks, 6 hours are reacted under the conditions of 75 DEG C to go out decontamination.Fully
After reaction, product is filtered, three times with ethyl alcohol washing, 24 hours are dried at 60 DEG C to get the organic bone of N porphyrins being coordinated to Ti
The carbon material of monatomic Ti dispersions derived from frame.Test shows that the content of monatomic Ti is 2.9%.
Embodiment 7
O porphyrins organic backbone and polypropylene hybrid that 10.0g Ag are coordinated are placed in reactor, in 100mL min-1
550 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 15 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 8 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 150mL is added
9mol L-1Acetic acid solution and be transferred in 500mL flasks, 12 hours are reacted under the conditions of 95 DEG C to go out decontamination.Fully reaction
Afterwards, product is filtered, three times with ethyl alcohol washing, dries at 60 DEG C 24 hours and spread out to get the O porphyrin organic backbones being coordinated to Ag
The carbon material of raw monatomic Ag dispersions.Test shows that the content of monatomic Ag is 3.8%.
Embodiment 8
N porphyrins organic backbone and polyethylene hybrid that 25.0g Zn are coordinated are placed in reactor, in 250mL min-1
1000 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 20 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 12 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 120mL1mol is added
L-1Sulfuric acid solution and be transferred in 500mL flasks, 24 hours are reacted under the conditions of 25 DEG C to go out decontamination.It, will fully after reaction
Product filters, and three times with ethyl alcohol washing, 24 hours is dried at 70 DEG C to get derived from the N porphyrin organic backbones being coordinated to Zn
The carbon material of monatomic Zn dispersions.Test shows that the content of monatomic Zn is 4.6%.
Embodiment 9
N porphyrins organic backbone and polystyrene hybrid that 12.0g Fe are coordinated are placed in reactor, in 500mL
min-1750 DEG C are warming up under the helium atmosphere of flow, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature
18 hours.Stop heating after constant temperature processing, is cooled to room temperature under helium protection.Then calcined product is taken out, is added
100mL1mol L-1Hydrofluoric acid solution and be transferred in 500mL flasks, 1 hour is reacted under the conditions of 40 DEG C to go out decontamination.It fills
Point reaction after, product is filtered, with ethyl alcohol washing three times, dried at 60 DEG C 24 hours it is organic to get the N porphyrins being coordinated to Fe
The carbon material of monatomic Fe dispersions derived from skeleton.Test shows that the content of monatomic Fe is 2.6%.
Embodiment 10
O porphyrins organic backbone and graphene hybrid that 5.0g Pt are coordinated are placed in reactor, in 150mL min-1Stream
1100 DEG C are warming up under the nitrogen atmosphere of amount, heating rate is 20 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 12 is small
When.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, 500mL is added
3mol L-1Salpeter solution and be transferred in 1L flasks, 3 hours are reacted under the conditions of 40 DEG C to go out decontamination.It, will fully after reaction
Product filters, and three times with ethyl alcohol washing, 24 hours is dried at 60 DEG C to get derived from the O porphyrin organic backbones being coordinated to Pt
The carbon material of monatomic Pt dispersions.Test shows that the content of monatomic Pt is 4.5%.
Embodiment 11
N porphyrins organic backbone and carbon black hybrid that 10.0g V are coordinated are placed in reactor, in 150mL min-1Flow
Argon gas atmosphere under be warming up to 400 DEG C, heating rate is 5 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 24 hours.It is permanent
Stop heating after temperature processing, is cooled to room temperature under protection of argon gas.Then calcined product is taken out, 250mL 5mol L are added-1
Hydrochloric acid solution and be transferred in 500mL flasks, 4 hours are reacted under the conditions of 70 DEG C to go out decontamination.Fully after reaction, by product
Filtering three times with ethyl alcohol washing dries 24 hours to get monatomic derived from the N porphyrin organic backbones being coordinated to V at 60 DEG C
The carbon material of V dispersions.Test shows that the content of monatomic V is 2.9%.
Embodiment 12
The N porphyrins organic backbone of the bis- coordinations of 15.0g Co, Ni and carbon nano-tube hybridization object are placed in reactor,
200mL min-1950 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 10 DEG C of min-1.Reactor reaches above-mentioned temperature
Afterwards, constant temperature 24 hours.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, is added
Enter 200mL 5mol L-1Sulfuric acid solution and be transferred in 500mL flasks, 12 hours are reacted under the conditions of 80 DEG C to go out decontamination.
Fully after reaction, product is filtered, three times with ethyl alcohol washing, 24 hours are dried at 60 DEG C to get to the N of the bis- coordinations of Co, Ni
The carbon material of monatomic Co, Ni dispersion derived from porphyrin organic backbone.Test shows that the content of monatomic Co is 2.6%；Dan Yuan
The content of sub- Ni is 2.6%.
Embodiment 13
S porphyrins organic backbone and graphene hybrid that 5.0g Cu are coordinated are placed in reactor, in 500mL min-1Stream
550 DEG C are warming up under the helium atmosphere of amount, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature 1 hour.
Stop heating after constant temperature processing, is cooled to room temperature under helium protection.Then calcined product is taken out, 150mL 9mol are added
L-1Acetic acid solution and be transferred in 500mL flasks, 6 hours are reacted under the conditions of 100 DEG C to go out decontamination.It, will fully after reaction
Product filters, and three times with ethyl alcohol washing, 24 hours is dried at 60 DEG C to get derived from the S porphyrin organic backbones being coordinated to Cu
The carbon material of monatomic Cu dispersions.Test shows that the content of monatomic Cu is 3.3%.
Embodiment 14
The O porphyrins organic backbone of the bis- coordinations of 25.0g Pt, Pd and graphene hybrid are placed in reactor, in 200mL
min-11000 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 10 DEG C of min-1.It is permanent after reactor reaches above-mentioned temperature
Temperature 12 hours.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, is added
500mL2mol L-1Hydrofluoric acid solution and be transferred in 1L flasks, 12 hours are reacted under the conditions of 60 DEG C to go out decontamination.Fully
After reaction, product is filtered, three times with ethyl alcohol washing, 24 hours are dried at 60 DEG C to get to the O porphyrins of the bis- coordinations of Pt, Pd
The carbon material of monatomic Pt, Pd dispersion derived from organic backbone.Test shows that the content of monatomic Pt is 2.9%；Monatomic Pd
Content be 2.1%.
Embodiment 15
N porphyrins organic backbone and polytetrafluoroethylene (PTFE) hybrid that 8.0g Ni are coordinated are placed in reactor, in 200mL
min-1600 DEG C are warming up under the nitrogen atmosphere of flow, heating rate is 10 DEG C of min-1.After reactor reaches above-mentioned temperature, constant temperature
3 hours.Stop heating after constant temperature processing, is cooled to room temperature under nitrogen protection.Then calcined product is taken out, is added
100mL2mol L-1Salpeter solution and be transferred in 500mL flasks, 4 hours are reacted under the conditions of 40 DEG C to go out decontamination.Fully
After reaction, product is filtered, three times with ethyl alcohol washing, 24 hours are dried at 60 DEG C to get the organic bone of N porphyrins being coordinated to Ni
The carbon material of monatomic Ni dispersions derived from frame.Test shows that the content of monatomic Ni is 3.4%.
Embodiment 16
S porphyrins organic backbone and polystyrene hybrid that 15.0g Au are coordinated are placed in reactor, in 400mL
min-11100 DEG C are warming up under the argon gas atmosphere of flow, heating rate is 20 DEG C of min-1.It is permanent after reactor reaches above-mentioned temperature
Temperature 8 hours.Stop heating after constant temperature processing, is cooled to room temperature under protection of argon gas.Then calcined product is taken out, is added
250mL1mol L-1Hydrofluoric acid solution and be transferred in 500mL flasks, 6 hours are reacted under the conditions of 25 DEG C to go out decontamination.It fills
Point reaction after, product is filtered, with ethyl alcohol washing three times, dried at 70 DEG C 24 hours it is organic to get the S porphyrins being coordinated to Au
The carbon material of monatomic Au dispersions derived from skeleton.Test shows that the content of monatomic Au is 4.0%.
Claims (9)
1. a kind of preparation method of the carbon material of single atomic dispersion, which is characterized in that this method contains following steps：
1) transition metal will be coordinated in the porphyrin organic backbone for being coordinated transition metal in porphyrin ring and carbon material or porphyrin ring
The hybrid that is formed of porphyrin organic backbone and polymer be positioned in reactor as precursor, in the carrier gas gas of inert gas
It is heated to 400-1100 DEG C under atmosphere；Wherein transition metal is coordinated in the form of single atomic dispersion in porphyrin organic backbone hydridization
Precursor is used as in object；
2) constant temperature is calcined for 1-48 hours after reactor reaches above-mentioned temperature, stops heating after calcining at constant temperature processing and in inertia
It is cooled to room temperature under gas shielded；
3) product after above-mentioned calcining is taken out, acid solution is added thereto to remove impurity, fully filters product after reaction
Washing, obtains the carbon material of transition metal single atomic dispersion.
2. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that the list
The carbon material of atom dispersion is one kind or several in transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au
Kind is scattered in monoatomic existence form in carbon material skeleton.
3. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that the porphin
The hybrid that quinoline organic backbone is formed with carbon material or porphyrin organic backbone with polymer is by porphyrin organic backbone and carbon material
Or porphyrin organic backbone is formed with polymer by intermolecular force；Its mesoporphyrin organic backbone is porphyrin and derivatives of porphyrin
The organic backbone connected by covalent bond；The mass ratio of carbon material and porphyrin organic backbone is 1:0.1-1:10；Polymer with
The mass ratio 1 of porphyrin organic backbone:0.1-1:10.
4. a kind of preparation method of the carbon material of single atomic dispersion according to claim 3, which is characterized in that the organic bone of porphyrin
In the hybrid that frame is formed with carbon material or porphyrin organic backbone with polymer, the miscellaneous original of inner ring of the porphyrin and derivatives of porphyrin
Son is the one or more of N, O and S；Inner ring coordination atom is in Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au
One or more, be coordinated in porphyrin inner ring to coordination atom single atomic dispersion；The porphyrin organic backbone is two dimension or three
Tie up structure.
5. a kind of preparation method of the carbon material of single atomic dispersion according to claim 3, it is characterised in that:The porphyrin
In the hybrid that organic backbone and carbon material or porphyrin organic backbone are formed with polymer, the carbon material be graphite, graphene,
Carbon nanotube, carbon fiber or carbon black；The polymer be polyethylene, polypropylene, polystyrene, polyaniline, Kynoar or
Polytetrafluoroethylene (PTFE).
6. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that described single former
The monatomic complexed transition metal atomic species with porphyrin organic backbone precursor of transition metal in the carbon material of son dispersion
It is identical.
7. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that described is lazy
Property gas be one kind in nitrogen, argon gas or helium, the flow of inert gas is 100-500mL min-1。
8. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that the acid
For the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid, molar concentration is 1-10mol L-1。
9. a kind of preparation method of the carbon material of single atomic dispersion according to claim 1, which is characterized in that the acid
The temperature of processing procedure is 25-100 DEG C, and the reaction time is 1-24 hours.
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