CN105293483B - A kind of method that original position prepares transient metal doped porous graphene - Google Patents

A kind of method that original position prepares transient metal doped porous graphene Download PDF

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CN105293483B
CN105293483B CN201510900841.2A CN201510900841A CN105293483B CN 105293483 B CN105293483 B CN 105293483B CN 201510900841 A CN201510900841 A CN 201510900841A CN 105293483 B CN105293483 B CN 105293483B
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transition metal
graphene
chitosan
doped porous
porous graphene
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CN105293483A (en
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木士春
刘小波
王哲
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a kind of method that original position prepares transient metal doped porous graphene.Specific steps include:The preparation of chitosan/transition metal particles complex:The salting liquid of transition metal is well mixed with chitosan aqueous solution, glacial acetic acid solution is added dropwise, is sufficiently stirred for being formed colloid, freeze-dried formation chitosan foam, the salt of the transition metal and the mass ratio of chitosan are 1:5‑50;Chitosan foam is placed in non-oxidizing atmosphere and calcined, the mixture of transition metal/graphene is made under the catalysis of transition metal;By the mixture and K of transition metal/graphene2HPO4Solid phase is blended, and is placed in non-oxidizing atmosphere and calcines after ball milling;Pickling removes which part transition metal and impurity, and vacuum drying is produced.Catalytic conversion and corrasion of the present invention by transition metal, using chitosan as raw material, remove transition metal particles with reference to pickling, prepare transient metal doped porous graphene, suitable for large-scale promotion.

Description

A kind of method that original position prepares transient metal doped porous graphene
Technical field
The present invention relates to porous carbon materials and field of nanometer material technology, specifically a kind of original position prepares transient metal doped many The method of hole graphene.
Background technology
Graphene is the two-dimentional allotrope of carbon.From 2004, Geim etc. [1] was successfully separated out graphene using adhesive tape Since, graphene rapidly becomes the study hotspot in the whole world.Graphene integrates numerous good characteristics, such as high carrier migration Rate, good translucency, high heat conductance, high mechanical properties and high electrochemical stability etc..Wherein, most peculiar part is stone The electric property that the unique electronic structure of black alkene is shown, electron-trajectory transport such as at room temperature, unusual quantum hall effect With quantum tunneling effect etc..Carbon atom in graphene is with SP2Hybridized orbit and adjacent carbon atom formation σ keys, remaining P electricity Sub-track then constitutes pi bond, therefore electron cloud is symmetric in carbon atom plane both sides.This bonding mode is similar with phenyl ring, So graphene can regard the condensed-nuclei aromatics being made up of a large amount of phenyl ring as.Although CNT and fullerene also have SP2Hydridization Structure, but the angle between the carbon atom of bonding is less than 120 °, 120 ° of intrinsic angle differences with graphene, this is just determined Graphene carbon atom it is active relatively low.The existing method for preparing graphene is mainly oxidation-reduction method, micromechanics stripping method, liquid Phase stripping method, epitaxial growth method, chemical vapour deposition technique and arc process etc..These methods exist that cost is higher and yield compared with Low the problem of, such as in oxidation-reduction method, graphene is easily reunited in the liquid phase, reduces the quality of graphene.
Recently, porous graphene material receives extensive research, and due to the pore structure of porous graphene in itself, it has Higher specific surface area and the passage for storing and transporting beneficial to electrons/ions, gas and liquid.Such as Ruoff [2] uses KOH Activation process graphene oxide, prepares the super capacitor material of higher energy density and specific capacitance.[3] such as wooden scholar's spring are used Acid treatment graphene oxide, obtains porous graphene, and the carrier of the noble metal catalyst as Proton Exchange Membrane Fuel Cells, Drastically increase the mass transfer ability of Catalytic Layer.Graphene is as a kind of new carbon material, and introducing will pole after loose structure The earth improves some shortcomings that graphene is present, and particularly the porous graphene after heterogeneous nonmetal doping can be extensive It is applied to energy storage and conversion art, such as fuel cell and lithium ion battery [4,5].
The technology of preparing of the catforming of current graphene is more ripe, chemical vapour deposition technique [6] be based on The catalytic action of metal (such as Ni-based, copper-based) is crossed, solid-state or gaseous carbon source are converted into graphene at a certain temperature Method.For the catalysis corrasion of transition metal, Chinese patent literature CN102849734A then discloses " a kind of with transition The method that metal or transistion metal compound prepare porous graphene for activator ", this method utilizes transition metal and its chemical combination Thing catalysis etching graphene sheet layer, loose structure is obtained with this.But this method is that, using graphene as raw material, cost is higher, no It is suitable for large-scale promotion.And for the report of transient metal doped graphene, such as Dai [7] is by cobalt acetate and graphene oxide Mixing, is made the graphene of cobaltosic oxide doping after hydro-thermal reaction, and the composite material exhibits go out excellent oxygen reduction activity. But do not possess loose structure with this obtained graphene, and the cobaltosic oxide of load easily comes off from graphenic surface.
Therefore, herein by the catalytic conversion and corrasion of transition metal and its compound, by the chitosan after carbonization Graphene is partially converted into, then pickling removes part metals particle, obtains the porous graphene material of transition metal original position doping Material.
[1]Novoselov K S,Geim A K,Morozov S V,et al.Electric field effect in atomically thin carbon films[J].science,2004,306(5696):666-669.
[2]Zhu Y,Murali S,Stoller M D,et al.Carbon-based supercapacitors produced by activation of graphene[J].Science,2011,332(6037):1537-1541.
[3]Cheng K,He D,Peng T,et al.Porous graphene supported Pt catalysts for proton exchange membrane fuel cells[J].Electrochimica Acta,2014,132:356- 363.
[4]Xiao J,Mei D,Li X,et al.Hierarchically porous graphene as a lithium–air battery electrode[J].Nano letters,2011,11(11):5071-5078.
[5]Han S,Wu D,Li S,et al.Porous graphene materials for advanced electrochemical energy storage and conversion devices[J].Advanced Materials, 2014,26(6):849-864.
[6]Reina A,Jia X,Ho J,et al.Large area,few-layer graphene films on arbitrary substrates by chemical vapor deposition[J].Nano letters,2008,9(1): 30-35.
[7]Liang Y,Li Y,Wang H,et al.Co3O4nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction[J].Nature materials,2011, 10(10):780-786.
The content of the invention
The technical problems to be solved by the invention are for transient metal doped porous graphene porous stone in the prior art There is provided a kind of method that original position prepares transient metal doped porous graphene for deficiency present in black alkene preparation.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of method that original position prepares transient metal doped porous graphene, specific steps include:
(1) preparation of chitosan/transition metal particles complex:The salting liquid of transition metal and chitosan aqueous solution are mixed Close uniform, glacial acetic acid solution is added dropwise, is sufficiently stirred for forming colloid, freeze-dried formation chitosan foam, the transition metal Salt and chitosan mass ratio be 1:5-50;
(2) by chitosan foam be placed in non-oxidizing atmosphere calcine, under the catalysis of transition metal be made transition metal/ The mixture of graphene;
(3) by the mixture and K of transition metal/graphene2HPO4Solid phase is blended, and non-oxidizing gas are placed in after ball milling Calcined in atmosphere;
(4) pickling removes which part transition metal and impurity, and transient metal doped porous graphite can be made in vacuum drying Alkene.
In such scheme, the transition metal described in step (1) is in platinum, palladium, iron, cobalt, nickel, copper, gold, silver, zinc, chromium One or more.
In such scheme, the chitosan aqueous solution concentration described in step (1) is 20mg/mL~50mg/mL.
In such scheme, the concentration of salt solution of the transition metal described in step (1) is 0.5mg/mL~10mg/mL.
In such scheme, the glacial acetic acid solution consumption described in step (1) is the 0.5%~3% of mixed liquor volume.
In such scheme, the mixing time described in step (1) is 1~12h.
In such scheme, non-oxidizing atmosphere described in step (2), (4) be one kind in argon gas, nitrogen, hydrogen or It is several.
In such scheme, the calcining heat described in step (2) is 700~1200 DEG C, and soaking time is 1~5h, heating speed Rate is 3~10 DEG C/min.
In such scheme, carbon material mixture and K described in step (3)2HPO4Mass ratio be 1~4:4~1, during ball milling Between be 4-6h.
In such scheme, the calcining heat described in step (3) is 700~1100 DEG C, and heating rate is 3~8 DEG C/min, is protected The warm time is 1~5h.
In such scheme, in step (4), one kind in sulfuric acid, hydrochloric acid, acetic acid, nitric acid, chloroazotic acid of described acid or It is several.
In such scheme, in step (4), the concentration of pickling is 1~6mol/L.
In such scheme, in step (4), the temperature of vacuum drying treatment is 40~80 DEG C, and drying time is 1~24h.
Transition metal salt and chitosan are mixed after gel by the present invention, and metal ion will effectively be adsorbed in chitosan In skeleton, dewater treatment is made using the method for lyophilized auxiliary, and in calcining carbonization in reacting furnace, obtain transistion metal compound with The mixture of carbon, in the process, metallic can play a part of catalyst and etching agent, and carbon material is catalytically conveted into stone Black alkene.Then K is utilized2HPO4At high temperature carbon material is carried out activation process to open carbon-coating, promote acid solution to penetrate into carbon-coating In, part metals particle is removed, so that transient metal doped porous graphene is made.
The invention has the advantages that:Catalytic conversion and corrasion of the present invention by transition metal, using chitosan as raw material, Chitosan nitrogenous characteristic in itself is taken full advantage of, transition metal particles is removed with reference to pickling, common carbon source can be converted into Metal-doped porous graphene is crossed, it is suitable for large-scale promotion.And this technique is relatively simple, the cycle is short and cost is relatively low, prepares Porous graphene pore structure enrich, pore-size distribution is wide, and hole density is big, passes through and changes the addition of transition metal salt and can adjust hole Density;It is with low cost not using graphene oxide or graphene as raw material, it can be mass-produced.It may be used on fuel cell In catalyst, lithium ion battery negative material and ultracapacitor, with extensive prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of transient metal doped porous graphene.
Wherein:(a), (b) is the porous graphene region without transition metal;(c) it is porous graphene cladding transition gold The region of category.
Fig. 2 is the Raman spectrogram of transient metal doped porous graphene.
Wherein:(a) it is the Raman spectrogram for the mixture for calcining obtained transition metal/graphene for the first time, (b) is warp Pickling removes the Raman spectrogram of transition metal.
Fig. 3 is the XRD spectrum of transient metal doped porous graphene.
Embodiment
Content for a better understanding of the present invention, is further illustrated below with reference to instantiation.But should refer to Go out, implementation of the invention is not limited to following several embodiments.
Embodiment 1
1g chitosans are scattered in 30ml deionized waters, 10mL acetic acid cobalt liquors are added, solution concentration is 10mg/mL, Ultrasonic 30min, then stirring 5h formation chitosan colloids under 2.5% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is turned Move in freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, Protective atmosphere is high-purity argon gas, and heating rate is 3 DEG C/min, and is incubated 2h at 800 DEG C, obtains transition metal/graphene Mixture.By transition metal/graphene mixture and K2HPO4By 1:3 mass ratio solid phase mixing, and in planetary ball mill Middle grinding 4h, transfers in vacuum tube furnace and calcines, protective atmosphere is high-purity argon gas, is risen to by 5 DEG C/min heating rate 900 DEG C, it is incubated 2h.Hydrochloric acid solution pickling of the reaction product through 6mol/L after calcining, and filtering and washing is to neutrality, it is true at 60 DEG C Sky is dried, and transition metal cobaltosic oxide doping porous graphene is made.As shown in Fig. 1 (a), the region is transmission electron microscope observing Under porous graphene low power image, with abundant porous network structure.After amplified, it is observed that obvious ring Shape graphene lattice fringe, and the removal that middle hole is due to transition metal is caused, such as shown in Fig. 1 (b).And in Fig. 1 (c) in, clearly cobaltosic oxide metal lattice striped is occurred in that, surrounding is then the graphene layer of cladding.Fig. 2 Raman spectrums Show, in 2700cm in the Raman spectrogram of the mixture of transition metal/graphene after calcining for the first time-1There is graphite in place The 2D peaks of alkene, I (D)/I (G) value is 1.13, shows just to have obtained I (D)/I after graphene, pickling by first time calcining (G) value rises to 1.53, and this is due to the removal of cobaltosic oxide and causes the formation of a large amount of hole defects.Fig. 3 is then four oxidations The XRD spectrum of three cobalt doped porous graphenes, wherein, 2 θ=21.8 ° are (002) peak of graphene, when 2 θ are 32 °, 37 °, 45 ° (220) of cobaltosic oxide, (311), (400) peak are corresponded to respectively.
Embodiment 2
1g chitosans are scattered in 50ml deionized waters, 8mL iron nitrate solutions are added, solution concentration is 5mg/mL, surpassed Sound 30min, then stirring 12h formation chitosan colloids under 0.9% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is turned Move in freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, Protective atmosphere is high pure nitrogen, and heating rate is 5 DEG C/min, and is incubated 2h at 700 DEG C, obtains transition metal/graphene Mixture.By transition metal/graphene mixture and K2HPO4By 1:4 mass ratio solid phase mixing, and in planetary ball mill Middle grinding 4h, transfers in vacuum tube furnace and calcines, protective atmosphere is high pure nitrogen, is risen to by 3 DEG C/min heating rate 800 DEG C, it is incubated 1h.Sulfuric acid solution pickling of the reaction product through 1mol/L after calcining, and filtering and washing is to neutrality, it is true at 40 DEG C Sky is dried, and transient metal doped porous graphene is made.
Embodiment 3
1g chitosans are scattered in 20ml deionized waters, 40mL acetic acid zinc solutions are added, solution concentration is 0.5mg/mL, Ultrasonic 30min, then stirring 8h formation chitosan colloids under 3% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is shifted Into freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, protected Shield atmosphere is high-purity argon gas, and heating rate is 4 DEG C/min, and is incubated 1h at 1000 DEG C, obtains the mixed of transition metal/graphene Compound.By transition metal/graphene mixture and K2HPO4By 1:2 mass ratio solid phase mixing, and in planetary ball mill Grinding 5h, transfers in vacuum tube furnace and calcines, protective atmosphere is high-purity argon gas, and 700 are risen to by 8 DEG C/min heating rate DEG C, it is incubated 3h.Acetum pickling of the reaction product through 2mol/L after calcining, and filtering and washing is to neutrality, vacuum at 70 DEG C Dry, transient metal doped porous graphene is made.
Embodiment 4
1g chitosans are scattered in 40ml deionized waters, the ammino platinum solution of 4mL dinitrosos two is added, solution concentration is 8mg/mL, ultrasonic 30min, then stirring 4h formation chitosan colloids under 0.5% glacial acetic acid solution, normal temperature are slowly added dropwise.Shell is gathered Carbohydrate gum body is transferred in freeze drier, and chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum In tube furnace, protective atmosphere is hydrogen, and heating rate is 6 DEG C/min, and is incubated 4h at 900 DEG C, obtains transition metal/graphite The mixture of alkene.By transition metal/graphene mixture and K2HPO4By 1:1 mass ratio solid phase mixing, and in planetary ball Grinding 5h in grinding machine, transfers in vacuum tube furnace and calcines, protective atmosphere is hydrogen, is risen to by 5 DEG C/min heating rate 1000 DEG C, it is incubated 2h.Wang aqueous solution pickling of the reaction product through 3mol/L after calcining, and filtering and washing is to neutrality, at 50 DEG C Vacuum drying, is made transient metal doped porous graphene.
Embodiment 5
1g chitosans are scattered in 30ml deionized waters, 5mL dichlorodiamine palladium solution are added, solution concentration is 10mg/ ML, ultrasonic 30min, then stirring 6h formation chitosan colloids under 2% glacial acetic acid solution, normal temperature are slowly added dropwise.By chitosan colloid It is transferred in freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace In, protective atmosphere is hydrogen, and heating rate is 5 DEG C/min, and is incubated 5h at 800 DEG C, obtains the mixed of transition metal/graphene Compound.By transition metal/graphene mixture and K2HPO4By 2:1 mass ratio solid phase mixing, and in planetary ball mill Grinding 4h, transfers in vacuum tube furnace and calcines, protective atmosphere is hydrogen, and 900 DEG C are risen to by 6 DEG C/min heating rate, It is incubated 4h.Wang aqueous solution pickling of the reaction product through 3mol/L after calcining, and filtering and washing is to neutrality, vacuum is done at 60 DEG C It is dry, transient metal doped porous graphene is made.
Embodiment 6
1g chitosans are scattered in 40ml deionized waters, 20mL nickel acetate solutions are added, solution concentration is 5mg/mL, surpassed Sound 30min, then stirring 8h formation chitosan colloids under 2.8% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is shifted Into freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, protected Shield atmosphere is high pure nitrogen, and heating rate is 10 DEG C/min, and is incubated 1h at 1100 DEG C, obtains transition metal/graphene Mixture.By transition metal/graphene mixture and K2HPO4By 3:1 mass ratio solid phase mixing, and in planetary ball mill Middle grinding 6h, transfers in vacuum tube furnace and calcines, protective atmosphere is high pure nitrogen, is risen to by 4 DEG C/min heating rate 1000 DEG C, it is incubated 2h.Hydrochloric acid solution pickling of the reaction product through 4mol/L after calcining, and filtering and washing is to neutrality, at 40 DEG C Vacuum drying, is made transient metal doped porous graphene.
Embodiment 7
1g chitosans are scattered in 30ml deionized waters, 10mL silver nitrate solutiones are added, solution concentration is 5mg/mL, surpassed Sound 30min, then stirring 1h formation chitosan colloids under 1.5% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is shifted Into freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, protected Shield atmosphere is high-purity argon gas, and heating rate is 8 DEG C/min, and is incubated 1h at 1200 DEG C, obtains the mixed of transition metal/graphene Compound.By transition metal/graphene mixture and K2HPO4By 1:1 mass ratio solid phase mixing, and in planetary ball mill Grinding 4h, transfers in vacuum tube furnace and calcines, protective atmosphere is high-purity argon gas, and 800 are risen to by 6 DEG C/min heating rate DEG C, it is incubated 5h.Salpeter solution pickling of the reaction product through 6mol/L after calcining, and filtering and washing is to neutrality, vacuum at 40 DEG C Dry, transient metal doped porous graphene is made.
Embodiment 8
1g chitosans are scattered in 40ml deionized waters, 10mL copper-baths are added, solution concentration is 20mg/mL, Ultrasonic 30min, then stirring 10h formation chitosan colloids under 1.25% glacial acetic acid solution, normal temperature are slowly added dropwise.By chitosan colloid It is transferred in freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace In, protective atmosphere is hydrogen, and heating rate is 4 DEG C/min, and is incubated 2h at 1000 DEG C, obtains transition metal/graphene Mixture.By transition metal/graphene mixture and K2HPO4By 1:4 mass ratio solid phase mixing, and in planetary ball mill Middle grinding 6h, transfers in vacuum tube furnace and calcines, protective atmosphere is hydrogen, and 1100 are risen to by 5 DEG C/min heating rate DEG C, it is incubated 2h.Salpeter solution pickling of the reaction product through 2mol/L after calcining, and filtering and washing is to neutrality, vacuum at 40 DEG C Dry, transient metal doped porous graphene is made.
Embodiment 9
1g chitosans are scattered in 20ml deionized waters, 5mL chlorauric acid solutions are added, solution concentration is 4mg/mL, surpassed Sound 30min, then stirring 8h formation chitosan colloids under 2% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is transferred to In freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, protected Atmosphere is high-purity argon gas, and heating rate is 8 DEG C/min, and is incubated 3h at 800 DEG C, obtains the mixing of transition metal/graphene Thing.By transition metal/graphene mixture and K2HPO4By 1:2 mass ratio solid phase mixing, and the powder in planetary ball mill 5h is ground, transfers in vacuum tube furnace and calcines, protective atmosphere is high-purity argon gas, and 800 are risen to by 5 DEG C/min heating rate DEG C, it is incubated 3h.Wang aqueous solution pickling of the reaction product through 3mol/L after calcining, and filtering and washing is to neutrality, vacuum at 40 DEG C Dry, transient metal doped porous graphene is made.
Embodiment 10
1g chitosans are scattered in 30ml deionized waters, 10mL acetic acid chromium solutions are added, solution concentration is 20mg/mL, Ultrasonic 30min, then stirring 5h formation chitosan colloids under 3% glacial acetic acid solution, normal temperature are slowly added dropwise.Chitosan colloid is shifted Into freeze drier, chitosan foam is made after dehydration completely.Then chitosan foam is placed in vacuum tube furnace, protected Shield atmosphere is high pure nitrogen, and heating rate is 4 DEG C/min, and is incubated 3h at 1100 DEG C, obtains the mixed of transition metal/graphene Compound.By transition metal/graphene mixture and K2HPO4By 4:1 mass ratio solid phase mixing, and in planetary ball mill Grinding 5h, transfers in vacuum tube furnace and calcines, protective atmosphere is high pure nitrogen, and 900 are risen to by 3 DEG C/min heating rate DEG C, it is incubated 1h.Salpeter solution pickling of the reaction product through 1mol/L after calcining, and filtering and washing is to neutrality, vacuum at 80 DEG C Dry, transient metal doped porous graphene is made.
The characterizing method of reference implementation example 1, has carried out transmission electron microscope etc. to the embodiment 2-10 materials prepared and has characterized, as a result Show that embodiment 2-10 has prepared transient metal doped porous graphene.

Claims (9)

1. a kind of method that original position prepares transient metal doped porous graphene, it is characterised in that:Specific steps include:
(1)The preparation of chitosan/transition metal particles complex:The salting liquid of transition metal is mixed with chitosan aqueous solution It is even, glacial acetic acid solution is added dropwise, is sufficiently stirred for forming colloid, freeze-dried formation chitosan foam, the salt of the transition metal Mass ratio with chitosan is 1:5-50;Step(1)Described transition metal be selected from platinum, palladium, iron, cobalt, nickel, copper, gold, silver, zinc, One or more in chromium;
(2)Chitosan foam is placed in 700 ~ 1200 DEG C of calcinings in non-oxidizing atmosphere, was made under the catalysis of transition metal Cross the mixture of Metal/grapheme;
(3)By the mixture and K of transition metal/graphene2HPO4Solid phase is blended, and is placed in after ball milling in non-oxidizing atmosphere Calcining;
(4)Pickling removes which part transition metal and impurity, and transient metal doped porous graphene can be made in vacuum drying.
2. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (1)Described chitosan aqueous solution concentration is 20mg/mL ~ 50mg/mL;Step(1)The concentration of salt solution of described transition metal For 0.5mg/mL ~ 10mg/mL.
3. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (1)Described glacial acetic acid solution consumption is the 0.5% ~ 3% of mixed liquor volume;Step(1)Described mixing time is 1 ~ 12h.
4. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (2)、(3)Described non-oxidizing atmosphere is the one or several kinds in argon gas, nitrogen, hydrogen.
5. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (2)Calcining soaking time used is 1 ~ 5h, and heating rate is 3 ~ 10 DEG C/min.
6. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (3)Described transition metal/graphene and K2HPO4Mass ratio be 1~4:4~1, Ball-milling Time is 4-6h.
7. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (3)Described calcining heat is 700 ~ 1100 DEG C, and heating rate is 3 ~ 8 DEG C/min, and soaking time is 1 ~ 5h.
8. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (4)In, the described sour one or several kinds in sulfuric acid, hydrochloric acid, acetic acid, nitric acid, chloroazotic acid.
9. the method that original position according to claim 1 prepares transient metal doped porous graphene, it is characterised in that:Step (4)In, the concentration of spent pickling acid is 1 ~ 6mol/L;The temperature of vacuum drying treatment is 40 ~ 80 DEG C, and drying time is 1 ~ 24h.
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