CN105293483A - In-situ preparation method of transition metal doped porous graphene - Google Patents
In-situ preparation method of transition metal doped porous graphene Download PDFInfo
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- CN105293483A CN105293483A CN201510900841.2A CN201510900841A CN105293483A CN 105293483 A CN105293483 A CN 105293483A CN 201510900841 A CN201510900841 A CN 201510900841A CN 105293483 A CN105293483 A CN 105293483A
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Abstract
The invention relates to an in-situ preparation method of transition metal doped porous graphene. The in-situ preparation method concretely comprises the following steps of preparing a chitosan/transition metal particle complex, namely uniformly mixing a salt solution of transition metal and a water solution of chitosan, dropwise adding a glacial acetic acid solution, sufficiently stirring to form a colloid, and carrying out freeze drying to obtain chitosan foam, wherein the mass ratio of the transition metal to the chitosan is 1:(5-50); calcining the chitosan foam in a non-oxidative atmosphere, and preparing a transition metal/graphene mixture under the catalysis of the transition metal; blending the transition metal/graphene mixture and a K2HPO4 solid, and calcining in a non-oxidative atmosphere after ball milling; and pickling to remove part of transition metal and impurities, and carrying out vacuum drying to obtain the transition metal doped porous graphene. The transition metal doped porous graphene is prepared by pickling chitosan serving as a raw material to remove transition metal particles by virtue of the catalytic conversion and etching effects of the transition metal, and therefore, the in-situ preparation method is suitable for large-scale popularization.
Description
Technical field
The present invention relates to porous carbon materials and field of nanometer material technology, is a kind of method that original position prepares transient metal doped porous graphene specifically.
Background technology
Graphene is the two-dimentional allotropic substance of carbon.From 2004, since Geim etc. [1] utilize adhesive tape successfully to isolate Graphene, Graphene becomes rapidly the study hotspot in the whole world.Graphene integrates numerous good characteristic, as high carrier mobility, good light transmission, high heat conductance, high mechanical strength and high electrochemical stability etc.Wherein, the most peculiar part is the electric property that the electronic structure of Graphene uniqueness shows, as the electron-trajectory transport under room temperature, unusual quantum hall effect and quantum tunneling effect etc.Carbon atom in Graphene is with SP
2hybridized orbital and adjacent carbon atom form σ key, and remaining P electronic orbit then forms π key, and therefore electronic cloud is symmetric in carbon atom plane both sides.This one-tenth key mode and phenyl ring similar, so Graphene can regard the condensed-nuclei aromatics be made up of a large amount of phenyl ring as.Although carbon nanotube and soccerballene also have SP
2hybrid structure, but the angle between the carbon atom of Cheng Jian is less than 120 °, and the 120 ° angles intrinsic from Graphene are different, and this activity just determining graphene carbon atom is lower.The existing method preparing Graphene is mainly oxidation reduction process, micromechanics stripping method, liquid phase stripping method, epitaxial growth method, chemical Vapor deposition process and arc process etc.These methods also exist the problem that cost is higher and productive rate is lower, and as in oxidation reduction process, Graphene is easily reunited in the liquid phase, reduce the quality of Graphene.
Recently, porous graphene material receives to be studied widely, due to the pore structure of porous graphene itself, and its passage that there is higher specific surface area and be beneficial to electrons/ions, gas and liquid storage and transport.As [2] such as Ruoff adopt KOH activation treatment graphene oxide, prepare the super capacitor material of higher energy density and ratio capacitance.Wood scholar's spring etc. [3] adopts acid treatment graphene oxide, obtains porous graphene, and the carrier of noble metal catalyst as Proton Exchange Membrane Fuel Cells, drastically increase the mass transfer ability of Catalytic Layer.Graphene is as a kind of novel carbon material, the some shortcomings that Graphene exists greatly will be improved after introducing vesicular structure, porous graphene particularly after heterogeneous nonmetal doping can be widely applied to energy storage and conversion art, as fuel cell and lithium ion battery etc. [4,5].
The technology of preparing of the catforming of current Graphene is comparatively ripe, chemical Vapor deposition process [6] is namely the katalysis based on transition metal (as Ni-based, copper base), at a certain temperature carbon source that is solid-state or gaseous state is converted into the method for Graphene.For the catalysis corrasion of transition metal, Chinese patent literature CN102849734A then discloses " a kind of with transition metal or transistion metal compound for the method for porous graphene prepared by activator ", the method utilizes transition metal and compound for catalysis etching graphene sheet layer thereof, obtains vesicular structure with this.But the method is raw material with Graphene, and cost is higher, is not suitable for promoting on a large scale.And for the report of transient metal doped Graphene, as cobaltous acetate mixes with graphene oxide by [7] such as Dai, the Graphene of obtained tricobalt tetroxide doping after hydro-thermal reaction, this composite material exhibits goes out excellent oxygen reduction activity.But do not possess vesicular structure with the Graphene that this obtains, and the tricobalt tetroxide of load easily comes off from graphenic surface.
Therefore, herein by catalytic conversion and the corrasion of transition metal and compound thereof, the chitosan after carbonization is partially converted into Graphene, and then pickling removes part metals particle, obtains the porous graphene material that transition metal is in-situ doped.
[1]NovoselovKS,GeimAK,MorozovSV,etal.Electricfieldeffectinatomicallythincarbonfilms[J].science,2004,306(5696):666-669.
[2]ZhuY,MuraliS,StollerMD,etal.Carbon-basedsupercapacitorsproducedbyactivationofgraphene[J].Science,2011,332(6037):1537-1541.
[3]ChengK,HeD,PengT,etal.PorousgraphenesupportedPtcatalystsforprotonexchangemembranefuelcells[J].ElectrochimicaActa,2014,132:356-363.
[4]XiaoJ,MeiD,LiX,etal.Hierarchicallyporousgrapheneasalithium–airbatteryelectrode[J].Nanoletters,2011,11(11):5071-5078.
[5]HanS,WuD,LiS,etal.Porousgraphenematerialsforadvancedelectrochemicalenergystorageandconversiondevices[J].AdvancedMaterials,2014,26(6):849-864.
[6]ReinaA,JiaX,HoJ,etal.Largearea,few-layergraphenefilmsonarbitrarysubstratesbychemicalvapordeposition[J].Nanoletters,2008,9(1):30-35.
[7]LiangY,LiY,WangH,etal.Co3O4nanocrystalsongrapheneasasynergisticcatalystforoxygenreductionreaction[J].Naturematerials,2011,10(10):780-786.
Summary of the invention
Technical problem to be solved by this invention is the deficiency for existing in porous graphene porous graphene preparation transient metal doped in prior art, provides a kind of original position to prepare the method for transient metal doped porous graphene.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Original position prepares a method for transient metal doped porous graphene, and concrete steps comprise:
(1) preparation of chitosan/transition metal particles complex body: the salts solution of transition metal is mixed with chitosan aqueous solution, drip glacial acetic acid solution, abundant stirring forms colloid, form chitosan foam through lyophilize, the salt of described transition metal and the mass ratio of chitosan are 1:5-50;
(2) chitosan foam is placed in non-oxidizing atmosphere to calcine, the mixture of obtained transition metal/Graphene under the catalysis of transition metal;
(3) by the mixture of transition metal/Graphene and K
2hPO
4solid phase is blended, is placed in non-oxidizing atmosphere calcines through ball milling;
(4) wherein section transitions metal and impurity are removed in pickling, and vacuum-drying can obtain transient metal doped porous graphene.
In such scheme, the transition metal described in step (1) be selected from platinum, palladium, iron, cobalt, nickel, copper, gold and 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 0.5% ~ 3% of mixed liquor volume.
In such scheme, the churning time described in step (1) is 1 ~ 12h.
In such scheme, step (2), non-oxidizing atmosphere described in (4) are one or several in argon gas, nitrogen, hydrogen.
In such scheme, the calcining temperature described in step (2) is 700 ~ 1200 DEG C, and soaking time is 1 ~ 5h, and temperature rise rate is 3 ~ 10 DEG C/min.
In such scheme, the carbon material mixture described in step (3) and K
2hPO
4mass ratio be 1 ~ 4:4 ~ 1, Ball-milling Time is 4-6h.
In such scheme, the calcining temperature described in step (3) is 700 ~ 1100 DEG C, and temperature rise rate is 3 ~ 8 DEG C/min, and soaking time is 1 ~ 5h.
In such scheme, in step (4), described acid be selected from sulfuric acid, hydrochloric acid, acetic acid, nitric acid, chloroazotic acid one or 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 time of drying is 1 ~ 24h.
After transition metal salt and chitosan are mixed and made into gel by the present invention, metal ion by active adsorption in chitosan skeleton, the auxiliary method of freeze-drying is adopted to make processed, and carbonization is calcined in Reaktionsofen, obtain the mixture of transistion metal compound and carbon, in the process, metallics can play the effect of catalyzer and etching agent, and carbon material is catalytically conveted to Graphene.Then K is utilized
2hPO
4at high temperature activation treatment is carried out to open carbon-coating to carbon material, promote that acid solution penetrates in carbon-coating, part metals particle is removed, thus obtained transient metal doped porous graphene.
Advantage of the present invention is: the present invention is by the catalytic conversion of transition metal and corrasion, take chitosan as raw material, take full advantage of the characteristic that chitosan itself is nitrogenous, combined acid washes away except transition metal particles, common carbon source can be converted into transient metal doped porous graphene, suitable for large-scale promotion.And this technique is comparatively simple, and the cycle is short and cost is lower, the porous graphene pore structure of preparation is enriched, and pore size distribution is wide, and hole density is large, by changing the density in the addition adjustable hole of transition metal salt; Not with graphene oxide or Graphene for raw material, with low cost, can be mass-produced.May be used on, in fuel-cell catalyst, lithium ion battery negative material and ultracapacitor, there is extensive prospect.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of transient metal doped porous graphene.
Wherein: (a), (b) are not containing the porous graphene region of transition metal; C () is the region of the coated transition metal of porous graphene.
Fig. 2 is the Raman spectrogram of transient metal doped porous graphene.
Wherein: (a) is the Raman spectrogram of the mixture calcining the transition metal/Graphene obtained for the first time, (b) is the Raman spectrogram through pickling removing transition metal.
Fig. 3 is the XRD figure spectrum of transient metal doped porous graphene.
Embodiment
In order to understand content of the present invention better, further illustrate below with reference to specific examples.But it is noted that enforcement of the present invention is not limited to following several embodiment.
Embodiment 1
Be scattered in 30ml deionized water by 1g chitosan, add 10mL cobaltous acetate solution, strength of solution is 10mg/mL, ultrasonic 30min, more slowly drips 2.5% glacial acetic acid solution, stirs 5h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high-purity argon gas, and temperature rise rate is 3 DEG C/min, and is incubated 2h at 800 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:3, and in planetary ball mill grinding 4h, transfer in vacuum tube furnace and calcine, protective atmosphere is high-purity argon gas, rises to 900 DEG C by the temperature rise rate of 5 DEG C/min, insulation 2h.Reaction product after calcining is through the hydrochloric acid soln pickling of 6mol/L, and filtering and washing is to neutral, vacuum-drying at 60 DEG C, obtained transition metal tricobalt tetroxide doping porous graphene.As shown in Fig. 1 (a), this region is the low power image of the porous graphene under transmission electron microscope observing, has abundant porous network structure.After amplifying, obvious ring-type Graphene lattice fringe can be observed, and the hole of centre is because removing of transition metal is caused, as shown in Fig. 1 (b).And in Fig. 1 (c), there is tricobalt tetroxide metal lattice striped clearly, be around then coated graphene layer.Fig. 2 Raman spectrum also shows, at 2700cm in the Raman spectrogram of the mixture of the transition metal/Graphene after first time calcining
-1there is the 2D peak of Graphene in place, I (D)/I (G) value is 1.13, show that calcining just obtains Graphene through first time, I (D) after pickling/I (G) value rises to 1.53, and this is the formation causing large number of orifices defect due to removing of tricobalt tetroxide.Fig. 3 is then the XRD figure spectrum of tricobalt tetroxide doping porous graphene, wherein, 2 θ=21.8 ° are (002) peak of Graphene, distinguish (220) of corresponding tricobalt tetroxide when 2 θ are 32 °, 37 °, 45 °, (311), (400) peak.
Embodiment 2
Be scattered in 50ml deionized water by 1g chitosan, add 8mL iron nitrate solution, strength of solution is 5mg/mL, ultrasonic 30min, more slowly drips 0.9% glacial acetic acid solution, stirs 12h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high pure nitrogen, and temperature rise rate is 5 DEG C/min, and is incubated 2h at 700 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:4, and in planetary ball mill grinding 4h, transfer in vacuum tube furnace and calcine, protective atmosphere is high pure nitrogen, rises to 800 DEG C by the temperature rise rate of 3 DEG C/min, insulation 1h.Reaction product after calcining is through the sulphuric acid soln pickling of 1mol/L, and filtering and washing is to neutral, vacuum-drying at 40 DEG C, obtained transient metal doped porous graphene.
Embodiment 3
Be scattered in 20ml deionized water by 1g chitosan, add 40mL acetic acid zinc solution, strength of solution is 0.5mg/mL, ultrasonic 30min, more slowly drips 3% glacial acetic acid solution, stirs 8h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high-purity argon gas, and temperature rise rate is 4 DEG C/min, and is incubated 1h at 1000 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:2, and in planetary ball mill grinding 5h, transfer in vacuum tube furnace and calcine, protective atmosphere is high-purity argon gas, rises to 700 DEG C by the temperature rise rate of 8 DEG C/min, insulation 3h.Reaction product after calcining is through the acetum pickling of 2mol/L, and filtering and washing is to neutral, vacuum-drying at 70 DEG C, obtained transient metal doped porous graphene.
Embodiment 4
Be scattered in 40ml deionized water by 1g chitosan, add 4mL dinitroso two ammino platinum solution, strength of solution is 8mg/mL, ultrasonic 30min, more slowly drips 0.5% glacial acetic acid solution, stirs 4h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is hydrogen, and temperature rise rate is 6 DEG C/min, and is incubated 4h at 900 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:1, and in planetary ball mill grinding 5h, transfer in vacuum tube furnace and calcine, protective atmosphere is hydrogen, rises to 1000 DEG C by the temperature rise rate of 5 DEG C/min, insulation 2h.Reaction product after calcining is through the wang aqueous solution pickling of 3mol/L, and filtering and washing is to neutral, vacuum-drying at 50 DEG C, obtained transient metal doped porous graphene.
Embodiment 5
Be scattered in 30ml deionized water by 1g chitosan, add 5mL dichlorodiamine palladium solution, strength of solution is 10mg/mL, ultrasonic 30min, more slowly drips 2% glacial acetic acid solution, stirs 6h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is hydrogen, and temperature rise rate is 5 DEG C/min, and is incubated 5h at 800 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 2:1, and in planetary ball mill grinding 4h, transfer in vacuum tube furnace and calcine, protective atmosphere is hydrogen, rises to 900 DEG C by the temperature rise rate of 6 DEG C/min, insulation 4h.Reaction product after calcining is through the wang aqueous solution pickling of 3mol/L, and filtering and washing is to neutral, vacuum-drying at 60 DEG C, obtained transient metal doped porous graphene.
Embodiment 6
Be scattered in 40ml deionized water by 1g chitosan, add 20mL nickel acetate solution, strength of solution is 5mg/mL, ultrasonic 30min, more slowly drips 2.8% glacial acetic acid solution, stirs 8h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high pure nitrogen, and temperature rise rate is 10 DEG C/min, and is incubated 1h at 1100 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 3:1, and in planetary ball mill grinding 6h, transfer in vacuum tube furnace and calcine, protective atmosphere is high pure nitrogen, rises to 1000 DEG C by the temperature rise rate of 4 DEG C/min, insulation 2h.Reaction product after calcining is through the hydrochloric acid soln pickling of 4mol/L, and filtering and washing is to neutral, vacuum-drying at 40 DEG C, obtained transient metal doped porous graphene.
Embodiment 7
Be scattered in 30ml deionized water by 1g chitosan, add 10mL silver nitrate solution, strength of solution is 5mg/mL, ultrasonic 30min, more slowly drips 1.5% glacial acetic acid solution, stirs 1h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high-purity argon gas, and temperature rise rate is 8 DEG C/min, and is incubated 1h at 1200 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:1, and in planetary ball mill grinding 4h, transfer in vacuum tube furnace and calcine, protective atmosphere is high-purity argon gas, rises to 800 DEG C by the temperature rise rate of 6 DEG C/min, insulation 5h.Reaction product after calcining is through the salpeter solution pickling of 6mol/L, and filtering and washing is to neutral, vacuum-drying at 40 DEG C, obtained transient metal doped porous graphene.
Embodiment 8
Be scattered in 40ml deionized water by 1g chitosan, add 10mL copper-bath, strength of solution is 20mg/mL, ultrasonic 30min, more slowly drips 1.25% glacial acetic acid solution, stirs 10h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is hydrogen, and temperature rise rate is 4 DEG C/min, and is incubated 2h at 1000 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:4, and in planetary ball mill grinding 6h, transfer in vacuum tube furnace and calcine, protective atmosphere is hydrogen, rises to 1100 DEG C by the temperature rise rate of 5 DEG C/min, insulation 2h.Reaction product after calcining is through the salpeter solution pickling of 2mol/L, and filtering and washing is to neutral, vacuum-drying at 40 DEG C, obtained transient metal doped porous graphene.
Embodiment 9
Be scattered in 20ml deionized water by 1g chitosan, add 5mL chlorauric acid solution, strength of solution is 4mg/mL, ultrasonic 30min, more slowly drips 2% glacial acetic acid solution, stirs 8h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high-purity argon gas, and temperature rise rate is 8 DEG C/min, and is incubated 3h at 800 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 1:2, and in planetary ball mill grinding 5h, transfer in vacuum tube furnace and calcine, protective atmosphere is high-purity argon gas, rises to 800 DEG C by the temperature rise rate of 5 DEG C/min, insulation 3h.Reaction product after calcining is through the wang aqueous solution pickling of 3mol/L, and filtering and washing is to neutral, vacuum-drying at 40 DEG C, obtained transient metal doped porous graphene.
Embodiment 10
Be scattered in 30ml deionized water by 1g chitosan, add 10mL chromium acetate solution, strength of solution is 20mg/mL, ultrasonic 30min, more slowly drips 3% glacial acetic acid solution, stirs 5h and form chitosan colloid under normal temperature.Chitosan colloid is transferred in freeze drier, obtained chitosan foam after dewatering completely.Then chitosan foam is placed in vacuum tube furnace, protective atmosphere is high pure nitrogen, and temperature rise rate is 4 DEG C/min, and is incubated 3h at 1100 DEG C, obtains the mixture of transition metal/Graphene.By transition metal/Graphene mixture and K
2hPO
4by the mass ratio solid phase mixing of 4:1, and in planetary ball mill grinding 5h, transfer in vacuum tube furnace and calcine, protective atmosphere is high pure nitrogen, rises to 900 DEG C by the temperature rise rate of 3 DEG C/min, insulation 1h.Reaction product after calcining is through the salpeter solution pickling of 1mol/L, and filtering and washing is to neutral, vacuum-drying at 80 DEG C, obtained transient metal doped porous graphene.
The characterizing method of reference example 1, has carried out the signs such as transmission electron microscope to material prepared by embodiment 2-10, and result shows that embodiment 2-10 has prepared transient metal doped porous graphene.
Claims (10)
1. original position prepares a method for transient metal doped porous graphene, it is characterized in that: concrete steps comprise:
(1) preparation of chitosan/transition metal particles complex body: the salts solution of transition metal is mixed with chitosan aqueous solution, drip glacial acetic acid solution, abundant stirring forms colloid, form chitosan foam through lyophilize, the salt of described transition metal and the mass ratio of chitosan are 1:5-50;
(2) chitosan foam is placed in non-oxidizing atmosphere to calcine, the mixture of obtained transition metal/Graphene under the catalysis of transition metal;
(3) by the mixture of transition metal/Graphene and K
2hPO
4solid phase is blended, is placed in non-oxidizing atmosphere calcines through ball milling;
(4) wherein section transitions metal and impurity are removed in pickling, and vacuum-drying can obtain transient metal doped porous graphene.
2. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the transition metal described in step (1) be selected from platinum, palladium, iron, cobalt, nickel, copper, gold and silver, zinc, chromium one or more.
3. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the chitosan aqueous solution concentration described in step (1) is 20mg/mL ~ 50mg/mL; The concentration of salt solution of the transition metal described in step (1) is 0.5mg/mL ~ 10mg/mL.
4. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the glacial acetic acid solution consumption described in step (1) is 0.5% ~ 3% of mixed liquor volume; Churning time described in step (1) is 1 ~ 12h.
5. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: step (2), non-oxidizing atmosphere described in (4) are one or several in argon gas, nitrogen, hydrogen.
6. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the calcining temperature described in step (2) is 700 ~ 1200 DEG C, and soaking time is 1 ~ 5h, and temperature rise rate is 3 ~ 10 DEG C/min.
7. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the carbon material mixture described in step (3) and K
2hPO
4mass ratio be 1 ~ 4:4 ~ 1, Ball-milling Time is 4-6h.
8. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: the calcining temperature described in step (3) is 700 ~ 1100 DEG C, and temperature rise rate is 3 ~ 8 DEG C/min, and soaking time is 1 ~ 5h.
9. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: in step (4), described acid be selected from sulfuric acid, hydrochloric acid, acetic acid, nitric acid, chloroazotic acid one or several.
10. original position according to claim 1 prepares the method for transient metal doped porous graphene, it is characterized in that: in step (4), and the concentration of pickling is 1 ~ 6mol/; The temperature of vacuum drying treatment is 40 ~ 80 DEG C, and time of drying is 1 ~ 24h.
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