CN104959134B - A kind of Heteroatom doping porous graphene elctro-catalyst and preparation and application and device - Google Patents
A kind of Heteroatom doping porous graphene elctro-catalyst and preparation and application and device Download PDFInfo
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- CN104959134B CN104959134B CN201510379585.7A CN201510379585A CN104959134B CN 104959134 B CN104959134 B CN 104959134B CN 201510379585 A CN201510379585 A CN 201510379585A CN 104959134 B CN104959134 B CN 104959134B
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Abstract
The invention belongs to carbon material and electrochemical field, a kind of Heteroatom doping porous graphene elctro-catalyst and its preparation and application and device are disclosed.Methods described is first by dense HNO3Add in graphene oxide water solution, sealing, ultrasonic reaction stands, poured into deionized water, centrifuges, and filters, and dries, obtains surface graphene oxide with holes；Surface graphene oxide with holes, Heteroatom doping source compound and solvent are well mixed, substrate surface is coated to, is freeze-dried, obtains solid film；The substrate for being loaded with solid film is placed in plasma high-temperature tubular reactor and reacted, Heteroatom doping porous graphene elctro-catalyst is obtained.Prepared elctro-catalyst has preferable hydrogen reduction electrocatalysis characteristic, in electrode material, with preferable electrochemical stability；It can be applied to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell and metal air battery cathodes Material Field.
Description
Technical field
The present invention relates to carbon material and electrochemical field, and in particular to a kind of Heteroatom doping porous graphene elctro-catalyst
And preparation method and application and device.
Background technology
Fuel cell (Fuel Cells) this chemical energy by fuel is efficient and is environmentally friendly directly translated into electric energy
New energy technology, because its have energy conversion efficiency height, effect on environment small (zero-emission or low emission), fuel variation
Many advantages, such as and receive significant attention；They are described as being the forth generation generation technology after waterpower, firepower, nuclear energy.And its
In Proton Exchange Membrane Fuel Cells be even more have the advantages that operating temperature is low, toggle speed is fast, be considered as most being hopeful replacement
Internal combustion engine turns into following automotive powerplant.At present, although the research to Proton Exchange Membrane Fuel Cells achieves to enter greatly very much
Exhibition, and there is the exemplary motor automobile using Proton Exchange Membrane Fuel Cells as power to emerge successively, but to realize PEM
The also substantial amounts of scientific and technical difficulty of fuel cell large-scale commercial application needs to go to capture.Wherein, cost height and short life
It is the two big outstanding problems for restricting Proton Exchange Membrane Fuel Cells development, and causes one of key factor of this two large problems to be
Elctro-catalyst.In the past, it is platinum or platinum alloy to be commercialized in fuel cell using most catalyst, but due to platinum scarcity of resources,
Expensive, mithridatism difference etc. limits its application in Proton Exchange Membrane Fuel Cells.Particularly negative electrode in battery, because of it
Oxygen reduction reaction (Oxygen reduction reaction, ORR) speed is far below the speed of anode fuel (such as hydrogen) oxidation reaction
Rate, so as to need the catalyst more high than anode to go to accelerate its oxygen reduction reaction process；Current pem fuel electricity
Pool cathode platinum carrying capacity accounts for 75% or so of the total platinum carrying capacity of battery.Therefore, developing low-cost, the ORR non-platinum catalysts of high activity come
Platinum carbon catalyst is substituted, it is considered to be reduction fuel cell cost, so as to realize the optimal path of its large-scale commercial application.
Graphene is because with unique physics, chemistry, mechanical performance, such as high theoretical specific surface area, excellent machinery is strong
Degree, good pliability and high electrical conductivity etc. and receive much concern, they be considered as capacitor, sensor, lithium ion battery,
The application prospect of light is suffered from terms of fuel cell.If the distinctive performance of graphene can be combined, carried out suitably
Good oxygen reduction catalytic activity is made it have after modification, so that applied to fuel battery cathod catalyst, it will be a meaning
The great work of justice.
Liu Yun boundarys seminar of Institute of Chemistry, Academia Sinica is made public for the first time using chemical vapour deposition technique and mixed within 2008
Miscellaneous graphene and preparation method thereof (CN101289181).Dai Hongjie seminars of other Stanford University have obtained nitrogen by electric heating
Doped graphene (Science 2009,324,768).So far, the preparation of doped graphene material and performance study are increasingly becoming
Focus of concern.(ACS Nano, 2010,4,1321-1326) has prepared N/C=4%'s with CVD for example, Qu etc.
Nitrogen-doped graphene, the number of plies is 2~8 layers.In 0.1M KOH solutions, with the working electrode of graphene modified although take-off potential ratio
The low 0.2V of Pt/C electrodes, but its current density is 3 times of Pt/C electrodes, and ORR reactions are carried out by 4 electronic processes.Parvez etc.
People (ACS Nano, 2012,6 (11), 9541-9550) is then predecessor with graphite oxide and cyanamide, by two-step thermal processing system
For nitrogen-doped graphene.First step heat treatment temperature is 500 DEG C, and the duration is 4 hours, and cyanamide is broken down into CN；Second step
Temperature is 800 DEG C, 900 DEG C or 1000 DEG C, forms the nitrogen-doped graphene of CN-G forms.TEM shows that this actual material is graphene
With the mixture of nitrogenous amorphous carbon.
The preparation method of current Heteroatom doping graphene film is mainly high-temperature direct thermal solution or chemical vapor deposition
Method.High-temperature direct thermal solution is that graphene oxide and Heteroatom doping source are (usual in higher temperature>800 DEG C) under, oxygen-containing function
Group's cracking produces a large amount of gases, and graphene oxide is reduced the graphene-doped bone of hetero atom simultaneously under the expansion of gas
Frame.Chemical vapour deposition technique generally synthesizes Heteroatom doping using carbon source and hetero atom source in the presence of metallic catalyst
Graphene, its synthesis temperature is generally also>800℃.Using both approaches, it has the disadvantage：1) operating condition is harsher, reaction
Temperature is high (generally>800 DEG C), the reaction time is long；2) reducing degree is not high, and C/O atomic ratios are only 10, thus have impact on hetero atom
The electric conductivity of doped graphene；3) doping level is not high, and Heteroatom doping amount is less than 10%, and whard to control；4) cost is prepared
It is high；5) graphene film is easily assembled made from, due to high-specific surface area, and graphene is easily gathered due to the strong Van der Waals force of interplanar
Collection.Therefore, this grapheme material, ion can only be migrated parallel on graphene planes direction, and perpendicular to its plane
Ion transfer speed on direction is relatively low.Hydrogen reduction occurs mainly in the edge of graphene film, and the practical efficiency of catalyst is low,
Greatly hinder application in the battery.
The content of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the invention is to provide a kind of Heteroatom doping many
The preparation method of hole graphene elctro-catalyst.The present invention using acid prepare different carbon/oxygen than surface graphene oxide with holes,
Surface graphene oxide with holes is mixed with Heteroatom doping source again, last using plasma method prepares out hetero atom
Adulterate porous graphene elctro-catalyst, by adjust various concentrations contain heteroatomic compound and plasma discharge parameter, can
To control heteroatomic doping content in elctro-catalyst, the state of foreign atom and structure etc..The reaction temperature of the present invention is low, anti-
Short between seasonable, prepared material structure is controllable.
Another object of the present invention is to provide the Heteroatom doping porous graphene prepared by above-mentioned preparation method
Elctro-catalyst.Elctro-catalyst specific surface area height prepared by the present invention, good electrical property, cost are low, oxygen reduction catalytic activity is good.
It is still another object of the present invention to provide the application of above-mentioned Heteroatom doping porous graphene elctro-catalyst.
It is still another object of the present invention to provide the device of the preparation method of Heteroatom doping porous graphene elctro-catalyst.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of Heteroatom doping porous graphene elctro-catalyst, specifically includes following steps：
(1) synthesis of surface graphene oxide with holes
Add water in graphene oxide, ultrasonic disperse obtains graphene oxide solution；Then under agitation, to
Dense HNO is added in container equipped with graphene oxide solution3, container sealing, ultrasonic reaction after standing, poured into deionized water,
Acid is removed in centrifugation, is purified, and is filtered, and is dried, is obtained surface graphene oxide with holes, standby；
(2) preparation of solid film
The surface graphene oxide with holes, Heteroatom doping source compound and solvent of step (1) is well mixed, applied
Covering liquid, is then coated to substrate surface by coating liquid, freeze-drying, obtains being supported on the surface graphene oxide with holes on substrate
With the solid film of the precursor containing hetero atom；
(3) prepared by the plasma method of Heteroatom doping porous graphene
The substrate of solid film that is loaded with of step (2) is placed in plasma high-temperature tubular reactor, using machinery
Pumping vacuum pump-down continues to be evacuated to 10 to 0.1~5Pa, then using molecular pump-4~10-3Pa, is passed through reducibility gas to pressure
It is by force 0.1~20Pa, plasma high-temperature tubular reactor is heated to 300~600 DEG C with 5~10 DEG C/min heating rates,
Radio-frequency power supply is opened, under conditions of radio-frequency power is 100~600W, 10~60min of plasma discharge is then shut off radio frequency
And heating power supply, cooling, 0.1~24h of immersion in diluted acid is put into, then net, drying is washed with deionized water, obtain Heteroatom doping many
Hole graphene elctro-catalyst.The structural representation of the plasma high-temperature tubular reactor is as shown in Figure 1.
The mass concentration of concentrated nitric acid described in step (1) is 60~65%；The quality percentage of the graphene oxide solution
Specific concentration is 0.1~1.0%；Dense HNO described in step (1)3Volume ratio with graphene oxide solution is (1~20)：1.
The volume ratio of deionized water and graphene oxide solution described in step (1) is (100~200) mL：(50~500) mL.
The frequency of ultrasonic reaction described in step (1) is that 20~100KHz, the power of ultrasonic reaction are 40~1000W；It is super
The temperature of phonoresponse is 4 DEG C~60 DEG C, and the ultrasonic reaction time is 0.5~10h；Time of repose described in step (1) is 1~3h.
The frequency of ultrasonic disperse described in step (1) is 20~100KHz, and the power of ultrasonic disperse is 40~1000W, is surpassed
The sound scattered time is 30~120min；The temperature dried described in step (1) is 40~60 DEG C, dry time for 12~
24h；The rotating speed of the stirring is 200~1000r/min.
Graphene oxide described in step (1) is prepared using improved Hummers methods, and specific preparation method is：
Under the conditions of ice-water bath, mass percent is added in sodium nitrate and graphite mixture for 95~98% concentrated sulfuric acid, stirring is anti-
Answer 10~60min；Potassium permanganate is gradually added, controlling reaction temperature is no more than 20 DEG C, and addition continues to react 6~24h after finishing,
Deionized water dilution is added, 30~60min of stirring reaction is warming up to 20~98 DEG C, reacts 12~48h, quality hundred is added dropwise
Fraction is 30~35% hydrogen peroxide, continues to react 30~60min after dripping, filtering is 5~10% with mass percent
HCl solution and deionized water are washed, untill sulfate radical-free is detected in filtrate；Finally by filter cake in 40~60 DEG C
12~24h is dried, graphene oxide is obtained；The potassium permanganate that is gradually added refers to that each addition of potassium permanganate is permanganic acid
The 1/60 of potassium gross weight, per 1~2min of minor tick；The rotating speed of the stirring is 200~1000r/min；The speed of the dropwise addition
For 5~10 drops/min；The heating rate is 10~20 DEG C/min；
The graphite powder：Sodium nitrate：The concentrated sulfuric acid：Potassium permanganate：Deionized water for dilution：The amount ratio of hydrogen peroxide is
(1~5) g：(1~5) g：(90~300) mL：(5~25) g：(50~300) mL：(50~100) mL.
The graphite powder is all kinds of native graphites or expanded graphite.Oxygen atomicity content accounts for total original in the graphene oxide
The 20-60% of subnumber.
Hybrid mode described in step (2) is one kind or several in ultrasonic mixing, mechanical agitation mixing, ball grinding stirring mixing
Kind.Incorporation time described in step (2) is 12~24h.
Surface graphene oxide with holes and the total quality hundred of Heteroatom doping source compound in coating liquid described in step (2)
It is 5~30% to divide specific concentration；The temperature of the freeze-drying is -28~-48 DEG C, and the time of freeze-drying is 12~48h.
Heteroatom doping source compound described in step (2) is solid-state and/or liquid heteroatomic compound, the hetero atom
Hetero atom is one or more of nitrogen phosphate and sulfur or boron in doping source compound.
Heteroatom doping source compound described in step (2) is urea, aniline, nitroaniline, benzyl disulfide, P- toluene
Sulfonic acid, 2 thiophene carboxaldehyde, triphenylphosphine, three naphthyl phosphines, tetraphenylphosphonibromide bromide, 1- butyl -3- methylimidazoles hexafluorophosphate,
Boric acid, thiocarbamide, Cys-S-2- thiophene or trifluoro borated amine (NH3BF3One or more of).
Solvent described in step (2) is volatile solvent；The solvent is in ethanol, methanol, toluene or tetrahydrofuran
More than one.
The mass ratio of surface graphene oxide with holes described in step (2) and Heteroatom doping source compound is 1：(0.5~
10)。
It is one kind in knife coating, spin-coating method, infusion method that coating liquid described in step (2), which is coated to the method for substrate surface,
Or several any combination.
Substrate described in step (2) should high temperature resistant, it is preferably one or more of in copper foil, iron foil, steel foil, nickel foil appoints
Meaning combination.The substrate high temperature resistant of the preferred material, thermal stability is good.
Reducibility gas described in step (3) is the mixed gas of protective gas and hydrogen；The protective gas be argon gas,
More than one in helium or nitrogen；The hydrogen is (0.05~10) with protective gas volume ratio：1.
Diluted acid described in step (3) is at least one of hydrochloric acid, sulfuric acid or nitric acid.The concentration of the diluted acid is
0.01mol/L~1mol/L.Drying temperature described in step (3) is 60~80 DEG C, and the drying time is 12~24h.
In the Heteroatom doping porous graphene elctro-catalyst, content of heteroatoms accounts for the 1.5~30% of total atom number, oxygen
Atomicity content accounts for the 1.2~8.5% of total atom number.
The Heteroatom doping porous graphene elctro-catalyst is prepared by above-mentioned preparation method.
Be applied to Proton Exchange Membrane Fuel Cells, the direct alcohols of the Heteroatom doping porous graphene elctro-catalyst fire
Expect battery and metal-air battery cathode material field.
The present invention using concentrated acid and graphite oxide alkene reaction prepare different carbon/oxygen than surface graphene oxide with holes,
Using plasma method prepares out Heteroatom doping porous graphene elctro-catalyst again, is mixed by the hetero atom for adjusting different amounts
Miscellaneous source compound and plasma discharge parameter, can control heteroatomic doping content in material, the state of foreign atom and
Structure etc..The introducing of porous graphene material mesopore not only provides for ion in the migration on graphene film in-plane
Passage, and be conducive to improving the pliability of graphene film, and the interaction of Van der Waals force between graphene film is reduced, promote
Enter the formation of three-dimensional porous grapheme material, effectively improve the conductive performance of ion, so as to improve the electrocatalysis of graphene
Energy.
Hetero atom source compound of the present invention has good dissolubility energy or solvent-dispersible energy, can be configured to uniform molten
Liquid, and the surface of substrate can be uniformly coated in, uniform and thin film layer is formed, so that it is porous to effectively reduce Heteroatom doping
The thickness of graphen catalyst layer.
A kind of special purpose device of the plasma preparation method of Heteroatom doping porous graphene elctro-catalyst, described etc.
Gas ions high-temperature tubular reactor includes plasma high-temperature quartz tube furnace 1, described plasma high-temperature quartz tube furnace 1
One end is provided with reducibility gas air inlet pipe 11, and the described plasma high-temperature quartz tube furnace other end is provided with exhaust tube 13
With exhaust tube 14, the described connection molecule pump 8 of exhaust tube 13, the described connection liquid nitrogen cold trap 4 of exhaust tube 14, the liquid nitrogen cold trap
4 are connected by pipeline with mechanical pump 5, and air intake duct is provided with described exhaust tube 14, and the air intake duct is provided with
Air shut-off valve door, the exhaust tube 14 is provided with the first control valve 9；Set on the pipeline of the liquid nitrogen cold trap and mechanical pump
Have and be provided with vacuum meter 12 on the 3rd control valve 16, the pipeline that the 3rd control valve 16 is connected with liquid nitrogen cold trap, it is described
Vacuum meter 12 is set with being provided with the 4th control valve 17, the described exhaust tube for being connected with molecular pump in the bypass of pipeline connection
There is the second control valve 10, described plasma high-temperature quartz tube furnace outer surface is wound with inductively coupled plasma coil
6, the two ends of described inductively coupled plasma coil connect radio frequency power source 7.15 be that substrate is placed in the middle of quartz tube furnace
Place, while being also heater strip center, is connected with digital display mass flowmenter 2 and tune in described reducibility gas air inlet pipe 11
Save valve 3.Described reducibility gas air inlet pipe connects reducibility gas air feed bottle respectively.
Plasma reaction device of the present invention is simple in construction, easy to operate, can largely be controlled using this device
Plasma doping and reduction reaction process, so as to obtain the oxygen reduction catalyst with required structure and performance.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) compared with general high-temperature direct thermal decomposition-reduction doping method, using plasma method of the present invention is not only reduced
Reaction temperature (plasma-assisted process typically can under relatively lower temp (≤500 DEG C) graphene is doped),
And the reaction time is shortened, also reduce cost；And, can be with by adjusting discharge parameter and content containing heteroatomic compound
Effectively control product doping and the uniformity of doping.
(2) Heteroatom doping porous graphene elctro-catalyst of the invention has preferable hydrogen reduction electrocatalysis characteristic, uses
In electrode material, with preferable electrochemical stability.
In a word, by using graphene oxide as matrix material, being used in the punching of monolithic surface of graphene oxide, plasma
The means such as thermal decomposition and reduction Heteroatom doping are aided in, grapheme material are not only realized both perpendicular to graphene film in-plane
On there is the abundant micro-nano duct of ion transmission, substantial amounts of hetero atom catalysis activity structure is contained again, and is also had concurrently simultaneously excellent
Electron transport property and hydrogen reduction electrocatalysis characteristic.
Brief description of the drawings
Fig. 1 is the structural representation of the plasma high-temperature tubular reactor of the present invention；Wherein 1- quartz tube furnaces, 2- matter
Amount flowmeter, 3- regulating valves (needle-valve), 4- liquid nitrogen cold traps, 5- mechanical pumps, 6- coils (copper tube coil), 7- radio frequency power sources,
8- molecular pumps, the control valves of 9- first (butterfly valve), the control valves of 10- second (butterfly valve), 11- reducibility gas air inlet pipe, 12- is true
Sky meter, 13- exhaust tubes (molecular pump exhaust tube), 14- exhaust tubes (mechanical pump exhaust tube), 15- sample mounting tables, 16- the 3rd is controlled
Valve processed, the control valves of 17- the 4th；
Fig. 2 is the SEM figures of N doping porous graphene elctro-catalyst prepared by embodiment 1；
Fig. 3 is N doping porous graphene elctro-catalyst and commercialization Pt/C catalysts prepared by embodiment 1~2
The linear scan curve of oxygen reduction reaction, 1 is the glass carbon electricity of N doping porous graphene elctro-catalyst modification prepared by embodiment 1
The linear scan curve of pole, 2 be the linear of the glass-carbon electrode of N doping porous graphene elctro-catalyst modification prepared by embodiment 2
Scanning curve, 3 be the linear scan curve for the glass-carbon electrode that commercialization Pt/C is modified；
Fig. 4 is that the glass-carbon electrode catalytic oxidation-reduction of N doping porous graphene elctro-catalyst modification prepared by embodiment 1 is anti-
The cyclic voltammetry curve answered；
Fig. 5 be embodiment 1 prepare N doping porous graphene elctro-catalyst under different potentials catalytic oxidation-reduction
Koutechy-Levich straight lines；
Fig. 6 is the song that N doping porous graphene elctro-catalyst prepared by embodiment 1 shifts electron number under different potentials
Line chart.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of preparation method of Heteroatom doping porous graphene elctro-catalyst, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared using improved Hummers methods, its technological process is as follows：
(1-1) assembles reaction bulb in ice-water bath, and (rotating speed of stirring be 500r/min) is to reaction under agitation
The solid mixture of 1g expanded graphites powder and 2.5g sodium nitrate is added in bottle, add 150mL mass percents for 95% it is dense
Sulfuric acid, reacts 30min in ice-water bath；Then, 60 times (per minor tick 1min) are divided to add 15g potassium permanganate, control reaction temperature
Spend for 0 DEG C, continue to react 12h；Add 150mL deionized waters to dilute, (rotating speed of stirring is 500r/ after stirring reaction 30min
Min), 98 DEG C are warming up to 10 DEG C/min heating rate, insulation reaction 48h, solution colour is obtained from black transitions into brown color
To the crude product of graphene oxide；
(1-2) the hydrogen peroxide reduction that (rate of addition is 5 drops/min) 50mL mass fractions are 35% is added dropwise into crude product
The oxidant of residual, continues to react 30min, solution is changed into glassy yellow after dripping off；Filter while hot, and be with mass fraction successively
5%HCl solution and deionized water washing are finally placed in 60 DEG C of vacuum drying untill sulfate radical-free is detected in filtrate
12h is dried in case, graphene oxide is obtained；
(2) synthesis of surface graphene oxide with holes
Deionized water is added in graphene oxide, ultrasonic disperse 60min (frequency is that 50KHz, power are 150W) is obtained
Graphene oxide solution, its mass percent concentration is 0.5%；Under agitation (rotating speed of stirring be 500r/min), to
It is 65% dense HNO that 250mL mass percent concentrations are added in the container of graphene oxide solution equipped with 50mL3, sealing container,
In 30 DEG C of ultrasonic reaction 1h (supersonic frequency is that 100KHz, ultrasonic power are 500W), stands after 1h, pour into 100mL deionization
In water, acid is removed in centrifugation, is purified, after filtering, in the vacuum drying chamber that gained solid is placed in 60 DEG C, is dried 12h, is produced surface band
Hole graphene oxide；
(3) preparation of solid film
The first ultrasonic mixing 60min of surface graphene oxide with holes, 100mg urea and ethanol prepared by 20mg steps (2)
(frequency is that 50KHz, power are 150W), is stirred for mixing 12h (rotating speed of stirring is 500r/min), obtains mass percent dense
The coating liquid for 30% is spent, coating liquid is then coated to copper foil surface using knife coating, (temperature is -48 DEG C, is done for freeze-drying
The dry time is 24h), obtain being supported on the solid film of substrate top surface graphene oxide@urea with holes；
(4) prepared by the plasma method of Heteroatom doping surface graphene with holes
The substrate of the solid film of surface graphene oxide@urea with holes will be loaded with, and to be placed in plasma high-temperature tubular type anti-
Device center is answered, removing impurity and vapor are vacuumized using mechanical pump, and is depressurized to 5Pa, molecule is then further used
Pump is evacuated to 10-3Pa, is then passed through N at one end2/H2Mixed gas (H2Percent by volume to pressure to be 5%) 10Pa,
Plasma high-temperature tubular reactor is heated to 600 DEG C with 6 DEG C/min heating rates, radio-frequency power supply is then opened, in radio frequency
Power be 500W under conditions of, carry out plasma discharge 30min, be then shut off radio frequency and heating power supply, be cooled to after room temperature,
The substrate of supported solid film is put into 0.5mol/L hydrochloric acid solutions and soaks 12h, the removal reactant that participation is reacted completely,
The accessory substance of production and other impurity, then be washed with deionized water only, 24h then are dried in 60 DEG C, N doping porous graphite is produced
Alkene elctro-catalyst.
It can be obtained by elementary analysis, nitrogen-atoms numbers account for total atom number in N doping porous graphene elctro-catalyst
12.3%, oxygen atomicity accounts for the 4.2% of total atom number.
Using SEM (Scanning Electron Microscopy, SEM) to manufactured in the present embodiment
N doping surface graphene elctro-catalyst with holes carries out the sign of microscopic appearance, as shown in Fig. 2 showing prepared by SEM photograph
Graphene be loose structure.Prepared elctro-catalyst electrochemical property test result is as illustrated in figures 3-6.
Fig. 3 is Different electrodes in O2To the linear scan curve of oxygen reduction in the 0.1mol/L potassium hydroxide systems of saturation
(LSV)；1 is the linear scan curve of the glass-carbon electrode of N doping porous graphene elctro-catalyst modification prepared by embodiment 1,2
The linear scan curve of the glass-carbon electrode of the N doping porous graphene elctro-catalyst modification prepared for embodiment 2,3 be commercialization
The linear scan curve of the glass-carbon electrode of Pt/C modifications.As can be seen from Figure 3, the N doping porous graphene electricity that prepared by embodiment 1 is urged
The glass-carbon electrode of agent modification is best to oxygen reduction catalytic activity, and the catalyst is similar with internationally recognized representative commercialization to urge
Agent is compared, and it is significantly improved to oxygen reduction catalytic activity.Test condition is the property using the glass-carbon electrode of modification as working electrode
It can test using three-electrode system (auxiliary electrode, reference electrode, working electrode), be carried out in 0.1mol/L potassium hydroxide solutions
Test.
Fig. 4 is that the glass-carbon electrode catalytic oxidation-reduction of N doping porous graphene elctro-catalyst modification prepared by embodiment 1 is anti-
The cyclic voltammetry curve answered.As shown in figure 4, being full of N in comparison solution2And O2When curve, be clear that in -0.2V
Near, by O2The curve obtained in environment has obvious hydrogen reduction peak to occur, it is shown that the N doping porous graphene is had
Hydrogen reduction catalytic performance.Test condition is the glass carbon for modifying N doping porous graphene elctro-catalyst made from experimental example 1
Electrode uses three-electrode system, is tested in 0.1mol/L potassium hydroxide solutions；Tested in -1.2~0V potential ranges
Cyclic voltammetric (CV) curve, it is 10mV s to sweep speed-1。
Fig. 5 be embodiment 1 prepare N doping porous graphene elctro-catalyst under different potentials catalytic oxidation-reduction
Koutechy-Levich straight lines；Fig. 6 is that N doping porous graphene elctro-catalyst prepared by embodiment 1 turns under different potentials
Move the curve map of electron number.From Fig. 5,6 it can be seen that the catalyst can effectively in reducing solution oxygen, can be achieved direct
4e processes.Test condition is that the catalytic oxidation-reduction LSV curves of elctro-catalyst are tested under different rotating speeds.
The preparation of each electrode：
The preparation of the glass-carbon electrode of N doping porous graphene elctro-catalyst modification prepared by embodiment 1：Weigh 4mg implementations
N doping porous graphene elctro-catalyst prepared by example 1, is added dropwise 87 μ L 15wt% perfluorinated sulfonic resin (Nafion) solution,
Then it is 2.5 to be scattered in 1mL volume ratios：It is that 50KHz, power are in frequency in the mixed solution of 1 water/isopropanol
Ultrasonic disperse 60min in 150W Ultrasound Instrument, obtains finely dispersed ink, takes 5 μ L ink droplets to be coated onto a diameter of 5mm glass carbon
The surface of electrode, after electrode is dried at room temperature for, obtains the glass-carbon electrode of N doping porous graphene modification.
The preparation of the glass-carbon electrode of N doping porous graphene modification prepared by embodiment 2：Nitrogen prepared by embodiment 2 is mixed
Miscellaneous porous graphene elctro-catalyst replaces N doping porous graphene elctro-catalyst prepared by embodiment 1, is prepared using embodiment 1
N doping porous graphene elctro-catalyst modification glass-carbon electrode preparation method, you can obtain required electrode.
The preparation of the glass-carbon electrode of commercial Pt/C modifications：Weigh 4mg commercializations Pt/C and (be purchased from Britain Johnson-Matthey
Company, mass ratio is the Nafion solution for the 5wt% for 40%) instilling 35 μ L, is then scattered in the ethanol that volume is 1mL
In, the ultrasonic disperse 60min in frequency is the Ultrasound Instrument that 50KHz, power are 150W obtains finely dispersed ink, takes 5 μ L ink
Water droplet is coated onto the surface of a diameter of 5mm glass-carbon electrode, after electrode is dried at room temperature for, and obtains the glass carbon electricity of commercial Pt/C modifications
Pole.
Embodiment 2
A kind of N doping porous graphene elctro-catalyst, specific preparation method is：(comparative example related to the present invention, it is high
Prepared by warm directly pyrolysis reduction method)
(1) synthesis of graphene oxide：Be the same as Example 1 is identical；
(2) synthesis of surface graphene oxide with holes：Be the same as Example 1 is identical；
(3) preparation of solid film：Be the same as Example 1 is identical；
(4) substrate for being loaded with surface graphene oxide with holes and the precursor containing hetero atom is placed in plasma high-temperature pipe
Formula reactor heated center position, is then passed through N at one end2/H2Mixed gas (H2Percent by volume for 5%), gaseous mixture
Flow is 50sccm, and plasma high-temperature tubular reactor is heated into 850 DEG C with 6 DEG C/min heating rates, and in this temperature
120min is stopped, heating power supply is then shut off, is cooled to after room temperature, the substrate for being loaded with solid film is put into 0.5mol/L salt
12h is soaked in acid solution, the reactant for not participating in reaction completely, the accessory substance and other impurity of production is removed, then use deionization
Water is cleaned, and 24h is then dried in 60 DEG C of baking oven, N doping porous graphene elctro-catalyst is produced；Can by elementary analysis
With, nitrogen-atoms numbers account for the 5.3% of total atom number in N doping porous graphene material, and oxygen atomicity accounts for total atom number
14.6%.The electrochemical property test result of N doping porous graphene elctro-catalyst manufactured in the present embodiment is as shown in Figure 3.
Embodiment 3
A kind of Heteroatom doping porous graphene elctro-catalyst, specific preparation method is：
(1) synthesis of graphene oxide：Be the same as Example 1 is identical；
(2) synthesis of surface graphene oxide with holes：Be the same as Example 1 is identical；
(3) surface graphene oxide with holes is mixed with benzyl disulfide
The first ultrasonic mixing of surface graphene oxide with holes, 100mg benzyl disulfides and ethanol prepared by 20mg steps (2)
60min (frequency is that 50KHz, power are 150W), is stirred for mixing 12h (rotating speed of stirring is 500r/min), obtains quality hundred
Point specific concentration is 30% coating liquid, and coating liquid then is coated into copper foil surface using knife coating, freeze-drying (temperature is-
48 DEG C, drying time is 24h), obtain being supported on the solid film of substrate top surface graphene oxide@benzyl disulfides with holes；
(4) prepared by the plasma method of Heteroatom doping surface graphene with holes
The substrate that the solid film of surface graphene oxide@benzyl disulfides with holes will be loaded with is placed in plasma high-temperature
Tubular reactor center, removing impurity and vapor are vacuumized using mechanical pump, and are depressurized to 5Pa, are then further made
10 are evacuated to molecular pump-3Pa, is then passed through N at one end2/H2Mixed gas (H2Percent by volume 5%) to pressure to be
10Pa, is heated to 600 DEG C with 6 DEG C/min heating rates by plasma high-temperature tubular reactor, then opens radio-frequency power supply,
Radio-frequency power is under conditions of 500W, progress plasma discharge 30min is then shut off radio frequency and heating power supply, is cooled to room
Wen Hou, the substrate of supported solid film is put into 0.5mol/L hydrochloric acid solutions and soaks 12h, is removed and is not participated in the anti-of reaction completely
Thing, the accessory substance and other impurity of production are answered, then is washed with deionized water only, then 24h is dried in 60 DEG C, produces sulfur doping porous
Graphene elctro-catalyst.
It can be obtained by elementary analysis, number of sulfur atoms accounts for total atom number in sulfur doping porous graphene elctro-catalyst
3.8%, oxygen atomicity accounts for the 5.8% of total atom number.
Resulting sulfur doping porous graphene is characterized using SEM, it is as a result similar to Example 1；As oxygen also
During the catalyst material of original reaction (test condition is same as Example 1), good performance is shown：Sulfur doping porous graphene
The glass-carbon electrode of modification has preferable catalytic activity to hydrogen reduction, and compared with being commercialized similar catalyst, it is urged hydrogen reduction
Change activity to be significantly improved；N is full of in comparison solution2And O2When cyclic voltammetry curve, by O2The curve obtained in environment has bright
Aobvious hydrogen reduction peak occurs, it is shown that the hydrogen reduction catalytic performance that the sulfur doping porous graphene has；Pass through different rotating speeds
Lower test catalytic oxidation-reduction LSV curves, it can be seen that the oxygen that the catalyst can effectively in reducing solution, can be achieved direct 4e
Process.
Embodiment 4
A kind of Heteroatom doping porous graphene elctro-catalyst, specific preparation method is：
(1) synthesis of graphene oxide：Be the same as Example 1 is identical；
(2) synthesis of surface graphene oxide with holes：Be the same as Example 1 is identical；
(3) surface graphene oxide with holes is mixed with triphenylphosphine
The first ultrasonic mixing of surface graphene oxide with holes, 100mg triphenylphosphines and ethanol prepared by 20mg steps (2)
60min (frequency is that 50KHz, power are 150W), is stirred for mixing 12h (rotating speed of stirring is 500r/min), obtains quality hundred
Point specific concentration is 30% coating liquid, and coating liquid then is coated into copper foil surface using knife coating, freeze-drying (temperature is-
48 DEG C, drying time is 24h), obtain being supported on the solid film of substrate top surface graphene oxide@triphenylphosphines with holes；
(4) prepared by the plasma method of Heteroatom doping porous graphene
The substrate of the solid film of surface graphene oxide@urea with holes will be loaded with, and to be placed in plasma high-temperature tubular type anti-
Device center is answered, removing impurity and vapor are vacuumized using mechanical pump, and is depressurized to 5Pa, molecule is then further used
Pump is evacuated to 10-3Pa, is then passed through N at one end2/H2Mixed gas (H2Percent by volume to pressure to be 5%) 10Pa,
Plasma high-temperature tubular reactor is heated to 600 DEG C with 6 DEG C/min heating rates, radio-frequency power supply is then opened, in radio frequency
Power be 500W under conditions of, carry out plasma discharge 30min, be then shut off radio frequency and heating power supply, be cooled to after room temperature,
The substrate of supported solid film is put into 0.5mol/L hydrochloric acid solutions and soaks 12h, the removal reactant that participation is reacted completely,
The accessory substance of production and other impurity, then be washed with deionized water only, 24h then are dried in 60 DEG C, phosphorus doping porous graphite is produced
Alkene elctro-catalyst.
It can be obtained by elementary analysis, phosphorus atoms number accounts for the 3.7% of total atom number in phosphorus doping porous graphene material,
Oxygen atomicity accounts for the 4.6% of total atom number.
Resulting phosphorus doping porous graphene is characterized using SEM, it is as a result similar to Example 1；As oxygen also
During the catalyst material of original reaction (test condition is same as Example 1), good performance is shown：Phosphorus doping porous graphene
The glass-carbon electrode of modification has preferable catalytic activity to hydrogen reduction, and the catalyst is compared with being commercialized similar catalyst, and its is right
Oxygen reduction catalytic activity is significantly improved；N is full of in comparison solution2And O2When cyclic voltammetry curve, by O2Obtained in environment
Curve has obvious hydrogen reduction peak to occur, it is shown that phosphorus doping porous graphene has hydrogen reduction catalytic performance；Turned by difference
The lower test catalytic oxidation-reduction LSV curves of speed, it can be seen that the oxygen that the catalyst can effectively in reducing solution, can be achieved direct
4e processes.
Embodiment 5
A kind of Heteroatom doping porous graphene elctro-catalyst, specific preparation method is：
(1) synthesis of graphene oxide：Be the same as Example 1 is identical；
(2) synthesis of surface graphene oxide with holes：Be the same as Example 1 is identical；
(3) surface graphene oxide with holes is mixed with trifluoro borated amine
The first ultrasonic mixing of surface graphene oxide with holes, 100mg trifluoros borated amine and ethanol prepared by 20mg steps (2)
60min (frequency is that 50KHz, power are 150W), is stirred for mixing 12h (rotating speed of stirring is 500r/min), obtains quality hundred
Point specific concentration is 30% coating liquid, and coating liquid then is coated into copper foil surface using knife coating, freeze-drying (temperature is-
48 DEG C, drying time is 24h), obtain being supported on the solid film of substrate top surface graphene oxide@trifluoro borated amines with holes；
(4) prepared by the plasma method of Heteroatom doping porous graphene
The substrate that the solid film of surface graphene oxide@trifluoro borated amines with holes will be loaded with is placed in plasma high-temperature
Tubular reactor center, removing impurity and vapor are vacuumized using mechanical pump, and are depressurized to 5Pa, are then further made
10 are evacuated to molecular pump-3Pa, is then passed through N at one end2/H2Mixed gas (H2Percent by volume 5%) to pressure to be
10Pa, is heated to 600 DEG C with 6 DEG C/min heating rates by plasma high-temperature tubular reactor, then opens radio-frequency power supply,
Radio-frequency power is under conditions of 500W, progress plasma discharge 30min is then shut off radio frequency and heating power supply, is cooled to room
Wen Hou, the substrate of supported solid film is put into 0.5mol/L hydrochloric acid solutions and soaks 12h, is removed and is not participated in the anti-of reaction completely
Thing, the accessory substance and other impurity of production are answered, then is washed with deionized water only, then 24h is dried in 60 DEG C, produces boron nitrogen co-doped
Porous graphene elctro-catalyst.
It can be obtained by elementary analysis, nitrogen-atoms numbers account for total atom number in nitrogen boron codope porous graphene material
5.7%, boron atom number accounts for the 2.7% of total atom number, and oxygen atomicity accounts for the 5.1% of total atom number.
Resulting nitrogen boron codope porous graphene is characterized using SEM, it is as a result similar to Example 1；As
During the catalyst material of oxygen reduction reaction (test condition is same as Example 1), good performance is shown：Nitrogen boron codope is more
The glass-carbon electrode of hole graphene modified has preferable catalytic activity to hydrogen reduction, and compared with being commercialized similar catalyst, its is right
Oxygen reduction catalytic activity is significantly improved；N is full of in comparison solution2And O2When cyclic voltammetry curve, by O2Obtained in environment
Curve has obvious hydrogen reduction peak to occur, it is shown that the hydrogen reduction catalytic performance that the nitrogen boron codope porous graphene has；
Pass through and catalytic oxidation-reduction LSV curves tested under different rotating speeds, it can be seen that the oxygen that the catalyst can effectively in reducing solution,
Direct 4e processes can be achieved.
Embodiment 6
A kind of preparation method of Heteroatom doping porous graphene elctro-catalyst, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared using improved Hummers methods, its technological process is as follows：
(1-1) assembles reaction bulb in ice-water bath, and (rotating speed of stirring be 1000r/min) is to reaction under agitation
The solid mixture of 5g expanded graphites powder and 5g sodium nitrate is added in bottle, the dense sulphur that 300mL mass percents are 95% is added
Acid, reacts 60min in ice-water bath；Then, 60 times (per minor tick 2min) are divided to add 25g potassium permanganate, controlling reaction temperature
For 10 DEG C, continue to react 24h；Add 300mL deionized waters to dilute, (rotating speed of stirring is 1000r/ after stirring reaction 60min
Min), 98 DEG C are warming up to 20 DEG C/min heating rate, insulation reaction 48h, solution colour is obtained from black transitions into brown color
To the crude product of graphene oxide；
(1-2) hydrogen peroxide that dropwise addition (rate of addition is 10 drops/min) 100mL mass fractions are 35% into crude product is also
The oxidant of original residual, continues to react 60min, solution is changed into glassy yellow after dripping off；Filter while hot, and be with mass fraction successively
10%HCl solution and deionized water washing are untill sulfate radical-free is detected in filtrate, and the vacuum for being finally placed in 60 DEG C is done
12h is dried in dry case, graphene oxide is obtained；
(2) synthesis of surface graphene oxide with holes
Deionized water is added in graphene oxide, ultrasonic disperse 30min (frequency is that 100KHz, power are 1000W) is obtained
To graphene oxide solution, its mass percent concentration is 1.0%；Under agitation (rotating speed of stirring is 1000r/min),
The dense HNO that 1000mL mass percent concentrations are 65% is added into the container of the graphene oxide solution equipped with 50mL3, sealing
Container, in 60 DEG C of ultrasonic reaction 10h (supersonic frequency is that 100KHz, ultrasonic power are 1000W), stands after 3h, pours into 200mL's
In deionized water, acid is removed in centrifugation, is purified, after filtering, in the vacuum drying chamber that gained solid is placed in 60 DEG C, is dried 12h, is produced
Surface graphene oxide with holes；
(3) preparation of solid film
The first ultrasonic mixing of surface graphene oxide with holes, 200mg urea and tetrahydrofuran prepared by 20mg steps (2)
30min (frequency is that 100KHz, power are 1000W), is stirred for mixing 20h (rotating speed of stirring is 1000r/min), obtains quality
Percent concentration is 15% coating liquid, and coating liquid then is coated into stainless steel foil surface, freeze-drying (temperature using spin-coating method
Spend for -38 DEG C, drying time is 18h), obtain being supported on the solid film of substrate top surface graphene oxide@urea with holes；
(4) prepared by the plasma method of Heteroatom doping porous graphene
The substrate of the solid film of surface graphene oxide@urea with holes will be loaded with, and to be placed in plasma high-temperature tubular type anti-
Device center is answered, removing impurity and vapor are vacuumized using mechanical pump, and is depressurized to 0.1Pa, then further uses and divides
Sub- pump is evacuated to 5 × 10-4Pa, is then passed through N at one end2/H2Mixed gas (H2Percent by volume 10%) to pressure to be
20Pa, is heated to 500 DEG C with 10 DEG C/min heating rates by plasma high-temperature tubular reactor, then opens radio-frequency power supply,
Under conditions of radio-frequency power is 600W, plasma discharge 60min is carried out, radio frequency and heating power supply is then shut off, is cooled to
After room temperature, the substrate of supported solid film is put into 1mol/L hydrochloric acid solutions and soaks 24h, removed and do not participate in the anti-of reaction completely
Thing, the accessory substance and other impurity of production are answered, then is washed with deionized water only, then 12h is dried in 100 DEG C, produces N doping many
Hole graphene elctro-catalyst.
It can be obtained by elementary analysis, nitrogen-atoms numbers account for total atom number in N doping porous graphene elctro-catalyst
14.3%, oxygen atomicity accounts for the 3.9% of total atom number.
Resulting N doping porous graphene is characterized using SEM, it is as a result similar to Example 1：As oxygen also
During the catalyst material of original reaction (test condition is same as Example 1), good performance is shown：N doping porous graphene
The glass-carbon electrode of modification has preferable catalytic activity to hydrogen reduction, with internationally recognized representative commercial similar catalyst phase
Than it is significantly improved to oxygen reduction catalytic activity；N is full of in comparison solution2And O2When cyclic voltammetry curve, by O2Environment
In obtained curve there is obvious hydrogen reduction peak to occur, it is shown that the hydrogen reduction catalytic that the N doping porous graphene has
Energy；Pass through and catalytic oxidation-reduction LSV curves are tested under different rotating speeds, it can be seen that the catalyst can be effectively in reducing solution
Oxygen, can be achieved direct 4e processes.
Embodiment 7
A kind of preparation method of Heteroatom doping porous graphene elctro-catalyst, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared using improved Hummers methods, its technological process is as follows：
(1-1) assembles reaction bulb in ice-water bath, and (rotating speed of stirring be 200r/min) is to reaction under agitation
The solid mixture of 1g expanded graphites powder and 1g sodium nitrate is added in bottle, the dense sulphur that 90mL mass percents are 95% is added
Acid, reacts 10min in ice-water bath；Then, 60 times (per minor tick 1min) are divided to add 5g potassium permanganate, controlling reaction temperature is
5 DEG C, continue to react 6h；(rotating speed of stirring is 200r/min) is added after the dilution of 50mL deionized waters, stirring reaction 30min,
98 DEG C are warming up to 10 DEG C/min heating rate, insulation reaction 12h, solution colour obtains oxygen from black transitions into brown color
The crude product of graphite alkene；
(1-2) the hydrogen peroxide reduction that (rate of addition is 5 drops/min) 50mL mass fractions are 35% is added dropwise into crude product
The oxidant of residual, continues to react 30min, solution is changed into glassy yellow after dripping off；Filter while hot, and be with mass fraction successively
5%HCl solution and deionized water washing are finally placed in 40 DEG C of vacuum drying untill sulfate radical-free is detected in filtrate
24h is dried in case, graphene oxide is obtained；
(2) synthesis of surface graphene oxide with holes
Deionized water is added in graphene oxide, ultrasonic disperse 30min (frequency is that 20KHz, power are 40W) is obtained
Graphene oxide solution, its mass percent concentration is 0.1%；Under agitation (rotating speed of stirring be 200r/min), to
It is 65% dense HNO that 500mL mass percent concentrations are added in the container of graphene oxide solution equipped with 500mL3, sealing appearance
Device, in 4 DEG C of ultrasonic reaction 0.5h (supersonic frequency is that 20KHz, ultrasonic power are 40W), stands after 1h, pour into 100mL go from
In sub- water, acid is removed in centrifugation, is purified, after filtering, in the vacuum drying chamber that gained solid is placed in 40 DEG C, is dried 24h, is produced surface
Graphene oxide with holes；
(3) preparation of solid film
The first ultrasonic mixing 120min of surface graphene oxide with holes, 10mg urea and toluene prepared by 20mg steps (2)
(frequency is that 20KHz, power are 40W), then ball milling mixing 3h (rotating speed is 800r/min), it is 5% to obtain mass percent concentration
Coating liquid, coating liquid is then coated to nickel foil surface using knife coating, (temperature is -28 DEG C, and drying time is for freeze-drying
24h), obtain being supported on the solid film of substrate top surface graphene oxide@urea with holes；
(4) prepared by the plasma method of Heteroatom doping porous graphene
The substrate of the solid film of surface graphene oxide@urea with holes will be loaded with, and to be placed in plasma high-temperature tubular type anti-
Device center is answered, removing impurity and vapor are vacuumized using mechanical pump, and is depressurized to 0.1Pa, then further uses and divides
Sub- pump is evacuated to 1 × 10-4Pa, is then passed through Ar/H at one end2Mixed gas (H2Percent by volume 5%) to pressure to be
10Pa, is heated to 300 DEG C with 5 DEG C/min heating rates by plasma high-temperature tubular reactor, then opens radio-frequency power supply,
Radio-frequency power is under conditions of 200W, progress plasma discharge 10min is then shut off radio frequency and heating power supply, is cooled to room
Wen Hou, the substrate of supported solid film is put into 0.01mol/L hydrochloric acid solutions and soaks 24h, is removed and is not participated in reaction completely
Reactant, the accessory substance and other impurity of production, then be washed with deionized water only, 24h then are dried in 40 DEG C, N doping are produced many
Hole graphene elctro-catalyst.
It can be obtained by elementary analysis, nitrogen-atoms numbers account for total atom number in N doping porous graphene elctro-catalyst
2.3%, oxygen atomicity accounts for the 8.5% of total atom number.
Resulting N doping porous graphene is characterized using SEM, it is as a result similar to Example 1；As oxygen also
During the catalyst material of original reaction (test condition is same as Example 1), good performance is shown：N doping porous graphene
The glass-carbon electrode of modification has preferable catalytic activity to hydrogen reduction, with internationally recognized representative commercial similar catalyst phase
Than it is significantly improved to oxygen reduction catalytic activity；N is full of in comparison solution2And O2When cyclic voltammetry curve, by O2Environment
In obtained curve there is obvious hydrogen reduction peak to occur, it is shown that the hydrogen reduction catalytic that the N doping porous graphene has
Energy；Pass through and catalytic oxidation-reduction LSV curves are tested under different rotating speeds, it can be seen that the catalyst can be effectively in reducing solution
Oxygen, can be achieved direct 4e processes.
Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；Although with reference to foregoing each reality
Example is applied the present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each
Technical scheme described in embodiment is modified, or carries out equivalent substitution to which part or all technical characteristic；And
These modifications are replaced, and the essence of appropriate technical solution is departed from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a kind of preparation method of Heteroatom doping porous graphene elctro-catalyst, it is characterised in that：Specifically include following steps：
(1) synthesis of surface graphene oxide with holes
Add water in graphene oxide, ultrasonic disperse obtains graphene oxide solution；Then under agitation, to equipped with
Dense HNO is added in the container of graphene oxide solution3, container sealing, ultrasonic reaction after standing, pours into deionized water, centrifuges
Acid is removed, is purified, is filtered, dries, obtains surface graphene oxide with holes, it is standby；
(2) preparation of solid film
The surface graphene oxide with holes, Heteroatom doping source compound and solvent of step (1) is well mixed, coated
Liquid, is then coated to substrate surface by coating liquid, freeze-drying, obtain being supported on surface graphene oxide with holes on substrate with
The solid film of the precursor containing hetero atom；Heteroatom doping source compound described in step (2) is solid-state and/or liquid hetero atom
Hetero atom is one or more of nitrogen phosphate and sulfur or boron in compound, the Heteroatom doping source compound；
(3) prepared by the plasma method of Heteroatom doping porous graphene
The substrate of solid film that is loaded with of step (2) is placed in plasma high-temperature tubular reactor, using mechanical pumping
Vacuum pump-down continues to be evacuated to 10 to 0.1~5Pa, then using molecular pump-4~10-3Pa, being passed through reducibility gas to pressure is
0.1~20Pa, 300~600 DEG C are warming up to by plasma high-temperature tubular reactor, are opened radio-frequency power supply, are in radio-frequency power
Under conditions of 100~600W, 10~60min of plasma discharge is then shut off radio frequency and heating power supply, cooling, is put into diluted acid
Middle immersion, then net, drying is washed with deionized water, obtain Heteroatom doping porous graphene elctro-catalyst.
2. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 1, it is characterised in that：Step
(1) mass concentration of concentrated nitric acid described in is 60~65%；The mass percent concentration of the graphene oxide solution be 0.1~
1.0%；Dense HNO described in step (1)3Volume ratio with graphene oxide solution is (1~20)：1；Described in step (1)
The volume ratio of deionized water and graphene oxide solution is (100~200) mL：(50~500) mL；
The frequency of ultrasonic reaction described in step (1) is that 20~100KHz, the power of ultrasonic reaction are 40~1000W；It is ultrasonic anti-
The temperature answered is 4 DEG C~60 DEG C, and the ultrasonic reaction time is 0.5~10h；Time of repose described in step (1) is 1~3h.
3. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 1, it is characterised in that：Step
(2) Heteroatom doping source compound described in is urea, aniline, nitroaniline, benzyl disulfide, P- toluenesulfonic acids, 2- thiophene
Formaldehyde, triphenylphosphine, three naphthyl phosphines, tetraphenylphosphonibromide bromide, 1- butyl -3- methylimidazoles hexafluorophosphate, boric acid, thiocarbamide,
One or more of Cys-S-2- thiophene or trifluoro borated amine；Solvent described in step (2) is volatile solvent；
The mass ratio of surface graphene oxide with holes described in step (2) and Heteroatom doping source compound is 1：(0.5~10)；
Reducibility gas described in step (3) is the mixed gas of protective gas and hydrogen；The protective gas is argon gas, helium
Or more than one in nitrogen；The volume ratio of the hydrogen and protective gas is (0.05~10)：1.
4. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 3, it is characterised in that：Step
(2) solvent described in is one or more of ethanol, methanol, toluene or tetrahydrofuran.
5. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 1, it is characterised in that：Step
(1) graphene oxide described in is prepared using improved Hummers methods, and specific preparation method is：In ice-water bath condition
Under, mass percent is added in sodium nitrate and graphite mixture for 95~98% concentrated sulfuric acid, 10~60min of stirring reaction；
Potassium permanganate is gradually added, controlling reaction temperature is no more than 20 DEG C, and addition continues to react 6~24h after finishing, and adds deionized water
Dilution, 30~60min of stirring reaction is warming up to 20~98 DEG C, reacts 12~48h, be added dropwise mass percent for 30~
35% hydrogen peroxide, continues to react 30~60min, filtering is 5~10%HCl solution with mass percent and is gone after dripping
Ionized water is washed, untill sulfate radical-free is detected in filtrate；Finally by filter cake in 40~60 DEG C dry 12~
24h, obtains graphene oxide.
6. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 5, it is characterised in that：It is described
It is gradually added potassium permanganate and refers to that each addition of potassium permanganate is the 1/60 of potassium permanganate gross weight, per 1~2min of minor tick；
The rotating speed of the stirring is 200~1000r/min；The speed of the dropwise addition is 5~10 drops/min；The heating rate be 10~
20℃/min；
The graphite：Sodium nitrate：The concentrated sulfuric acid：Potassium permanganate：Deionized water for dilution：The amount ratio of hydrogen peroxide is (1~5)
g：(1~5) g：(90~300) mL：(5~25) g：(50~300) mL：(50~100) mL.
7. the preparation method of Heteroatom doping porous graphene elctro-catalyst according to claim 1, it is characterised in that：Step
(1) frequency of ultrasonic disperse described in is 20~100KHz, and the power of ultrasonic disperse is 40~1000W, the time of ultrasonic disperse
For 30~120min；The temperature dried described in step (1) is 40~60 DEG C, and the dry time is 12~24h；
Hybrid mode described in step (2) is one or more of ultrasonic mixing, mechanical agitation mixing or ball grinding stirring mixing；Step
Suddenly incorporation time described in (2) is 12~24h；
Surface graphene oxide with holes and the total mass percent of Heteroatom doping source compound in coating liquid described in step (2)
Concentration is 5~30%；The temperature of the freeze-drying is -28~-48 DEG C, and the time of freeze-drying is 12~48h；
Coating liquid described in step (2) be coated to the method for substrate surface in knife coating, spin-coating method, infusion method it is a kind of with
On；Substrate described in step (2) is more than one in copper foil, steel foil, iron foil or nickel foil；
Diluted acid described in step (3) is at least one of hydrochloric acid, sulfuric acid or nitric acid；The concentration of the diluted acid is 0.01mol/
L~1mol/L；Drying temperature described in step (3) is 60~80 DEG C, and the drying time is 12~24h；Described in step (3)
Heating rate is 5~10 DEG C/min；Soak time described in step (3) is 0.1~24h.
8. a kind of preparation method by any one of the claim 1~7 Heteroatom doping porous graphene elctro-catalyst is medium
Special purpose device prepared by processes, it is characterised in that：
Described plasma high-temperature tubular reactor includes plasma high-temperature quartz tube furnace, described plasma high-temperature
Quartz tube furnace one end is provided with reducibility gas air inlet pipe, and the described plasma high-temperature quartz tube furnace other end is provided with
2 exhaust tubes, an exhaust tube connection molecule pump, another exhaust tube connects liquid nitrogen cold trap, and the liquid nitrogen cold trap passes through pipeline and machine
Tool pump is connected；Described plasma high-temperature quartz tube furnace outer surface is wound with inductively coupled plasma coil, described
The two ends connection radio frequency power source of inductively coupled plasma coil；Set on the exhaust tube being connected with liquid nitrogen cold trap free
Gas air inlet pipe, the air intake duct is provided with air shut-off valve door, and the exhaust tube being connected with liquid nitrogen cold trap is provided with the
Be provided with the 3rd control valve on one control valve, the pipeline of the liquid nitrogen cold trap and mechanical pump, the 3rd control valve with
It is provided with the pipeline of liquid nitrogen cold trap connection in vacuum meter, the bypass of the vacuum meter and pipeline connection and is provided with the 4th control valve
Door, the described exhaust tube for being connected with molecular pump is provided with the second control valve, described reducibility gas air inlet pipe and connected
There are digital display mass flowmenter and control valve.
9. a kind of Heteroatom doping porous graphene electricity prepared by any one of claim 1~7 preparation method is urged
Agent.
10. the application of Heteroatom doping porous graphene elctro-catalyst according to claim 9, it is characterised in that：It is described miscellaneous
Atom doped porous graphene elctro-catalyst is applied to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell and metal-sky
Pneumoelectric pool cathode Material Field.
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| CN105668724A (en) * | 2016-03-18 | 2016-06-15 | 常州大学 | One-step synthesized nitrogen and sulfur co-doped graphene aerosol and electro-adsorption removal of various heavy metal ions thereby |
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| CN102583339B (en) * | 2012-01-20 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene from three-dimensional porous carbon material and three-dimensional porous graphene |
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| US20150147642A1 (en) * | 2013-11-26 | 2015-05-28 | Toyota Motor Engineering & Manufacturing North America, Inc. | Boron-doped graphene sheet as sodium-ion battery anode |
| CN104671237B (en) * | 2015-02-04 | 2016-08-17 | 浙江大学 | A kind of devices and methods therefor preparing graphene film based on plasma |
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