CN107236966A - A kind of carbon silica aerogel electrode containing N prepares activation method - Google Patents

A kind of carbon silica aerogel electrode containing N prepares activation method Download PDF

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CN107236966A
CN107236966A CN201710307355.9A CN201710307355A CN107236966A CN 107236966 A CN107236966 A CN 107236966A CN 201710307355 A CN201710307355 A CN 201710307355A CN 107236966 A CN107236966 A CN 107236966A
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silica aerogel
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赵红颖
陈英
赵国华
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Tongji University
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    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract

Activation method is prepared the present invention relates to a kind of carbon silica aerogel electrode containing N, N is mixed in carbon aerogels skeleton situ, and the carbon aerogels CO that adulterated to N2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doping carbon aerogels.Compared with prior art, the present invention passes through CO due to making N atoms be evenly dispersed into carbon aerogels matrix using incorporation N in situ2And N2Activation, prepared N carbon silica aerogel electrodes of mixing are in production H2O24 times are improved than carbon aerogels, also has that preparation method is easy, electrode easily shapes in addition, catalytic reaction activity is high, the advantages of be easy to recycle.

Description

A kind of carbon silica aerogel electrode containing N prepares activation method
Technical field
The invention belongs to carbon material field, activation method is prepared more particularly, to a kind of carbon silica aerogel electrode containing N.
Background technology
Hydrogen peroxide (H2O2) it is a kind of important chemicals, it is widely used in bleaching agent, chemosynthesis reaction thing, fire Arrow propellant, antiseptic and Water warfare reagent etc..H2O2As oxidant in use, because accessory substance is H2O, therefore be a kind of The oxidant of green.Electrochemical in-situ reduces O2Produce H2O2, overcome H2O2Because store and conveyer belt come danger, and not by The limitation of preparation condition, is a kind of very promising technology.Therefore, how O is efficiently controlled2Reduction makes it send out as much as possible Raw two electron reductions produce H2O2, just turn into the focus and difficulties of research.
The property and structure of cathode material are for O2Reducing activity has important influence.Cathode material is to O2Two electronics are also The selectivity of original reaction is relevant with the active site species of material surface, and catalytic reaction activity and the electrification of cathode material Learn active area, electric conductivity and mass-transfer performance relevant.Wherein, carbon material is because good conductivity, hydrogen gas evolution overpotential are high, chemistry is steady It is qualitative and for H2O2Low catalytic activity and be widely used in electro-catalysis and produce H2O2Research.According to literature survey, it is used for Electrochemical reduction O2Produce H2O2Carbon material mainly have graphite, activated carbon fiber, reticulated vitreous carbon, carbon felt/graphite felt, carbon sea Tender carbon/PTFE combination electrode materials etc..Carbon material electro-catalysis produces H2O2Often carried out in alkaline medium, especially oxygen function The carbon material surface (such as quinonyl) of change, can significantly increase the activity that its electro-catalysis reduces oxygen.But, hydroxide ion meeting It is catalyzed H2O2Decompose, and H2O2Acid medium is frequently necessary in actual applications.On carbon-based electrode, ORR is in acid medium High overpotential is needed, and quinonyl can not be catalyzed ORR in sour environment.Therefore, how carbon electrode is improved in acid medium Electrocatalysis characteristic, just turn into our focus of attention.
Chinese patent CN 104446330B disclose a kind of preparation method of superhigh specific surface area nitrating carbon aerogels, with Melamine, resorcinol and formaldehyde are raw material, and triblock copolymer F68 is template, and sodium hydroxide is catalyst, through molten Glue-gel reaction, exchange of solvent, constant pressure and dry and high temperature cabonization obtain nitrating carbon aerogels；Again at high temperature with carbon dioxide Activated as activator, the nitrating carbon aerogels of superhigh specific surface area are obtained, by with melamine, resorcinol and first Aldehyde is used as precursors, it is ensured that the stability and uniformity of nitrogen are mixed in obtained material, adds triblock copolymer F68 is as template, for forming micron-sized duct in carbon aerogels and greatly improving traditional aeroge constant pressure and dry The serious contraction collapse phenomenon occurred in preparation process；Activation process is carried out to nitrating carbon aerogels using carbon dioxide, it is micro- The presence in meter level duct, which has, to be deep into material internal beneficial to carbon dioxide and performs etching, so that the specific surface area of material obtains pole Big lifting.Compared with this patent, the nitrating carbon aerogels preparation method of the application is simpler, to nitrating carbon aerogels activation temperature And method is optimized.Make the raising of the more favourable ORR activity of nitrating carbon aerogels, the type for mixing nitrogen is varied with temperature, entered Row analysis, the nitrogen for obtaining graphite mould is conducive to 2e-ORR activity, the carbon aerogels after being modified produce more H2O2.It can be used for The cathode material of electric Fenton-like system, electronic generation H2O2, Fenton activity is improved, faster degradation of contaminant expands nitrating carbon gas Gel application field.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can improve life H2O2Yield, reduce cost, and the preparation method simply carbon silica aerogel electrode containing N prepares activation method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of carbon silica aerogel electrode containing N prepares activation method, mixes N in carbon aerogels skeleton situ, and N is adulterated Carbon aerogels CO2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doping carbon aerogels, adopts Use following steps：
(1) resorcinol, formaldehyde, sodium carbonate are dissolved in water, then add N sources, stir after close in container Envelope, 20~30 DEG C of constant temperature is placed in 24~30 hours by the container, 40~50 DEG C of constant temperature 24~30 hours, 85~90 DEG C of constant temperature 70 To occur polymerization, N wet gels are mixed in formation within~75 hours, then soak the gel prepared in acetone at ambient temperature Stain 3~5 days, changes an acetone daily, for replacing the water in gel, after dipping terminates, dry 2 at ambient temperature~ 3 days, the xerogel of a large amount of structural integrities is obtained, polycondensation reaction occurs under suitable lower temperature and is formed for resorcinol, formaldehyde Phenolic resin, during polymerization, forms stable network structure, is impregnated 3~5 days using in acetone, one is changed daily Secondary acetone, prevents from causing its network knot natural air drying or high temperature drying moisture evaporation speed are too fast for the water replaced in gel Structure will not be collapsed, and this method is workable, convenient and simple.Then these xerogel are placed in the heating of tube furnace Program, in nitrogen Gas velocity under 300~400mL/min nitrogen atmosphere, 600-700 DEG C is risen to 1~2 DEG C of heating rate per minute, and Kept for 4~5 hours at such a temperature, room temperature is then down to phase same rate, the bulk for having obtained structural integrity mixes N carbon airsettings Gel electrode；
(2) the N carbon silica aerogel electrodes of mixing that step (1) is prepared are placed in the heating of tube furnace Program, in carbon dioxide Flow velocity for 30~40mL/min carbon dioxide atmosphere under, rise to 750-850 DEG C with 4 DEG C of speed per minute, at such a temperature Kept for 1-2 hours, be then down to phase same rate after room temperature, obtain the block CO of structural integrity2Activate N carbon doping aeroges Electrode；
(3) the block CO for preparing step (2)2Activation N carbon doping silica aerogel electrodes are placed in tube furnace Program liter Temperature, under 200~300mL/min of nitrogen flow rate nitrogen atmosphere, 750~850 DEG C are risen to 4~5 DEG C of speed per minute, Kept for 1~2 hour at this temperature, room temperature is then down to phase same rate, the block CO of structural integrity is obtained2And N2N carbon is mixed in activation Aeroge, as product.
Resorcinol described in step (1)：Formaldehyde：Water：The mol ratio of sodium carbonate is 1：2~3：16~19： 0.0007 ~0.001
As preferred embodiment, resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is preferably 1：2： 17.5： 0.0008。
N sources described in step (1) are acetonitrile, and addition accounts for the 3%~10% of the gross mass of raw material.Mix N content With the difference of activation temperature, there is different degrees of reduction, the defect of carbon material increases, increase avtive spot.With activation temperature 600-900 DEG C of change, has for N doping configurations and significantly affects.Experiments verify that in 700-800 DEG C or so CO2Reaming, can Effectively increase N adulterate carbon aerogels specific surface area, for N adulterate configuration also can with the change of temperature, mutually conversion and Reduce.We control the change of activation temperature, using the change of XPS analytical elements composition and valence state, contain in material is ensured A certain amount of N and activation temperature during optimal catalytic performance.Through the electrode after optimal activation temperature activation, with high proportion Graphite mould N and oxidized form N, the avtive spot for having stronger adsorption capacity to oxygen can be formed, catalytic activity has obtained significantly carrying It is high.ORR tests show that take-off potential is moved with N incorporation on the occasion of direction, realizes the raising of carbon material catalytic activity.Thing Reason resistance diminishes, and good conductivity, the specific surface area of material is significantly improved.
Pass through CO2After activation, N content is mixed with the difference of activation temperature, there is different degrees of reduction, carbon material Defect is more, increases avtive spot.Activation temperature also has on doping configuration to be significantly affected, with graphite mould N and oxidized form N ratio Example increase, forms the avtive spot for having stronger adsorption capacity to oxygen, and catalytic activity has obtained significant raising.ORR, which is tested, to be shown, Take-off potential is moved with N incorporation on the occasion of direction, realizes the raising of carbon material catalytic activity.Physical resistance diminishes, conductive Property is good, and the specific surface area of material is significantly improved.
Further pass through N2After activation, ensureing that N content is constant or somewhat increases, mixing the middle graphite mould and oxygen of N carbon materials The ratio of the nitrogen of change type is further improved, ORR increased activities, is more beneficial for 2e-ORR reacts, and improves H2O2Yield, material Specific surface area is changed less.
Using the product prepared as negative electrode, its Anodic is boron-doped diamond (BDD) membrane electrode, 0.05M's Na2SO4(PH=3) H is determined under chem workstation, constant voltage to be used in supporting electrolyte2O2Yield.Before reaction In 0.05M Na2SO4 (PH=3) solution, oxygen is first aerated 20~30 minutes with 200~300mL/min speed, in reaction During oxygen aeration rate keep it is constant.
Compared with prior art, the present invention possesses advantages below：
(1) bulk is constructed out using one-step method and mixes N carbon aerogels, make N homoepitaxials in situ in the three dimensional network of carbon aerogels In network structure, cost is low, and method is simple, easy to operate.
(2) by controlling suitable CO2Activation and N2Activation, can regulate and control to mix N carbon aerogels material specific surface areas, improve stone Black type N and oxidized form N ratio, increase avtive spot, improve ORR activity, so as to improve electro-catalysis generation H2O2Amount.
(3) compared with undoped with carbon aerogels, energy consumption is low, H2O2Output increased 4 times.
Brief description of the drawings
Fig. 1 be using different materials as negative electrode, boron-doped diamond (BDD) membrane electrode as anode, under constant voltage 0.05M Na2SO4H is produced to carry out electro-catalysis in electrolyte2O2Amount.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following examples will be helpful to this area Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the general of this area For logical technical staff, without departing from the inventive concept of the premise, various modifications and improvements can be made.These are belonged to Protection scope of the present invention.
Embodiment 1
One kind is used for electro-catalysis in situ and produces H2O2, preparation method is easy, catalytic reaction activity is high, be easy to what is recycled N carbon silica aerogel electrodes are mixed as negative electrode, and the specific preparation process for mixing N carbon silica aerogel electrodes is as follows：
(1) appropriate resorcinol, formaldehyde, water, sodium carbonate are weighed, then with resorcinol：Formaldehyde：Water：Sodium carbonate Mol ratio is 1：2：17.5：0.0008 mixing, it is rear among injection cuboid glass container after stirring to seal.This is held Device is placed in 20~30 DEG C of constant temperature 24~30 hours, 40~50 DEG C of constant temperature 24~30 hours, 85~90 DEG C of constant temperature 70~75 hours with Generation polymerization, forms wet gel.Then by the gel prepared at ambient temperature in acetone impregnate 3~5 days, daily An acetone is changed, for replacing the water in gel, after dipping terminates, dries 2~3 days at ambient temperature, obtains a large amount of The xerogel of structural integrity.Then these xerogel are placed in the heating of tube furnace Program, are 300~400mL/ in nitrogen flow rate Under min nitrogen atmosphere, 800-950 DEG C is risen to 1~2 DEG C of heating rate per minute, and holding 4~5 is small at such a temperature When, room temperature is then down to phase same rate, the block carbon silica aerogel electrode (CA) of structural integrity has been obtained.
(2) appropriate resorcinol, formaldehyde, water, sodium carbonate are weighed, then with resorcinol：Formaldehyde：Water：Sodium carbonate Mol ratio is 1：2：17.5：0.0008 mixing, after uniform solution is formed, N sources acetonitrile is added into precursor solution, It is rear among injection cuboid glass container after stirring to seal.The container is placed in 20~30 DEG C of constant temperature 24~30 hours, 40~50 DEG C of constant temperature 24~30 hours, to occur polymerization, N wet gels were mixed in formation in 70~75 hours for 85~90 DEG C of constant temperature.So The gel prepared is impregnated 3~5 days in acetone at ambient temperature afterwards, an acetone is changed daily, for replacing gel In water, dipping terminate after, at ambient temperature dry 2~3 days, obtain the xerogel of a large amount of structural integrities.Then by this A little xerogel are placed in the heating of tube furnace Program, in the case where nitrogen flow rate is 300~400mL/min nitrogen atmosphere, with 1~2 DEG C Heating rate per minute rises to 600-700 DEG C, and is kept for 4~5 hours at such a temperature, is then down to room with phase same rate Temperature, the bulk for having obtained structural integrity mixes N carbon silica aerogel electrodes (NCA).
(3) CO for mixing N carbon aerogels (NCA) according to prepared by claim 22Activation method, the activation method is as follows： N aeroges (NCA) electrode of mixing prepared by claim 2 is placed in the heating of tube furnace Program, is 30 in carbon dioxide flow rate Under~40mL/min carbon dioxide atmosphere, 750-850 DEG C is risen to 4 DEG C of speed per minute, keeps 1-2 small at such a temperature When, then it is down to phase same rate after room temperature, has obtained the block CO of structural integrity2Activate N carbon doping silica aerogel electrodes (NCA-CO2)。
(4) N for mixing N carbon aerogels (NCA) according to prepared by claim 32Activation method, the activation method is as follows： By CO in claim 32The electrode for mixing N carbon aerogels (NCA) of activation is placed in the heating of tube furnace Program, in nitrogen flow rate Under 200~300mL/min nitrogen atmosphere, 750~850 DEG C are risen to 4~5 DEG C of speed per minute, 1 is kept at such a temperature ~2 hours, room temperature is then down to phase same rate, the block CO of structural integrity has been obtained2And N2N carbon aerogels (NCA) are mixed in activation Electrode (NCA-CO2-N2)。
Embodiment 2
By CA, NCA-CO in embodiment 12And NCA-CO2-N2It is separately in electrocatalytic reaction system, measurement is produced H2O2Amount, as the negative electrode in electrocatalytic reaction system, its Anodic is boron-doped diamond (BDD) membrane electrode, is used Glass cement, which is fixed, " mixes the area about 3cm of N silica aerogel electrodes2, using chem workstation, under constant voltage, PH=3 0.05M Na2SO4To carry out before electrocatalytic reaction, reaction solution in supporting electrolyte in oxygen with 200~250mL/min speed First it is aerated 20~30 minutes, oxygen aeration rate keeps constant during electrocatalytic reaction, takes a sample per 30min, makes H is determined with ultraviolet specrophotometer2O2Yield.
Embodiment 3
Repeat embodiment more than 2 times, mix N aeroges (NCA) electrode and still keep higher catalytic activity.
Fig. 1 is with block carbon silica aerogel electrode (CA), CO2Activation block mixes N carbon silica aerogel electrodes and CO2、 N2Activation block Shape mixes N carbon silica aerogel electrodes as negative electrode, when boron-doped diamond (BDD) membrane electrode is as anode, in 0.05M under constant voltage Na2SO4H is produced to carry out electro-catalysis in electrolyte2O2.Wherein accompanying drawing is the electronic generation H of Different electrodes under three-electrode system2O2 Figure.Wherein CA-1.3 carbon silica aerogel electrodes, are the electrode undoped with N；750C-NCA-1.1 is 750 DEG C of CO2Activation block is mixed N carbon silica aerogel electrodes；850C-NCA-1.1 is 850 DEG C of CO2Activation block mixes N carbon silica aerogel electrodes, 750C-750N-NCA- 1.1 i.e. 750 DEG C of CO2After activation, then carry out 750 DEG C of N2High-temperature calcination bulk mixes N carbon silica aerogel electrodes 750C-750N-NCA-1.1； 750C-850N-NCA-1.1 i.e. 750 DEG C CO2After activation, then carry out 850 DEG C of N2High-temperature calcination bulk mixes N carbon silica aerogel electrodes.
After nitrogen-doped carbon aeroge and activation, the surface hydrophilic and hydrophobic of carbon aerogels changes, and is conducive to O2Molecule Absorption, and the incorporation of nitrogen causes carbon material, and surface defect increases, and avtive spot increases, and increases the activity of ORR reactions. CO2Activation mainly play reaming, beneficial to O2Absorption and accelerate mass transfer.
Embodiment 4
A kind of carbon silica aerogel electrode containing N prepares activation method, mixes N in carbon aerogels skeleton situ, and N is adulterated Carbon aerogels CO2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doping carbon aerogels, adopts Use following steps：
(1) resorcinol, formaldehyde, sodium carbonate are dissolved in water, resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is 1：2：16：0.0007, then add acetonitrile as N sources, the addition in N sources accounts for the 3% of the gross mass of raw material, stir after Sealed in container, the container is placed in 20 DEG C of constant temperature 30 hours, 40 DEG C of constant temperature 30 hours, 85 DEG C of constant temperature 75 hours is to polymerize N wet gels are mixed in effect, formation, then impregnate 3 days the gel prepared in acetone at ambient temperature, change once daily Acetone, for replacing the water in gel, after dipping terminates, dries 2 days, obtains the dry of a large amount of structural integrities at ambient temperature Then these xerogel are placed in the heating of tube furnace Program by gel, in the case where nitrogen flow rate is 300mL/min nitrogen atmosphere, 600 DEG C are risen to 1 DEG C of heating rate per minute, and is kept for 4 hours at such a temperature, room temperature is then down to phase same rate, The bulk for having obtained structural integrity mixes N carbon silica aerogel electrodes；
(2) the N carbon silica aerogel electrodes of mixing that step (1) is prepared are placed in the heating of tube furnace Program, in carbon dioxide Flow velocity is under 30mL/min carbon dioxide atmosphere, 750 DEG C is risen to 4 DEG C of speed per minute, and holding 1 is small at such a temperature When, then it is down to phase same rate after room temperature, obtains the block CO of structural integrity2Activate N carbon doping silica aerogel electrodes；
(3) the block CO for preparing step (2)2Activation N carbon doping silica aerogel electrodes are placed in tube furnace Program liter Temperature, under nitrogen flow rate 200mL/min nitrogen atmosphere, rises to 750 DEG C with 4 DEG C of speed per minute, keeps at such a temperature 1 hour, room temperature is then down to phase same rate, the block CO of structural integrity is obtained2And N2N carbon aerogels are mixed in activation, as produce Product.
Using the product prepared as negative electrode, anode is boron-doped diamond (BDD) membrane electrode, 0.05M's Na2SO4(PH=3) H is determined under chem workstation, constant voltage to be used in supporting electrolyte2O2Yield.Determine H2O2Before yield In 0.05M Na2SO4(PH=3) in solution, oxygen is first aerated 20 minutes with 200mL/min speed, is then reacted, instead Oxygen aeration rate keeps constant during answering.
Embodiment 5
A kind of carbon silica aerogel electrode containing N prepares activation method, mixes N in carbon aerogels skeleton situ, and N is adulterated Carbon aerogels CO2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doping carbon aerogels, adopts Use following steps：
(1) resorcinol, formaldehyde, sodium carbonate are dissolved in water, resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is 1：2：17.5：0.0008, acetonitrile is then added as N sources, and the addition in N sources accounts for the 3% of the gross mass of raw material, after stirring Sealed in container, the container is placed in 20 DEG C of constant temperature 30 hours, 40 DEG C of constant temperature 30 hours, 85 DEG C of constant temperature 75 hours are poly- to occur Cooperation is used, and N wet gels are mixed in formation, then impregnates 3 days the gel prepared in acetone at ambient temperature, one is changed daily Secondary acetone, for replacing the water in gel, after dipping terminates, dries 2 days, obtains a large amount of structural integrities at ambient temperature Then these xerogel are placed in the heating of tube furnace Program by xerogel, in the nitrogen atmosphere that nitrogen flow rate is 300mL/min Under, 600 DEG C are risen to 1 DEG C of heating rate per minute, and kept for 4 hours at such a temperature, room is then down to phase same rate Temperature, the bulk for having obtained structural integrity mixes N carbon silica aerogel electrodes；
(2) the N carbon silica aerogel electrodes of mixing that step (1) is prepared are placed in the heating of tube furnace Program, in carbon dioxide Flow velocity is under 30mL/min carbon dioxide atmosphere, 750 DEG C is risen to 4 DEG C of speed per minute, and holding 1 is small at such a temperature When, then it is down to phase same rate after room temperature, obtains the block CO of structural integrity2Activate N carbon doping silica aerogel electrodes；
(3) the block CO for preparing step (2)2Activation N carbon doping silica aerogel electrodes are placed in tube furnace Program liter Temperature, under nitrogen flow rate 200mL/min nitrogen atmosphere, rises to 750 DEG C with 4 DEG C of speed per minute, 1 is kept at such a temperature Hour, room temperature is then down to phase same rate, the block CO of structural integrity is obtained2And N2N carbon aerogels are mixed in activation, as produce Product.
Using the product prepared as negative electrode, anode is boron-doped diamond (BDD) membrane electrode, 0.05M's Na2SO4(PH=3) H is determined under chem workstation, constant voltage to be used in supporting electrolyte2O2Yield.Determine H2O2Before yield In 0.05M Na2SO4(PH=3) in solution, oxygen is first aerated 20 minutes with 200mL/min speed, is then reacted, instead Oxygen aeration rate keeps constant during answering.
Embodiment 6
A kind of carbon silica aerogel electrode containing N prepares activation method, mixes N in carbon aerogels skeleton situ, and N is adulterated Carbon aerogels CO2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doping carbon aerogels, adopts Use following steps：
(1) resorcinol, formaldehyde, sodium carbonate are dissolved in water, resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is 1：3：19：0.001, then add acetonitrile as N sources, the addition in N sources accounts for the 10% of the gross mass of raw material, stir after Sealed in container, the container is placed in 30 DEG C of constant temperature 24 hours, 50 DEG C of constant temperature 24 hours, 90 DEG C of constant temperature 70 hours is to polymerize N wet gels are mixed in effect, formation, then impregnate 5 days the gel prepared in acetone at ambient temperature, change once daily Acetone, for replacing the water in gel, after dipping terminates, dries 3 days, obtains the dry of a large amount of structural integrities at ambient temperature Then these xerogel are placed in the heating of tube furnace Program by gel, in the case where nitrogen flow rate is 400mL/min nitrogen atmosphere, 700 DEG C are risen to 2 DEG C of heating rates per minute, and is kept for 5 hours at such a temperature, room temperature is then down to phase same rate, The bulk for having obtained structural integrity mixes N carbon silica aerogel electrodes；
(2) the N carbon silica aerogel electrodes of mixing that step (1) is prepared are placed in the heating of tube furnace Program, in carbon dioxide Flow velocity is under 40mL/min carbon dioxide atmosphere, 850 DEG C is risen to 4 DEG C of speed per minute, and holding 2 is small at such a temperature When, then it is down to phase same rate after room temperature, obtains the block CO of structural integrity2Activate N carbon doping silica aerogel electrodes；
(3) the block CO for preparing step (2)2Activation N carbon doping silica aerogel electrodes are placed in tube furnace Program liter Temperature, under nitrogen flow rate 300mL/min nitrogen atmosphere, rises to 850 DEG C with 5 DEG C of speed per minute, keeps at such a temperature 2 hours, room temperature is then down to phase same rate, the block CO of structural integrity is obtained2And N2N carbon aerogels are mixed in activation, as produce Product.
Using the product prepared as negative electrode, anode is boron-doped diamond (BDD) membrane electrode, 0.05M's Na2SO4(PH=3) H is determined under chem workstation, constant voltage to be used in supporting electrolyte2O2Yield.Determine H2O2Before yield In 0.05M Na2SO4(PH=3) in solution, oxygen is first aerated 30 minutes with 300mL/min speed, is then reacted, instead Oxygen aeration rate keeps constant during answering.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (7)

1. a kind of carbon silica aerogel electrode containing N prepares activation method, it is characterised in that mix N in carbon aerogels skeleton situ, And the carbon aerogels CO that adulterated to N2And N2Activation, adjusts the hydrophilic and hydrophobic of aeroge, prepares with high catalytic activity N doped carbons Aeroge, using following steps：
(1) resorcinol, formaldehyde, sodium carbonate are dissolved in water, then add N sources, stirred after being sealed in container, will The container is placed in 20~30 DEG C of constant temperature 24~30 hours, 40~50 DEG C of constant temperature 24~30 hours, and 85~90 DEG C of constant temperature 70~75 are small When to occur polymerization, N wet gels are mixed in formation, and the gel prepared is then impregnated into 3~5 in acetone at ambient temperature My god, an acetone is changed daily, for replacing the water in gel, after dipping terminates, is dried 2~3 days, is obtained at ambient temperature To the xerogel of a large amount of structural integrities, these xerogel are then placed in the heating of tube furnace Program, nitrogen flow rate be 300~ Under 400mL/min nitrogen atmosphere, 600-700 DEG C is risen to 1~2 DEG C of heating rate per minute, and keep 4 at such a temperature ~5 hours, room temperature is then down to phase same rate, the bulk for having obtained structural integrity mixes N carbon silica aerogel electrodes；
(2) the N carbon silica aerogel electrodes of mixing that step (1) is prepared are placed in the heating of tube furnace Program, in carbon dioxide flow rate Under 30~40mL/min carbon dioxide atmosphere, to rise to 750-850 DEG C with 4 DEG C of speed per minute, keeping at such a temperature 1-2 hours, then it is down to phase same rate after room temperature, obtains the block CO of structural integrity2Activate N carbon dopings aeroge electricity Pole；
(3) the block CO for preparing step (2)2Activation N carbon doping silica aerogel electrodes are placed in the heating of tube furnace Program, Under 200~300mL/min of nitrogen flow rate nitrogen atmosphere, 750~850 DEG C are risen to 4~5 DEG C of speed per minute, in the temperature Degree is lower to be kept for 1~2 hour, is then down to room temperature with phase same rate, is obtained the block CO of structural integrity2And N2N carbon airsettings are mixed in activation Glue, as product.
2. a kind of carbon silica aerogel electrode containing N according to claim 1 prepares activation method, it is characterised in that step (1) Described in resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is 1：2~3：16~19：0.0007~0.001.
3. a kind of carbon silica aerogel electrode containing N according to claim 2 prepares activation method, it is characterised in that step (1) Described in resorcinol：Formaldehyde：Water：The mol ratio of sodium carbonate is preferably 1：2：17.5：0.0008.
4. a kind of carbon silica aerogel electrode containing N according to claim 1 prepares activation method, it is characterised in that step (1) Described in N sources be acetonitrile.
5. a kind of carbon silica aerogel electrode containing N according to claim 1 or 4 prepares activation method, it is characterised in that step (1) addition in N sources accounts for the 3%~10% of the gross mass of raw material in.
6. a kind of carbon silica aerogel electrode containing N according to claim 1 prepares activation method, it is characterised in that will prepare Obtained product is as negative electrode, and anode is boron-doped diamond (BDD) membrane electrode, in 0.05M Na2SO4(PH=3) it is support Used in electrolyte under chem workstation, constant voltage and determine H2O2Yield.
7. a kind of carbon silica aerogel electrode containing N according to claim 6 prepares activation method, it is characterised in that determine H2O2 In 0.05M Na before yield2SO4(PH=3) in solution, oxygen is first aerated 20~30 minutes with 200~300mL/min speed, Then reacted, oxygen aeration rate keeps constant in course of reaction.
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