CN104862808B - A kind of Fe-N-C nanometer fiber net and preparation method thereof - Google Patents
A kind of Fe-N-C nanometer fiber net and preparation method thereof Download PDFInfo
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Abstract
A kind of Fe N C nano fleece and preparation method thereof, described Fe N C nano fleece is made in accordance with the following methods: (1) preparation spinning solution: ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are mixed, ultrasonic disperse, obtain spinning solution；(2) electrostatic spinning；(3) solvent atmosphere processes: is placed in suitable solvents atmosphere process, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibril net；(4) pre-oxidation: pre-oxidize in air atmosphere；(5) pyrolysis: pre-oxidized fibers net is pyrolyzed with tripolycyanamide, obtains the nanometer fiber net after carbonization；(6) acid treatment: acid treatment, washing, dry；(7) finally it is pyrolyzed, obtains Fe N C nano fleece.Preparation method of the present invention is simple, is produced on a large scale, and obtained Fe N C nano fleece diameter Distribution is uniform, and size is 200～500nm, and nanofiber is connected with each other, and good conductivity has wide application prospect.
Description
Technical field
The present invention relates to a kind of fleece and preparation method thereof, be specifically related to a kind of Fe-N-C nanometer fiber net and preparation method thereof.
Background technology
Existing low-temperature fuel cell cathode catalysis kinetics is slow, and conventional Pt/C catalyst is due to expensive and scarcity of resources, the serious popularization and application restricting fuel cell.And transition metal nitrogen carbon compound (M-N-C, M=Fe, Co etc.) catalytic performance is high, low price, by researcher extensive concern.Precursor pyrolysis and hot pressing have the Nomenclature Composition and Structure of Complexes can design and regulate and control, the advantage such as molding and handling ease, be one of main method preparing ceramic composite materials at present.At present, conventional method prepare M-N-C catalyst is to select suitable carbon, nitrogen, transition metal precursor, is pyrolyzed at a suitable temperature after mixing, and preparation technology is simply it is considered to be the method for preparing catalyst of great potential.Method of electrostatic spinning is that precursor solution relies on thousand of high-pressure electrostatic power to several ten thousand volts to stretch the effective ways preparing nanofiber; in addition to the advantage such as possess that equipment is simple, cost is low and the suitability is wide, electrospinning process is used to facilitate implementation the large-scale production of nanofiber.But, mutually overlap between nanofiber prepared by routine intravenous electrical spinning method, introduce contact resistance, hinder electric charge transmission between the fibers.
Yan et al. (X. Yan, L.
Gan, Y. Lin, L. Bai, T. Wang, X. Wang, J. Luo and J. Zhu, Controllable
synthesis and enhanced electrocatalysis of iron-based catalysts derived from
Electrospun nanofibers. Small, 2014, DOI:10.1002./small.201401213.) by PAN and Fe (NO3)3It is blended in DMF, after obtaining fibril felt by electrostatic spinning, directly pre-oxidation and pyrolysis, prepared Fe-N-C nanofiber mutually overlaps, contact resistance between fiber can increase electric charge transport resistance between the fibers, the electric conductivity causing fiber felt declines, and reduces the electro catalytic activity of fiber felt.Jeong et al. (B. Jeong, D.
Shin, H. Jeon, J. D. Ocon, B. S. Mun, J. Baik, H. Shin and J. Lee, Excavated
Fe-N-C sites for enhanced electrocatalytic acticity in the oxygen reduction
Reaction. ChemSusChem, 2014,7,1289-1294.) by PAN and Fe (acac)3Being blended in DMF, the nanofiber mats of preparation is after ball milling, although expose more avtive spot, but the fiber of fracture and broken pore structure can hinder electric charge transmission and electrolyte transmission in the catalyst, cause the electrocatalytic oxidation reducing property of fiber felt to reduce.
Summary of the invention
The technical problem to be solved is to provide that a kind of technical process is simple, facilitate implementation large-scale production, Fe-N-C nanometer fiber net that obtained nanometer fiber net is connected with each other, charge transfer resistance is low and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of Fe-N-C nanometer fiber net, makes in accordance with the following methods:
(1) preparation spinning solution: ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are added in reactor with the ratio of 0.5～6:10:100 and mixes, then ultrasonic disperse, obtain spinning solution；
(2) electrostatic spinning: step (1) gained spinning solution carries out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibril felt；
(3) solvent atmosphere processes: step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril felt is placed in the suitable solvents atmosphere of polyvinylpyrrolidone process, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibril net；
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril net is pre-oxidized in air atmosphere, obtains pre-oxidized fibers net；
(5) pyrolysis: step (4) gained pre-oxidized fibers net and tripolycyanamide are concurrently placed under inert atmosphere protection with mass ratio 1:8～12 and are pyrolyzed, be cooled to room temperature, obtain the nanometer fiber net after carbonization；
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is carried out acid treatment, then is washed with deionized to neutrality, dry；
(7) finally pyrolysis: the nanometer fiber net after being dried by step (6) gained is pyrolyzed under inert atmosphere protection, is cooled to room temperature, obtains Fe-N-C nanometer fiber net.
Further, in step (3), the suitable solvents atmosphere of described polyvinylpyrrolidone refers to the air atmosphere that suitable solvents relative humidity is 50～90RH% of polyvinylpyrrolidone.Described relative humidity be in air the absolute humidity of water or solvent with should at a temperature of the ratio of saturated humidity of water or solvent.
Further, in step (3), the temperature that described solvent atmosphere processes is 15～60 DEG C (preferably 20～40 DEG C), and the time is 20～60h(preferably 22～30h).
Further, in step (3), the suitable solvents of described polyvinylpyrrolidone includes one or more in ethanol, water or dimethylformamide.
Processing through step (3) suitable solvents atmosphere, the nanofiber mats being mutually lapped can become interconnective nanometer fiber net under the action of the solvent.
In step (1), selected ferric acetyl acetonade, polyvinylpyrrolidone and ethanol suitable ratio beneficially electrostatic spinning obtains the fiber of uniform diameter.
Further, in step (1), the K value of described polyvinylpyrrolidone is 30～90.
Further, in step (1), the frequency of described ultrasonic disperse is 15～20 kHz, and the time is 1～3h.Can get finely dispersed spinning solution in this operating condition.
Further, in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV(preferably 15～20kV), needle point is 10～30cm(preferably 15～20cm to the vertical dimension of receiving screen), feeding rate is 5～30 μ L/min(preferably 10～20 μ L/min), spinning temperature is 10～60 DEG C (preferably 15～30 DEG C), and relative air humidity is 20～80RH%.Described receiving screen is flat board aluminium foil.The fibre diameter obtained in the range of above-mentioned parameter is less, and is evenly distributed.
Further, in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.Pre-oxidation makes fibril crosslink, and prevents fiber from occurring doubling phenomena, suitable Pre oxidation and time can ensure that fiber is full cross-linked in pyrolytic process.
Further, in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h(preferably 1～5h).In practical operation, pre-oxidized fibers net can be covered on tripolycyanamide.Described inert atmosphere is high-purity argon gas or the high pure nitrogen of purity >=99.99%.The pyrolysis of step (5) pre-oxidation can be made after the abundant carbonization of fiber, tripolycyanamide fully decompose distillation, nitrogen element is incorporated in fiber formation Fe-N-C or nitrogen-doped carbon, as avtive spot performance electrocatalysis；The pyrolysis of step (7) is the small-molecule substance in order to contain in fiber after removing acidifying.
Further, in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.Acid treatment can be pyrolyzed with removing step (5) after Fe and Fe that contain of fiber surface3O4。
The present invention is by being dissolved in ferric acetyl acetonade and polyvinylpyrrolidone in alcohol solvent, use electrostatic spinning technique and polymer pyrolysis technology, process through electrostatic spinning, solvent atmosphere, pre-oxidize, be pyrolyzed, acid treatment and being finally pyrolyzed, obtain porous and interconnective Fe-N-C nanometer fiber net.
Present invention have the advantage that Fe-N-C nanofiber web preparation method is simple, it is simple to large-scale production；Fe-N-C nanometer fiber net is non-woven fabrics state, even in fiber diameter distribution, and diameter is 200～500nm；Solve and connect for overlap joint between nanofiber prepared by common electrostatic spinning, the problem causing introducing contact resistance, it is connected with each other between Fe-N-C nanofiber network fiber of the present invention, charge transfer resistance is little；Fe-N-C or nitrogen-doped carbon in nanometer fiber net can be as the avtive spots of electrocatalytic reaction；Fibrous inside contains abundant pore structure, and specific surface area is big；Prepared Fe-N-C nanometer fiber net has wide application prospects at self-supporting catalyst and fuel cell cathode catalyst field.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net；
Fig. 2 is the SEM figure of comparative example 1 gained Fe-N-C nanofiber mats；
Fig. 3 is the graph of pore diameter distribution of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net；
Fig. 4 is the full spectrogram of XPS of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net；
Fig. 5 is the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net and the electrochemical impedance spectroscopy comparison diagram of comparative example 1 gained Fe-N-C nanofiber mats；
Fig. 6 is the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net and the hydrogen reduction performance comparison figure of comparative example 1 gained Fe-N-C nanofiber mats.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
The used nitrogen of the embodiment of the present invention is the high pure nitrogen of purity >=99.99%；Other chemical reagent used, if no special instructions, is all obtained by routine business approach.
Embodiment
1
(1) preparation spinning solution: ferric acetyl acetonade, polyvinylpyrrolidone (K value is 90) and ethanol are mixed, then 20 with the ratio of mass ratio 2:10:100
Under kHz supersonic frequency, carry out ultrasonic disperse 2h, obtain spinning solution；
(2) electrostatic spinning: using internal diameter is that the metal needle of 0.8mm is as shower nozzle, spinning voltage is 15kV, the vertical dimension of needle point to receiving screen is 15cm, feeding rate is 15 μ L/min, spinning temperature is 20 DEG C, relative air humidity is 40RH%, silk received by flat board aluminium foil, and step (1) gained spinning solution carries out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibril felt；
(3) solvent atmosphere processes: be placed in malaria atmosphere by step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril felt, the relative humidity of steam is 70RH%, the temperature processed is 25 DEG C, and the time is 24h, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibril net；
(4) pre-oxidation: be placed in pre-oxidation furnace by step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril net, in air atmosphere, with the ramp of 3 DEG C/min to 260 DEG C, then is incubated 2h and carries out pre-oxidation treatment, obtain pre-oxidized fibers net；
(5) pyrolysis: step (4) gained pre-oxidized fibers net and tripolycyanamide are concurrently placed in pyrolysis oven with mass ratio 1:10; under nitrogen protection, with the ramp of 5 DEG C/min to 900 DEG C, then it is incubated 2h and is pyrolyzed; it is cooled to room temperature, obtains the nanometer fiber net after carbonization；
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is placed in the H that concentration is 0.5mol/L2SO4In solution, at 80 DEG C, carry out acid treatment 8h, then be washed with deionized to neutrality, dry；
(7) finally pyrolysis: the nanometer fiber net after being dried by step (6) gained is placed in pyrolysis oven, under nitrogen protection, with the ramp of 5 DEG C/min to 900 DEG C, then is incubated 1h and is pyrolyzed, be cooled to room temperature, obtain Fe-N-C nanometer fiber net.
As shown in Figure 1, it is connected with each other between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention, i.e. the part of fiber overlap joint is melted under solvent action is integrated, thering is provided continuous passage for electric charge transmission, fibre diameter size is 250～300 nm, after testing, its surface is loose structure, and pore structure the most mesoporous (as shown in Figure 3), beneficially electrolyte are in fibrous inside transmission, improve electrocatalysis characteristic；As shown in Figure 4, Fe-N-C nanometer fiber net is mainly made up of C, Fe, O and N element, Fe-N-C and N-C key therein can be favorably improved electrocatalytic oxidation reducing property as the avtive spot of electrocatalytic reaction.
Embodiment
2
(1) preparation spinning solution: ferric acetyl acetonade, polyvinylpyrrolidone (K value is 30) and ethanol are mixed, then 15 with the ratio of mass ratio 5:10:100
Under kHz supersonic frequency, carry out ultrasonic disperse 3h, obtain spinning solution；
(2) electrostatic spinning: using internal diameter is that the metal needle of 0.8mm is as shower nozzle, spinning voltage is 20kV, the vertical dimension of needle point to receiving screen is 20cm, feeding rate is 10 μ L/min, spinning temperature is 20 DEG C, relative air humidity is 20RH%, silk received by flat board aluminium foil, and step (1) gained spinning solution carries out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibril felt；
(3) solvent atmosphere processes: be placed in the dry air atmosphere containing ethanol by step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril felt, the relative humidity of alcohol vapor is 50RH%, the temperature processed is 25 DEG C, time is 24h, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibril net；
(4) pre-oxidation: be placed in pre-oxidation furnace by step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril net, in air atmosphere, with the ramp of 1 DEG C/min to 280 DEG C, then is incubated 1h and carries out pre-oxidation treatment, obtain pre-oxidized fibers net；
(5) pyrolysis: step (4) gained pre-oxidized fibers net and tripolycyanamide are concurrently placed in pyrolysis oven with mass ratio 1:10; under nitrogen protection, with the ramp of 10 DEG C/min to 800 DEG C, then it is incubated 2h and is pyrolyzed; it is cooled to room temperature, obtains the nanometer fiber net after carbonization；
(6) acid treatment: be placed in the HCl solution that concentration is 1.0 mol/L by the nanometer fiber net after step (5) gained carbonization, at 60 DEG C, carries out acid treatment 10h, then is washed with deionized to neutrality, dry；
(7) finally pyrolysis: the nanometer fiber net after being dried by step (6) gained is placed in pyrolysis oven, under nitrogen protection, with the ramp of 10 DEG C/min to 800 DEG C, then is incubated 1h and is pyrolyzed, be cooled to room temperature, obtain Fe-N-C nanometer fiber net.
Being connected with each other between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention, i.e. the part of fiber overlap joint is melted under solvent action is integrated, and provides continuous passage for electric charge transmission, and fibre diameter size is 220～260 nm；After testing, its surface is loose structure, and pore structure is the most mesoporous, and beneficially electrolyte transmits at fibrous inside, improves electrocatalysis characteristic；Fe-N-C nanometer fiber net prepared by this example is mainly made up of C, Fe, O and N element, Fe-N-C and N-C key therein can play electrocatalysis as the avtive spot of electrocatalytic reaction.The peak current density J of Fe-N-C nanometer fiber netP=1.10mA·cm-2, illustrate that the electron transport ability of interconnective Fe-N-C nanoweb structures and electro catalytic activity are high.
Comparative example
1
This comparative example preparation technology is with embodiment 1, and it differs only in: not carrying out step (3) solvent atmosphere and process, final products therefrom is Fe-N-C nanofiber mats.
As shown in Figure 1, it is connected with each other between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention 1, i.e. the part of fiber overlap joint is melted under solvent action is integrated, as shown in Figure 2, it is non-woven fabrics distributions without fiber in the Fe-N-C nanofiber mats of comparative example 1 gained of solvent atmosphere process, diameter Distribution is uniform, mutually overlaps between nanofiber；From the Fe-N-C nanometer fiber net obtained by embodiment in Fig. 51 and the electrochemical impedance spectroscopy relative analysis of the Fe-N-C nanofiber mats obtained by comparative example 1, the electric charge transmission resistance of Fe-N-C nanometer fiber net is 4.3 Ω, the electric charge transmission resistance of Fe-N-C nanofiber mats is 7.0 Ω, illustrates that interconnective nanoweb structures can effectively reduce electric charge transport resistance in the fibre；It will be appreciated from fig. 6 that test through electrocatalytic oxidation reduction reaction, the peak current density J of the Fe-N-C nanometer fiber net obtained by embodiment 1P=1.02mA·cm-2, higher than the J of the Fe-N-C nanofiber mats obtained by comparative example 1P=0.76mA·cm-2, the nanofiber mats being connected with each other the electron transport ability of the Fe-N-C nanometer fiber net of structure and electro catalytic activity higher than bridging arrangement is equally described.
Claims (38)
1. a Fe-N-C nanometer fiber net, it is characterised in that make in accordance with the following methods:
(1) preparation spinning solution: ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are added in reactor with the ratio of 0.5～6:10:100 and mixes, then ultrasonic disperse, obtain spinning solution；
(2) electrostatic spinning: step (1) gained spinning solution carries out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibril felt；
(3) solvent atmosphere processes: step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril felt is placed in the suitable solvents atmosphere of polyvinylpyrrolidone process, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibril net；
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibril net is pre-oxidized in air atmosphere, obtains pre-oxidized fibers net；
(5) pyrolysis: step (4) gained pre-oxidized fibers net and tripolycyanamide are concurrently placed under inert atmosphere protection with mass ratio 1:8～12 and are pyrolyzed, be cooled to room temperature, obtain the nanometer fiber net after carbonization；
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is carried out acid treatment, then is washed with deionized to neutrality, dry；
(7) finally pyrolysis: the nanometer fiber net after being dried by step (6) gained is pyrolyzed under inert atmosphere protection, is cooled to room temperature, obtains Fe-N-C nanometer fiber net.
Fe-N-C nanometer fiber net the most according to claim 1, it is characterised in that: in step (3), the suitable solvents atmosphere of described polyvinylpyrrolidone refers to the air atmosphere that suitable solvents relative humidity is 50～90RH% of polyvinylpyrrolidone.
Fe-N-C nanometer fiber net the most according to claim 1 or claim 2, it is characterised in that: in step (3), the temperature that described solvent atmosphere processes is 15～60 DEG C, and the time is 20～60h.
Fe-N-C nanometer fiber net the most according to claim 1 or claim 2, it is characterised in that: in step (3), the suitable solvents of described polyvinylpyrrolidone includes one or more in ethanol, water or dimethylformamide.
5. state Fe-N-C nanometer fiber net according to claim 3, it is characterised in that: in step (3), the suitable solvents of described polyvinylpyrrolidone includes one or more in ethanol, water or dimethylformamide.
Fe-N-C nanometer fiber net the most according to claim 1 or claim 2, it is characterised in that: in step (1), the K value of described polyvinylpyrrolidone is 30～90.
Fe-N-C nanometer fiber net the most according to claim 3, it is characterised in that: in step (1), the K value of described polyvinylpyrrolidone is 30～90.
Fe-N-C nanometer fiber net the most according to claim 4, it is characterised in that: in step (1), the K value of described polyvinylpyrrolidone is 30～90.
Fe-N-C nanometer fiber net the most according to claim 1 or claim 2, it is characterised in that: in step (1), the frequency of described ultrasonic disperse is 15～20
KHz, the time is 1～3h.
Fe-N-C nanometer fiber net the most according to claim 3, it is characterised in that: in step (1), the frequency of described ultrasonic disperse is 15～20
KHz, the time is 1～3h.
11. Fe-N-C nanometer fiber nets according to claim 4, it is characterised in that: in step (1), the frequency of described ultrasonic disperse is 15～20
KHz, the time is 1～3h.
12. Fe-N-C nanometer fiber nets according to claim 5, it is characterised in that: in step (1), the frequency of described ultrasonic disperse is 15～20
KHz, the time is 1～3h.
13. Fe-N-C nanometer fiber nets according to claim 1 or claim 2, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV, needle point is 10～30cm to the vertical dimension of receiving screen, feeding rate is 5～30 μ L/min, and spinning temperature is 10～60 DEG C, and relative air humidity is 20～80RH%.
14. Fe-N-C nanometer fiber nets according to claim 3, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV, needle point is 10～30cm to the vertical dimension of receiving screen, feeding rate is 5～30 μ L/min, and spinning temperature is 10～60 DEG C, and relative air humidity is 20～80RH%.
15. Fe-N-C nanometer fiber nets according to claim 4, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV, needle point is 10～30cm to the vertical dimension of receiving screen, feeding rate is 5～30 μ L/min, and spinning temperature is 10～60 DEG C, and relative air humidity is 20～80RH%.
16. Fe-N-C nanometer fiber nets according to claim 5, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV, needle point is 10～30cm to the vertical dimension of receiving screen, feeding rate is 5～30 μ L/min, and spinning temperature is 10～60 DEG C, and relative air humidity is 20～80RH%.
17. Fe-N-C nanometer fiber nets according to claim 6, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: using internal diameter is that the metal needle of 0.5～1.5mm is as shower nozzle, spinning voltage is 12～25kV, needle point is 10～30cm to the vertical dimension of receiving screen, feeding rate is 5～30 μ L/min, and spinning temperature is 10～60 DEG C, and relative air humidity is 20～80RH%.
18. Fe-N-C nanometer fiber nets according to claim 1 or claim 2, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
19. Fe-N-C nanometer fiber nets according to claim 3, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
20. Fe-N-C nanometer fiber nets according to claim 4, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
21. Fe-N-C nanometer fiber nets according to claim 5, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
22. Fe-N-C nanometer fiber nets according to claim 6, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
23. Fe-N-C nanometer fiber nets according to claim 7, it is characterised in that: in step (4), the process of described pre-oxidation be the ramp with 1～5 DEG C/min to 240～280 DEG C, then be incubated 1～3h.
24. Fe-N-C nanometer fiber nets according to claim 1 or claim 2, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
25. Fe-N-C nanometer fiber nets according to claim 3, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
26. Fe-N-C nanometer fiber nets according to claim 4, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
27. Fe-N-C nanometer fiber nets according to claim 5, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
28. Fe-N-C nanometer fiber nets according to claim 6, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
29. Fe-N-C nanometer fiber nets according to claim 7, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
30. Fe-N-C nanometer fiber nets according to claim 8, it is characterised in that: in step (5), (7), the process of described pyrolysis be the ramp with 1～10 DEG C/min to 800～1000 DEG C, then be incubated 0.8～8h.
31. Fe-N-C nanometer fiber nets according to claim 1 or claim 2, it is characterized in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
32. Fe-N-C nanometer fiber nets according to claim 3, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
33. Fe-N-C nanometer fiber nets according to claim 4, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
34. Fe-N-C nanometer fiber nets according to claim 5, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
35. Fe-N-C nanometer fiber nets according to claim 6, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
36. Fe-N-C nanometer fiber nets according to claim 7, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
37. Fe-N-C nanometer fiber nets according to claim 8, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
38. Fe-N-C nanometer fiber nets according to claim 9, it is characterised in that: in step (6), the acid used by described acid treatment is sulphuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1～1.0mol/L, and the temperature of acid treatment is 60～90 DEG C, and the time is 5～10h.
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