CN109449448A - A kind of fuel battery cathod catalyst and its preparation method and application - Google Patents

A kind of fuel battery cathod catalyst and its preparation method and application Download PDF

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CN109449448A
CN109449448A CN201811223442.7A CN201811223442A CN109449448A CN 109449448 A CN109449448 A CN 109449448A CN 201811223442 A CN201811223442 A CN 201811223442A CN 109449448 A CN109449448 A CN 109449448A
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preparation
nitrogen
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amino
terephthalic acid
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CN109449448B (en
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周瑜
王宗花
张艳
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Qingdao University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

This disclosure relates to a kind of fuel battery cathod catalyst and its preparation method and application, using 2- amino-terephthalic acid (TPA) and molysite as raw material, metallic iron-organic framework materials are prepared using solvent process for thermosynthesizing, metallic iron-organic framework materials are used into N, dinethylformamide washing is filtered afterwards three times, by the dry acquisition presoma of filtered precipitating, by presoma at 550~650 DEG C, it is roasted under atmosphere of inert gases, then carrying out acid processing can be obtained nitrogen Fe2O3 doping carbon nanomaterial, wherein, the solvent that solvent process for thermosynthesizing uses is N, dinethylformamide organic solvent.The nitrogen Fe2O3 doping carbon nanomaterial of preparation method preparation has excellent oxygen reduction catalytic activity, preferable take-off potential and carrying current, stable methanol tolerance performance, and electron transfer number is close to four electron transfers.

Description

A kind of fuel battery cathod catalyst and its preparation method and application
Technical field
The disclosure belongs to field of fuel cell technology, and in particular to a kind of fuel battery cathod catalyst and preparation method thereof And application.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
In view of the growing energy needs of people, emerging energy conversion device becomes research hotspot.For example, novel Electrochemical energy reforming unit presents great application prospect for meeting the growing energy demand of people.About existing The research of fuel cell, the oxygen reduction catalyst of fuel cell include noble metal catalyst, non-precious metal catalyst and carbon-based non- Metallic catalyst etc..Wherein noble metal catalyst mainly includes platinum, palladium etc., the disadvantage is that price is more expensive；Non-precious Metal Catalysts Agent mainly includes iron, cobalt etc., the disadvantage is that stability is poor；It is a kind of non-involved in 108281679 A of CN before applicant Metal porous C catalyst, this nitrogen-doped carbon compound have in terms of although having preferable stability but catalytic performance it is certain not Foot, in addition, need to carry out to boil for a long time (5 ± 0.5h) when removal remains in the hydrone or unreacted ligand in hole, Time consumption and energy consumption further limits its business and uses on a large scale.Therefore, exploring the new and effective electrochemical material of one kind seems It is particularly important.
Summary of the invention
For background above technology, the disclosure provides a kind of fuel battery cathod catalyst and its preparation method and application. Compared with the nitrogen-doped carbon nano material in 108281679 A of CN, the fuel battery cathod catalyst that the application is prepared has There are more excellent oxygen reduction catalytic activity, better take-off potential and carrying current, preferable stability and methanol tolerance Can, electron transfer number is more nearly four electron transfers.
The disclosure specifically uses following technical scheme:
Firstly, present disclose provides a kind of preparation methods of fuel battery cathod catalyst, method includes the following steps:
Using 2- amino-terephthalic acid (TPA) and molysite as raw material, preparing metallic iron-using solvent process for thermosynthesizing has machine frame Metallic iron-organic framework materials are placed in n,N-Dimethylformamide after washing and filter by frame material, and filtered precipitating is dry Dry acquisition presoma roasts presoma under 550~650 DEG C, atmosphere of inert gases, and then carrying out acid processing can obtain Obtain nitrogen Fe2O3 doping carbon nanomaterial, wherein the solvent that solvent process for thermosynthesizing uses is n,N-Dimethylformamide organic solvent.
The disclosure also protect the nitrogen Fe2O3 doping carbon nanomaterial being prepared using the above method and its preparing fuel Application in cell cathode catalyst.
Secondly, a kind of fuel cell is provided, and its main feature is that: using above-mentioned nitrogen Fe2O3 doping carbon nanomaterial as fuel electricity Pool cathode catalyst.
Further it is provided that a kind of application of above-mentioned nitrogen Fe2O3 doping carbon nanomaterial in electro-catalysis.
Compared with the relevant technologies that the present inventor knows, the one of technical solution of the disclosure has following beneficial to effect Fruit:
The disclosure is prepared for nano-scale iron-organic framework materials by direct solvent thermal method, and with this metallic iron- Organic framework materials are prepared for nitrogen Fe2O3 doping carbon nanomaterial catalyst material by high temperature cabonization for presoma.With CN before Nitrogen-doped carbon nano material in 108281679 A is compared, and the fuel battery cathod catalyst in the disclosure its catalytic performance is more It is good, it is more nearly ideal four electron transfer reaction, and also have preferably methanol resistance and stability.Disclosure synthesis It the development of base metal carbon material oxygen reduction catalyst and applies and has important prospect in terms of fuel cell.Moreover, and CN Nitrogen-doped carbon nano material in 108281679 A is compared, and preparation process time-consuming is short, is consumed energy low.
Detailed description of the invention
The Figure of description for constituting disclosure a part is used to provide further understanding of the disclosure, the signal of the disclosure Property embodiment and its explanation for explaining the disclosure, do not constitute the improper restriction to the disclosure.
Fig. 1 is electron microscope picture, wherein the scanning electron microscope (SEM) photograph of a:N-C-Fe-600 presoma, b:N-C-Fe-600 Scanning electron microscope (SEM) photograph, the transmission electron microscope picture of c:N-C-Fe-600 presoma, the transmission electron microscope picture of d:N-C-Fe-600.
Fig. 2 is XRD spectra, wherein a: for the XRD spectra of presoma, b: for the XRD spectra of N-C-Fe-600.
Fig. 3 is the high-resolution xps energy spectrum of N-C-Fe-600, wherein a: element species spectrogram, the high-resolution XPS energy of b:C1s Spectrum, the high-resolution xps energy spectrum of c:N1s, the high-resolution xps energy spectrum of d:Fe2p.
Fig. 4 is the Raman spectrogram of N-C-Fe-600.
Fig. 5 is the BET spectrogram of N-C-Fe-600.
Fig. 6 is the thermogravimetric spectrogram of the presoma of N-C-Fe-600.
Fig. 7 is the 0.1molL that the material under different temperatures is saturated in oxygen-1Linear scan curve in KOH solution.
In Fig. 8, a:N-C-Fe-600 modified electrode is 50mVs in scanning speed-1Cyclic voltammetry curve；B:N-C- The linear scan curve and ring-disc electrode test curve when revolving speed is 1600rpm of Fe-600, scanning speed 5mVs-1； Linear scan curve of the c:N-C-Fe-600 under different rotating speeds；The Koutecky-Levich (K-L) of d:N-C-Fe-600 is bent Line.
Fig. 9 is the 0.1molL that N-C-Fe-600 modified electrode and business Pt/C are saturated in oxygen-1It is steady in KOH solution Qualitative test (a) and methanol resistance test (b).
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation and/or their combination.
Molysite described herein is the compound for being dissolved in the water and ionizing out iron ion, such as iron chloride, ferric sulfate, nitric acid Iron etc..
Solvent process for thermosynthesizing described herein refers in the pressure vessel of sealing, is with n,N-Dimethylformamide The mixture of organic solvent and water is solvent, the chemical reaction carried out under conditions of high temperature and pressure.
Herein described inert gas refers to the gas for being difficult to that combustion reaction occurs with organic matter or carbon, such as nitrogen, argon gas Deng.
As background technique is introduced, exist in the prior art that noble metal catalyst is expensive, Non-precious Metal Catalysts The deficiency of agent stability difference, in order to solve technical problem as above, present applicant proposes a kind of systems of nitrogen-doped carbon nano material The application of standby and its electrocatalytic oxidation reduction.
As background technique is introduced, in 108281679 A of CN non-metallic catalyst catalytic performance exist it is certain not Foot, in order to solve technical problem as above, the present disclosure proposes a kind of preparation method of fuel battery cathod catalyst, this method The following steps are included:
Using 2- amino-terephthalic acid (TPA) and molysite as raw material, preparing metallic iron-using solvent process for thermosynthesizing has machine frame Metallic iron-organic framework materials are placed in n,N-Dimethylformamide after washing and filter by frame material, and filtered precipitating is dry Dry acquisition presoma roasts presoma under 550~650 DEG C, atmosphere of inert gases, and then carrying out acid processing can obtain Obtain nitrogen Fe2O3 doping carbon nanomaterial.Wherein, the solvent that solvent process for thermosynthesizing uses is n,N-Dimethylformamide.
The crystal morphology obtained in solvent thermal reaction using different solvents is different.The application selects DMF, makes to obtain Polyhedral Particles shape pattern is presented in the nitrogen Fe2O3 doping carbon nanomaterial matrix obtained.
In one of the disclosure or some specific embodiments, the 2- amino-terephthalic acid (TPA) and molysite rub You are than being 1:1.
In one of the disclosure or some specific embodiments, the 2- amino-terephthalic acid (TPA) and N, N- diformazan The adding proportion of base formamide is (1~2) mmol:(25~35) mL.
In one of the disclosure or some specific embodiments, by 2- amino-terephthalic acid (TPA) and iron salt dissolved in In n,N-Dimethylformamide, solvent process for thermosynthesizing is used after 2- amino-terephthalic acid solution is mixed with iron salt solutions It is reacted.
Further, by 1.3838mmol 2- amino-terephthalic acid (TPA) and 1.3838mmol iron salt dissolved in 30mL N, In the solution of dinethylformamide, solvent-thermal process is used after 2- amino-terephthalic acid solution is mixed with iron salt solutions Method is reacted.
In one of the disclosure or some specific embodiments, the temperature of solvent-thermal process is 110~130 DEG C, is closed It is 19~21h at the time.If temperature is high or low, the crystallization degree for obtaining material is bad；Further, the temperature of solvent-thermal process It is 120 DEG C.
In one of the disclosure or some specific embodiments, the inert gas is argon gas.
In one of the disclosure or some specific embodiments, the heating rate of the roasting is 2~4 DEG C of min-1, further preferably 3 DEG C of min-1。
In one of the disclosure or some specific embodiments, the calcining time is 3~4h.
Maturing temperature not only will affect the variation of iron in nitrogen Fe2O3 doping carbon nanomaterial, but also will affect Fe2O3 doping carbon and receive The structure and microscopic appearance of rice material, and then influence the catalytic performance of fuel battery cathod catalyst.At one of the disclosure or In some specific embodiments, the maturing temperature is 595~605 DEG C；Further, the maturing temperature is 600 DEG C.
In one of the disclosure or some specific embodiments, the filtered precipitating is washed laggard three times Row drying.Further, it is washed using n,N-Dimethylformamide solution.
It carries out repeatedly washing the unreacted ligand gone to remain in hole using n,N-Dimethylformamide (DMF), simultaneously Metallic iron-organic framework materials will not be dissolved, material structure is avoided damage to, have the function that activation.And 108281679 A of CN Middle needs are boiled the hydrone or unreacted ligand that (5 ± 0.5h) removal remains in hole for a long time, are otherwise entrained in Hydrone or unreacted ligand in hole will affect the catalytic stability of material and the ability of methanol tolerance.
In one of the disclosure or some specific embodiments, the drying is vacuum drying.The drying time For 11~13h.
In one of the disclosure or some specific embodiments, the acid that the acid processing uses is hydrochloric acid.Further , the concentration of hydrochloric acid is 2M.
In a typical embodiment of the disclosure, the nitrogen Fe2O3 doping carbon for providing a kind of above-mentioned preparation method acquisition is received Rice material.The material is the porous carbon materials of nitrogen, Fe2O3 doping, has relatively uniform pore size distribution, the size in hole is about 19nm；Its Polyhedral Particles shape is presented in microscopic appearance, and is covered by fluffy substance.The shape characteristic of the material increases the ratio table of material Area and cellular structure, compared to the strip structure of material N-C-Al-900 in 108281679 A of CN, the material of the application It is more conducive to the progress of oxygen reduction reaction.
In another typical embodiment of the disclosure, above-mentioned nitrogen Fe2O3 doping carbon nanomaterial is provided and is preparing fuel Application in cell cathode catalyst.
In another typical embodiment of the disclosure, a kind of fuel cell is provided, above-mentioned nitrogen Fe2O3 doping carbon is received Rice material is as fuel battery cathod catalyst.
Further, the fuel cell is methanol fuel cell.
In another typical embodiment of the disclosure, a kind of above-mentioned nitrogen Fe2O3 doping carbon nanomaterial is provided in electricity Application in catalysis.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool The technical solution of the disclosure is described in detail in the embodiment of body.
Embodiment 1
A kind of preparation method of nitrogen Fe2O3 doping carbon nanomaterial, comprising the following steps:
1) nano-scale iron-organic framework materials presoma preparation: 1.3838mmol 2- amino -1,4- is weighed Terephthalic acid (TPA), while weighing 1.3838mmol Iron trichloride hexahydrate and being dissolved in 30mL n,N-Dimethylformamide, stirring is to filling It is added in ptfe autoclave after dividing dissolution, reaction kettle is sealed, is reacted 20 hours under the conditions of 120 DEG C, it is then cold But room temperature is arrived, above-mentioned reaction solution is filtered, precipitating is washed three times with n,N-Dimethylformamide, it is dry to be then placed in vacuum oven Dry 12h obtains brown-black powder product.
2) preparation of nitrogen Fe2O3 doping carbon nanomaterial (N-C-Fe): nano-scale iron-prepared by step 1) is organic Frame material presoma is put into tube furnace, with 3 DEG C of min under argon atmosphere-1Rate be warming up to 600 DEG C, roast 3h system Nitrogen Fe2O3 doping carbon nanomaterial is obtained, 2M HCl treatment is then used, obtained material designation is N-C-Fe-600.
Embodiment 2
The embodiment is same as Example 1, the difference is that, the embodiment is under argon atmosphere with 3 DEG C of min-1's Rate is warming up to 550 DEG C, and nitrogen Fe2O3 doping carbon nanomaterial is made in roasting 3h, then uses 2M HCl treatment, obtained material designation For N-C-Fe-550.
Embodiment 3
The embodiment is same as Example 1, the difference is that, the embodiment is under argon atmosphere with 3 DEG C of min-1's Rate is warming up to 650 DEG C, and nitrogen Fe2O3 doping carbon nanomaterial is made in roasting 3h, then uses 2M HCl treatment, obtained material designation For N-C-Fe-650.
Embodiment 4
The embodiment is same as Example 1, the difference is that, the embodiment is under argon atmosphere with 3 DEG C of min-1's Rate is warming up to 700 DEG C, and nitrogen Fe2O3 doping carbon nanomaterial is made in roasting 3h, then uses 2M HCl treatment, obtained material designation For N-C-Fe-700.
Embodiment 5
The embodiment is same as Example 1, the difference is that, the embodiment is under argon atmosphere with 3 DEG C of min-1's Rate is warming up to 800 DEG C, and nitrogen Fe2O3 doping carbon nanomaterial is made in roasting 3h, then uses 2M HCl treatment, obtained material designation For N-C-Fe-800.
Embodiment 6
The embodiment is same as Example 1, the difference is that, the embodiment is under argon atmosphere with 3 DEG C of min-1's Rate is warming up to 500 DEG C, and nitrogen Fe2O3 doping carbon nanomaterial is made in roasting 3h, then uses 2M HCl treatment, obtained material designation For N-C-Fe-500.
Embodiment 7
Electrocatalytic oxidation reduction test, comprising the following steps:
1) glass-carbon electrode (diameter 3mm) is handled by following steps: first carrying out polishing throwing with 0.3 μm of alumina powder Light obtains the surface of mirror-smooth, successively uses dehydrated alcohol and deionized water supersound washing later, is then dried up with nitrogen With spare.
2) working electrode prepare it is as follows: by synthetic N-C-Fe sample 1mg be scattered in 50 μ L mass fractions be 0.5% Nafion aqueous solution, in the ethyl alcohol of 300 μ L and the deionized water of 300 μ L, so that material is uniformly dispersed by ultrasound, pipette about 8 μ L drop is dried to be measured at room temperature in processed glassy carbon electrode surface；Rotating disk electrode (r.d.e) (diameter 5mm) is by identical Mode pipettes 20 μ L drops in electrode surface, is placed to dry at room temperature to be measured.
3) three electron system tests are carried out with electrochemical workstation (CHI), had both used platinum filament as to electrode, silver/silver chlorate (saturation potassium chloride) electrode be reference electrode, in modification catalyst glass-carbon electrode as working electrode.In oxygen saturation 0.1mol·L-1Electrocatalytic oxidation reduction test is carried out in KOH solution, and to be continued in linear sweep test and stability test It is passed through oxygen.
Test result and discussion in embodiment 1
1, the structural characterization of N-C-Fe-600
Fig. 1 a and Fig. 1 b are respectively the scanning electron microscope (SEM) photograph of N-C-Fe-600 carbonization front and back, from the figure we can see that come, Material morphology produces apparent variation after 600 DEG C of high-temperature process, and edge occurs significantly compared with original pattern Carbonized path.Fig. 1 a can clearly be observed that the polyhedron that average diameter is 200nm or so and length is 250nm or so Grain.Then, at 600 DEG C in Ar carbonization treatment 4 hours and be converted into N-C-Fe.Polyhedral surface becomes coarse, and by Fluffy substance covering, the shape characteristic of the material increase specific surface area and the duct of material；Fig. 1 c and Fig. 1 d are respectively N- The transmission electron microscope picture of the N-C-Fe-600 of C-Fe-600 carbonization front and back, it can be seen that material after carbonization occurs centainly because of high temperature Degree is collapsed, but there are still and these ducts are conducive to the progress of oxygen reduction reaction for its overall skeleton and pattern.
Fig. 2 a is presoma (NH2- MIL-88 (Fe)) XRD, Fig. 2 b is the XRD diagram of N-C-Fe-600, from Fig. 2 a and mark Quasi- NH2The diffraction maximum of-MIL-88 (Fe) compares, it can be seen that this material successfully synthesizes NH substantially2-MIL-88(Fe) The namely presoma of N-C-Fe-600.It can be seen that carbonization MOF is primarily present unformed carbon, Fe from Fig. 2 b3C, Fe tri- Kind species.It is to show that product is mainly made of the agraphitic carbon of disordered structure there are two broad peaks at 23 ° and 44 ° at 2 angles θ, Respectively correspond two diffraction maximums of graphite.Fe is formd in the material of carbonization3C, and Fe has been corresponded to well3The diffraction of C Peak.There is also the corresponding diffraction maximums of Fe simultaneously for material after carbonization.The formation of this graphitized carbon has well the material Electric conductivity plays an important role.
Fig. 3 a is the xps energy spectrum figure of N-C-Fe-600, the presence of carbon, nitrogen, oxygen, ferro element demonstrate successfully synthesize nitrogen, The carbon material of Fe2O3 doping.Fig. 3 b be N-C-Fe-600 XPS in C1s high-resolution xps energy spectrum, 284.8eV, 286.9eV, Peak at 288.9eV respectively corresponds C=C, C=O, C-N key.The presence of C-N key also further illustrates N and is successfully doped in In product.Fig. 3 c is the high-resolution xps energy spectrum of N1s in the XPS of N-C-Fe-600, and three peaks in figure respectively correspond pyridine type Nitrogen (N1s:398.53eV), pyrroles's type nitrogen (N1s:400.15eV), graphite mould nitrogen (N1s:401.02eV).Fig. 3 d is N-C-Fe- The high-resolution xps energy spectrum of Fe2p in 600 XPS, the peak at 710.7eV and 724.3eV respectively correspond Fe2p3/2 and Fe2p1/2.Show that there is Fe and Fe in material3C。
Fig. 4 is the Raman spectrogram of N-C-Fe-600, and for the carbon in more careful description material, Raman spectrum is a kind of Widely used tool, for characterizing the detailed construction feature of carbon-based material.Spectrum shows two main peaks, respectively due to 1360cm-11590cm at graphite material of the D- at place with peak and missing-1G- band peak (Fig. 3 a) at place.ID/IGRatio can mark Show that level of graphitization (unordered degree and defect level) very significant and edge plane of the carbon in N-C-Fe-600 material is unordered. Defect sturcture can provide ORR active site, be conducive to during electro-catalysis electronics in material conduction and ORR reaction into Row.
Fig. 5 is N-C-Fe-600 specific surface area test chart under 77K condition of nitrogen gas, specific surface area size 136.309cc/ g.As seen from the figure, after carbonization material absorption/desorption isotherm, illustrating material, there are meso-hole structures.Illustration is carbon material in Fig. 5 Graph of pore diameter distribution, by illustration it can be seen that product have relatively uniform pore size distribution, pore size is about 19nm.This carbon material Porous structure greatly improve the specific surface area of material, for improve electrochemical process activity and catalyst surface The mass transfer and diffusion important in inhibiting of electrolyte.
Fig. 6 is N-C-Fe-600 presoma (NH2- MIL-88) thermogravimetric spectrogram, thermogravimetric spectrogram is a kind of analysis of material The effective ways of thermal stability.Have before 600 DEG C apparent twice weightless, be the loss of the water and ligand in material, 600 DEG C it The weight of material continuously declines afterwards, illustrates the structure of material as the rising of temperature has occurred that apparent collapsing.Therefore 600 Degree is optimum carburizing temperature.
2, the Electrochemical Characterization of N-C-Fe
Fig. 7 is the catalyst material (NH obtained under different carburizing temperatures2- MIL-88, the N-C-Fe-500 in embodiment 6, N-C-Fe-600 in embodiment 1, the N-C-Fe-700 in embodiment 4, the N-C-Fe-800 in embodiment 5), it is saturated in oxygen 0.1molL-1Linear scan curve (LSV) in KOH solution.It has used rotating disk electrode (r.d.e) (RDE), has schemed in test process 7 revolving speed is 1600rpm.As seen from the figure, compared with other several materials, N-C-Fe-600 have better take-off potential (- 0.15V) current density (the 5.1mAcm of He Geng great-2)。
Fig. 8 a is the cyclic voltammetry curve of N-C-Fe-600 catalyst material, as can be seen from Figure, in oxygen saturation Under the conditions of, there is the characteristic peak of apparent oxygen reduction reaction, illustrates that this material has apparent electro-catalysis for oxygen reduction reaction Activity, the current potential of reduction peak are -0.28V.Fig. 8 b is the 0.1molL that N-C-Fe-600 modified electrode is saturated in oxygen-1KOH Linear scan curve and ring-disc electrode test curve in solution, revolving speed 1600rpm, scanning speed 5mVs-1.Utilize with Lower formula calculates electron transfer number (n) of catalyst during hydrogen reduction:
N=4Id/(Id+Ir)/N (1)
IdFor the size (5.10mA/cm of test process mid-game electric current2), IrFor the size of circular current in test process (0.012mA/cm2), N is the collection coefficient (0.43) of Pt ring.
By calculating it is found that electron transfer number of catalyst during hydrogen reduction is close to ideal four electronics transfers n =3.7.
While in order to probe into the reaction mechanism of the reaction, the disclosure is using rotating circular disk voltammetry for N-C-Fe-600's The dynamics of electrocatalytic oxidation reduction reaction is further studied.Its polarization curve is the 0.1mol in oxygen saturation L-1Change the obtained Fig. 8 c of revolving speed in KOH solution it is found that in the voltage range of -0.8~0V, Limited diffusion current density with The increase of revolving speed and increase.Fig. 8 d is its corresponding Koutecky-Levich (K-L) curve, as seen from the figure curve line Sexual intercourse is good, and for this explanation under different voltage, N-C-Fe-600 has similar electron transfer number, and oxygen reduction reaction meets First-order kinetics.The electron transfer number (n) of oxygen reduction reaction and dynamic (dynamical) limiting current density be by RDE, and It is calculated on the basis of K-L equation, specific equation are as follows:
1/J=1/JL+1/JK=1/B ω0.5+1/JK (2)
B=0.62nFCO(DO)2/3v-1/6 (3)
JK=nFkCO (4)
Wherein, J is current density obtained in test, JKIt is kinetic limiting current density, JLIt is that diffusion limiting current is close Degree, ω are the angular velocity of rotations of motor, and n is the electronics transfer sum of oxygen reduction reaction, and F is Faraday constant (96485C mol-1)。COIt is the volumetric concentration of oxygen, DOIt is diffusion coefficient of the oxygen in KOH electrolyte, v is that the dynamic of electrolyte is glutinous Degree, k is electron transfer rate constant.And in 0.1molL-1In KOH solution, CO=1.2 × 10-6mol·cm-3, DO=1.9 ×10-5cm2·s-1, v=1.0 × 10-2cm2·s-1.According to above-mentioned formula, n can be obtained by calculating K-L slope of a curve The electron transfer number of N-C-Fe-600 is 3.7, and the electron transfer number of material N-C-Al-900 is in 108281679 A of CN 3.3, as a result illustrate that the catalytic process of N-C-Fe-600 material is closer to four electron transfer reactions.The raising of the performance, one It is the pattern and porous structure for being the Polyhedral Particles shape of the application material, second is that being the porous carbon materials in the application Nonmetallic iron is adulterated, active site is increased, improves catalytic performance.
The stability and methanol tolerance performance of material are also to measure catalyst in the main indicator of fuel cell practical application.This It is disclosed in the 0.1molL of oxygen saturation-1The stability and methanol resistance of N-C-Fe-600 catalyst have been carried out in KOH solution Test.By Fig. 9 a it is found that after running 30000s, the loss of N-C-Fe-600 catalyst material is considerably less than business Pt/C, possesses Better stability.In Fig. 9 b, after 1M methanol is added, N-C-Fe-600 catalyst material only has the variation of minimum amplitude, and quotient Industry Pt/C then has biggish curent change, illustrates that the methanol tolerance performance of N-C-Fe-600 catalyst is substantially better than Pt/C.These knots Fruit shows that this material has great potential application value in direct methanol fuel cell.In 108281679 A of CN Material N-C-Al-900 is compared, and obtained catalyst catalytic performance is more preferable, is more nearly ideal four electron transfer reaction, and Also there are preferably methanol resistance and stability.
Above-described embodiment is the preferable embodiment of the disclosure, but embodiment of the present disclosure is not by above-described embodiment It limits, made changes, modifications, substitutions, combinations, simplifications under other any spiritual essence and principles without departing from the disclosure, It should be equivalent substitute mode, be included within the protection scope of the disclosure.

Claims (10)

1. a kind of preparation method of fuel battery cathod catalyst, characterized in that method includes the following steps:
Using 2- amino-terephthalic acid (TPA) and molysite as raw material, metallic iron-organic frame material is prepared using solvent process for thermosynthesizing Metallic iron-organic framework materials are placed in n,N-Dimethylformamide after washing and filter by material, and the drying of filtered precipitating is obtained Presoma is obtained, presoma is roasted under 550~650 DEG C, atmosphere of inert gases, then carrying out acid processing can be obtained nitrogen Fe2O3 doping carbon nanomaterial, wherein the solvent that solvent process for thermosynthesizing uses is n,N-Dimethylformamide organic solvent.
2. preparation method as described in claim 1, it is characterized in that: 2- amino-terephthalic acid (TPA) and molysite molar ratio For 1:1；
Alternatively, the adding proportion of the 2- amino-terephthalic acid (TPA) and n,N-Dimethylformamide be (1~2) mmol:(25~ 35)mL。
3. preparation method as described in claim 1, it is characterized in that: by 2- amino-terephthalic acid (TPA) and iron salt dissolved in N, N- In dimethylformamide, carried out after 2- amino-terephthalic acid solution is mixed with iron salt solutions using solvent process for thermosynthesizing Reaction；
Further, by 1.3838mmol 2- amino-terephthalic acid (TPA) and 1.3838mmol iron salt dissolved in 30mL N, N- bis- In the solution of methylformamide, solvent process for thermosynthesizing is used after 2- amino-terephthalic acid solution is mixed with iron salt solutions It is reacted.
4. preparation method as described in claim 1, it is characterized in that: the temperature of solvent-thermal process is 110~130 DEG C, when synthesis Between be 19~21h.
5. preparation method as described in claim 1, it is characterized in that: the inert gas is argon gas；Alternatively,
The heating rate of the roasting is 2~4 DEG C of min-1, further preferably 3 DEG C of min-1；Alternatively,
The calcining time is 3~4h；Alternatively,
The filtered precipitating be dried after washing three times；
The drying is vacuum drying, and the drying time is 11~13h；
The acid that the acid processing uses is hydrochloric acid, and further, the concentration of hydrochloric acid is 2M.
6. preparation method as described in claim 1, it is characterized in that: the maturing temperature is 595~605 DEG C, further, institute Stating maturing temperature is 600 DEG C.
7. the nitrogen Fe2O3 doping carbon nanomaterial being prepared using method according to any one of claims 1 to 6.
8. nitrogen Fe2O3 doping carbon nanomaterial as claimed in claim 7 is preparing the application in fuel battery cathod catalyst.
9. a kind of fuel cell, it is characterized in that: using nitrogen Fe2O3 doping carbon nanomaterial as claimed in claim 7.
10. application of the nitrogen Fe2O3 doping carbon nanomaterial as claimed in claim 7 in electro-catalysis.
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