CN110137518A - A kind of self-supported Fe-N-C oxygen reduction catalyst and preparation method thereof - Google Patents

A kind of self-supported Fe-N-C oxygen reduction catalyst and preparation method thereof Download PDF

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CN110137518A
CN110137518A CN201910483401.XA CN201910483401A CN110137518A CN 110137518 A CN110137518 A CN 110137518A CN 201910483401 A CN201910483401 A CN 201910483401A CN 110137518 A CN110137518 A CN 110137518A
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edtafena
self
supported
oxygen reduction
reduction catalyst
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CN110137518B (en
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严祥辉
蒙紫薇
黄红明
房国丽
许皓
薛同
沈宏芳
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North Minzu University
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Shenzhen City Cuiyun Valley Technology Ltd
North Minzu 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
    • H01M4/96—Carbon-based electrodes
    • 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

The invention belongs to non-precious metal catalyst technical fields in electro-catalysis, and in particular to self-supported Fe-N-C oxygen reduction catalyst derived from a kind of EDTAFeNa and preparation method thereof.The mesoporous pore size of the self-supported Fe-N-C oxygen reduction catalyst is 3.9 ± 0.2nm, and specific surface area is 385 ± 2m2g‑1, Fe constituent content is 0.4 ± 0.02at.%, and N element content is 2.6 ± 0.2at.%, and C element content is 93 ± 2at.%；The self-supported Fe-N-C oxygen reduction catalyst is that mesopore molecular sieve and sodium iron ethylene diamine tetra acetate are obtained by heat treatment-etching-acid processing-heat treatment under mixing evaporation drying-inert gas shielding.Not only catalyst activity, selectivity are high, it can be achieved that efficient electric catalytic oxidation-reduction reacts (ORR) in the alkaline electrolyte by the present invention, and preparation method route is flexible, elastic space is big, operation is controllable, is easy to large-scale production.

Description

A kind of self-supported Fe-N-C oxygen reduction catalyst and preparation method thereof
Technical field
The invention belongs to non-precious metal catalyst technical fields in electro-catalysis, and in particular to a kind of EDTAFeNa is derivative certainly Load Fe-N-C oxygen reduction catalyst and preparation method thereof.
Background technique
Fuel cell directly and efficiently can convert electric energy for the chemical energy contained in fuel molecule, and only generation pair Environment unpolluted water provides a kind of new approach for the effective use of existing fossil energy.Since it is with light, high Effect, quick start, service life length, low-corrosiveness, it is environmental-friendly the features such as, in electric car power supply, mobile power source, portable power And power plant application etc. will have very big application prospect.Nevertheless, realizing fuel cell in the world in a short time Civil nature, commercialization and industrial application still suffer from huge challenge in range, wherein hinder its be commercialized process it is crucial because Element be first the presently used electrode material of fuel cell (Pt or Pt base catalyst) natural resources shortage, it is expensive, cause to fire Expect that battery cost is excessively high.In order to solve this problem, exploitation can substitute Pt for the cheap of fuel battery negative pole hydrogen reduction (ORR) Non-precious metal catalyst (NPMCs) is one of the important goal that scientific research person pursue always.
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to provide self-supported Fe-N-C oxygen derived from a kind of EDTAFeNa Reducing catalyst, the existing meso-hole structure of the catalyst, very big specific surface area have high level and uniform N doping again simultaneously.
The second object of the present invention is to provide the preparation method of the self-supported Fe-N-C oxygen reduction catalyst, this method Synthetic route is flexible, elastic space is big, operation is controllable, relative inexpensiveness, is easy to large-scale production.
The present invention is achieved through the following technical solutions:
The mesoporous pore size of a kind of self-supported Fe-N-C oxygen reduction catalyst, the self-supported Fe-N-C oxygen reduction catalyst is 3.9 ± 0.2nm, specific surface area are 385 ± 2m2g-1, Fe constituent content be 0.4 ± 0.02at.%, N element content be 2.6 ± 0.2at.%, C element content are 93 ± 2at.%；
The self-supported Fe-N-C oxygen reduction catalyst includes mesopore molecular sieve and sodium iron ethylene diamine tetra acetate (EDTAFeNa), the mass ratio of the mesopore molecular sieve and sodium iron ethylene diamine tetra acetate is 1:1~20；
The mesopore molecular sieve is one or more of SBA-15, MCM-41, MCM-48 or KIT-6 composition.Wherein Mesopore molecular sieve is used as from hard template is sacrificed, and EDTAFeNa has both iron, nitrogen and carbon matrix precursor.
The preparation method of self-supported Fe-N-C oxygen reduction catalyst, includes the following steps:
1) first mesopore molecular sieve is add to deionized water, adds sodium iron ethylene diamine tetra acetate and be uniformly dispersed, then Above-mentioned suspended matter is evaporated, dry, is ground, solid powder A is obtained；
2) by A obtained in step 1) under slumpability gas shield, 650~750 are warming up to 10 ± 2 DEG C/min DEG C keep 1-3h, then after cooled to room temperature grind uniformly, obtain catalyst precarsor, be labeled as EDTAFeNa-HT1 (MMS)；
3) by catalyst precarsor EDTAFeNa-HT1 (MMS) obtained in step 2) with acid or alkali ethanol water into Row etching obtains the precursor EDTAFeNa-ET (MMS) of desiliconization；
4) the carry out acid by EDTAFeNa-ET (MMS) obtained in step 3) in 70~90 DEG C, 0.5~2M handles 0.5 ~for 24 hours, it finishes and is filtered, dried, obtain the precursor EDTAFeNa-AL (MMS) for eliminating part iron species；
5) by EDTAFeNa-AL (MMS) obtained in step 4), in 180~220mLmin-1Under flowing gas protection, 600~1000 DEG C are warming up to 10 ± 2 DEG C/min and keeps 0.5~3h, then cooled to room temperature, this work-in-process label For EDTAFeNa-AL-HT2 (MMS), the i.e. self-supported Fe-N-C catalyst.Wherein, in EDTAFeNa-AL-HT2 (MMS) AL be to be shown to be sour processing, be the abbreviation of English Acid-leaching from naming.
Preferably, the mesopore molecular sieve and sodium iron ethylene diamine tetra acetate be add to deionized water dispersion can be it is super Sound dispersion passes through solid phase mechanical mixture.
Preferably, other nitrogenous small molecule compounds can also be added simultaneously in step 1)；The nitrogenous small molecule chemical combination Object is melamine, urea, pyrroles, one or several compositions in ethylenediamine.
Preferably, activator KOH, K can also be added simultaneously in step 1)2CO3、(NH4)2CO3、ZnCO3In one or Several compositions.
Preferably, the slumpability gas is N2Or He.
Preferably, performed etching in step 3) with the ethanol water of acid or alkali, specifically: by EDTAFeNa-HT1 (MMS) it is added in the ethanol-water solution for the NaOH that molar concentration is 1.5~2.5M, in 55~65 DEG C of 20~25h of stirring, so It washed repeatedly 3 times, filtered, dry with deionized water and ethyl alcohol afterwards；The volume ratio of ethyl alcohol and water is 1 in the ethanol-water solution: 1.When being performed etching with the ethanol water of acid, preferably HF.
Preferably, acid is HCl, H in the processing of acid described in step 4)2SO4Or HNO3Solution.
Preferably, the flowing gas is inert gas or active gases NH in step 5)3。
Traditional Fe-N-C material preparation method based on carbon carrier, nitrogenous precursor and metal salt, due to being heat-treated In the process, nitrogenous precursor degrades and is carbonized, in addition to carrying out non-uniform N doping to carbon carrier, while also inevitably The duct of carbon carrier is blocked to some extent, therefore in several key factors such as aperture, specific surface area, the active sites for influencing ORR Between density and distribution, it is constantly present a tradeoff compromise.
The present invention uses ordered mesoporous molecular sieve to sacrifice hard template, it is therefore an objective to which being cut out using its mesoscopic structure is had greatly The mesoporous Fe-N-C material of specific surface area is conducive to the exposure of active sites and the mass transfer diffusion of bottom product, promotes electronics transfer speed Rate, another purpose are that the interaction of its duct abundant and EDTAFeNa can be improved carbonization yield, while reduce N element Loss；The unique cheap organic and inorganic compound EDTAFeNa of selection has both Fe, N and C presoma, it is therefore an objective to can reduce The cost of raw material is also avoided that structural complexity caused by interacting as multicomponent presoma；In addition only pass through cracking A kind of presoma of EDTAFeNa can obtain the carbon material of Fe, N codope, and this auto-dope will be expected to obtain more evenly The active sites of distribution and its density of raising；It is seen using Jie that acid processing can remove nonactive Fe species and further controlled material Structure；To which the active non-precious metal catalyst of excellent ORR has been provided in collaboration.
Compared with the prior art, the present invention has the following beneficial effects:
1) preparation process is used only cheap organic and inorganic compound EDTAFeNa and has both Fe, N and C presoma；
2) preparation process is hard template using SBA-15 and combines acid processing, can effectively improve N doping and graphite Change degree creates the mesoporous and big specific surface area of narrow ditribution, removes nonactive or promotes ORR that 2e occurs-Selective reaction way The crystalline state Fe species of diameter, the quick transmission so as to substance and electronics for ORR process provide channel；
3) under alkaline condition, the starting of self-supported mesoporous Fe-N-C material catalysis ORR and half wave potential and high potential Lower dynamics current density is catalyzed ORR close to commercialization Pt/C catalyst with the 4e of energy conversion efficiency-Reaction path It carries out；
4) the catalyst usage range is wide, can be used as the cathodic oxygen reduction catalyst of various fuel cells.
The method of the present invention for preparing self-supported Fe-N-C catalyst derived from EDTAFeNa, reagent needed for preparation process Small toxicity, safety and environmental protection, component be few, low raw-material cost, and preparation process is flexible, elastic space is big, operation is controllable, yield is high, It is easy to large-scale production.
Detailed description of the invention
Fig. 1 is the N of EDTAFeNa-HT2, EDTAFeNa-HT1 and EDTAFeNa-AL2Suction/desorption isotherm and aperture point Cloth.
Fig. 2 is the magnetic hysteresis loop of EDTAFeNa-HT2, EDTAFeNa-HT1 and EDTAFeNa-AL.
Fig. 3 is the TEM photo of EDTAFeNa-HT2.
Fig. 4 is Fe species size statistic distribution map in the TEM photo of EDTAFeNa-HT2.
Fig. 5 is the small angle XRD spectra of EDTAFeNa-HT2 (SBA-15) and EDTAFeNa-AL-HT2 (SBA-15).
Fig. 6 is the wide-angle XRD spectra of EDTAFeNa-HT2 (SBA-15) and EDTAFeNa-AL-HT2 (SBA-15).
Fig. 7 is the N of EDTAFeNa-HT2 (SBA-15) and EDTAFeNa-AL-HT2 (SBA-15)2Suction/desorption isotherm and Pore-size distribution.
Fig. 8 is EDTAFeNa-HT2 (SBA-15) and the XPS of EDTAFeNa-AL-HT2 (SBA-15) is composed entirely.
Fig. 9 is the magnetic hysteresis loop of EDTAFeNa-HT2 (SBA-15) and EDTAFeNa-AL-HT2 (SBA-15).
Figure 10 is in O2EDTAFeNa-HT2 (SBA-15), EDTAFeNa-AL-HT2 (SBA- in the 0.1M KOH of saturation 15) (room temperature sweeps fast 10mV s with the polarization curve of Pt/C catalysis ORR-1, revolving speed 1600rpm).
Figure 11 is that EDTAFeNa-HT2 (SBA15) is catalyzed under the polarization curve and different potentials of ORR each under different rotating speeds O2Molecule reacts the electron number of transfer.
Figure 12 is that EDTAFeNa-AL-HT2 (SBA15) is catalyzed under the polarization curve and different potentials of ORR often under different rotating speeds A O2Molecule reacts the electron number of transfer.
Specific embodiment
The present invention is described in further detail With reference to embodiment, to help those skilled in the art's reason The solution present invention.
Embodiment 1
1) it takes 2g EDTAFeNa to be put into quartz boat and is placed in tube furnace, in 200mL min-1N2Under protection, with 10 DEG C/ Min is warming up to 700 DEG C of holding 2h, and cooled to room temperature, then uniformly, this work-in-process is named as EDTAFeNa- for grinding HT1。
2) take 0.25g EDTAFeNa-HT1 in 80 DEG C, the H of 30ml 0.5M2SO4Acid processing 0.5h is carried out in solution, is finished It filtered, dried, this work-in-process is named as EDTAFeNa-AL.
3) 0.15g EDTAFeNa-AL is taken to continue in 200mL min-1N2Under protection, 900 DEG C are warming up to simultaneously with 10 DEG C/min 2h is kept, then cooled to room temperature, spare after grinding uniformly, the sample that this stage obtains is labeled as EDTAFeNa-HT2.
This preparation process does not use SBA-15 as hard template, but has used acid treatment step, will be as control catalysis Agent uses SBA-15 as hard template with following, while the catalyst for having carried out sour processing preparation is compared.
The N of the EDTAFeNa-HT2 of the present embodiment synthesis2Suction/desorption isotherm and pore-size distribution and magnetic hysteresis loop are such as Fig. 1, shown in 2；TEM (transmission electron microscope) and the distribution of Fe species size statistic are as shown in Figure 3,4.
Embodiment 2
1) it takes the homemade SBA-15 of 0.4g to be added in 45mL deionized water, adds 7.88gEDTAFeNa, magnetic agitation Then above-mentioned suspended matter is evaporated, dries, grinds by 0.5h, ultrasonic disperse 2h, obtain solid powder A.
2) 1g A sample is taken, in 200mL min-1N2Under protection, 700 DEG C of holding 1-3h are warming up to 10 DEG C/min, then It is ground uniformly after cooled to room temperature, obtains catalyst precarsor, be named as EDTAFeNa-HT1 (SBA-15).
3) alcohol-water (1:1, V:V) for taking 0.25g EDTAFeNa-HT1 (SBA-15) to be added to 25mL 2M NaOH is molten In liquid, 60 DEG C of stirrings for 24 hours, then washed repeatedly 3 times, filtered, dry with deionized water and ethyl alcohol, this alkaline etching process be for The SBA-15 template in sample is removed, the precursor C of desiliconization is obtained, is named as EDTAFeNa-ET (SBA-15).
4) 0.15g EDTAFeNa-ET (SBA-15) is taken, in 200mL min-1N2Under protection, it is warming up to 10 DEG C/min 900 DEG C and 2h is kept, then cooled to room temperature, this work-in-process is labeled as EDTAFeNa-HT2 (SBA-15).
This preparation process has used SBA-15 as hard template, but without using H2SO4Solution carries out sour processing, Reng Jiangzuo For comparative catalyst, use SBA-15 as hard template with following, while the catalyst for having carried out sour processing preparation is compared.
Embodiment 3
Experimental procedure is same as Example 2, difference be in experimental procedure 3) and 4) between increase a step acid handle, Experimental method is with the experimental procedure 2 in embodiment 1), the sample finally obtained is named as EDTAFeNa-AL-HT2 (SBA-15).
EDTAFeNa-HT2 (the SBA- that the EDTAFeNa-AL-HT2 (SBA-15) and embodiment 2 of the present embodiment synthesis are synthesized 15) small angle, wide-angle XRD spectra are as shown in Figure 5,6；N2Suction/desorption isotherm, pore-size distribution and texture parameter such as Fig. 7 and table 1 It is shown；XPS is composed entirely and surface-element composition is as shown in Fig. 8 and table 2；Magnetic hysteresis loop is as shown in Figure 9.
Embodiment 4
Weigh 3mg embodiment 1,2,3 preparation self-supported Fe-N-C catalyst, be distributed to 0.5mL 5wt%Nafion and In the mixed solution of deionized water (1/9, V/V), then it is suspended to pipette the above-mentioned evenly dispersed catalyst of 15 μ L by ultrasonic disperse 1h Liquid is coated to polished glassy carbon electrode surface, dry under infrared lamp, working electrode is used as after solvent volatilizees completely, so Afterwards using platinum filament as to electrode, Ag/AgCl electrode is as reference electrode by CV, and LSV electrochemical method test material is in 0.1M ORR activity in KOH.
Embodiment 5
A kind of self-supported Fe-N-C oxygen reduction catalyst, is prepared by following methods:
1) it takes the SBA-15 of 0.4g to be added in 45mL deionized water, adds 7.88g EDTAFeNa, magnetic agitation Then above-mentioned suspended matter is evaporated, dries, grinds by 0.5h, ultrasonic disperse 2h, obtain solid powder A.
2) 1g A sample is taken, in 200mL min-1N2Under protection, 700 DEG C of holding 2.5h are warming up to 5 DEG C/min, then certainly It is ground uniformly after being so cooled to room temperature, obtains catalyst precarsor, be labeled as EDTAFeNa-HT1 (SBA-15).
3) alcohol-water (1:1, V:V) for taking 0.25g EDTAFeNa-HT1 (SBA-15) to be added to 25mL 2M NaOH is molten In liquid, 60 DEG C of stirrings for 24 hours, then washed repeatedly 3 times, filtered, dry with deionized water and ethyl alcohol, this alkaline etching process be for The SBA-15 template in sample is removed, the precursor C of desiliconization is obtained, is named as EDTAFeNa-ET (SBA-15).
4) take 0.25g EDTAFeNa-ET (SBA-15) in 80 DEG C, the H of 30ml 0.5M2SO4Sour processing is carried out in solution 0.5h is finished and is filtered, dried, this work-in-process is named as EDTAFeNa-AL (SBA-15).
5) 0.15g EDTAFeNa-AL (SBA-15) is taken, in 200mL min-1N2Under protection, it is warming up to 10 DEG C/min 900 DEG C and 2h is kept, then cooled to room temperature, this work-in-process is labeled as EDTAFeNa-AL-HT2 (SBA-15), i.e. institute The self-supported Fe-N-C catalyst stated.
Embodiment 6
A kind of self-supported Fe-N-C oxygen reduction catalyst, is prepared by following methods:
1) it takes the MCM-48 of 0.4g to be added in 45mL deionized water, adds 6g EDTAFeNa, magnetic agitation 2h, Gu Above-mentioned suspended matter, is then evaporated, dries, grinds, obtain solid powder A by mechanical kilowatt mixing dispersion 2h.
2) 1g A sample is taken, in 200mL min-1Under He protection, 650 DEG C of holding 3h are warming up to 15 DEG C/min, then certainly It is ground uniformly after being so cooled to room temperature, obtains catalyst precarsor, be labeled as EDTAFeNa-HT1 (MCM-48).
3) alcohol-water (1:1, V:V) for taking 0.25g EDTAFeNa-HT1 (MCM-48) to be added to 25mL 2M NaOH is molten In liquid, 55 DEG C of stirrings for 24 hours, then washed repeatedly 3 times, filtered, dry with deionized water and ethyl alcohol, this alkaline etching process be for The MCM-48 template in sample is removed, the precursor C of desiliconization is obtained, is named as EDTAFeNa-ET (MCM-48).
4) take 0.25g EDTAFeNa-ET (MCM-48) in 75 DEG C, the HNO of 30ml 2M3Sour processing is carried out in solution 0.5h is finished and is filtered, dried, this work-in-process is named as EDTAFeNa-AL (MCM-48).
5) 0.15g EDTAFeNa-AL (MCM-48) is taken, in 200mL min-1NH3Under protection, it is warming up to 10 DEG C/min 950 DEG C and 2h is kept, then cooled to room temperature, this work-in-process is labeled as EDTAFeNa-AL-HT2 (MCM-48), i.e. institute The self-supported Fe-N-C catalyst stated.
Embodiment 7
A kind of self-supported Fe-N-C oxygen reduction catalyst, is prepared by following methods:
1) it takes the KIT-6 of 0.4g to be added in 45mL deionized water, adds 7.88g EDTAFeNa, magnetic agitation Then above-mentioned suspended matter is evaporated, dries, grinds by 0.5h, ultrasonic disperse 2h, obtain solid powder A.
2) 1g A sample is taken, in 200mL min-1N2Under protection, 750 DEG C of holding 1h are warming up to 10 DEG C/min, then certainly It is ground uniformly after being so cooled to room temperature, obtains catalyst precarsor, be labeled as EDTAFeNa-HT1 (KIT-6).
3) 0.25g EDTAFeNa-HT1 (KIT-6) is taken to be added to alcohol-water (1:1, V:V) solution of 25mL 2M NaOH In, 70 DEG C of stirrings for 24 hours, then washed repeatedly 3 times, filtered, dry with deionized water and ethyl alcohol, this alkaline etching process be in order to The KIT-6 template in sample is removed, the precursor C of desiliconization is obtained, is named as EDTAFeNa-ET (KIT-6).
4) 0.25g EDTAFeNa-ET (KIT-6) is taken to carry out sour processing in 75 DEG C, the HC1 solution of 30ml 0.5M 0.5h is finished and is filtered, dried, this work-in-process is named as EDTAFeNa-AL (KIT-6).
5) 0.15g EDTAFeNa-AL (KIT-6) is taken, in 200mL min-1N2Under protection, 900 are warming up to 10 DEG C/min DEG C and keep 2h, then cooled to room temperature, this work-in-process is labeled as EDTAFeNa-AL-HT2 (KIT-6), i.e., described Self-supported Fe-N-C catalyst.
In the embodiment of the present invention, the business 20%Pt/C for comparison is the production of Johnson Matthey company.Such as without spy Do not mentionlet alone bright, characterization employed in embodiment and electro-chemical test means are this field conventional technology.
The structural property parameter of the self-supported Fe-N-C oxygen reduction catalyst of table 1
Sample SBET(m2g-1) V(cm3g-1) Dp(nm)
EDTAFeNa-HT1 17 0.03 4.0
EDTAFeNa-AL 225 0.41 3.9
EDTAFeNa-HT2 295 0.51 3.9
EDTAFeNa-HT2(SBA-15) 93 0.30 3.9
EDTAFeNa-AL-HT2(SBA-15) 385 0.83 3.9
The surface-element of the self-supported Fe-N-C oxygen reduction catalyst of table 2 forms
The self-supported Fe-N-C oxygen reduction catalyst of table 3 is catalyzed the reactivity parameter of ORR in 0.1M KOH
By table 1-3 as it can be seen that the narrow mesoporous pore size of self-supported Fe-N-C catalyst is distributed (~3.9nm), big specific surface area (385m2g-1), high degree of graphitization, higher N content and low surface Fe constituent content (< 0.5at.%).Starting and half Wave potential is all only 10mV lower than business Pt/C catalyst (JM, 20wt%Pt).
The polarization curve of series self-supported Fe-N-C catalyst and Pt/C catalyst ORR prepared by embodiment 1,2,3 And onset potential (the E obtainedonset), half wave potential (E1/2), limiting current density (JL) and dynamics current density (Jk) as schemed 10 and table 3 shown in；Prepared by the EDTAFeNa-HT2 (SBA-15) and embodiment 3 that ORR is prepared in embodiment 2 under different rotating speeds The K-L equation model line (built-in figure) under polarization curve and corresponding different potentials on EDTAFeNa-AL-HT2 (SBA-15) Respectively as is illustrated by figs. 11 and 12.
Fig. 1,2 show the N of 1 three phases product EDTAFeNa- (HT1, AL, HT2) of embodiment2Adsorption desorption curve, hole Diameter distribution and magnetic hysteresis loop, in conjunction with texture parameter in table 1, a large amount of magnetic Fe species can effectively be removed by showing acid processing, Regulate and control the mesoscopic structure of sample simultaneously, obtaining has large specific surface area (> 220m2g-1) micro--mesoporous material.Fig. 3,4 are shown The TEM photo of embodiment 1 product EDTAFeNa-HT2 and the Fe species size statistic distribution of production, it can be seen that remaining Fe Species are wrapped in graphene or graphite-structure, and particle size is nanoscale, show only to crack a kind of forerunner of EDTAFeNa Body combines acid processing particle size caused by the Fe species generated aggregation can inhibited to a certain degree to increase and remove surface Fe Species.Fig. 5,6,7,8 and 9 respectively illustrate the EDTAFeNa-HT2 (SBA-15) that embodiment 2 and embodiment 3 synthesize and The small angle of EDTAFeNa-AL-HT2 (SBA-15), wide-angle XRD spectra, N2Suction/desorption isotherm, pore-size distribution, XPS compose entirely and As a result magnetic hysteresis loop demonstrates in conjunction with the data of table 1 and 2 and uses ordered mesoporous molecular sieve SBA-15 same for sacrifice hard template When by acid handle, can cut out with certain ordered degree, bigger serface, narrow pore-size distribution, high degree of graphitization and The mesoporous Fe-N-C material of higher N content, and almost all of crystalline state iron species such as α-Fe, Fe3C and Fe3O4It can be removed Fall.
Figure 10,11,12 and table 3 respectively illustrate 3 samples of the terminal stage of the synthesis of embodiment 1,2 and 3 and Pt/C is urged Agent is in O2The chemical property of ORR, the EDTAFeNa-AL- that embodiment 3 synthesizes as the result is shown are catalyzed in the 0.1M KOH of saturation HT2 (SBA-15) has highest catalytic performance, E to ORRonset、E1/2、JLAnd Jk(0.87V) respectively be up to 0.96V, 0.83V、4.20mA cm-2With 1.32mA cm-2, only with the E of Pt/ConsetAnd E1/210mV is differed, and is catalyzed ORR with 4 electronics Reaction path carries out, and discloses using SBA-15 as hard template, cheap organic and inorganic compound EDTAFeNa has both Fe, N and C Presoma, the mesoscopic structure of the EDTAFeNa-AL-HT2 (SBA-15) of acquisition, high degree of graphitization, higher N content are advantageous Cause in the exposure of active sites, the mass transfer diffusion of bottom product and the increase of active site density to promote electron transfer rate The active raising of ORR；The EDTAFeNa-HT2 (SBA-15) and EDTAFeNa-AL- synthesized additionally by comparative example 2 and 3 The synthetic method of HT2 (SBA-15) catalysis ORR can reduce the cost of raw material, and have process route flexible, elastic empty Between it is big, operation is controllable the features such as, under the preparation condition of optimization, very it is potential cooperate with out have to ORR it is more excellent active Non-precious metal catalyst.

Claims (10)

1. a kind of self-supported Fe-N-C oxygen reduction catalyst, which is characterized in that the self-supported Fe-N-C oxygen reduction catalyst Mesoporous pore size is 3.9 ± 0.2nm, and specific surface area is 385 ± 2m2g-1, Fe constituent content is 0.4 ± 0.02at.%, and N element contains Amount is 2.6 ± 0.2at.%, and C element content is 93 ± 2at.%；
The self-supported Fe-N-C oxygen reduction catalyst includes mesopore molecular sieve and sodium iron ethylene diamine tetra acetate, the mesoporous molecular The mass ratio of sieve and sodium iron ethylene diamine tetra acetate is 1:1~20；The mesopore molecular sieve be SBA-15, MCM-41, MCM-48 or One or more of KIT-6 composition.
2. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as described in claim 1, which is characterized in that including as follows Step:
1) first mesopore molecular sieve is add to deionized water, adds sodium iron ethylene diamine tetra acetate and is uniformly dispersed, it then will be upper It states suspended matter to be evaporated, dry, grind, obtains solid powder A；
2) by A obtained in step 1) under slumpability gas shield, 650~750 DEG C of guarantors are warming up to 10 ± 2 DEG C/min 1~3h is held, is then ground uniformly after cooled to room temperature, obtains catalyst precarsor, is labeled as EDTAFeNa-HT1 (MMS), Wherein MMS is the english abbreviation of mesopore molecular sieve, can be one or more of SBA-15, MCM-41, MCM-48 or KIT-6 Composition；
3) ethanol water of catalyst precarsor EDTAFeNa-HT1 (MMS) acid obtained in step 2) or alkali is carved Erosion obtains the precursor EDTAFeNa-ET (MMS) of desiliconization；
4) EDTAFeNa-ET (MMS) obtained in step 3) is carried out to sour processing in 70~90 DEG C, the solution of 0.5~2M 0.5~for 24 hours, it finishes and is filtered, dried, obtain the precursor EDTAFeNa-AL (MMS) for eliminating part iron species；
5) by EDTAFeNa-AL (MMS) obtained in step 4), in 180~220mL min-1Under flowing gas protection, with 10 ± 2 DEG C/min is warming up to 600~1000 DEG C and keeps 0.5~3h, and then cooled to room temperature, this work-in-process are labeled as EDTAFeNa-AL-HT2 (MMS), the i.e. self-supported Fe-N-C catalyst.
3. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 1) In, the mesopore molecular sieve and sodium iron ethylene diamine tetra acetate are add to deionized water dispersing mode and are ultrasonic disperses or pass through Solid phase mechanical mixture.
4. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 1) In, other nitrogenous small molecule compounds can also be added simultaneously；The nitrogenous small molecule chemical combination be melamine, urea, pyrroles, One or several compositions in ethylenediamine.
5. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 1) In, KOH, K can also be added simultaneously2CO3、(NH4)2CO3、ZnCO3In one or several compositions.
6. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 2) In, the slumpability gas is N2Or He.
7. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 3) In, it is performed etching with the ethanol water of acid or alkali, specifically: it is 1.5 that EDTAFeNa-HT1 (MMS), which is added to molar concentration, In the ethanol-water solution of the NaOH of~2.5M, in 55~65 DEG C of 20~25h of stirring, then repeat to wash with deionized water and ethyl alcohol It washs 3 times, filter, is dry；The volume ratio of ethyl alcohol and water is 1:1 in the ethanol-water solution.
8. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 3) In, it is performed etching with the ethanol water of acid or alkali, specifically: it is 1.5 that EDTAFeNa-HT1 (MMS), which is added to molar concentration, In the ethanol-water solution of the HF of~2.5M, in 55~65 DEG C of 20~25h of stirring, then with deionized water and ethyl alcohol repeated washing 3 Secondary, suction filtration, drying.
9. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 4) In, acid is HC1, H in the acid processing2SO4Or HNO3Solution.
10. the preparation method of self-supported Fe-N-C oxygen reduction catalyst as claimed in claim 2, which is characterized in that step 5) In, the flowing gas is inert gas or active gases NH3。
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