CN109659570A - The application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide - Google Patents

The application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide Download PDF

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CN109659570A
CN109659570A CN201910019516.3A CN201910019516A CN109659570A CN 109659570 A CN109659570 A CN 109659570A CN 201910019516 A CN201910019516 A CN 201910019516A CN 109659570 A CN109659570 A CN 109659570A
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organic framework
metal organic
framework compound
hollow microsphere
properties
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CN109659570B (en
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韩午丽
王凯佩
高宇
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Yangtze University
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Yangtze University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9075Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention discloses a kind of application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide, the metal organic framework compound hollow microsphere is used for fuel cell ORR catalyst, for the oxygen reduction reaction of catalytic cathode.For the metal organic framework compound using obtaining following preparation method, the preparation method includes: that (1) provides Properties of Polystyrene Nano Particles;(2) it loads on Properties of Polystyrene Nano Particles using Fe, Co as the MOF derivative of metal ion center, i.e. presoma;(3) presoma is calcined and carries out high temperature cabonization, remove Properties of Polystyrene Nano Particles;(4) sulfur doping is carried out to carbonized product.The metal organic framework compound hollow microsphere has excellent electro catalytic activity, can be used as fuel cell ORR elctro-catalyst.Its optimal Limited diffusion current density is 4.1mA/cm‑2, the theoretical limit diffusion current density for having been approached noble metal catalyst platinum carbon is 6mA/cm‑2, but cost is less expensive.

Description

The application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide
Technical field
The invention belongs to the applied technical fields of metal organic framework compound (MOF) derivative, and in particular to one kind is negative The application for carrying the metal organic framework compound hollow microsphere of iron cobalt sulfide, can be applied to fuel cell ORR catalyst.
Background technique
Fuel cell is a kind of environmental-friendly, efficient new energy, by the oxidized of anode and the oxygen of cathode Restore two half-reaction compositions.Oxidizing reaction rate is far longer than reduction reaction rate, therefore, improves the oxygen reduction reaction of cathode Rate is particularly important.And cathode reaction dynamic process is extremely slow, commercial Pt catalyst is expensive at present, becomes One of the bottleneck of fuel cell large-scale use.The Pt catalyst for thering is studies have shown that fuel battery negative pole to use account for battery at This about 40%.So cheap, low pollution, the alternative Pt's of catalytic performance, the fuel cell yin for being easy to be mass produced Pole oxygen reduction catalyst just seems most important.
In short, the key for the ORR catalyst to be had excellent performance be to design and synthesizing activity site dispersion degree it is high, The porous carbon materials of large specific surface area.
Summary of the invention
The object of the present invention is to provide a kind of applications of metal organic framework compound hollow microsphere.
The metal organic framework compound hollow microsphere preparation process of the load iron cobalt sulfide is simple, it is at low cost, and It is environmentally protective, it is used for the oxygen reduction reaction that fuel cell ORR catalyst is used to catalytic cathode, catalytic effect is excellent.
Using obtaining following preparation method, the preparation method includes: the metal organic framework compound
(1) Properties of Polystyrene Nano Particles is provided;
(2) it loads on Properties of Polystyrene Nano Particles using Fe, Co as the MOF derivative of metal ion center, i.e. presoma;
(3) presoma is calcined and carries out high temperature cabonization, remove Properties of Polystyrene Nano Particles;
(4) sulfur doping is carried out to carbonized product.
Further, the metal organic framework compound hollow microsphere of load iron cobalt sulfide is urged for fuel cell ORR Agent, a kind of specific embodiment are as follows:
The metal organic framework compound hollow microsphere of load iron cobalt sulfide is made as catalyst pulp, by catalyst Slurry is made on fuel battery cathode material.
Specifically, catalyst pulp is made by mixing by metal organic framework compound, binder, dispersing agent and pore creating material It obtains.
When making catalyst pulp, nafion, PVB, PTFE, PVDF is can be used in bonding agent, and dosage is that metal has machine frame The 5%~15% of frame compound quality;The deionized water and liquid alcohol centainly matched, such as ethyl alcohol, second two can be used in dispersing agent Alcohol, isopropanol etc., dosage are the 10%~50% of metal organic framework compound quality;Pore creating material is filled by the alcohol in dispersing agent When.
Specifically, catalyst pulp is made in fuel battery negative pole material by the mode that coating, hot pressing or roll-in can be used On material.
Further, the Properties of Polystyrene Nano Particles synthesizes with the following method:
The aqueous solution that (1a) prepares emulsifier is placed in reaction vessel, is placed in the aqueous solution of emulsifier in inert atmosphere To remove the polymerization inhibitor in emulsifier;
(1b) is warming up to reflux temperature, instills initiator into reaction vessel at reflux later, and react;
(1c) styrene monomer and assistant for emulsifying agent are added into reaction vessel;
(1d) is warming up to reflux temperature again, reacts at reflux later, is cooled to room temperature after the reaction was completed;
The aqueous solution of inorganic salts is added in reaction vessel and is demulsified by (1e), obtains suspension;
(1f) carries out decompression suction filtration to suspension or centrifuge is centrifuged, and is successively washed again later, depressurizes suction filtration, dries It does to get Properties of Polystyrene Nano Particles;
The entire synthesis process of Properties of Polystyrene Nano Particles carries out in an inert atmosphere.
The emulsifier uses lauryl sodium sulfate, and the initiator uses potassium peroxydisulfate or ammonium persulfate, described to help Emulsifier uses n-butanol, and the aqueous solution of the inorganic salts uses the aqueous solution of potassium chloride.
Further, the molar ratio of Fe and Co is 1:(1~3 in the MOF structure).
Further, load is using Fe, Co as the MOF derivative of metal ion center on Properties of Polystyrene Nano Particles, tool Body are as follows:
(2a) Properties of Polystyrene Nano Particles is scattered in the first dispersing agent, obtains dispersion liquid A;
(2b) disperses source of iron and cobalt source in the second dispersing agent, obtains dispersion liquid B;Second dispersing agent and the first dispersing agent It is identical;
2-methylimidazole is dissolved in ethyl alcohol by (2c), obtains solution C;
Dispersion liquid B is instilled dispersion liquid A and stirred by (2d), and solution C is added later, is stirred to react;
(2e) successively carries out vacuum rotary steam to reactant solution, is cooled to room temperature, recrystallizes, depressurizing suction filtration, drying, obtains Product;
The source of iron FeCl3Or Fe (NO3)3·6H2O;The cobalt source is CoCl2·6H2O or Co (NO3)2·6H2O。
Further, sulfur doping is carried out to carbonized product, specifically:
By carbonized product and sulphur source ground and mixed, calcined in inert atmosphere later;The sulphur source is thiocarbamide.
The invention has the advantages that and the utility model has the advantages that
The present invention urges the ORR that the metal organic framework compound hollow microsphere of load iron cobalt sulfide is used as fuel cell Agent, the metal organic framework compound hollow microsphere of the load iron cobalt sulfide is using Fe, Co as metal ion center and packet The MOF derivative being rolled on Properties of Polystyrene Nano Particles is presoma, then is modified by sulphur atom doping MOF structure. Due to the porous structure of metal organic framework compound hollow microsphere, large specific surface area, and reactivity attachment point is more, thus With excellent electronics and reduzate transmission performance.
By verification experimental verification, the metal organic framework compound hollow microsphere of the load iron cobalt sulfide has excellent electricity Catalytic activity can be used as fuel cell ORR elctro-catalyst.The metal organic framework compound of the load iron cobalt sulfide is hollow micro- The optimal Limited diffusion current density of ball is 4.1mA/cm-2, have been approached the theoretical limit dissufion current of noble metal catalyst platinum carbon Density is 6mA/cm-2, but cost is less expensive.
Detailed description of the invention
Fig. 1 is the XRD characterization figure of 1-1-ZIF@PS-C-S;
Fig. 2 is the XRD characterization figure of 1-2-ZIF@PS-C-S;
Fig. 3 is the XRD characterization figure of 1-3-ZIF@PS-C-S;
The nitrogen saturation that Fig. 4 is 1-1-ZIF@PS-C-S and the CV cyclic voltammogram under oxygen saturation;
The nitrogen saturation that Fig. 5 is 1-2-ZIF@PS-C-S and the CV cyclic voltammogram under oxygen saturation;
The nitrogen saturation that Fig. 6 is 1-3-ZIF@PS-C-S and the CV cyclic voltammogram under oxygen saturation.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
It should be noted that " Properties of Polystyrene Nano Particles " to be abbreviated as to " PS microballoon " hereinafter, by emulsifier " dodecyl Sodium sulphate " is abbreviated as " SDS ", and initiator " potassium peroxydisulfate " is abbreviated as " KPS ".
Embodiment 1
PS microballoon can directly be bought, and can also voluntarily be prepared, and the present embodiment will provide a kind of preparation method of PS microballoon, The preparation method of certain PS microballoon is not limited to this.
The step of PS microballoon, is successively as follows in the present embodiment:
(1) 0.3g SDS is dissolved in the deionized water of 180ml, SDS solution is obtained, SDS solution is placed in there-necked flask, and Polymerization inhibitor in nitrogen removing SDS is led to SDS solution.
(2) SDS solution in there-necked flask is warming up to 80 DEG C, at reflux, it is water-soluble that KPS is quickly instilled into there-necked flask Liquid, drop finish, and react 15min.The KPS aqueous solution instilled is obtained in the deionized water for 0.3g KPS is added 15ml.
(3) mixed liquor of styrene monomer and n-butanol is slowly added dropwise into there-necked flask, drop finishes, and reacts 30min.The mixing Liquid is obtained by 0.3g styrene monomer and the mixing of 0.2g n-butanol.
(4) it is added at one time 9.7g styrene monomer into there-necked flask, reacts 2h at reflux.
(5) cooled to room temperature.
(6) at room temperature, Klorvess Liquid is added into there-necked flask in a small amount of multiple method, until there is obvious sediment, Stop the addition of Klorvess Liquid;It keeps being stirred liquid in there-necked flask while Klorvess Liquid is added.
(7) it stands and is demulsified for 24 hours.
(8) decompression suction filtration is carried out to the suspension obtained after demulsification or centrifuge is centrifuged, later to the white solid of acquisition It is successively filtered using washing, decompression, drying, white powder product, that is, PS microballoon of acquisition.
(9) the mixed liquor decompression after demulsification is filtered or is centrifuged with centrifuge, obtained white solid is successively with distillation Twice, decompression filters for water and ethanol washing, drying;The PS microballoon of white powder is obtained, structural formula is
It should be noted that the whole process of synthesis PS microballoon will carry out in inert atmosphere protection.
Embodiment 2-4 will provide the synthetic example of three kinds of presomas, and the molar ratio of Fe, Co are followed successively by three kinds of presomas 1:1,1:2,1:3 are respectively corresponded and are named as 1-1-ZIF@PS, 1-2-ZIF@PS and 1-3-ZIF@PS.
PS microballoon employed in embodiment 2-4 is 1 product of embodiment.
Embodiment 2
The present embodiment will provide the MOF derivative 1-1-ZIF@synthetic example of PS, and steps are as follows:
(1) in there-necked flask, the PS microballoon of 0.27g is dispersed in 5ml deionized water and 20ml ethyl alcohol, 30 DEG C of temperature control, For mechanical stirring to evenly dispersed, gained dispersion liquid is denoted as dispersion liquid A.
(2) by the FeCl of 0.78g3With the CoCl of 1.142g2·6H2O is dispersed in 15ml ethyl alcohol, gained dispersion liquid It is denoted as dispersion liquid B.
(3) 2-methylimidazole of 2.362g is dissolved in 25ml ethyl alcohol, acquired solution is denoted as solution C.
(4) dispersion liquid B is slowly dropped in dispersion liquid A, mixed liquor quickly becomes brown blue in there-necked flask, and to mixing Liquid is vigorously stirred 30min.
(5) solution C is added at one time in there-necked flask, mixed liquor rapidly goes to brownish black in there-necked flask at this time, stirred Night reaction.
(6) vacuum rotary steam is carried out to reactant in there-necked flask, after natural cooling, successively carries out ethyl alcohol recrystallization, decompression It filters, filter cake drying, obtains bluish violet product 1-1-ZIF@PS.
Embodiment 3
The present embodiment will provide the MOF derivative 1-2-ZIF@synthetic example of PS, and steps are as follows:
(1) in there-necked flask, the PS microballoon of 1.08g is dispersed in 10ml deionized water and 50ml ethyl alcohol, 30 DEG C of temperature control, For mechanical stirring to evenly dispersed, gained dispersion liquid is denoted as dispersion liquid A.
(2) by the FeCl of 1.04g3With the CoCl of 3.05g2·6H2O is dispersed in 45ml ethyl alcohol, gained dispersion liquid note For dispersion liquid B.
(3) 2-methylimidazole of 9.448g is dissolved in 80ml ethyl alcohol, acquired solution is denoted as solution C.
(4) dispersion liquid B is slowly dropped in dispersion liquid A, mixed liquor quickly becomes brown blue in there-necked flask, and to mixing Liquid is vigorously stirred 30min.
(5) solution C is added at one time in there-necked flask, mixed liquor rapidly goes to brownish black in there-necked flask at this time, stirred Night reaction.
(6) vacuum rotary steam is carried out to reactant in there-necked flask, after natural cooling, successively carries out ethyl alcohol recrystallization, decompression It filters, filter cake drying, obtains bluish violet product 1-1-ZIF@PS.
Embodiment 4
The present embodiment will provide the MOF derivative 1-3-ZIF@synthetic example of PS, and steps are as follows:
(1) in there-necked flask, the PS microballoon of 0.54g is dispersed in 10ml deionized water and 40ml ethyl alcohol, 30 DEG C of temperature control, For mechanical stirring to evenly dispersed, gained dispersion liquid is denoted as dispersion liquid A.
(2) by the FeCl of 0.78g3With the CoCl of 3.426g2·6H2O is dispersed in 30ml ethyl alcohol, gained dispersion liquid It is denoted as dispersion liquid B.
(3) 2-methylimidazole of 4.724g is dissolved in 80ml ethyl alcohol, acquired solution is denoted as solution C.
(4) dispersion liquid B is slowly dropped in dispersion liquid A, mixed liquor quickly becomes brown blue in there-necked flask, and to mixing Liquid is vigorously stirred 30min.
(5) solution C is added at one time in there-necked flask, mixed liquor rapidly goes to brownish black in there-necked flask at this time, stirred Night reaction.
(6) vacuum rotary steam is carried out to reactant in there-necked flask, after natural cooling, successively carries out ethyl alcohol recrystallization, decompression It filters, filter cake drying, obtains bluish violet product 1-3-ZIF@PS.
Embodiment 5
The present embodiment will provide the implementation of the high temperature cabonization of presoma 1-1-ZIF@PS, 1-2-ZIF@PS, 1-3-ZIF@PS Example.
Presoma 1-1-ZIF@PS, 1-2-ZIF@PS and 1-3-ZIF@PS are respectively placed in different porcelain boats, porcelain boat is put Enter tube furnace, high-temperature calcination is carried out under air atmosphere.Calcine technology parameter are as follows: with 2.5 DEG C/min heating rate by tube furnace Interior temperature rises to 500 DEG C, and keeps the temperature 3h.Calcining is completed, and through cooled to room temperature, grinds 2h to calcined product using mortar. Products therefrom, which respectively corresponds, is named as 1-1-ZIF@PS-C, 1-2-ZIF@PS-C, 1-3-ZIF@PS-C.
Embodiment 6
The present embodiment will provide the sulfur doping of carbonized product 1-1-ZIF@PS-C, 1-2-ZIF@PS-C, 1-3-ZIF@PS-C Embodiment.
1-1-ZIF@PS-C, 1-2-ZIF@PS-C, 1-3-ZIF@PS-C are mixed with thiocarbamide according to the mass ratio of 1:2 respectively It closes, and is fully ground 4h with mortar, be respectively placed in different porcelain boats later.Porcelain boat is put into tube furnace, in nitrogen atmosphere into Row high-temperature calcination.Calcine technology parameter are as follows: tubular type in-furnace temperature is risen to 600 DEG C with 2.5 DEG C/min heating rate, and is kept the temperature 3h.Calcining is completed, and through cooled to room temperature, grinds 2h to calcined product using mortar.Products therefrom, which respectively corresponds, to be named as 1-1-ZIF@PS-C-S、1-2-ZIF@PS-C-S、1-3-ZIF@PS-C-S。
Fig. 1 is the XRD characterization figure of 1-1-ZIF@PS-C-S, by right with the JPC-DS card (JCPDS99-0109) of standard Than, it can be seen that Fig. 1 is iron cobalt sulfide Fe0.8Co0.2S phase, 2 angles θ be iron cobalt sulfide at 29.97 °, 33.90 °, 43.78 ° Fe0.8Co0.2The characteristic peak of S respectively corresponds (200), (201), (202) crystal face, and peak type is sharp, regular, half-peak breadth is relatively narrow, explanation Crystallinity is fine.There is no miscellaneous peak, illustrates the iron cobalt sulfide Fe for pure phase0.8Co0.2S.The characteristic peak of elemental sulfur is not shown, Illustrate that sulphur is fully doped and enters lattice, the not remaining sulphur simple substance in surface.Also the not no disperse broad peak of amorphous carbon, explanation PS microballoon is by except making a gift of to the greatest extent during high temperature cabonization under air atmosphere.
Fig. 2 and Fig. 3 is respectively the XRD characterization figure of 1-2-ZIF@PS-C-S, 1-3-ZIF@PS-C-S, by with standard JPC-DS card (JCPDS99-0109) comparison, 2 angles θ are to respectively correspond iron cobalt sulfide at 29.97 °, 33.90 °, 43.78 ° Fe0.8Co0.2(200) of S, (201), (202) crystal face.But compared to Figure 1, hence it is evident that find out, with Co content in compound Increasing, characteristic peak remitted its fury, half-peak breadth increases, illustrate that distortion of lattice degree increases, crystallinity decline, i.e. crystallinity 1-3-ZIF@ PS-C-S<1-2-ZIF@PS-C-S<1-1-ZIF@PS-C-S.In addition, it is metallic cobalt that 2 angles θ, which are corresponding at 45.8 ° and 53.3 °, The diffraction maximum of nano particle (111), (200) crystal face illustrates compared to Fig. 1, with the increase of Co content, occur in the composite Cobalt nano-particle.
Embodiment 7
The present embodiment is 1-1-ZIF@PS-C-S, the electrocatalysis characteristic of 1-2-ZIF@PS-C-S, 1-3-ZIF@PS-C-S try It tests, by the metal organic framework compound hollow microsphere of load iron cobalt sulfide known to electrocatalysis characteristic test, to oxygen Reduction has good electro catalytic activity, can be used as the catalyst of fuel battery negative pole oxygen reduction reaction.
Electrocatalysis characteristic test procedure is as follows:
(1) 1-1-ZIF@PS-C-S, 1-2-ZIF@PS-C-S, 1-3-ZIF@PS-C- is respectively adopted in preparation work electrode S modifies glass-carbon electrode.
The modification of glass-carbon electrode, specifically:
(1a) is cleaned and is polished to glass-carbon electrode;
(1b) weighs 6 product 5mg of embodiment, is added in the centrifuge tube of 2ml.Take the deionization of 80 μ L respectively with liquid-transfering gun Water, the isopropanol of 900 μ L, 20 μ L nafion, be added centrifuge tube in, ultrasonic 40min, obtain ink;
(1c) in three times with liquid-transfering gun is every time dried in the air the ink droplet of 6 μ L in glassy carbon electrode surface using drop-coating naturally It is dry.
(2) the present embodiment electrocatalysis characteristic test is all made of three-electrode system, the electrochemical workstation of morning China 660E, the U.S. Pine rotating disk electrode (r.d.e), pine rotating disk electrode (r.d.e) diameter be 5mm, area 0.19625cm2, reference electrode is saturation Mercury/mercuric oxide electrode is platinum electrode to electrode, and electrolyte is the KOH solution of 0.1M, is configured using deionized water.
Electrochemical property test is carried out using cyclic voltammetry (CV) and linear sweep voltammetry (LSV).CV experiment condition Are as follows: the KOH solution of 0.1M prepared using deionized water first leads to N240min reaches saturation, with 0.5VS-1Sweep speed scanning 100 Circle carries out electrode activation;Logical O is changed again240min reaches saturation, with 50mVS-1It sweeps speed and obtains CV figure.LSV experiment condition are as follows: O2 The KOH solution of the 0.1M of saturation sweeps fast 5mVS-1, rotation speed change from high to low, successively 2000rpm, 1600rpm, 1200rpm, 800rpm、400rpm。
CV cyclic voltammetric result is shown in that Fig. 4-6, Fig. 4 are 1-1-ZIF@PS-C-S as catalyst, electrocatalytic oxidation reducing electrode When CV cyclic voltammogram, it can be seen from the figure that nitrogen saturation electrolyte in there are not redox peaks, in contrast, In the electrolyte of oxygen saturation, there are apparent redox peaks in the place -0.3V, it was confirmed that 1-1-ZIF@PS-C-S has preferably The electro catalytic activity to oxygen reduction.Fig. 5 is 1-2-ZIF@PS-C-S as catalyst, CV when electrocatalytic oxidation reducing electrode Cyclic voltammogram, comparison nitrogen saturation and the CV of oxygen saturation electrolyte scheme, hence it is evident that find out that 1-2-ZIF@PS-C-S also has electricity Catalytic activity, potential corresponding to peak value are -0.28V.Fig. 6 is 1-3-ZIF@PS-C-S as catalyst, electrocatalytic oxidation reduction CV cyclic voltammogram when electrode, the CV figure in oxygen saturation electrolyte equally obviously have a redox peaks, and spike potential is- 0.24V。
The oxygen reduction of catalyst cathode is the process that chemical energy is converted to electric energy, the electricity of reduction corresponding to reduction peak Position is bigger, then the catalytic activity of elctro-catalyst is better.Therefore, 1-1-ZIF@PS-C-S, 1-2-ZIF@PS-C-S, 1-3-ZIF@ The electro catalytic activity sequence of PS-C-S are as follows: 1-3-ZIF@PS-C-S > 1-2-ZIF@PS-C-S > 1-1-ZIF@PS-C-S.Compare XRD The analysis of figure is as a result, illustrate that metal organic framework compound hollow microsphere of the present invention has good ORR activity, and increase Co gold Metal nano-particle content can effectively improve its catalytic activity.
LSV cyclic voltammetric the results are shown in Table 1, spread electricity for the limit of the glass-carbon electrode after catalyst modification under different rotating speeds Current density (unit: mA/cm-2).LSV polarization curve data reflect the power of Cathodic oxygen reduction.Platform is spread in the limit Area, Limited diffusion current density is bigger, then hydrogen reduction power is more sufficient.As can be seen from Table 1, for same catalyst, with Revolving speed increase, Limited diffusion current density increases therewith, this similarly proved in CV cyclic voltammetric result about this three Kind catalyst all has the active conclusion of preferable ORR.When the revolving speed of rotating disk electrode (r.d.e) is 1600rpm, commercial noble metal The theoretical limit diffusion current density of catalyst platinum carbon is 6mA/cm-2.The limit of catalyst of the present invention at 1600 rpm is compared to expand Current density is dissipated, the Limited diffusion current density of 1-1-ZIF@PS-C-S is 3.2mA/cm-2, the limit expansion of 1-2-ZIF@PS-C-S Dissipating current density is 3.6mA/cm-2, the Limited diffusion current density of 1-3-ZIF@PS-C-S is 4.1mA/cm-2.It can be seen that 1-1- The electro catalytic activity sequence of ZIF@PS-C-S, 1-2-ZIF@PS-C-S, 1-3-ZIF@PS-C-S are as follows: 1-3-ZIF@PS-C-S > 1- 2-ZIF@PS-C-S>1-1-ZIF@PS-C-S.This also demonstrates the analysis result of CV cyclic voltammetric result: load iron cobalt of the present invention The metal organic framework compound hollow microsphere of sulfide has good ORR activity, and the content for increasing Co can be mentioned effectively Its high catalytic activity.
The Limited diffusion current density of glass-carbon electrode after the modification of 1 catalyst of table
400rpm 800rpm 1200rpm 1600rpm 2000rpm
1-1-ZIF@PS-C-S 2.6mA/cm-2 2.8mA/cm-2 3.1mA/cm-2 3.2mA/cm-2 3.5mA/cm-2
1-2-ZIF@PS-C-S 2.4mA/cm-2 2.9mA/cm-2 3.4mA/cm-2 3.6mA/cm-2 3.9mA/cm-2
1-3-ZIF@PS-C-S 3mA/cm-2 3.3mA/cm-2 3.8mA/cm-2 4.1mA/cm-2 4.3mA/cm-2
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.

Claims (9)

1. a kind of application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide, it is characterized in that:
The metal organic framework compound hollow microsphere is used for fuel cell ORR catalyst, for the hydrogen reduction of catalytic cathode Reaction;
Using obtaining following preparation method, the preparation method includes: the metal organic framework compound
(1) Properties of Polystyrene Nano Particles is provided;
(2) it loads on Properties of Polystyrene Nano Particles using Fe, Co as the MOF derivative of metal ion center, i.e. presoma;
(3) presoma is calcined and carries out high temperature cabonization, remove Properties of Polystyrene Nano Particles;
(4) sulfur doping is carried out to carbonized product.
2. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as described in claim 1, special Sign is:
The metal organic framework compound hollow microsphere is used for fuel cell ORR catalyst, specifically:
Metal organic framework compound is made as catalyst pulp, catalyst pulp is made in fuel battery cathode material On.
3. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as claimed in claim 2, special Sign is:
Metal organic framework compound is made as catalyst pulp, specifically:
Metal organic framework compound, binder, dispersing agent and pore creating material are mixed and are made as catalyst pulp.
4. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as claimed in claim 2, special Sign is:
By the way of coating, hot pressing or roll-in, catalyst pulp is made on fuel battery cathode material.
5. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as described in claim 1, special Sign is:
The Properties of Polystyrene Nano Particles synthesizes with the following method:
The aqueous solution that (1a) prepares emulsifier is placed in reaction vessel, is placed in the aqueous solution of emulsifier in inert atmosphere to go Except the polymerization inhibitor in emulsifier;
(1b) is warming up to reflux temperature, instills initiator into reaction vessel at reflux later, and react;
(1c) styrene monomer and assistant for emulsifying agent are added into reaction vessel;
(1d) is warming up to reflux temperature again, reacts at reflux later, is cooled to room temperature after the reaction was completed;
The aqueous solution of inorganic salts is added in reaction vessel and is demulsified by (1e), obtains suspension;
(1f) carries out decompression suction filtration to suspension or centrifuge is centrifuged, and is successively washed again later, depressurizes suction filtration, drying, i.e., Obtain Properties of Polystyrene Nano Particles;
The entire synthesis process of Properties of Polystyrene Nano Particles carries out in an inert atmosphere.
6. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as claimed in claim 5, special Sign is:
The emulsifier uses lauryl sodium sulfate, and the initiator uses potassium peroxydisulfate or ammonium persulfate, described to help emulsification Agent uses n-butanol, and the aqueous solution of the inorganic salts uses the aqueous solution of potassium chloride.
7. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as described in claim 1, special Sign is:
The molar ratio of Fe and Co is 1:(1~3 in the MOF structure).
8. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as described in claim 1, special Sign is:
It is loaded on Properties of Polystyrene Nano Particles using Fe, Co as the MOF derivative of metal ion center, specifically:
(2a) Properties of Polystyrene Nano Particles is scattered in the first dispersing agent, obtains dispersion liquid A;
(2b) disperses source of iron and cobalt source in the second dispersing agent, obtains dispersion liquid B;Second dispersing agent and the first dispersing agent phase Together;
2-methylimidazole is dissolved in ethyl alcohol by (2c), obtains solution C;
Dispersion liquid B is instilled dispersion liquid A and stirred by (2d), and solution C is added later, is stirred to react;
(2e) successively carries out vacuum rotary steam to reactant solution, is cooled to room temperature, recrystallizes, depressurizing suction filtration, drying, is produced Object;
The source of iron FeCl3Or Fe (NO3)3·6H2O;The cobalt source is CoCl2·6H2O or Co (NO3)2·6H2O。
9. the application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide as described in claim 1, special Sign is:
Sulfur doping is carried out to carbonized product, specifically:
By carbonized product and sulphur source ground and mixed, calcined in inert atmosphere later;The sulphur source is thiocarbamide.
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