CN112909270A - Preparation and application of multistage composite oxygen reduction catalyst - Google Patents
Preparation and application of multistage composite oxygen reduction catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000001301 oxygen Substances 0.000 title claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 15
- 230000009467 reduction Effects 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims description 28
- 239000000243 solution Substances 0.000 claims abstract description 45
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 230000000813 microbial effect Effects 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- -1 transition metal cyanide compound Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 58
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
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- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Classifications
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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
- H01M4/90—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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of environmental engineering, and particularly relates to a preparation method of an air cathode oxygen reduction catalyst of a microbial fuel cell, which is used for treating organic matters in a polluted water source. The invention provides a preparation method of an oxygen reduction catalyst for an air cathode of a microbial fuel cell, which comprises the following steps: a. respectively preparing two solutions of a transition metal cyanide compound aqueous solution (A solution) and a transition metal soluble salt aqueous solution (B solution); dispersing a certain amount of phthalocyanine in an absolute ethyl alcohol solution, and recording the solution as a solution C; b. under the condition of magnetic stirring, firstly adding the solution A into the solution C, fully stirring, then dropwise and slowly adding the solution B into the solution, and continuously stirring after dropwise adding is finished to uniformly mix the solution A and the solution C. The preparation process is simple, the used raw materials are common compounds, and the preparation process is simple and easy to obtain, and provides convenient conditions for large-scale preparation of the catalyst.
Description
The technical field is as follows:
the invention belongs to the field of environmental engineering, and particularly relates to a preparation method of an air cathode oxygen reduction catalyst of a microbial fuel cell, which is used for treating organic matters in a polluted water source.
Technical background:
microbial Fuel Cells (MFCs) are devices that directly convert chemical energy of organic substances in sewage into electrical energy by using microorganisms. The sewage treatment device can generate clean and pollution-free electric energy while treating sewage, and is therefore considered to be a green and environment-friendly sustainable sewage treatment device. However, in a microbial fuel cell using oxygen as a cathode electron acceptor, the oxygen reduction reaction at the cathode is slow, limiting the improvement in cell performance. Researches show that the cathode reaction activation potential can be reduced by attaching a high-activity catalyst on a cathode, the oxygen reduction reaction rate is increased, and the service performance of the MFCs is improved. Among these catalysts, noble metals such as Pt have a good catalytic effect, but their price is high, resulting in a high cost of the microbial fuel cell. Therefore, there is a trend toward the development of highly efficient and inexpensive non-noble metal catalysts. In the prior non-noble metal oxygen reduction catalysts, carbon and nitrogen catalysts containing transition metals such as Fe and Co have been disclosed in the prior art, but the preparation methods of the catalysts are complicated and expensive materials such as melamine, dimethylformamide, zeolite imidazole organic framework-8 (ZIF-8), porphyrin and the like are often used, so that the preparation methods are difficult to industrially produce.
Prussian-like blue is a compound having a metal-cyanide coordination structure. By carrying out pyrolysis on the prussian-like blue, the prussian-like blue can be converted into a graphene-coated alloy structure. Chinese patent CN106622235B discloses a method for preparing a graphene-coated alloy nano-catalyst for converting carbon dioxide into carbon monoxide, which comprises mixing two kinds of metal powders to form an anode, using a graphite rod as a cathode, and performing a discharge reaction in a reaction chamber of a mixed gas of methane and a dopant gas for 1-6 hours to obtain the graphene-coated alloy nano-catalyst. Such processes are relatively harsh. Chinese patent CN 106825552B discloses a method of distributing graphene oxide on the surface of alloy powder by using electrostatic interaction, and then reducing graphene oxide into graphene in a vacuum furnace. Although the preparation method ensures that the graphene is distributed on the surface of the metal alloy, the raw material uses the relatively expensive titanium alloy, so that the production cost is increased, and the large-scale production is difficult. Both the chinese patent CN 107497495A and the chinese patent CN 109174105A relate to the preparation of catalysts with prussian-like blue PBA as precursors, but the performance and stability of the catalysts need to be improved.
In order to improve the stability of the air cathode catalyst of the microbial fuel cell and reduce the production cost, the method takes phthalocyanine and Prussian-like blue as composite precursors, under the condition of high-temperature calcination, a graphene structure converted from cyanide in the Prussian-like blue and sponge carbon derived from the phthalocyanine can form a layer of surface carbon, and finally the transition metal/graphene/sponge carbon multi-stage composite catalyst is obtained, so that metal ions in the catalyst are protected, the stability and the activity of the catalyst are improved, and important reference is provided for realizing large-scale preparation of the catalyst.
The invention content is as follows:
the invention aims to provide a preparation method of an oxygen reduction catalyst for an air cathode of a microbial fuel cell, wherein the catalyst has an excellent multi-stage composite structure of transition metal/graphene/sponge carbon. The multi-stage composite catalyst prepared by the invention has better catalytic action on the air cathode oxygen reduction reaction of the microbial fuel cell, the preparation process is simpler, the used raw materials are common compounds, and the multi-stage composite catalyst is simple and easy to obtain, and provides better convenient conditions for the mass preparation of the catalyst.
The preparation method comprises the following steps:
a. respectively preparing two solutions of a transition metal cyanide compound aqueous solution (A solution) and a transition metal soluble salt aqueous solution (B solution); dispersing a certain amount of phthalocyanine in an absolute ethyl alcohol solution, and recording the solution as a solution C;
b. under the condition of magnetic stirring, firstly adding the solution A into the solution C, fully stirring, then dropwise and slowly adding the solution B into the solution, and continuously stirring after dropwise adding is finished to uniformly mix the solution A and the solution C;
c. performing solid-liquid separation on the mixture in the step (b) through a centrifugal machine, reserving solid matters, and washing with clean water for multiple times;
d. putting the solid obtained in the step (c) into a vacuum drying oven for drying at the temperature of 60-100 ℃ for 12-36 h;
e. grinding the dried solid obtained in the step (d), calcining at 500-1000 ℃ for 1-4h under the condition of nitrogen or argon, and naturally cooling to room temperature after calcining to obtain a calcined product;
f. washing the calcined product obtained in the step (e) with dilute hydrochloric acid, ethanol and clear water for three times respectively, and then placing the calcined product in a vacuum drying oven for drying at the drying temperature of 60-100 ℃ for 12-36h to finally obtain the transition metal/graphene/sponge carbon multistage composite catalyst;
further, in the production method of the present application, the transition metal cyanide compound has M1xM2(CN)yWherein x is 1-4, y is 3-6, M1＝Na，K；M2＝Fe，Co)；
Further, in the preparation method of the present application, the transition metal in the transition metal salt is selected from one or more of Cu, Zn, and Mn;
further, in the preparation method, the concentration of the A solution and the B solution is between 0.1 and 2mol/L, and the concentration of the C solution is between 2 and 10 g/L; the volume ratio of the three solutions A, B and C is 1: 1: 1-5;
the application discloses a preparation method of a transition metal/graphene/sponge carbon multistage composite catalyst and application of the transition metal/graphene/sponge carbon multistage composite catalyst in a microbial fuel cell;
the beneficial effect of this application lies in: the method comprises the following steps of (1) obtaining a transition metal/graphene/sponge carbon multistage composite catalyst by using cheap and easily-obtained raw materials and a simple process flow and taking Prussian-like blue loaded sponge carbon as a precursor; on one hand, the size of the transition metal is less than 100nm, and the transition metal is wrapped by the dissolved carbon formed by the graphene layer and the sponge carbon, so that the stability and the catalytic activity of the transition metal are improved; on the other hand, the nitrogen-containing graphene and the sponge carbon are mutually fused, so that the catalytic effect and the stability of the catalyst are further enhanced. The catalyst prepared by the invention is used in the air cathode of the microbial fuel cell, so that the resistance of oxygen reduction reaction can be greatly reduced, the output power density of the cell is improved, and the industrial application of the microbial fuel cell is promoted.
Description of the drawings:
FIG. 1 is a transmission electron scan of an Fe-Cu/graphene/sponge carbon composite catalyst in one embodiment
FIG. 2 first embodiment of the linear scan curve
FIG. 3 is a graph of the output power density of a microbial fuel cell in accordance with a first embodiment
The specific implementation mode is as follows:
implementation mode one
Respectively preparing 0.50mol/L phthalocyanine ethanol solution, 0.13mol/L potassium hexacyanoferrate and 0.40mol/L copper nitrate aqueous solution. Under the condition of magnetic stirring, firstly adding a potassium hexacyanoferrate solution into a phthalocyanine ethanol solution, then slowly adding a copper nitrate solution into the mixed solution, and continuing stirring for 3 hours after the dropwise addition is finished. Then solid-liquid separation is carried out by a centrifugal machine to obtain a solid product, and the solid product is washed by clear water for a plurality of times. And (3) drying the solid obtained by centrifugation in a vacuum drying oven at the drying temperature of 80 ℃ for 12 h. And grinding the obtained dry solid, placing the ground dry solid in a tubular furnace, introducing nitrogen, setting the calcining temperature to 850 ℃ and the calcining time to be 2.5 h. And (3) washing the calcined product with 0.1M HCl, ethanol and clear water respectively, and then placing the washed calcined product in a vacuum drying oven for drying at the drying temperature of 80 ℃ for 14h to finally obtain the iron-copper/graphene/sponge carbon multistage composite catalyst.
An electron transmission electron microscope image of the iron-copper/graphene/sponge carbon composite catalyst is shown in fig. 1. CN groups in the Prussian-like blue are converted into graphene layers to wrap the surfaces of the metal alloys, and the graphene layers and the sponge carbon on the outermost layer form a surface blending phenomenon, so that the transition metal/graphene/sponge carbon composite catalyst is constructed. This structure facilitates the shuttling of air and the transfer of electrons, and thus the reduction of oxygenAnd (3) carrying out the reaction. The prepared iron-copper/graphene/sponge carbon composite catalyst is used as a catalyst layer of an air cathode (blank sponge carbon is used as a control), electrochemical characterization is carried out, and a linear sweep voltammetry curve is shown in fig. 2. The results show that the iron-copper/graphene/sponge carbon multistage composite catalyst can greatly promote the electrochemical reaction of the system, and the iron-copper/graphene/sponge carbon composite catalyst has larger catalytic activity. The prepared iron-copper/graphene/sponge carbon composite catalyst was used as a catalyst layer of an air cathode (blank sponge carbon was used as a control) for battery performance characterization, and the results are shown in fig. 3. As can be seen from the results, the output power of the iron-copper/graphene/sponge carbon multistage composite catalyst reaches 1837mW m-2The output power density of the blank sponge carbon is more than five times, which shows that the iron-copper/graphene/sponge carbon multistage composite catalyst can promote the electricity generating capacity of the microbial fuel cell, and provides reference for the development of the microbial fuel cell.
Claims (6)
1. A preparation method of a multistage composite oxygen reduction catalyst is characterized by comprising the following steps: the preparation method mainly comprises the following steps:
a. preparing a transition metal cyanide aqueous solution, and recording the solution as A; preparing a transition metal salt aqueous solution, and recording the transition metal salt aqueous solution as a B solution; dispersing phthalocyanine in absolute ethyl alcohol solution, and recording as C solution;
b. under the condition of magnetic stirring, firstly adding the solution A into the solution C, fully stirring, then dropwise and slowly adding the solution B into the solution, and continuously stirring after dropwise adding is finished to uniformly mix the solution A and the solution C;
c. performing solid-liquid separation on the mixture in the step (b) through a centrifugal machine, reserving solid matters, and washing with clean water for multiple times;
d. putting the solid obtained in the step (c) into a vacuum drying oven for drying at the temperature of 60-100 ℃ for 12-36 h;
e. grinding the dried solid obtained in the step (d), calcining at 500-1000 ℃ for 1-4h under the condition of high-purity nitrogen or high-purity argon, and naturally cooling to room temperature after calcining to obtain a calcined product;
f. and (e) washing the calcined product obtained in the step (e) with dilute hydrochloric acid, ethanol and clear water for three times, then placing the washed calcined product in a vacuum drying oven for drying at the drying temperature of 60-100 ℃ for 12-36h, and finally obtaining the transition metal/graphene/sponge carbon multistage composite catalyst.
2. The method for producing a multistage composite oxygen-reducing catalyst according to claim 1, characterized in that: the transition metal cyanide has M1xM2(CN)yWherein x is 1-4, y is 3-6, M1＝Na，K；M2＝Fe，Co。
3. The method for producing a multistage composite oxygen-reducing catalyst according to claim 1, characterized in that: the transition metal in the transition metal salt is selected from one or more of Cu, Zn and Mn.
4. The method for producing a multistage composite oxygen-reducing catalyst according to claim 1, characterized in that: the concentration of the A and B solutions is between 0.1 and 2mol/L, and the concentration of the C solution is between 2 and 10 g/L.
5. The method for producing a multistage composite oxygen-reducing catalyst according to claim 1, characterized in that: the volume ratio of the three solutions A, B and C is 1: 1: 1 to 5.
6. The method for using the multistage composite oxygen reduction catalyst according to claim 1, wherein: the method is suitable for preparing the catalyst for the oxygen reduction reaction, and is particularly suitable for preparing the air cathode catalyst of the microbial fuel cell.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114447348A (en) * | 2022-01-28 | 2022-05-06 | 曲阜师范大学 | Preparation method of oxygen reduction catalyst combining metal/covalent organic framework compound with titanium aluminum carbide |
| CN116161678A (en) * | 2022-12-07 | 2023-05-26 | 大连理工大学 | Preparation method of efficient wave-absorbing composite material CoFe@CNTs |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114447348A (en) * | 2022-01-28 | 2022-05-06 | 曲阜师范大学 | Preparation method of oxygen reduction catalyst combining metal/covalent organic framework compound with titanium aluminum carbide |
| CN114447348B (en) * | 2022-01-28 | 2023-08-11 | 曲阜师范大学 | Oxygen reduction catalyst of metal/covalent organic framework compound combined titanium aluminum carbide and preparation method and application thereof |
| CN116161678A (en) * | 2022-12-07 | 2023-05-26 | 大连理工大学 | Preparation method of efficient wave-absorbing composite material CoFe@CNTs |
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