CN109037713A - The preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst - Google Patents

The preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst Download PDF

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CN109037713A
CN109037713A CN201810811336.4A CN201810811336A CN109037713A CN 109037713 A CN109037713 A CN 109037713A CN 201810811336 A CN201810811336 A CN 201810811336A CN 109037713 A CN109037713 A CN 109037713A
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iron
catalyst
preparation
oxygen reduction
biological carbon
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李俊
范泽宇
董莹莹
张亮
付乾
朱恂
廖强
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Chongqing 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
    • H01M4/90—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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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  • Microbiology (AREA)
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Abstract

The invention discloses the preparation methods of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst, it is characterised in that: the following steps are included: A, mixing with iron salt solutions or iron content organic solution chlorella pyrenoidosa powder and ultrasonic vibration；B, again that obtained product is dry under the conditions of 80 DEG C~100 DEG C；C, then the product after drying is placed in electric tube furnace, and be pyrolyzed under an inert atmosphere；D, the product obtained after pyrolysis cleans after ball mill grinding, then with hydrochloric acid, obtains catalyst；The present invention solves the problems such as existing Pt/C catalyst at high price, scarcity of resources, easily poison, and has the characteristics that at low cost, preparation method is simple, can be widely used in the fields such as the energy, chemical industry, environmental protection.

Description

The preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst
Technical field
The present invention relates to microbiological fuel cells, more particularly to Novel iron N doping mesoporous biological carbon oxygen reduction catalyst Preparation method.
Background technique
Microbiological fuel cell (MFC, Microbial Fuel Cell) is a kind of novel microbial energy conversion skill Art, the microbial film of anode growth, which can degrade, the organic matter in sewage and generates electronics, and electronics passes through external circuit arrival Cathode is simultaneously transmitted to cathode electronics receptor and produces electricl energy.MFC mostly uses air cathode at present.This is primarily due to the oxygen in air Itself is cheap and easy to get, and not will increase additional system operation cost.Therefore MFC cathod catalyst hydrogen reduction (ORR, Oxygen reduction reaction) transmitting in cathode of activity and oxygen is the electricity generation performance for influencing battery entirety Principal element.
ORR catalyst mostly uses noble metal or precious metal alloys material, such as metal platinum or platinum cobalt alloy etc. at present, it can To be effectively reduced the overpotential during ORR.But there are some the shortcomings that being difficult to avoid that, such as price are high for precious metal material The problem of expensive, reserves are limited and easily poison inactivation, therefore more and more researchers are desirable with non-noble metallic materials substitution Precious metal material, wherein the ORR catalyst of Fe-N-C type receives extensive attention with its outstanding catalytic performance.For example, Liu et al. people (LIU Yingying, Ruan J, SANG Shangbin, et al.Iron and Nitrogen co-doped Carbon Derived from Soybeans as Efficient Electro-catalysts for the Oxygen Reduction Reaction [J] .Electrochimica Acta, 2016,215:388-397) it is big by pyrolysis natural material Bean powder end and FeCl3Mixture, be prepared for a kind of Fe3O4With the high-performance carbonaceous ORR catalyst of N co-doped.They have found High-performance is higher from catalyst degree of graphitization, and the total content of pyridine-N and graphite-N are higher, while obtaining higher Fe3O4Content and specific surface area.Cui et al. (CUI Xiaoyang, YANG Ahubin, YAN Xingxu, et al.Pyridinic-Nitrogen-Dominated Graphene Aerogels with Fe-N-C Coordination for Highly Efficient Oxygen Reduction Reaction[J].Advanced Functional Materials, 2016,26:5708-5717) graphene aerogel that a kind of pyridine nitrogen accounts for main N doping has been synthesized, discovery contains There is the sample of Fe-N-C types of functional groups to have the take-off potential and higher carrying current of corrigendum.Therefore, high performance iron is prepared The biological carbon oxygen reduction catalyst of N doping has good actual application prospect.
Summary of the invention
It is mesoporous for the Novel iron N doping of microbiological fuel cell technical problem to be solved by the present invention lies in providing The preparation method of biological carbon oxygen reduction catalyst.
It is above-mentioned mentioned in order to solve the problems, such as, the technical scheme is that Novel iron N doping mesoporous biological carbon oxygen is also The preparation method of raw catalyst, it is characterised in that: the following steps are included:
A, chlorella pyrenoidosa powder is mixed to simultaneously ultrasonic vibration with iron salt solutions or iron content organic solution, obtains aggregate sample Product；
B, again that obtained product is dry under the conditions of 80 DEG C~100 DEG C, obtain desciccate；
C, then the product after drying is placed in electric tube furnace, and be pyrolyzed under an inert atmosphere, after tentatively obtaining pyrolysis Catalyst sample；
D, the product obtained after pyrolysis cleans after ball mill grinding, then with hydrochloric acid, obtains catalyst.
The present invention uses stainless (steel) wire as supporting layer, and carbon black uses pressure sintering as gas diffusion layers, combined catalyst Air cathode is made, in conjunction with carbon brush anode, is assembled into high-performance single-chamber microbial fuel cell.
Concrete principle of the invention is: the present invention is made using chlorella pyrenoidosa (Chlorella pyrenoidosa, CP) For the nitrogen source and carbon source of ORR catalyst.Chlorella pyrenoidosa is that one is natural and cheap microalgae (19 $/kg).It is logical 55% to 60% protein (different according to condition of culture), 6% water and unsaturated fat are often accounted for containing quality Acid, carbohydrate, fiber, minerals and vitamins etc..During high temperature cabonization, this not only obtains catalyst itself and enriches Pore structure directly carry out the nitrogen P elements that guarantee the transmission of substance in electrode, while be rich in chlorella pyrenoidosa from mixing It is miscellaneous；900 DEG C of high temperature cabonization ensure that char-forming material has good electric conductivity.The present invention is made using exogenous iron containing compounds Synthesized Fe/N-C catalyst for source of iron, the catalyst of ferro element doping has richer mesoporous and macropore, be ion and The transmission of oxygen and the discharge of product water provide channel.
Chlorella pyrenoidosa of the present invention is rich in nitrogen P elements, and auto-dope can further increase active site, and then effective Oxygen Adsorption and catalysis reaction are carried out, so that carbonaceous cathodes have preferable hydrogen reduction performance；Chlorella pyrenoidosa of the present invention at This is low in cost and easily available, environmentally friendly；The present invention carries out ferro element doping, further changes catalyst surface defect level and hole Gap structure enhances catalytic performance；Iron N doping mesoporous biological carbon hydrogen reduction of the present invention for microbiological fuel cell is catalyzed Agent is as a kind of new microbiological fuel cell yin non-metallic catalyst, alternative high due to its good electrocatalysis characteristic Expensive commercial Pt/C catalyst solves the problems such as existing Pt/C catalyst at high price, scarcity of resources, easily poison, in micro- life The fields such as the reduction of object fuel cell electrocatalytic oxidation, sewage treatment have a wide range of applications.
The preferred side of the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to the present invention Case, the iron salt solutions are iron chloride, frerrous chloride or ironic citrate；Iron content organic solution is ferrocene or FePC.
The preferred side of the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to the present invention The mass ratio of case, chlorella pyrenoidosa powder and iron salt solutions or the ferro element in iron content organic solution be 28~32:5.04~ 6.16。
The preferred embodiment of the preparation method of iron N doping mesoporous biological carbon oxygen reduction catalyst according to the present invention, heat The method of solution is: dry sample is placed in high-temperature tubular electric furnace, nitrogen is vacuumized and fill, later with 3 DEG C~5 DEG C/ Minute rate be warming up to 300 DEG C, be then warming up to 900 DEG C with 8 DEG C~10 DEG C/min of rate, be carbonized 2 under nitrogen atmosphere ~2.5 hours, then natural cooling waited for that furnace temperature is down to 100 DEG C or less taking-up products.
The preferred side of the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to the present invention Case, ball mill grinding time are 10~12 hours.
The beneficial effect of the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst of the present invention is: Catalyst prepared by the present invention can effectively carry out Oxygen Adsorption and catalysis reaction, so that carbonaceous cathodes have preferable hydrogen reduction Performance and catalytic performance are a kind of new microbiological fuel cell yin non-metallic catalyst, the commercial Pt/C of alternative valuableness Catalyst solves the problems such as existing Pt/C catalyst at high price, scarcity of resources, easily poison, has at low cost, preparation method The features such as simple, can be widely used in the fields such as the energy, chemical industry, environmental protection, have a good application prospect.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst of the present invention.
Fig. 2 is the iron N doping mesoporous biological carbon hydrogen reduction that 1,2 gained of the embodiment of the present invention is used for microbiological fuel cell The nitrogen adsorption desorption curve and distribution of pores figure of catalyst.
Fig. 3 a is the resulting oxygen reduction catalyst CP-FeCl of embodiment 13SEM (scanning electron under different enlargement ratios Microscope) figure；
Fig. 3 b is the resulting oxygen reduction catalyst CP-FeCl of embodiment 22SEM (scanning electron under different enlargement ratios Microscope) figure；
Fig. 4 a is the resulting oxygen reduction catalyst CP-FeCl of embodiment 13XPS (X-ray photoelectron spectroscopic analysis) figure.
Fig. 4 b is the resulting oxygen reduction catalyst CP-FeCl of embodiment 22XPS (X-ray photoelectron spectroscopic analysis) figure.
Fig. 5 is that (linear voltammetric scan is bent by LSV of embodiment 1, the 2 and Pt/C catalyst at rotating ring disk electrode (r.r.d.e) 1600rmp Line) figure.
Fig. 6 a is that embodiment 1,2 and Pt/C catalyst is assembled into the power density curve graph after battery respectively.
Fig. 6 b is that embodiment 1,2 and Pt/C catalyst is assembled into the anode and cathode polarization curve after battery respectively.
Specific embodiment
The present invention is further described specifically below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
Referring to Fig. 1, the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst, comprising the following steps:
A, by 30g chlorella pyrenoidosa powder and 100ml, 1molL-1FeCl3Simultaneously ultrasonic vibration 2 is small for iron salt solutions mixing When, obtain mixing sample；
B, again that obtained product is 6~8 hours dry under the conditions of 80 DEG C~100 DEG C, the product after being dried；
C, then the product after drying is placed in electric tube furnace, nitrogen is vacuumized and fill, later with 3 DEG C~5 DEG C/minute The rate of clock is warming up to 300 DEG C, is then warming up to 900 DEG C, under nitrogen atmosphere, nitrogen stream with 8 DEG C~10 DEG C/min of rate Amount control is in 35cm3/ min~40cm3/ min is carbonized 2~2.5 hours；Then natural cooling waits for that furnace temperature is down to 100 DEG C or less and is taken Product out, the catalyst sample after being tentatively pyrolyzed；
D, the product obtained after pyrolysis cleans after ball mill grinding 10~12 hours, then with 1M hydrochloric acid, is catalyzed Agent CP-FeCl3。
Embodiment 2, iron salt solutions are 100ml, 1molL unlike the first embodiment-1FeCl2Solution obtains catalyst CP-FeCl2。
Comparative catalyst CP-FeCl3With catalyst CP-FeCl2, referring to figure, 2, from figure 2 it can be seen that the valence of ferro element State has significant impact to catalyst pores gap structure.The shape of all nitrogen Adsorption and desorption isotherms belongs to IUPAC classification IV type, P/P0Show mesoporous presence in the curve that 0.3-0.4 range occurs.Referring to table 1, table 1 is embodiment 1,2 institute of embodiment Obtain catalyst CP-FeCl3And CP-FeCl2Specific surface area and distribution of pores data.
Table 1
It can be seen that CP-FeCl from the data in table 12Compared to CP-FeCl3There is higher BET specific surface area, but CP-FeCl3There is bigger Kong Rong.This shows that divalent Fe2O3 doping makes CP-FeCl2Form more micropores.The formation of micropore can be with Bigger specific surface area is obtained to expose more active sites；And the CP-FeCl of trivalent Fe2O3 doping3With more Mesoporous and macropore.Although its specific surface area is smaller, a large amount of mesoporous and macropore presence can for ion and oxygen transmission with And the discharge of product water provides channel.
As best shown in figures 3 a and 3b, CP-FeCl2With CP-FeCl3Microscopic appearance it is substantially similar, but CP-FeCl2Surface is formed Some small protrusions and hole, and it is significantly less than CP-FeCl in size3, this also intuitively demonstrates CP-FeCl2Surface Form a large amount of micropore.
As shown in Fig. 4 a, 4b, two kinds of catalyst are all successfully mixed with nitrogen, CP-FeCl2And CP-FeCl3Middle nitrogen is former Atomic ratio shared by son is respectively 1.65% and 1.55%, this illustrates shadow of the valence state to the total doping of nitrogen for adulterating ferro element Sound is very little.According to existing research and document, nitrogen XPS spectrum, which can be fitted, is divided into four peaks: in 398.7eV or so The peak pyridinic-N, at the peak pyrrolic-N of 400.1eV or so, 401.2eV or so the peak graphitic-N and At the peak oxidized-N of 402.4eV or so.
Referring to table 2, table 2 is embodiment 1,2 gained catalyst CP-FeCl of embodiment3And CP-FeCl2XPS spectrum swarming Fitting data is specifically reflected in conjunction with energy position and each nitrogen-containing functional group proportion.
Table 2
The valence state that can be seen that ferro element from the data in Fig. 4 a, 4b and table 2 has larger shadow to nitrogenous luminous energy group type Ring: more oxygen elements form the oxide of iron in conjunction with ferro element after mixing iron first, thus oxidized-N do not occur Peak occurs.Secondly, CP-FeCl3The content of middle pyridinic-N is much higher than CP-FeCl2, while pyrrolic-N content will be lower than CP-FeCl2, this illustrates Fe3+Be conducive to have the pyridinic-N functional group of oxygen reduction activity to be formed.In addition CP-FeCl2In The content of graphitic-N is slightly above CP-FeCl3, indicate CP-FeCl2There is bigger carrying current.
As shown in figure 5, CP-FeCl3Take-off potential and half wave potential compared with CP-FeCl2Polarization.This shows CP-FeCl3More Good ORR catalytic activity.Its reason is primarily due to CP-FeCl3Possess more mesoporous and macroporous structure structure, it is effective strong Change substrate transmitting, is conducive to the transmitting of reactant and the discharge of product；In addition, the pyridinic-N of its high level is also Hydrogen reduction provides more active sites.From this figure it can be seen that CP-FeCl2Carrying current be slightly above CP-FeCl3, This is primarily due to CP-FeCl2Caused by middle graphitic-N content is higher.Although CP-FeCl2And CP-FeCl3Carrying current It is not much different with Pt/C, the hydrogen reduction starting of Pt/C is 0.242V vs.Ag/AgCl most just.But CP-FeCl3Half wave potential It is slightly positive in Pt/C, CP-FeCl3Electron transfer number reached 3.89, illustrate its catalysis ORR react with four electron reaction processes Based on, the above results illustrate CP-FeCl2It is a kind of cheap catalyst that can substitute Pt/C.
Embodiment 3, iron salt solutions are 100ml, 1molL unlike the first embodiment-1Ironic citrate FeC6H5O7Solution, Obtain catalyst CP-FeC6H5O7。
Embodiment 4, unlike the first embodiment by 28g chlorella pyrenoidosa powder and 100ml, 1molL-1Ferrocene The mixing of Ferrocene solution, obtains catalyst CP-Ferrocene.
Embodiment 5, unlike the first embodiment by 32g chlorella pyrenoidosa powder and 100ml, 1molL-1FePC The mixing of Iron (II) phthalocyanine solution, obtains catalyst CP-FePc.
Embodiment 6, respectively with CP-FeCl3、CP-FeCl2With Pt/C be catalyst make MFC, use stainless (steel) wire as Air cathode is made using pressure sintering as gas diffusion layers, combined catalyst in supporting layer, carbon black, in conjunction with carbon brush anode, assembling At high-performance single-chamber microbial fuel cell.As shown in Figure 6 a, with CP-FeCl3For the highest maximum of the MFC of catalyst production Power density is 2358.37 ± 90mWm-2, greater than using Pt/C as cathod catalyst MFC maximum power density (1846.3 ± 66mW·m-2).It can be seen that anode performance difference very little from the anode and cathode polarization curve of Fig. 6 b simultaneously.The above results explanation, MFC electricity generation performance difference is mainly caused by cathod catalyst is different.With CP-FeCl3Why can be obtained for the cathode of catalyst Maximum performance has benefited from wherein the presence of a large amount of mesoporous and macropore, enhances the transmitting of reactant and product in Catalytic Layer It excludes, reduces resistance to mass tranfer.Meanwhile existing for catalyst it is a large amount of it is heteroatomic be doped to cathode reaction provide it is a large amount of anti- Active site is answered to enhance battery electricity generation ability.
Chlorella pyrenoidosa powder used in all embodiments of the invention is purchased from Xi'an Tian Bin Bioisystech Co., Ltd, Nafion membrane solution is purchased from DuPont Corporation, and carbon black (Vulcan XC72) is purchased from Carbot company, commercial 20% platinum carbon catalysis Agent and ptfe emulsion (polytetrafluoroethylene, PTFE, mass fraction ω=60%) are gloomy purchased from upper Haihe River Electric Applicance Co., Ltd.Other reagents are that analysis is pure, are purchased from Chengdu Ke Long chemical reagent factory.Water used in experimentation is equal For deionized water.
The preparation of air cathode is using Don et al. (DONG Heng, YU Hongbing, WANG Xin, et al.A Novel Structure of Scalable Air-cathode without Nafion and Pt by Rolling Activated Carbon and PTFE as Catalyst Layer in Microbial Fuel Cells[J].Water Research, 2012,46:5777-5787.) hot-press method reported in document.Air cathode consists of three parts, and is respectively Gas diffusion layers, Catalytic Layer, and the stainless steel mesh sheet played a supporting role between gas diffusion layers and Catalytic Layer.It will be commercial Carbon black and PTFE emulsion are pressed in stainless (steel) wire on piece according to the mass ratio 3:2 heat of mixing.Similarly, catalyst and PTFE emulsion quality Than for 4:1.The carrying capacity of gas diffusion layers carbon black is 30mgcm-2, Catalytic Layer catalyst loading is 10mgcm-2。
Microbiological fuel cell uses single cell structure, is made of organic glass.Chamber be diameter be 3cm, length 4cm Cylinder.Anode use diameter for 2.5cm, length be 2.5cm carbon brush and place in the chamber, air cathode is another mounted in MFC Side and gas diffusion layers side exposure in air.All MFC use 50 Ω sequence batch initiations.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this The range of invention is defined by the claims and their equivalents.

Claims (5)

1. the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst, it is characterised in that: the following steps are included:
A, chlorella pyrenoidosa powder is mixed to simultaneously ultrasonic vibration with iron salt solutions or iron content organic solution, obtains mixture；
B, again that step A mixture obtained is dry under the conditions of 80 DEG C~100 DEG C, obtain desciccate；
C, then desciccate is placed in electric tube furnace, and be pyrolyzed under an inert atmosphere, obtain catalyst first sample；
D, the catalyst first sample obtained after pyrolysis is cleaned after ball mill grinding, then with hydrochloric acid, obtains catalyst.
2. the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to claim 1, feature Be: the iron salt solutions are iron chloride, frerrous chloride or ironic citrate；Iron content organic solution is ferrocene or phthalocyanine Iron.
3. the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to claim 1 or 2, special Sign is: the mass ratio of chlorella pyrenoidosa powder and iron salt solutions or the ferro element in iron content organic solution is 28~32: 5.04~6.16.
4. the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to claim 3, feature Be: the method for pyrolysis is: dry sample being placed in high-temperature tubular electric furnace, nitrogen is vacuumized and fill, later with 3 DEG C ~5 DEG C/min of rate is warming up to 300 DEG C, then 900 DEG C is warming up to 8 DEG C~10 DEG C/min of rate, in nitrogen atmosphere Lower carbonization 2~2.5 hours, then natural cooling waits for that furnace temperature is down to 100 DEG C or less taking-up products.
5. the preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst according to claim 4, feature Be: the ball mill grinding time is 10~12 hours.
CN201810811336.4A 2018-07-23 2018-07-23 The preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst Pending CN109037713A (en)

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CN110429309A (en) * 2019-08-12 2019-11-08 重庆大学 Based on monoblock type carbonaceous from breathing cathode without film aminic acid fuel battery preparation method
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888318A (en) * 2019-02-13 2019-06-14 上海交通大学 A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal-
CN110429309A (en) * 2019-08-12 2019-11-08 重庆大学 Based on monoblock type carbonaceous from breathing cathode without film aminic acid fuel battery preparation method
CN110429309B (en) * 2019-08-12 2020-12-29 重庆大学 Preparation method of membrane-free formic acid fuel cell based on integral carbonaceous self-breathing cathode
CN113134354A (en) * 2021-03-09 2021-07-20 四川轻化工大学 Preparation method of high-efficiency oxygen reduction reaction catalyst

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