CN109103464A - A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell - Google Patents
A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell Download PDFInfo
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- CN109103464A CN109103464A CN201811002897.6A CN201811002897A CN109103464A CN 109103464 A CN109103464 A CN 109103464A CN 201811002897 A CN201811002897 A CN 201811002897A CN 109103464 A CN109103464 A CN 109103464A
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- catalyst
- uio66
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/9008—Organic or organo-metallic compounds
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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
- 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
Abstract
The present invention relates to bioelectrochemistry technical fields, specifically disclose the preparation method, Catalytic Layer and microbiological fuel cell of a kind of Catalytic Layer.Then deionized water is added dropwise comprising steps of S1, mix acetylene black and Co/UiO66 catalyst in the preparation method of Catalytic Layer；S2, perfluorosulfonic acid type polymer solution solution and pure aqueous isopropanol are added, stirred evenly, obtain suspension；S3, suspension is applied on carbon cloth, forming coating on carbon cloth, it is dry, obtain Catalytic Layer.In the preparation method of Catalytic Layer provided by the present invention, creatively using Co/UiO66 catalyst as raw material, compared with noble metal platinum and its noble metal composite, the raw material sources of Co/UiO66 catalyst are extensive, cheap, are a kind of good oxygen reduction reaction catalyst.Applied in microbiological fuel cell, can be improved the stability of microbiological fuel cell, reduce its operating cost, improve cathode electronics delivery rate.
Description
Technical field
The present invention relates to bioelectrochemistry fields, more particularly to a kind of preparation method of Catalytic Layer, Catalytic Layer and micro- life
Object fuel cell.
Background technique
Energy and environment problem is that the project of whole mankind's facing and modern industrialization develop difficulty urgently to be resolved
One of topic.Environmental problem is not only related to the survival and development of mankind itself, manner of breathing same as the survival and reproduction of other biological
It closes.With human development and industry prosperity, the exploitation of the energy is also to increasingly sharpen to the destruction of environment, the exploitation of new clean energy resource
On a large scale using extremely urgent；The exploitation of biomass energy and efficient utilize are to solve the problems, such as environmental pollution and energy shortage
One of effective way is of great significance to realization social sustainable development.Microbiological fuel cell has in field of waste water treatment
It hopes while improving environment and energy problem.
Microbiological fuel cell (Microbial Fuel Cell, MFC) will be changed using microorganism as biocatalyst
Learn one kind " green " device that can be converted into electric energy.Electronics is generated in the electricity-producing microorganism energy oxidation of organic compounds of MFC anode
And proton, after microorganism-capturing to anode, by external circuit by electronics transfer to cathode, proton is also by proton exchange membrane
It is sent to cathode, proton and electron acceptor is finally made to react and generate electric current.Compared with other fuel cells, MFC is net
Electric energy can be harvested while changing sewage, and does not bring secondary pollution；, operating condition low with maintenance cost be mild, biology
The advantages that compatibility is good is a kind of new high-efficiency electrochemical techniques, obtains the extensive concern of domestic and foreign scholars.
Although the potentiality of microbiological fuel cell have applications well in following development, due to its output power
Still lower, material cost is higher, is not met by the demand of modern industry, needs the high Microbial fuel of preparation catalytic activity
The cathod catalyst of battery can not only significantly improve the electricity generation performance of microbiological fuel cell, moreover it is possible to take for expensive Pt/
C catalyst is of great significance for the large-scale application of MFC so that overall cost be greatly reduced and improve stability.
Summary of the invention
The present invention is directed to overcome the deficiencies of existing technologies, the preparation method, Catalytic Layer and biology combustion of a kind of Catalytic Layer are provided
Expect battery, solves to exist in the prior art lower output power and higher cost etc. in the utilization of microbiological fuel cell and ask
Topic.
To achieve the above object, the invention adopts the following technical scheme:
The present invention provides a kind of preparation method of Catalytic Layer, the preparation method comprising steps of S1, by acetylene black and Co/
The mixing of UiO66 catalyst, is then added dropwise from water；S2, perfluorosulfonic acid type polymer (Nafion) solution and pure is added
Aqueous isopropanol stirs evenly, and obtains suspension；S3, the suspension is coated on carbon cloth, is formed and is applied on the carbon cloth
Layer, it is dry, obtain Catalytic Layer.
Preferably, the mass ratio of the acetylene black and the Co/UiO66 catalyst is (3~5): 1；The deionized water
Mass ratio with the Co/UiO66 catalyst is (10~15): 1.
Preferably, the concentration of the Nafion solution is 3%~5%, the concentration of the pure aqueous isopropanol is 95%~
99%.
Preferably, the mass ratio of the Co/UiO66 catalyst and the Nafion solution, the pure aqueous isopropanol is
1:(30~35): (25~30).
Preferably, the coating with a thickness of 0.3mm~0.5mm.
Preferably, the Co/UiO66 catalyst preparation method comprising steps of
S11,2- amino terephthalic acid (TPA), chlorination zirconia material and n,N-Dimethylformamide are mixed, it is mixed obtains first
Close solution；First mixed solution placement is reacted at the first temperature, obtains yellowish mixture of colours dope；S12, it uses respectively
Yellowish mixture of colours dope described in n,N-Dimethylformamide and methanol agitator treating, centrifugal treating is dry, obtains solid
Body；The solid body, cobalt nitrate and methanol are mixed, the second mixed solution is obtained；Second mixed solution is placed
It reacts at the second temperature, obtains the yellowish mixture of colours dope for mixing Co；S13, with methanol wash described in mix the yellowish mixture of colours of Co
Dope, centrifugal treating is dry, obtains the solid body for mixing Co；The solid body for mixing Co is placed at a temperature of third
High temperature sintering is carried out, the Co/UiO66 catalyst is obtained.
Preferably, in the step S11,2- amino terephthalic acid (TPA), chlorination zirconia material and n,N-Dimethylformamide
Mass ratio between three is 1:(1~2): (261~262)；In the step S12, cobalt nitrate, solid body and methanol three
Mass ratio between person is 1:(11~12): (68~69).
On the other hand, the present invention provides a kind of Catalytic Layer, and the Catalytic Layer is made by above-mentioned preparation method.
On the other hand, the present invention also provides a kind of microbiological fuel cell, including diffusion layer, carbon based layer, carbon cloth layer and
Catalytic Layer, wherein the Catalytic Layer uses above-mentioned Catalytic Layer.Preferably, the Catalytic Layer with a thickness of 0.4mm~0.5mm.
It is creative using Co/UiO66 catalyst as raw material in the preparation method of Catalytic Layer provided by the present invention, and it is expensive
Metal platinum and its noble metal composite are compared, and the raw material sources of Co/UiO66 catalyst are extensive, cheap, are a kind of good
Oxygen reduction reaction catalyst.Catalytic Layer obtained by preparation method of the invention is applied in microbiological fuel cell, it can
The stability of microbiological fuel cell is improved, its operating cost is reduced, improves cathode electronics delivery rate.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the structural schematic diagram that microbiological fuel cell loads Catalytic Layer cathode provided in an embodiment of the present invention；
Fig. 2 is the corresponding Catalytic Layer of 1-4 of the embodiment of the present invention for the voltage pattern after microbiological fuel cell；
Fig. 3 is the corresponding Catalytic Layer of 1-4 of the embodiment of the present invention for the power density diagram after microbiological fuel cell.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The specific embodiment of the invention provides the preparation method, Catalytic Layer and microbiological fuel cell of a kind of Catalytic Layer, solution
Lower output power certainly exists in the prior art in the utilization of microbiological fuel cell and the problems such as higher cost.
The specific embodiment of the invention provides a kind of preparation method of Catalytic Layer, comprising:
S1, acetylene black and Co/UiO66 catalyst are mixed, is then added dropwise from water；S2, to add Nafion molten
Liquid and aqueous isopropanol, stir evenly, and obtain suspension；S3, the suspension is coated on carbon cloth, the shape on the carbon cloth
It is dry at coating, obtain Catalytic Layer.
Wherein, the Co/UiO66 catalyst preparation method comprising steps of
S11,2- amino terephthalic acid (TPA), chlorination zirconia material and n,N-Dimethylformamide are mixed, it is mixed obtains first
Close solution；First mixed solution placement is reacted at the first temperature, obtains yellowish mixture of colours dope；S12, it uses respectively
Yellowish mixture of colours dope described in n,N-Dimethylformamide and methanol agitator treating, centrifugal treating is dry, obtains solid
Body；The solid body, cobalt nitrate and methanol are mixed, the second mixed solution is obtained；Second mixed solution is placed
It reacts at the second temperature, obtains the yellowish mixture of colours dope for mixing Co；S13, with methanol wash described in mix the yellowish mixture of colours of Co
Dope, centrifugal treating is dry, obtains the solid body for mixing Co；The solid body for mixing Co is placed at a temperature of third
High temperature sintering is carried out, the Co/UiO66 catalyst is obtained.
Specifically, the preparation method of Catalytic Layer includes: in the embodiment of the present invention
S1, acetylene black and Co/UiO66 catalyst are mixed, wherein acetylene black and the mass ratio of Co/UiO66 catalyst are
(3~5): 1；Then be added dropwise the deionized water and Co/UiO66 catalyst being added dropwise from water mass ratio be (10~
15):1；S2, the Nafion solution that concentration is 3%~5% and the aqueous isopropanol that concentration is 95%~99% are added,
There is no limit for the addition sequence of Nafion solution and aqueous isopropanol, wherein Co/UiO66 catalyst and Nafion solution, isopropyl
The mass ratio of alcoholic solution is 1:(30~35): (25~30) stir evenly, and obtain suspension；S3, suspension is applied to carbon cloths
On, the coating with a thickness of 0.3mm~0.5mm is formed on carbon cloth, it is dry, obtain Catalytic Layer.
Wherein, Co/UiO66 catalyst preparation method comprising steps of S1, by 2- amino terephthalic acid (TPA), zirconium chloride material
Material and n,N-Dimethylformamide mixing, wherein 2- amino terephthalic acid (TPA), chlorination zirconia material and N, N- dimethyl formyl
Mass ratio between amine three is 1:(1~2): (261~262) obtain the first mixed solution；It, will in preferred embodiment
After 2- amino terephthalic acid (TPA), chlorination zirconia material and n,N-Dimethylformamide mix in proportion, in 20 DEG C~30 DEG C environment
At a temperature of, preferably 25 DEG C, by magnetic agitation 5min~10min, obtain the first mixed solution；S2, described first is mixed
Solution placement reacts at the first temperature, wherein the first temperature be 110 DEG C~130 DEG C, preferably 120 DEG C, at the first temperature
The reaction time of reaction is 36h~60h, preferably 48h, obtains yellowish mixture of colours dope；S3, N, N- dimethyl methyl are used respectively
Yellowish mixture of colours dope, centrifugal filtration described in amide and methanol agitator treating, obtain the first precipitating, the revolving speed of centrifugation
7000~9000r/min, preferably 8000r/min, the time of centrifugation are 5min~10min, precipitate drying for first, specifically exist
It is dried in vacuum oven, the operating temperature of vacuum oven is 70 DEG C~90 DEG C, and preferably 80 DEG C, the dry time is
12h~36h preferably for 24 hours obtains solid body；In preferred embodiment, after centrifugal filtration, is shaken and washed with methanol
And ultrasound 1min~5min, re-dry obtain solid body；S4, the solid body, cobalt nitrate and methanol are mixed,
In, the mass ratio between cobalt nitrate, solid body and methanol three is 1:(11~12): (68~69) obtain the second mixing
Solution；Second mixed solution placement is reacted at the second temperature, wherein second temperature is 30 DEG C~50 DEG C, preferably
40 DEG C, the reaction time reacted at the second temperature is 12h~36h, and preferably for 24 hours, the yellowish mixture of colours for obtaining mixing Co is sticky
Object；S5, with methanol wash described in mix the yellowish mixture of colours dope of Co, centrifugal filtration obtains the second precipitating, the revolving speed of centrifugation
7000~9000r/min, preferably 8000r/min, the time of centrifugation are 5min~10min, precipitate drying for second, specifically exist
It is dried in vacuum oven, the operating temperature of vacuum oven is 70 DEG C~90 DEG C, and preferably 80 DEG C, the dry time is
12h~36h preferably for 24 hours obtains the solid body for mixing Co；S6, the solid body for mixing Co is placed at a temperature of third
Carry out high temperature sintering, specifically, the temperature range of third temperature be 700 DEG C~1000 DEG C, can respectively 700 DEG C, 800 DEG C,
High temperature sintering is carried out under the conditions of 900 DEG C or 1000 DEG C, the time of high temperature sintering is 1h~3h, preferably 2h；It is further preferred that
High temperature sintering temperature is 900 DEG C, the solid body for mixing Co is placed at a temperature of third when carrying out high temperature sintering, is passed through nitrogen
Gas obtains the Co/UiO66 catalyst as doped raw material.Specifically, in 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C conditions
The catalyst that lower progress high temperature sintering obtains is denoted as Co/UiO66-700 catalyst, Co/UiO66-800 catalyst, Co/ respectively
UiO66-800 catalyst, Co/UiO66-900 catalyst and Co/UiO66-1000 catalyst.
More specifically, the preparation method of Catalytic Layer includes: in the embodiment of the present invention
S1, by acetylene black and Co/UiO66 catalyst according to mass ratio (3~5): 1 is placed into proportion container, to ingredient
Be added dropwise in container with Co/UiO66 catalyst quality ratio be 1:(11~12) deionized water；Specifically, by acetylene black
It is placed on pan paper, then weighed Co/UiO66 catalyst is placed into pan paper, and by acetylene black and Co/UiO66
Catalyst is uniformly mixed；Further, deionization is instilled into the proportion container that placed acetylene black and Co/UiO66 catalyst
Water, it should be noted that when instilling deionized water to proportion container, needing drop by drop to instill, making acetylene black and Co/
UiO66 catalyst and deionized water mixing are more uniform, and when instilling deionized water, do not need to be stirred.
S2, into proportion container, addition and Co/UiO66 catalyst quality ratio are 1:(31~32): the concentration of (26~27)
It is 99% aqueous isopropanol for 5%Nafion solution and concentration and stirs evenly, the addition of Nafion solution and aqueous isopropanol
There is no limit obtain suspension to sequence；Specifically, first adding into proportion container with Co/UiO66 catalyst quality ratio is 1:
The concentration of (31~32) is 5% Nafion solution, then adds into proportion container and be with Co/UiO66 catalyst quality ratio
1:(26~27) concentration be 99% aqueous isopropanol；Then by the Co/UiO66 catalyst being put into proportion container (as
Pulvis), concentration is 5%Nafion solution and concentration is 99% aqueous isopropanol (as solvent) sealing, then be placed into vibrator
On, centrifugal force stirring is obtained by vibrator proportion container, when on vibrator, the revolving speed of vibrator is not more than proportion container
250 revolution per seconds, so that the solution and pulvis in proportion container are sufficiently mixed, to obtain uniformly mixed suspension.
In the specific embodiment of the invention, the density for the Nafion solution that selected concentration is 5% is 0.92~
0.94g/ml, correspondingly, the density for the aqueous isopropanol that concentration is 99% are 0.785g/ml.Specifically, acetylene black, Co/
UiO66 catalyst, deionized water, the mass ratio for the aqueous isopropanol that the Nafion solution and concentration that concentration is 5% are 99%
Unit is gram.
S3, suspension is applied on carbon cloth, thickness is formed on carbon cloth between the coating of 0.3mm~0.5mm, will be with applying
After at least drying for 24 hours of the carbon cloth of layer, Catalytic Layer is obtained.It should be noted that being answered when suspension is applied on carbon cloth
This is avoided the other side suspension is applied to carbon cloth as far as possible.
Further, it is coated on carbon cloth after certain thickness suspension, needs to be dried, under normal circumstances, needed
Carbon cloth is dried by hair dryer.In embodiments of the present invention, due to being coated with suspension on carbon cloth, and in order to prevent
Leading to carbon cloth and suspension due to high temperature in the drying process, its is destructurized, it is preferable that needs to be arranged hair dryer and adopts
It is blown with cold wind, or when being blown using hot wind, it should the distance between carbon cloth and hair dryer air outlet be kept to be greater than 70~100cm
Between, and it is additionally provided with partition between carbon cloth and hair dryer air outlet, it, can be to avoid high temperature by the partition and setting distance
Destroy the structure of carbon cloth and suspension.
In practical applications, the carbon cloth coated with suspension will at least be dried for 24 hours, after carbon cloth is dry for 24 hours, can obtain
To Catalytic Layer, and the Catalytic Layer is Co/UiO66 Catalytic Layer.
It is creative using Co/UiO66 catalyst as raw material in the preparation method of Catalytic Layer provided by the present invention, and it is expensive
Metal platinum and its noble metal composite are compared, and the raw material sources of Co/UiO66 catalyst are extensive, cheap, are a kind of good
Oxygen reduction reaction catalyst.Catalytic Layer obtained by preparation method of the invention is applied in microbiological fuel cell, it can
The stability of microbiological fuel cell is improved, its operating cost is reduced, improves cathode electronics delivery rate.It solves in the prior art
The problems such as there are lower output power in the utilization of microbiological fuel cell and higher costs.
The embodiment of the present invention also provides a kind of microbiological fuel cell, including diffusion layer, carbon based layer, carbon cloth layer and catalysis
Layer.Wherein, Catalytic Layer is Catalytic Layer obtained by preparation method through the invention, Catalytic Layer with a thickness of 0.4mm~
0.5mm。
Catalytic Layer is applied to by the present invention by loading to the Catalytic Layer containing Co/UiO66 catalyst on carbon cloth
In microbiological fuel cell, the cathode that microbiological fuel cell load has Co/UiO66 carbon cloth is obtained.It is specific as shown in fig. 1,
For the structural schematic diagram of microbiological fuel cell load C o/UiO66 catalyst cathode provided in an embodiment of the present invention, the microorganism
Fuel cell includes including diffusion layer, carbon based layer 1-3, carbon cloth layer 1-2 and Catalytic Layer 1-1.Catalysis provided in an embodiment of the present invention
The thickness of layer is between 0.4~0.5mm.
It is described in detail below in conjunction with specific embodiment.
Embodiment 1
The Co/UiO66-700 catalyst of 0.0442g and 0.1768g acetylene black are placed into proportion container, held to ingredient
It is added dropwise in device with Co/UiO66-700 catalyst quality than the deionized water for 1:11；
Being added according to this into proportion container with Co/UiO66-700 catalyst quality than the concentration for 1:31:26 is 5%
Nafion solution and pure aqueous isopropanol simultaneously stir, and obtain suspension；
Suspension is applied to form thickness between the coating of 0.3mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After drying 25h less, Catalytic Layer is obtained.
Embodiment 2
The Co/UiO66-800 catalyst of 0.0442g and 0.1768g acetylene black are placed into proportion container, held to ingredient
It is added dropwise in device with Co/UiO66-800 catalyst quality than the deionized water for 1:12；
Being added according to this into proportion container with Co/UiO66-800 catalyst quality than the concentration for 1:32:17 is 5%
Nafion solution and pure aqueous isopropanol simultaneously stir, and obtain suspension；
Suspension is applied to form thickness between the coating of 0.5mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After few drying for 24 hours, Catalytic Layer is obtained.
Embodiment 3
The Co/UiO66-900 catalyst of 0.0442g and 0.1768g acetylene black are placed into proportion container, held to ingredient
It is added dropwise in device with Co/UiO66-900 catalyst quality than the deionized water for 1:11.5；
It is added according to this with Co/UiO66-900 catalyst quality than being for the concentration of 1:31.5:26.5 into proportion container
5% Nafion solution and pure aqueous isopropanol simultaneously stir, and obtain suspension；
Suspension is applied to form thickness between the coating of 0.4mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After few drying for 24 hours, Catalytic Layer is obtained.
Embodiment 4
The Co/UiO66-1000 catalyst of 0.0442g and 0.1768g acetylene black are placed into proportion container, to ingredient
0.5ml deionized water is added dropwise in container；
The Nafion solution that 1.5ml concentration is 5% and the isopropyl that 1.5ml concentration is 99% are sequentially added into proportion container
Alcoholic solution simultaneously stirs, and obtains suspension；
Suspension is applied to form thickness between the coating of 0.3mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After few drying for 24 hours, Catalytic Layer is obtained.
Embodiment 5
The Co/UiO66-900 catalyst of 0.0442g and 0.1326g acetylene black are placed into proportion container, held to ingredient
It is added dropwise in device with Co/UiO66-900 catalyst quality than the deionized water for 1:11.5；
It is added according to this with Co/UiO66-900 catalyst quality than being for the concentration of 1:31.5:26.5 into proportion container
5% Nafion solution and pure aqueous isopropanol simultaneously stir, and obtain suspension；
Suspension is applied to form thickness between the coating of 0.4mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After few drying for 24 hours, Catalytic Layer is obtained.
Embodiment 6
The Co/UiO66-1000 catalyst of 0.0442g and 0.221g acetylene black are placed into proportion container, held to ingredient
It is added dropwise in device with Co/UiO66-900 catalyst quality than the deionized water for 1:11.5；
It is added according to this with Co/UiO66-900 catalyst quality than being for the concentration of 1:31.5:26.5 into proportion container
5% Nafion solution and pure aqueous isopropanol simultaneously stir, and obtain suspension；
Suspension is applied to form thickness between the coating of 0.4mm, extremely by the carbon cloth of coating on carbon cloth, on carbon cloth
After few drying for 24 hours, Catalytic Layer is obtained.
Performance test
Catalytic Layer made from the corresponding preparation method of 1-4 of the embodiment of the present invention is applied to it in microbiological fuel cell
Afterwards, the output voltage that different Catalytic Layers correspond to microbiological fuel cell is tested, Fig. 2 is the voltage of corresponding microorganism fuel cell
Figure.It can be seen from the figure that the corresponding maximum output voltage of each battery is respectively 298mV, 334mV, 397mV and 380mV,
In, where the microorganism fuel cell cathode of the Co/UiO66 catalyst load in embodiment 3 after 900 DEG C of Temperature Treatments
Microbiological fuel cell can reach larger output voltage.
The power density that different Catalytic Layers correspond to microbiological fuel cell is tested, it is specific as shown in Figure 3.It can from figure
Out, the corresponding peak power output of each battery is respectively 346mW/m3、590mW/m3、1369mW/m3And 1193mW/m3.And with
Pt/C be catalyst apply in microbiological fuel cell usually caused by power density be 229mW/m2, this will be well below
Power density caused by microbiological fuel cell provided in an embodiment of the present invention.This shows catalysis provided in an embodiment of the present invention
Layer is applied can replace Pt/C to be supported on cathode as agent to be applied in microbiological fuel cell in microbiological fuel cell.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method of Catalytic Layer, which is characterized in that the preparation method comprising steps of
S1, acetylene black and Co/UiO66 catalyst are mixed, deionized water is then added dropwise；
S2, perfluorosulfonic acid type polymer solution and pure aqueous isopropanol are added, stirred evenly, obtain suspension；
S3, the suspension is coated on carbon cloth, forms coating on the carbon cloth, it is dry, obtain Catalytic Layer.
2. a kind of preparation method as described in claim 1, which is characterized in that the acetylene black and the Co/UiO66 catalyst
Mass ratio be (3~5): 1；The mass ratio of the deionized water and the Co/UiO66 catalyst is (10~15): 1.
3. a kind of preparation method as described in claim 1, which is characterized in that the concentration of the perfluorosulfonic acid type polymer solution
It is 3%~5%, the concentration of the pure aqueous isopropanol is 95%~99%.
4. a kind of preparation method as described in claim 1, which is characterized in that the Co/UiO66 catalyst and the perfluor sulphur
Acid-based polymer solution, the pure aqueous isopropanol mass ratio be 1:(30~35): (25~30).
5. a kind of preparation method as described in claim 1, which is characterized in that the coating with a thickness of 0.3mm~0.5mm.
6. a kind of preparation method as described in claim 1, which is characterized in that the preparation method packet of the Co/UiO66 catalyst
Include step:
S11,2- amino terephthalic acid (TPA), chlorination zirconia material and n,N-Dimethylformamide are mixed, it is molten obtains the first mixing
Liquid；First mixed solution placement is reacted at the first temperature, obtains yellowish mixture of colours dope；
S12, the respectively yellowish mixture of colours dope described in n,N-Dimethylformamide and methanol agitator treating, centrifugal treating are done
It is dry, obtain solid body；The solid body, cobalt nitrate and methanol are mixed, the second mixed solution is obtained；By described second
Mixed solution placement is reacted at the second temperature, obtains the yellowish mixture of colours dope for mixing Co；
S13, with methanol wash described in mix the yellowish mixture of colours dope of Co, centrifugal treating is dry, obtains the solid body for mixing Co；
The solid body for mixing Co is placed at a temperature of third and carries out high temperature sintering, obtains the Co/UiO66 catalyst.
7. a kind of preparation method as claimed in claim 6, which is characterized in that in the step S11,2- amino terephthaldehyde
Mass ratio between acid, chlorination zirconia material and N,N-dimethylformamide three is 1:(1~2): (261~262)；The step
In rapid S12, the mass ratio between cobalt nitrate, solid body and methanol three is 1:(11~12): (68~69).
8. a kind of Catalytic Layer, which is characterized in that the Catalytic Layer passes through preparation method described in any one of claim 1-7
It is made.
9. a kind of microbiological fuel cell, including diffusion layer, carbon based layer, carbon cloth layer and Catalytic Layer, which is characterized in that the catalysis
Layer uses Catalytic Layer according to any one of claims 8.
10. microbiological fuel cell as claimed in claim 9, which is characterized in that the Catalytic Layer with a thickness of 0.4mm~
0.5mm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811002897.6A CN109103464A (en) | 2018-08-30 | 2018-08-30 | A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344380A (en) * | 2015-12-08 | 2016-02-24 | 镇江市高等专科学校 | Metal organic frame/graphene carried palladium nano-composite catalyst and preparing method and application thereof |
| CN105633418A (en) * | 2015-12-25 | 2016-06-01 | 华南理工大学 | Pt/UIO-66 composite material for lithium air battery negative electrode and preparation method for Pt/UIO-66 composite material |
| CN106111207A (en) * | 2016-06-27 | 2016-11-16 | 镇江市高等专科学校 | A kind of organic metal framework/nano-stannic oxide/Graphene composite photocatalyst material and its production and use |
| CN106784895A (en) * | 2017-01-06 | 2017-05-31 | 华南理工大学 | A kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof |
| CN107442176A (en) * | 2017-06-26 | 2017-12-08 | 湖北大学 | A kind of ammonia borane hydrolysis releases hydrogen ruthenium phosphorus alloy manometer load-type catalyst and preparation method thereof |
| CN107949941A (en) * | 2015-09-08 | 2018-04-20 | 庄信万丰燃料电池有限公司 | Redox reactions catalyst |
| CN108428903A (en) * | 2018-04-04 | 2018-08-21 | 广州大学 | A kind of charcoal catalyst, the preparation method and microbiological fuel cell of Catalytic Layer |
-
2018
- 2018-08-30 CN CN201811002897.6A patent/CN109103464A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107949941A (en) * | 2015-09-08 | 2018-04-20 | 庄信万丰燃料电池有限公司 | Redox reactions catalyst |
| CN105344380A (en) * | 2015-12-08 | 2016-02-24 | 镇江市高等专科学校 | Metal organic frame/graphene carried palladium nano-composite catalyst and preparing method and application thereof |
| CN105633418A (en) * | 2015-12-25 | 2016-06-01 | 华南理工大学 | Pt/UIO-66 composite material for lithium air battery negative electrode and preparation method for Pt/UIO-66 composite material |
| CN106111207A (en) * | 2016-06-27 | 2016-11-16 | 镇江市高等专科学校 | A kind of organic metal framework/nano-stannic oxide/Graphene composite photocatalyst material and its production and use |
| CN106784895A (en) * | 2017-01-06 | 2017-05-31 | 华南理工大学 | A kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof |
| CN107442176A (en) * | 2017-06-26 | 2017-12-08 | 湖北大学 | A kind of ammonia borane hydrolysis releases hydrogen ruthenium phosphorus alloy manometer load-type catalyst and preparation method thereof |
| CN108428903A (en) * | 2018-04-04 | 2018-08-21 | 广州大学 | A kind of charcoal catalyst, the preparation method and microbiological fuel cell of Catalytic Layer |
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