CN105789663B - The porous nickel of graphene modified makees the method for cathodic reduction carbon dioxide in a kind of microbiological fuel cell - Google Patents

The porous nickel of graphene modified makees the method for cathodic reduction carbon dioxide in a kind of microbiological fuel cell Download PDF

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Publication number
CN105789663B
CN105789663B CN201610280992.7A CN201610280992A CN105789663B CN 105789663 B CN105789663 B CN 105789663B CN 201610280992 A CN201610280992 A CN 201610280992A CN 105789663 B CN105789663 B CN 105789663B
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porous nickel
reduced
cathode
source
catholyte
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CN105789663A (en
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柳丽芬
李益华
杨凤林
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Dalian University of Technology
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Dalian University of Technology
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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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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
    • 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 new energy and environmental protection and contamination control field, the porous nickel for providing graphene modified in a kind of microbiological fuel cell makees the method for cathodic reduction carbon dioxide.Under conditions of the electricity production power supply of biological anode, the HCO in catholyte3 ‑And CO2Mainly it is reduced into ethyl alcohol.Biological anode is graphite particle load Shewanella, and the porous nickel materials that cathode is modified using porous nickel or reduced graphene each lead into N2And CO2The cathode reduction products of formation are to lead to N2When catholyte in HCO3 ‑It is main to be reduced to ethyl alcohol, and acetone is by-product；Logical CO2, HCO3 ‑While being reduced to ethyl alcohol, part CO2It is also reduced to CO；CO2Reduction reaction is contributed to carry out, improves the generating rate and production quantity of reduzate.Porous nickel electrode by reduced graphene after modifying, and transmission electronic capability is further promoted, and system capacity efficiency and product yield have very big promotion.

Description

The porous nickel of graphene modified makees cathodic reduction dioxy in a kind of microbiological fuel cell Change the method for carbon
Technical field
The invention belongs to new energy and environmental protection and contamination control field, are related to CO2Under biological production electro ultrafiltration The method of reduction, especially with porous nickel and the porous nickel of graphene functionalized as cathode by CO2The method of reduction.
Background technology
With the development of global economy, the demand to the energy is growing, CO2As the final product after using energy source, Discharge capacity is increasing year by year.To alleviate greenhouse effects, by CO2Carry out the focus that recycling transforms into social concerns at this stage.It will CO2The method of reduction conversion has：Photosynthesis, electro-catalysis reduction, photo catalytic reduction and CO2Catalyzed copolymerization etc..Its product has：First The small organic molecules such as acid, methanol, formaldehyde and CH4、CO、H2、O2Wait gases.
As global energy is in short supply and environmental pollution increasingly sharpens, carrying out energy recovery to pollutant has important reality Meaning.Biological production power technology, that is, microbiological fuel cell of waste water under the action of anode biological production electricity bacterium, will pollute in waste water The energy that object contains releases, and oxidation stain produce bear proton and electronics, in cathode O2It is reduced to form water.The technology exists While handling pollutant effluents, the energy conversion in waste water for electric energy and is exported, realizes the recycling of the waste water energy.It will Waste water electricity production technology is used to restore CO2, compared with other photocatalysis and electro-catalysis reduction technique, more energy-saving and environmental protection.Using useless Aquatic products power technology, at normal temperatures, using the electric energy of generation by CO2Reduction, yet there are no report.
Invention content
The object of the present invention is to provide one kind using porous Ni-base material as cathode, in microbiological fuel cell system, Anode bacterium conversion water pollutant is for electron, and cathode is in alkali bicarbonate system by CO2(or Alkali absorption formation HCO3 -) reduction method.Also, after porous nickel materials are carried out graphene functionalized, the system is to HCO3 -‐CO2Absorb production Object reducing property is substantially improved.
Technical scheme of the present invention：
The porous nickel of graphene modified makees the method for cathodic reduction carbon dioxide in a kind of microbiological fuel cell, and step is such as Under：
Porous nickel sheet is immersed in 0.5-2g L-1Graphene oxide dispersion in, ultrasound, stand, drying；By above-mentioned baking Dry porous nickel sheet is placed in excessive hydrazine hydrate solution, is placed in autoclave, and 100-150 DEG C of heating is no less than 8h, and taking-up is spent Ionized water is cleaned, and drying obtains the porous nickel of graphene modified；
In double-chamber microbiological fuel cell, anode chamber is separated with cathode chamber by amberplex；Anode is using load The carbon material of bacterium is produced electricity, outer connecting resistance makees cathode with the porous nickel of graphene modified；Anolyte takes simulation sewage；Catholyte Using 0.3-0.5M potassium bicarbonate solutions, addition 0.1-0.5M electrolyte (sodium sulphate, potassium chloride, sodium chloride etc.)；Anode anaerobism, Cathode is aerated, with 0.01-0.1m3h-1Rate is passed through CO2Or N2, when being passed through CO2When, CO2A gas part is converted into catholyte Bicarbonate ion, fraction are reduced to CO, and bicarbonate is reduced to ethyl alcohol in catholyte, and acetone is by-product.When being passed through N2When, bicarbonate radical is reduced to ethyl alcohol in catholyte, and acetone is by-product.
The amberplex is proton exchange membrane or cation-exchange membrane.
The carbon material is graphite particle, carbon felt or carbon particle.
The anolyte includes carbon source, nitrogen source, phosphorus source and electrolyte, wherein, glucose, sodium acetate or sucrose are as carbon Source, ammonium chloride is as nitrogen source, and potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or disodium hydrogen phosphate are as phosphorus source, C:N:P It is 150:5:1, supply the bacterium energy.
Beneficial effects of the present invention：
(1) principle of waste water electricity production can be realized using microbiological fuel cell, while waste water electricity production is carried out, by environment Medium temperature chamber effect gas CO2It is restored, realizes waste recycling, energy-saving and environmental protection are realized in this technological design in energy consumption.
(2) in general waste water electricity production system, O2As electron acceptor, nickel material is generally required as cathode by pre-oxidation Processing, prevents nickel material by O2Oxidation.This experimental design realizes nickel material and makees cathode and without any pretreatment, CO2Be passed through Existing oxygen molecule in system can be excluded, protects cathode material.
(3) this experiment uses graphene modified Porous nickel cathode, accelerates electron-transport efficiency and cathodic reduction performance, is promoted System production capacity and cathodic reduction produce rate.
Description of the drawings
Fig. 1 be in microbiological fuel cell (graphene modified) Porous nickel cathode to HCO3 --CO2Absorption product reduction fortune Row schematic diagram.
Fig. 2 is that concentration is the ethyl alcohol of 100ppm and the GC-MS result figures of acetone hybrid standard sample and reaction product.○ Represent hybrid standard sample, represents reaction product, and abscissa is appearance time, and ordinate is peak area.
Fig. 3 is that the Porous nickel cathode that reduced graphene is modified in microbiological fuel cell is being passed through CO2When polarization curve And power density curve；Abscissa is electric current, and left side ordinate is potential, and right side ordinate is power density, ● represent polarization Curve, ▲ expression power density curve.
In figure：1 amberplex；2 cathode chambers；The porous nickel of 3 graphene modifieds；4 aerators；5 outer connecting resistances；6 carbon Stick；7 anode chambers；The graphite particle of 8 electricity production bacterium loads.
Specific embodiment
Below in conjunction with technical solution and attached drawing, the specific embodiment that the present invention will be described in detail.
Embodiment 1
In dual chamber biology electricity production system, the graphite particle of load Shewanella is added in anode, electronics is exported with carbon-point, External 500 Ω resistance, is wired to cathode, and cathode places multilayer chip porous nickel, proton is used between anode and cathode Exchange membrane separates, as shown in Figure 1.Anolyte adds in bacteriotrophy liquid (C:N:P=100:5:1), catholyte prepares 0.5M KHCO3With 0.2M Na2SO4Common 200mL.In these cases, continuously it is passed through 0.1m3h-1N2Gas.After reacting 6h, product warp Gas chromatograph-mass spectrometer (GC-MS) (GC-MS) is analyzed, and determines HCO3 -Ethyl alcohol is reduced to, acetone is generated as by-product, such as attached drawing Shown in 2.
Embodiment 2
In 1 system of example, reaction system composition is constant, by N2It is changed to CO2Gas, holding throughput are 0.1m3h-1, it is cloudy Pole liquid prepares 0.3M KHCO3With 0.2M Na2SO4Common 200mL.After reacting 6h, analyzed through GC-MS, liquid product for ethyl alcohol and Acetone, ethyl alcohol are principal product, there is CO generations in gas-phase product, compare the above process, determine part CO2HCO is formed by absorption3 -, HCO3 -While being further reduced to ethyl alcohol and acetone, part CO2It is reduced to CO.Meanwhile CO2Presence promote ethyl alcohol Deng generation.
Embodiment 3
In 2 system of example, anode and cathode liquid is constant, and reaction system composition is constant, and throughput is changed to 0.02m3h-1, instead It after answering 6h, is analyzed through GC-MS, liquid product is ethyl alcohol and acetone, and ethyl alcohol is principal product, there is CO generations in gas-phase product；Together When, liquid-phase reaction product generates ethyl alcohol and acetone.
Embodiment 4
In 2 system of example, closed circuit is changed to open a way, remaining condition is constant, CO2Throughput is 0.1m3h-1, test Product after reaction 6h, analysis result obtains, and under open-circuit condition, organic matter yield is lower, HCO3 -And CO2Reduction conversion ratio is lower.It says Bright closed circuit promotes system cathode HCO3-CO2 -The progress of absorption product reduction reaction.
Embodiment 5
In example 2, cathode material is used instead to the porous nickel of reduced graphene modification, which uses It is as follows：Porous nickel is soaked in 0.5g L-1In graphene oxide dispersion, ultrasound is stood, drying, 100 DEG C in autoclave 8h is reacted, is washed with deionized, is dried.Example 1-3 is repeated, it is found that product yield has very big promotion, illustrates to restore graphite The load of alkene improves its catalytic reduction performance.Measuring open circuit potential in its reaction process reaches 0.63V, production capacity maximum work simultaneously Rate density reaches 17W m-3, as shown in Figure 3；The power density promotes 15 times or more compared with porous nickel makees cathode；It reacted System electric current is 0.5-1.5mA in journey, has slow downward trend with the consumption electric current of reactant；Its product formation improves Nearly 2 times, TOC contents reach 150mg/L in water outlet.
Embodiment 6
In example 5, the porous method for preparing nickel of reduced graphene modification is as follows：Porous nickel is soaked in 2g L-1Oxygen In graphite alkene dispersion liquid, ultrasound is stood, drying, and 120 DEG C of reaction 12h, are washed with deionized in autoclave, dry.Weight Multiple example 1-3, can obtain the effect of example 5.

Claims (5)

1. the porous nickel of graphene modified makees the method for cathodic reduction carbon dioxide in a kind of microbiological fuel cell, feature exists In step is as follows：
Porous nickel sheet is immersed in 0.5-2g L-1Graphene oxide dispersion in, ultrasound, stand, drying；By above-mentioned drying Porous nickel sheet is placed in excessive hydrazine hydrate solution, is placed in autoclave, and 100-150 DEG C of heating is no less than 8h, taking-up deionization Water is cleaned, and drying obtains the porous nickel of graphene modified；
In double-chamber microbiological fuel cell, anode chamber is separated with cathode chamber by amberplex；Anode is produced electricity using load The carbon material of bacterium, outer connecting resistance make cathode with the porous nickel of graphene modified, form closed circuit；Anolyte is dirty using simulation Water, catholyte use 0.3-0.5M potassium bicarbonate solutions, add 0.1-0.5M electrolyte；Anode anaerobism, cathode aeration, with 0.01-0.1m3h-1Rate is passed through CO2Or N2, when being passed through CO2When, CO2A gas part be converted into catholyte bicarbonate radical from Son, fraction are reduced to CO, and bicarbonate is reduced to ethyl alcohol in catholyte, and acetone is by-product；When being passed through N2When, catholyte Middle bicarbonate radical is reduced to ethyl alcohol, and acetone is by-product.
2. according to the method described in claim 1, it is characterized in that, the amberplex is proton exchange membrane or cation Exchange membrane.
3. method according to claim 1 or 2, which is characterized in that the carbon material is carbon felt or carbon particle.
4. method according to claim 1 or 2, which is characterized in that the anolyte include carbon source, nitrogen source, phosphorus source and Electrolyte, wherein, glucose, sodium acetate or sucrose as carbon source, ammonium chloride as nitrogen source, potassium dihydrogen phosphate, sodium dihydrogen phosphate, Dipotassium hydrogen phosphate or disodium hydrogen phosphate are as phosphorus source, C:N:P is 150:5:1, supply the bacterium energy.
5. according to the method described in claim 3, it is characterized in that, the anolyte includes carbon source, nitrogen source, phosphorus source and electrolysis Matter, wherein, glucose, sodium acetate or sucrose are as carbon source, and ammonium chloride is as nitrogen source, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid Hydrogen dipotassium or disodium hydrogen phosphate are as phosphorus source, C:N:P is 150:5:1, supply the bacterium energy.
CN201610280992.7A 2016-04-29 2016-04-29 The porous nickel of graphene modified makees the method for cathodic reduction carbon dioxide in a kind of microbiological fuel cell Expired - Fee Related CN105789663B (en)

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