CN107275651A - A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing - Google Patents

A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing Download PDF

Info

Publication number
CN107275651A
CN107275651A CN201710421229.6A CN201710421229A CN107275651A CN 107275651 A CN107275651 A CN 107275651A CN 201710421229 A CN201710421229 A CN 201710421229A CN 107275651 A CN107275651 A CN 107275651A
Authority
CN
China
Prior art keywords
fuel cell
microbiological fuel
hydrogen
washed
method described
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710421229.6A
Other languages
Chinese (zh)
Inventor
张凯旋
王玉生
次素琴
陈思
付倩
卢恋月
刘琪凯
苏晓明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang Hangkong University
Original Assignee
Nanchang Hangkong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanchang Hangkong University filed Critical Nanchang Hangkong University
Priority to CN201710421229.6A priority Critical patent/CN107275651A/en
Publication of CN107275651A publication Critical patent/CN107275651A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing, fuel battery cathode material uses titania nanotube, the decomposition water under light conditions, produces hydrogen；Comprise the following steps：The deionized water of measured amounts, absolute ethyl alcohol adds P25, NaOH solid wherein；Ultrasound is simultaneously stirred, bottom does not have attachment, it is poured into the liner of reactor and adds stirring magneton, oil bath, sample takes out and is first washed with deionized, and then with HCl centrifuge washings repeatedly, then is washed with deionized water to neutrality, dried in vacuum drying chamber, finally calcining can prepare titania nanotube in tube furnace.Titania nanotube is applied on microorganism fuel cell cathode, microbiological fuel cell produces hydrogen through running after a while in the case of sunshine irradiation.The present invention improves titania nanotube photocatalytic hydrogen production by water decomposition ability using photoelectric-synergetic effect, while can generate electricity, handles organic pollution, simple system, hydrogen generation efficiency is high.

Description

A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing
Technical field
The invention belongs to microbiological fuel cell field, specifically related to a kind of TiO2The making of microbiological fuel cell hydrogen manufacturing Method.
Background technology
Microbiological fuel cell be it is a kind of the chemical energy stored in debirs can be converted into electric energy it is renewable, Clean energy technology, is had broad prospects in waste water resource using aspect.Electrode material is used as electrochemical reaction and electronics The important place of transmission, is the important component of energy storage conversion devices, and the performance to electrochemical energy is played to pass weight The effect wanted.Therefore cathode material has very important meaning to the performance for lifting microbiological fuel cell.The calorific value of hydrogen Height, combustion velocity is fast, water is produced after releasing energy and renewable, is acknowledged as a kind of cleaning green energy resource.At present, produce The method of hydrogen has many kinds, chemical hydrogen manufacturing, water electrolysis hydrogen production, biological hydrogen production etc..Wherein chemical hydrogen manufacturing is mostly by natural gas The reformation of the compounds such as oil is made, and is current hydrogen manufacturing mode most widely used in the world.Water electrolysis hydrogen production is a kind of complete The hydrogen manufacturing mode of cleaning, but its energy consumption is larger, is subject to certain restrictions at the scene in terms of hydrogen manufacturing.Biological hydrogen production is with organic waste Thing is raw material, and hydrogen is produced by microbial fermentation, but fermentation and hydrogen production can not make organic matter exhaustive oxidation, and production hydrogen rate is relatively low.
The microbiological fuel cell production hydrogen studied at present is mostly catalyst using platinum, but platinum price is costly, limitation Its application in practice, while main method is applied voltage.Cathode microbial fuel by catalyst of titanium dioxide Battery can have higher power output, cheap and easy to get, and the dielectric constant of titanium dioxide is higher, therefore with excellent electrical property Energy.Titanium dioxide has the performance of semiconductor, at the same can ultraviolet irradiation under decomposition water, produce hydrogen.
The content of the invention
The present invention relates to a kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing, anode of microbial fuel cell is decomposed Organic matter, electronics and proton are provided for negative electrode, and negative electrode uses titania nanotube material also primary electron and photochemical catalyzing Hydrogen manufacturing, the hydrogen produced is collected by vacuum collection airbag.It is simple in construction, fewer than traditional microbiological fuel cell hydrogen manufacturing extraneous electricity The input of pressure, supplied for electronic and proton are stopped than traditional photocatalysis water hydrogen manufacturing, improve decomposition efficiency.
The present invention adopts the following technical scheme that, a kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing, its feature exists It is as follows in method and step：
(1) 30ml deionized water is measured, absolute ethyl alcohol 30ml adds 2g P25 (titanium dioxide granules wherein）、10 Mol/L NaOH solution 30ml；2 h of ultrasound, stir 12 h, are well mixed it, bottom does not have attachment, is poured into The liner of reactor（100ml) and it is put into drying box 180 DEG C of reaction 24h；
(2) sample takes out and is first washed with deionized, then multiple with 0.01 mol/L HCl centrifuge washings, then spends Ion is washed to neutrality, dries 10 h under the conditions of 40 DEG C in vacuum drying chamber（Note aqueous in material before drying Amount, first can carry out suction filtration to solid）, last 350 DEG C of (nitrogen protection) calcining, 4 h in tube furnace.(5 DEG C of programming rate/ min)；
（3）Sample 20mg plus 30uL adhesive plus 120 μ L deionizations are taken, ultrasonic 30min is applied on 1*2cm carbon cloth；Ventilation Drying 24h can be assembled on microorganism fuel cell cathode；
（4）Double-chamber microbiological fuel cell, centre takes PEM to separate, and tinfoil parcel anode prevents ultraviolet from irradiating； Negative electrode is sealed, and uses incandescent lamp（Or ultraviolet）Irradiation, gas is collected using vacuum bag.
In step (4) of the present invention, microbiological fuel cell, which is used, uses PEM between double-chamber structure, dual chamber Separate, anode is sodium acetate using the sludge in domestication sewage treatment plant, anode nutriment, and cathode solution is buffer solution.
In step (4) of the present invention, it is characterised in that Cathode buffer liquid concentration is 0.1M.
It is an advantage of the invention that：The microbiological fuel cell hydrogen manufacturing new method of the present invention, is acted on, negative electrode using photoelectric-synergetic Titania nanotube photocatalytic hydrogen production by water decomposition ability is improved, anode can be produced electricity, and anode can be with synchronization process organic contamination Thing.
Brief description of the drawings
Fig. 1 produces hydrogen schematic diagram for the microbiological fuel cell of the present invention.
Fig. 2 is titania nanotube XRD diffraction patterns of the invention.
In figure, 1- carbon brush, 2- instrument connections, 3- liquid-changing holes, 4- anodes, 5- test systems, 6- external resistances, 7- clips, 8- PEM, 9- magnetons, 10- carbon cloths, 11- negative electrodes, 12- flexible pipes, 13- vacuum bags.
Embodiment
Below in conjunction with the accompanying drawings and the invention will be further described by embodiment, but it should be noted that embodiment not Constitute the restriction to the claimed scope of the invention.
In Fig. 1, microbiological fuel cell of the invention production hydrogen schematic diagram, mainly by 1- carbon brush, 2- instrument connections, 3- changes liquid Hole, 4- anodes, 5- test systems, 6- external resistances, 7- clips, 8- PEMs, 9- magnetons, 10- coating graphene-titanium dioxides Titanium carbon cloth, 11- negative electrodes, 12- flexible pipes, 13- vacuum bags composition.It is characterized in that passing through 8- protons between 4- anodes and 11- negative electrodes Exchange membrane, which separates to combine using 7- clips, 2- instrument connections and 3- liquid-changing holes on composition main part, 4- anodes, 4- sun Be inside pole inside 1- carbon brush position, 4- anodes inside 1- carbon brush and 11- negative electrodes 10- coating graphene-titanium dioxide carbon cloths by 6- external resistances are connected, and 5- test systems are connect in the connection of 6- external resistances, and 9- magnetons respectively have one in 4- anodes and 11- negative electrodes, and 11- is cloudy It is 10- coating graphene-titanium dioxide carbon cloths inside pole, 11- negative electrodes and 13- vacuum bags, metal contact is connected by 12- flexible pipes Gap at AB glue seal.
Case study on implementation
A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing, it is characterised in that method and step is as follows：
(1) deionized water of measured amounts, adds 0.1g P25 (titanium dioxide granules wherein）, 4 g NaOH consolidate Body, the concentration for finally ensureing NaOH solution is 10mol/L.2 h of ultrasound, stir 12 h, are well mixed it, bottom is not attached Thing, the liner of reactor is poured into（25ml) and stirring magneton is put into, is transferred in oil bath that (magneton is still in a kettle. Still in stirring during reaction) 120 DEG C of reaction 24h.
(2) sample takes out and is first washed with deionized, then multiple with 0.01 mol/L HCl centrifuge washings, then uses Deionized water is washed till neutrality, dries 10 h under the conditions of 40 DEG C in vacuum drying chamber（Note aqueous in material before drying Amount, first can carry out suction filtration to solid）, last 400 DEG C of (nitrogen protection) calcining, 2 h in tube furnace.(5 DEG C of programming rate/ min)。
(3) sample 20mg plus 30 μ L adhesives plus 120 μ L deionizations are taken, ultrasonic mixing 30min is applied to 1*2cm carbon On cloth.Aeration-drying 24h can be assembled on microorganism fuel cell cathode.
(4) double-chamber microbiological fuel cell, centre takes PEM to separate, and tinfoil parcel anode prevents ultraviolet from shining Penetrate.Negative electrode is sealed, and uses incandescent lamp（Or ultraviolet）Irradiation, gas is collected using vacuum bag.Anode is using domestication sewage disposal Sludge in factory, anode nutriment is sodium acetate, and cathode solution buffer concentration is 0.1M/L.

Claims (7)

1. a kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing, it is characterised in that method and step is as follows：
(1) 10 mol/L NaOH solution 30ml, absolute ethyl alcohol 30ml are measured, 2g P25 is added wherein；2 h of ultrasound, 12 h are stirred, are well mixed it, bottom does not have attachment, is poured into the liner of reactor and is put into 180 in drying box DEG C reaction 24h；
(2) sample takes out and is first washed with deionized, then multiple with 0.01 mol/L HCl centrifuge washings, then spends Ion is washed to neutrality, dries 10 h under the conditions of 40 DEG C in vacuum drying chamber, finally 350 DEG C of 4 h of calcining in tube furnace；
（3）Sample 20mg plus 30uL adhesive plus 120 μ L deionizations are taken, ultrasonic 30min is applied on 1*2cm carbon cloth；Ventilation Drying 24h can be assembled on microorganism fuel cell cathode；
（4）Microbiological fuel cell is double-chamber structure, and centre takes PEM to separate, and tinfoil parcel anode prevents ultraviolet Irradiation；Negative electrode is sealed, and is irradiated using incandescent lamp, and gas is collected using vacuum bag.
2. according to the method described in claim 1, it is characterised in that：Described step (1) naoh concentration is 10mol/ L30ml, absolute ethyl alcohol is 30ml, and P25 is ultrasonic mixing 2h before 2g, hydro-thermal reaction, stirs 12h.
3. according to the method described in claim 1, it is characterised in that：Described step (1) hydrothermal temperature is 180 DEG C, when Between be 24h.
4. according to the method described in claim 1, it is characterised in that：Described step (2) sample is washed with deionized water to neutrality, 10 h are dried under the conditions of 40 DEG C in vacuum drying chamber, (nitrogen protection) 350 DEG C of calcining 4h (programming rates 5 in tube furnace ℃/min)。
5. according to the method described in claim 1, it is characterised in that：Described step (3) sample 20mg adds 30 μ L Nafion molten Liquid, 120 μ L deionizations, ultrasonic mixing 30min.
6. according to the method described in claim 1, it is characterised in that：Described step (4) microbiological fuel cell uses dual chamber Separated between structure, dual chamber using PEM, anode is using the sludge in domestication sewage treatment plant, anode nutriment Sodium acetate, cathode solution is buffer solution.
7. according to the method described in claim 1, it is characterised in that：Described step (4) Cathode buffer liquid concentration is 0.1M/ L。
CN201710421229.6A 2017-06-07 2017-06-07 A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing Pending CN107275651A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710421229.6A CN107275651A (en) 2017-06-07 2017-06-07 A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710421229.6A CN107275651A (en) 2017-06-07 2017-06-07 A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing

Publications (1)

Publication Number Publication Date
CN107275651A true CN107275651A (en) 2017-10-20

Family

ID=60066974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710421229.6A Pending CN107275651A (en) 2017-06-07 2017-06-07 A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing

Country Status (1)

Country Link
CN (1) CN107275651A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112458487A (en) * 2020-09-03 2021-03-09 南昌航空大学 Medium-alkali asymmetric microbial electrolytic cell and application thereof in hydrogen production

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080213632A1 (en) * 2007-02-10 2008-09-04 Noguera Daniel R Light-powered microbial fuel cells
CN102381727A (en) * 2011-04-02 2012-03-21 中国海洋大学 Process for preparing titanium dioxide mesoporous nano-belt material by solvothermal method
CN104311142A (en) * 2014-09-30 2015-01-28 东南大学 Vertically grown TiO2 nanosheet and preparation method thereof
CN105308782A (en) * 2013-06-20 2016-02-03 加利福尼亚大学董事会 Self-biased and sustainable microbial electrohydrogenesis device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080213632A1 (en) * 2007-02-10 2008-09-04 Noguera Daniel R Light-powered microbial fuel cells
CN102381727A (en) * 2011-04-02 2012-03-21 中国海洋大学 Process for preparing titanium dioxide mesoporous nano-belt material by solvothermal method
CN105308782A (en) * 2013-06-20 2016-02-03 加利福尼亚大学董事会 Self-biased and sustainable microbial electrohydrogenesis device
CN104311142A (en) * 2014-09-30 2015-01-28 东南大学 Vertically grown TiO2 nanosheet and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QING-YUN CHEN等: "Hydrogen production on TiO2 nanorod arrays cathode coupling with bio-anode with additional electricity generation", 《JOURNAL OF POWER SOURCES》 *
YAN-RONG HE等: "Hydrogen production in a light-driven photoelectrochemical cell", 《APPLIED ENERGY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112458487A (en) * 2020-09-03 2021-03-09 南昌航空大学 Medium-alkali asymmetric microbial electrolytic cell and application thereof in hydrogen production

Similar Documents

Publication Publication Date Title
CN107012474B (en) A kind of method of large-scale solar energy photocatalysis-photoelectrocatalysis hydrogen production by water decomposition
Xiao et al. Hybrid microbial photoelectrochemical system reduces CO2 to CH4 with 1.28% solar energy conversion efficiency
He et al. Hydrogen production in a light-driven photoelectrochemical cell
He et al. NiFe-layered double hydroxide decorated BiVO4 photoanode based bi-functional solar-light driven dual-photoelectrode photocatalytic fuel cell
CN103367759B (en) Visible-light response type photocatalysis wastewater fuel cell, manufacture method thereof and application thereof
Wan et al. A solar assisted microbial electrolysis cell for hydrogen production driven by a microbial fuel cell
CN105709793B (en) Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst, preparation method and application of cadmium sulfide nano-particles modification
CN110424022A (en) Compound MIL-101 hetero-junctions light anode of nanometer rods alpha-ferric oxide and preparation method thereof
CN105749914B (en) A kind of method of symmetrical difunctional photochemical catalyst, dual chamber Photoreactor and photocatalytic reduction of carbon oxide
CN112125390A (en) Device for assisting in strengthening biological anode to degrade antibiotics by adopting photocatalysis
CN104971720A (en) Bismuth tungstate nanocomposite, and preparation method and application thereof
CN103668305A (en) Guide-plate microbial electrolysis cell embedded with multi-electrode system and use method thereof
CN108773852A (en) A kind of preparation method of crystal face hetero-junctions rutile crystal type titanium dioxide optical catalyst and production hydrogen application
Liu et al. An effective self-driven PFC-PEC hybrid system for hydrogen generation from organic substance
Wang et al. When MoS 2 meets TiO 2: facile synthesis strategies, hybrid nanostructures, synergistic properties, and photocatalytic applications
CN110112449A (en) A kind of efficient photocatalysis cathode type microbiological fuel cell for restoring carbon dioxide and the method for restoring carbon dioxide using it
CN104817190B (en) A kind of Bioelectrochemical device and the method that utilize solar energy fall dirt to produce hydrogen
CN113896275A (en) Photoelectrocatalysis reactor
CN106238081A (en) Preparation has the WO of high activity photoelectrocatalysis decomposition water performance3the method of nanometer thorn/CoPi complex light anode
CN107275651A (en) A kind of TiO2The preparation method of microbiological fuel cell hydrogen manufacturing
CN108821394B (en) Preparation method of iron (II) molybdate/graphene oxide catalytic electrode
CN103981558A (en) Tantalum nitride nanotube array electrode and preparation method thereof
CN106906487A (en) A kind of method that carbon dioxide by photoelectric catalytic reduction prepares ethanol
CN105088266A (en) Method for compounding co-catalyst on semiconductor material to manufacture photoelectric chemical cell nano-structure photoelectrode
KR100999080B1 (en) Flat-type device for enzymatic hydrogen production by using anodized tubular TiO2 electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20171020

WD01 Invention patent application deemed withdrawn after publication