Mechanism of Energy Generation of Microbial Fuel Cells

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1 20 7Π PROGRESS IN CHEMISTRY Vol. 20 No. 7Π8 Aug., , ( ; ) (MFC),, MFC MFC MFC 5,,, : TM : A : X(2008) 07Π Mechanism of Energy Generation of Microbial Fuel Cells Lu Na 1,2 Zhou Shungui 2 Ni Jinren (11Department of Environmental Engineering, Peking University, Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing , China ; 21Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco2Environment and Soil Sciences, Guangzhou , China) Abstract Microbial fuel cells ( MFCs) are the emerging technology for producing electricity directly from biodegradable organic matter using bacteria as catalyst. One of the most promising applications for MFCs is to use them simultaneously treating organic wastes while accomplishing power generation. The main problems for MFC are low electron transfer and power density. The electron transfer from the microbial cell to the fuel cell anode, as a process that links microbiology and electrochemistry, represents a key factor that defines the MFC power and energy output. In the paper, five key steps including fuel bio2oxidation, electron transfer to anode, electron transfer through the external circuit, proton diffusion and cathode reaction for electricity generation by MFC systems are identified and discussed in detail. Finally, the potential study directions in the future are prospected. Key words microbial fuel cells ; mechanism of energy generation ; electron transfer ; output power 1,, (microbial fuel cell,mfc) [1,2 ],MFC, : (1), ; (2), ; (3), ; (4), Logan [3 6 ] : , : (No ) (No ) 3 3 e2mail pku. edu. cn

2 ,,MFC 1911, Potter [7 ], MFC, MFC, 10 WΠm 2, MFC,, MFC, MFC 2 MFC MFC,, 1 MFC [3,8,9 ], MFC 5 : (1), ; (2), ; (3) ; (4), ; (5) ( ),, ( ), (electricigenic respiration),, [10 ] Fe ( ) ( ),,, Fe ( ) [10 ] Fe ( ), Fe ( ),, Fe ( ),, 1 :11 ;21 ;31 ;41 ;51 Fig. 1 Steps of electron2transfer in MFC system. 11fuel biooxidation, 21electron transfer to anode, 31resistance, 41proton diffusion, and 51cathode reaction MFC,,,,,, NADH Q [11 ] Kim [9 ] MFC, ;,,, ;,,,, MFC, 1, MFC MFC,,,, MFC,, [12 ] [13 ] [14 ] [15 ] MFC MFC( MFC)

3 7Π Table 1 Anodic microorganisms and their electron transfer types microorganism bacterial example transfer type electron acceptor ref. mediator2driven microorganisms Butyribacterium methylotrophicum exogenous mediators neutral red 13 Desulfovibrio desulfurcans primary metabolites as mediators S 2-16 Pseudomonas aeruginosa secondary metabolites as mediators pyocyanin 40,41 electricigens Geobacteraceae membrane2driven cytochrome Rhodoferax ferrireducens cytochrome 24 Clostridium butyricum cytochrome 23 Shewanella putrefaciens cytochrome 18 H 2 H 2 S ( ), ( Escherichia coli) Desulfobulbaceae Harbermann [16 ] Desulfovibrio desulfurcans, MFC, 212,, ( Pseudomonas aeruginosa [17 ] ) MFC, ( ), 2,,, 4 : MFC, 4,, [9,18 ] ( ), MFC, 2 Table 2 Development of anodic electron2transfer mechanisms in [9,19 ] MFC MFC MFC( MFC), [19 21 ], [22 ] ( Shewanella putrefaciens ) [18 ] ( Clostridium butyricum ) [23 ] ( Rhodoferax ferrireducens) [24 ] [25 ( Geobacteraceae) 27 ] ( Aeromonas hydrophila) MFC, MFC 16S rdna, MFC,,, 3615 % Gammaproteobacteria 2710 % Firmicutes [28 ] ;, Deltaproteobacteria, 70 %, 1713 % Gammaprote2 obacteria [29 ] ; 4019 % Betaproteobacteria 2712 % Alphaproteobacteria, Deltaproteobacteria Gammaproteobacteria [20 ] ; [30 ] year finder viewpoint ref Potter demonstrating the production of electrical energy (the first reported MFC) 1931 Cohen proposing the introduction of electromotively active redox substances 1991 Harbermann & Pommer proposing the production of reduced primary metabolites as redox mediators 1999 Kim, et al demonstrating some microorganisms possessing membrane bound cytochromes to transfer electrons 2000 Newman & Kolter 2005 Reguera, Lovley,et al proposing the secondary metabolites being involved in extracellular electron transfer processes proposing the electron2transfer mechanism of electronically conducting nanowires , 41,,, 34

4 :A ;B ;C ;D Fig. 2 Identified anodic electron2transfer mechanisms in MFC. A) cell2membrane2bound cytochromes, B) electrically conductive nanowires, C) redox mediators, and D) oxidation of primary metabolites 0147 gπl),, (12 h 3 C),,,, Kim [18 ] , MFC,, (pili),, (nanowire) [34 ], 3 5 nm, MFC, Reguera [34 ] (AFM) G. sulfurreducens :,,,, ( ),,,, NADH Q [11,31 ] :,, C,, [32 ],, 2 B, Kim [9 ],,,, NADH Q,, C 21212,,, Geobacter sulferreducens 100 ( ), C [33 ],,, ( Shewanella, putrefaciens ) [18 ] ( Rhodoferax ferrireducens) [24 ] [25 ( Geobacteraceae) 27 ] ( Aeromonas hydrophila), ( Clostridium butyricum) [23 ], : , C, 2 A Geobacter Desulfuromonas Shewanella,, Kim [9 ] MFC,, ( ( ), ,

5 7Π8 1237,MFC,, MFC 2 C,,, ;,, : (1), ; (2),, ; (3), ; (4), ; (5), [14 ] [16 ] Fe ( ) EDTA [35 ] [12 ] [13 ], 3, Park [36 ],, 10,,,, [37 ] 3 MFC [38 ] Table 3 Exogenous redox mediators and their potentials used for MFC [38 ] substance class redox mediator redox potential phenazines neutral red safranine phenazine ethosulfate 0106 phenothiazines new methylene blue toluidine blue o thionine phenoxazines resorufin gallocyanine 0102 quinones 22hydroxy21,42naphthoquinone anthraquinone22,62disulfonate ,, MFC, ;,, MFC , ( [39 ) 41 ],, (pyocyanine) ,42 (ACNQ) [39 ] MFC,, 2 C,,, ;,,,,, [17,19 ], Rabaey [17 ] Pseudomonas aeruginosa MFC (pyocyanine) phenazine212carboxamide MFC,,16S rrna,mfc Lactobacillus Enterococcus [19 ] MFC, C [38 ],,, [10,42 ],,, MFC H 2 H 2 S ( ),, 2 D,,,,, MFC, MFC,

6 :, MFC, [43 ], MFC [44 ],, (1) SO H e - S H 2 O (1) Harbermann [16 ] Desulfovibrio desulfuricans MFC,,,, [43 ],,,, Harbermann [16 ], S 2 -,, : MFC,,, Schrgder [45 ] E. coli K12,, maπm 2, 213, MFC,,,,,, ;,,,,, Menicucci [46 ],,,,, MFC, MFC, ;,, MFC 214, MFC, MFC, MFC, [2 ], [47 ] MFC,, ph,, MFC :,Nafion,, (10-2 SΠcm) Logan [48 ],, MFC,, MFC, Min [49 ], Liu [47 ] MFC,, Nafion MFC ,,,, ;,,,,,,, Liu [47 ], MFC Nafion MFC 3,, 28 %,MFC,, MFC,, 14 % [50 ] 215, ( ),, MFC

7 7Π8 1239,, ( ), MFC,, Oh [51 ], MFC 22 % Cheng [52 ], 2 mgπcm mgπcm 2,, MFC, Morris [53 ] PbO 2, Pt 117,,, 319,,,, MFC,, [54 ],, MFC,, [55 ],,,, Oh [51 ] 50 % 80 %,,,,,,,, Rhoads [56 ],, ( ) mv 3 MFC MFC,, : ( ), ; ( ),,, MFC MFC 5,,, MFC,, MFC MFC, : (1),, MFC (2) MFC Fe ( ),Fe ( ) MFC (3),, MFC, MFC, MFC [ 1 ] Park D H, Zeikus J G. Biotechnol. Bioeng., 2003, 81 : [ 2 ] Gil G C, Chang I S, Kim B H, et al. Biosen. Bioelectron., 2003, 18 : [ 3 ] Liu H, Ramnarayanan R, Logan B E. Environ. Sci. Technol., 2004, 38 : [ 4 ] Liu H, Logan B E. Environ. Sci. Technol., 2004, 38 (14) : [ 5 ] Min B, Logan B E. Environ. Sci. Technol., 2004, 38 (21) : [ 6 ] He Z, Minteer S D, Angenent L T. Environ. Sci. Technol., 2005, 39(14) : [ 7 ] Potter M C. Proc. R. Soc. Lond. B, 1911, 84 : [ 8 ] ( Guan Y), ( Zhang X). ( Progress in Chemistry), 2007, 19(1) : [ 9 ] Kim H J, Park H S, Hyun M S, et al. Enzyme Microbiol. Technol., 2002, 30 : [10] Lovley D R. Nat. Rev. Microbiol., 2006, 4 :

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