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A comprehensive review of microbial electrochemical
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H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807 1797. dozens of functions have been discovered Almost all MESs share one inorganic electron donors mainly waste materials and transfer elec. common principle in the anode in which biodegradable substrates trons to the anode electrode The electrons can be captured directly. such as waste materials are oxidized by microorganisms and generate through an external circuit for electricity generation or used for chemi. electrical current The current can be captured directly for electricity cal production The microbial oxidation reaction in the anode chamber. generation microbial fuel cells MFCs Fornero et al 2010 Liu and is a shared principle for almost all MES reactors as shown in Table 1. Logan 2004 Ren et al 2007 or used to produce H2 and other value However how to use these electrons on the cathode side shows the. added chemicals microbial electrolysis cells MECs Cheng et al beauty of this platform technology because any reduction based reac. 2009 Liu et al 2010 Logan et al 2008 The electrons can also be tion can be realized in the cathode chamber which creates numerous. used in the cathode chamber to synthesize organic compounds micro possibilities Based on the different functions the MES platform has. bial electrosynthesis MES or remediate contaminants microbial been speci ed into many different names that some researchers name. remediation cells MRCs Aulenta et al 2008 Butler et al 2010 them MXCs where X stands for different applications Harnisch and. Gregory and Lovley 2009 Lovley and Nevin 2011 Rabaey and Schr der 2010 Torres et al 2010 Table 1 summarizes all the reactor. Rozendal 2010 The potential across the electrodes can also drive desa acronyms to date and demonstrates the shared principle on the anode. lination microbial desalination cells MDCs Cao et al 2009 Jacobson and the versatile functions on the cathode. et al 2011 Luo et al 2011 Luo et al 2012c Mehanna et al 2010 The Ideal anodic reactions in MESs generally include dynamic and effec. production of current associated with microbial catabolism was rst tive microbial activity and community higher substrate conversion rate. reported a century ago by Potter 1911 but research interests in this and electron transfer ef ciency and lower material and system costs. concept have only blossomed in the past decade resulting in an expo MESs employ a unique group of microbes called electrochemically ac. nential growth in the number of journal articles Fig 1 There are tive bacteria EAB exoelectrogen electricigen or anode respiring. several excellent reviews that provided information on the history bacteria ARB to convert the chemical energy stored in organic or inor. and development of MESs Borole et al 2011 Schr der 2011 2012 ganic substrates to electrical energy during their anaerobic respiration. Sleutels et al 2012 and the substrates materials and microbial com Logan 2009 Lovley 2006 Park et al 2001 Torres et al 2009 Such. munities in different systems Hamelers et al 2010 Logan 2009 microorganisms are able to transfer electrons out of cell membranes. Lovley 2006 Pant et al 2010 Wei et al 2011 but there has been to the electrode either directly through membrane bound protein. no comprehensive or quantitative review that directly addresses one structures such as pili c type cytochrome and laments or using mo. fundamental factor where all the known functions were originated bile electron shuttles such as mediators for indirect electron transfer. from and all future functions will be based upon As shown in Table 1 For example recent studies showed that Geobacter sulfurreducens re. this article aims to provide the rst complete review with the goal to quires conductive pili as nanowires for cell to cell electron conduction. summarize all the functions with different acronyms that have been de and c type cytochrome OmcZ to promote electron transfer onto the elec. veloped using this platform to date and shed light on future system de trode Lovley 2011 Summers et al 2010 In contrast Shewanella spe. velopment for energy and environmental science and engineering cies were reported to make both direct electrode contact through. Different groups have also used bioelectrochemical systems BESs or conductive laments and indirect electron transfer via mediators such. MXCs for this technology platform but because BESs were also used in as ribo avin or avin adenine mononucleotide FMN Canstein et al. other studies to represent cell free enzyme based systems while system 2008 Gorby et al 2006 Marsili et al 2008 Many other bacteria can. acronyms have far beyond the X of MXCs this review uses MESs to rep produce and use soluble redox mediators or electron shuttles which. resent the overall technology platform Harnisch and Schr der 2010 transport the electrons from the cell to the electrode For example. Logan and Rabaey 2012 Rozendal et al 2008 Torres et al 2010 Pseudomonas species can produce phenazines as extracellular electron. shuttles and other bacteria can use externally provided mediators. 2 The shared principle in the anode chamber such as neutral red anthraquinone 2 6 disulfonate AQDS thionine. methyl viologen methyl blue and some humics Aulenta et al 2008. Compared to traditional chemical fuel cells the MES platform uses Milliken and May 2007 Park and Zeikus 2000 Rabaey et al 2005a. low cost and self sustaining microorganisms to oxidize organic and Scott and Murano 2007 Thurston et al 1985. Fig 1 Number of published journal articles on MESs containing the phrases microbial fuel cell microbial electrolysis cell microbial electrosynthesis or microbial desalination cell. Source Scopus on 7 1 2013 document type Journal Language English duplicates were removed from searching results. Summary of all types of MESs with different acronyms. Types of MESs Electron donor for anode oxidization Electron acceptor for cathode Main products Ref. MFC based systems for electricity generation, Microbial fuel cells MFCs in general Any biodegradable material Oxygen potassium ferricyanide Electricity Kim et al 1999 Tanaka et al 1983. or other oxidants, 1 Tubular microbial fuel cell tubular MFC Acetate glucose domestic wastewater hospital Potassium ferricyanide Electricity Rabaey et al 2005b. wastewater digester ef uent from a potato,processing plant. H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807. 2 Up ow microbial fuel cell UMFC Sucrose Potassium ferricyanide oxygen Electricity He et al 2005 He et al 2006. 3 Baf ed air cathode microbial fuel Glucose liquid from corn stover steam explosion Oxygen Electricity Feng et al 2010. cell BAFMFC process, 4 Up ow anaerobic sludge blanket Glucose sul de Oxygen sulfer Electricity Zhang et al 2012. reactor microbial fuel cell UASB MFC, 5 Slalom ow cassette electrode microbial Starch yeast extract peptone plant oil detergent Oxygen Electricity Miyahara et al 2013.
fuel cell sCE MFC, 6 Plug ow microbial fuel cell PF MFC Wastewater sodium acetate Oxygen Electricity Karra et al 2013. 7 Complete mixing microbial fuel cell Wastewater sodium acetate Oxygen Electricity Karra et al 2013. 8 Stacked microbial fuel cell stacked MFC Sodium acetate Potassium ferricyanide Electricity Aelterman et al 2006. 9 Submersible microbial fuel cell SBMFC Domestic wastewater Oxygen Electricity Zhang and Angelidaki 2012c. 10 Benthic microbial fuel cell BMFC Sediment Oxygen Electricity Gong et al 2011 Nielsen et al 2007. Tender et al 2008, 11 Sediment microbial fuel cell AKA benthic Acetate and other fermentation products in the Oxygen Electricity Lovley 2006. unattended generator or BUG sediment, 12 Self stacked submersible microbial fuel Sediment acetate Oxygen Electricity Zhang and Angelidaki 2012b. cell SSMFC, 13 Microbial remediation cell MRC Diesel ethanol 1 2 dichloroethane pyridine Chlorinated solvents Reduced non toxic chemicals Aulenta et al 2008 Butler et al 2010. phenol perchlorate chromium Gregory and Lovley 2009 Kim et al. and uranium 2007,Luo et al 2009 Morris et al 2009,Pham et al 2009 Zhang et al 2009.
T Zhang et al 2010, 14 Photo microbial fuel cell p MFC Water Potassium ferricyanide Electricity Thorne et al 2011. 15 Microbial photoelectrochemical solar cell Marine sediment Oxygen Electricity glucose oxygen Malik et al 2009. 16 Solar powered microbial fuel cell Succinate propionate Oxygen Electricity hydrogen Cho et al 2008 Strik et al 2010. 17 Photobioelectrochemical fuel cell Organic acids alcohols Potassium ferricyanide Electricity hydrogen Rosenbaum et al 2005. 18 Photosynthetic microbial fuel cells PMFCs Water Oxygen Electricity Zou et al 2009. 19 Photosynthetic electrochemical cell Water glucose Potassium ferricyanide Electricity Yagishita et al 1997. 20 Solar driven microbial Trypticase soy broth TSB Proton Electricity Qian et al 2010. photoelectrochemical cell solar MPC, 21 Plant microbial fuel cell PMFC Plant derived organics root exudates Oxygen potassium ferricyanide Electricity Deng et al 2012. 22 Phototrophic microbial fuel cells Sediment Oxygen Electricity He et al 2009. phototrophic MFCs, 23 Photosynthetic algal microbial fuel cell Algae Potassium ferricyanide Electricity Strik et al 2008b. 24 Microbial electrochemical snorkel MES Wastewater Oxygen Treated wastewater no Erable et al 2011. AKA short circuited microbial fuel cell electricity. 25 Acid mine drainage fuel cell AMD FC Ferrous ion Oxygen Electricity removing iron Cheng et al 2007. Types of MESs Electron donor for anode oxidization Electron acceptor for cathode Main products Ref. 26 Integrated photobioelectrochemical system Wastewater Oxygen Electricity algal biomass Xiao et al 2012. 27 Osmotic microbial fuel cell OsMFC Sodium acetate Oxygen Diluted draw solution Zhang et al 2011. electricity, 28 Microbial reverse electrodialysis cell MRC Sodium acetate Oxygen Electricity Cusick et al 2012 Kim and Logan 2011b. 29 Microbial reverse electrodialysis Sodium acetate Oxygen Electricity acid alkali Zhu et al 2013. chemical production cell MRCC,MEC based systems for chemical production.
Microbial electrolysis cells MECs in general Any biodegradable material Proton Hydrogen hydrogen peroxide Cheng et al 2009 Liu et al 2005b. methane sodium hydroxide Rabaey et al 2010 Rozendal et al 2009. 30 Bioelectro chemically assisted microbial Wastewater Proton Hydrogen Ditzig et al 2007. reactor BEAMR, 31 Solar powered microbial electrolysis fuel Acetate Proton Hydrogen Chae et al 2009. 32 Microbial reverse electrodialysis Acetate Proton Hydrogen Kim and Logan 2011a. electrolysis cell MREC, 33 Microbial electrolysis struvite precipitation Sodium acetate Proton Hydrogen struvite Cusick and Logan 2012. 34 Submersible microbial electrolysis cell SMEC Acetate Proton Hydrogen Zhang and Angelidaki 2012a. H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807. MES based systems for chemical production, Microbial electrosynthesis MES in general Organic hydrogen sul de water Acetic acid or other organics Ethanol acetate 2 oxobutyrate Gong et al 2013 Nevin et al 2010. carbon dioxide formate Nevin et al 2011 Rabaey and. Rozendal 2010 Rabaey et al 2011,Steinbusch et al 2010. 35 Microbial carbon capture cell MCC Glucose Carbon dioxide Algal biomass electricity Wang et al 2010. MDC based systems for water desalination and bene cial reuse. Microbial desalination cells MDCs in general Any biodegradable material Oxygen potassium ferricyanide Desalinated water Cao et al 2009. organics or other oxidants, 36 Microbial saline wastewater electrolysis cell MSC Sodium acetate Hydrogen Treated saline wastewater Kim and Logan 2013b.
electricity, 37 Osmotic MDC OsMDC MODC Sodium acetate xylose wastewater Oxygen potassium ferricyanide Desalinated water electricity Kim and Logan 2013a Zhang and He. proton 2012, 38 Microbial desalination cell with capacitive adsorption Sodium acetate Potassium ferricyanide Desalinated water Forrestal et al 2012a. capability cMDC, 39 Microbial desalination cell packed with ion exchange Sodium acetate Oxygen Desalinated water electricity Morel et al 2012. resin R MDC, 40 Microbial electrolysis desalination cell MEDC Sodium acetate Proton Hydrogen desalinated water Luo et al 2011. 41 Microbial electrolysis desalination and chemical Sodium acetate Oxygen Desalinated water sodium Chen et al 2012. production hydroxide,cell MEDCC hydrochloric acid, 42 Microbial capacitive desalination cell MCDC Sodium acetate Oxygen Desalinated water Forrestal et al 2012b.
43 Capacitive deionization coupled with microbial fuel Sodium acetate Potassium ferricyanide Desalinated water Yuan et al 2012. cell CDI MFC, 44 Up ow microbial desalination cell UMDC Sodium acetate Oxygen Desalinated water electricity Jacobson et al 2011. 45 Stacked microbial desalination cell SMDC Sodium acetate Oxygen Desalinated water electricity Chen et al 2011. 46 Recirculation microbial desalination cell rMDC Xylose Oxygen Desalinated water electricity Qu et al 2012. 47 Submerged microbial desalination denitri cation Sodium acetate Nitrate Electricity nitrogen Zhang and Angelidaki 2013. cell SMDDC, 1800 H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807. Using microorganisms as biocatalysts MESs can theoretically con combination of multiple functions in one system and they are generally. vert any biodegradable substrate into energy and chemicals Besides straightforward such as microbial electrolysis desalination cell MEDC. simple sugars and derivatives used in most lab scale studies many com Luo et al 2011 microbial electrolysis desalination and chemical. plex waste materials have also been utilized such as different wastewa production cell MEDCC Chen et al 2012 osmotic microbial fuel. ters from municipal and industrial sources biomass wastes and cell OsMFC Zhang et al 2011 and microbial electrolysis struvite. inorganic substrates such as ammonia sul de and acid mine drainage precipitation cell MESC Cusick and Logan 2012 etc. Cheng et al 2007 Kuntke et al 2012 Pant et al 2010 Rabaey et al. 2006 Velasquez Orta et al 2009 The utilization of complex waste ma 4 MFC based systems for electricity generation. terials generally requires the cooperation of polymer degrading bacte. ria and electrochemically active bacteria with the rst group breaking 4 1 Wastewater microbial fuel cells wastewater MFCs. down the complex polymers such as cellulose or protein into simple. organic matter such as volatile fatty acids alcohol or amino acids and MFCs refer to the reactor systems that focus on electricity production. then the second group oxidizes these simple organic products with from biodegradable materials Table 1 provides a complete list of differ. the anode serving as the electron acceptor Freguia et al 2008 ent MFCs to date by our best count Early lab scale MFC studies mostly. Parameswaran et al 2009 Ren et al 2007 2008 In terms of waste used acetate glucose or other simple substrates to characterize the per. treatment in the anode chamber MESs represent a new generation of formance of materials reactor con gurations or microbial activities. technology because they carry the potential to transform traditional Liu et al 2005a Rabaey et al 2003 The rst MFC study that used. energy intensive treatment focused processes into integrated systems real wastewater as the substrate was reported in 2004 Liu et al. that recover energy nutrient water and other value added products 2004 and since then hundreds of studies have been published to report. power production from different substrates including both organic and. 3 The diverse application possibilities in the cathode chamber inorganic waste streams using various electrode or separator materials. and reactor con gurations Several review articles have provided com. As shown in Table 1 there have been 47 systems presented so far prehensive information on the substrates Pant et al 2010 electrode. with different functions or system constructions that were developed materials Wei et al 2011 separator materials X Zhang et al. using the MES platform and people used different acronyms to 2010 and reactor con gurations Logan et al 2006 used in different. represent the various functions and systems Though no speci c rules MFC studies. have been established to name the different reactors this article at Classic MFC designs include the single chamber air cathode MFCs. tempts for the rst time to summarize and categorize all the systems SCMFCs developed by Liu and Logan which for the rst time eliminat. that have been reported so far and provides some insights on future ed the membrane and therefore signi cantly reduced system internal. technology development resistance and cost Fig 3A Liu and Logan 2004 Liu et al 2005a Tu. In many cases the different MESs can be summarized as MXCs in bular designs Tubular MFCs with different ow patterns simpli ed. which the X simply presents the main function and bene t of a speci c construction processes and optimized systems with increased electrode. cell For example a microbial fuel cell MFC is the very original type of surface area and reduced system resistance He et al 2005 Rabaey. MES whose main function is direct electricity generation Fig 2A et al 2005b A baf ed air cathode microbial fuel cell BAFMFC was. Logan et al 2006 When an external power source is added in an designed to increase organic loading rate Feng et al 2010 and stacked. MFC reactor to reduce cathode potential the system becomes a micro MFCs were able to increase direct voltage or current output while also. bial electrolysis cell MEC where hydrogen gas and other products enhance substrate oxidation Aelterman et al 2006 Other MFC sys. can be generated Fig 2B Cheng et al 2009 Ditzig et al 2007 tems used in wastewater applications include submersible MFCs. Logan et al 2008 Rabaey et al 2010 Rozendal et al 2009 If the SBMFCs Zhang and Angelidaki 2012c which may convert the infor. main function of the system is to use the cathode to reduce oxidized mation of substrate concentration toxicity or dissolved oxygen concen. contaminants such as uranium perchlorate or chlorinated solvents tration into electronic signals as MFC sensors. the cell can be named a microbial remediation cell MRC Aulenta The main advantages of using MFCs in wastewater treatment come. et al 2008 Butler et al 2010 Gregory and Lovley 2009 and if the from the savings of aeration energy and sludge disposal Oh et al. main goal of the system is to synthesize value added chemicals through 2010 Ren 2013 Xiao et al 2012 For traditional activated sludge sys. microbially catalyzed cathodic reductions the system can be named mi tems aeration can amount to 45 75 of plant energy costs so the con. crobial electrosynthesis MES which can be a little confusing with the version of aeration tank to MFC units is very bene cial because it not. general microbial electrochemical system acronym Fig 2C Lovley only eliminates aeration energy consumption studies also showed. and Nevin 2011 Rabaey and Rozendal 2010 Another system called that the MFC can produce 10 20 more energy that can be used for. a microbial desalination cell MDC Fig 2D Cao et al 2009 Kim other processes Huggins et al 2013 Pant et al 2010 The reported. and Logan 2011a includes additional chambers between the anode maximum power density from lab scale air cathode MFCs has reached. and cathode and uses the internal potential to drive water desalination 2 87 kW m3 making it promising for commercialization development. There are also many different sub systems within each main catego Fan et al 2012 even though the system scale up remains a major. ry Take MFCs as an example based on different substrates used in MFC challenge Another main bene t of MFC systems is the low biomass pro. reactors there are wastewater MFCs sediment or benthic MFCs etc Liu duction The MFC is a bio lm based system and the cell yield of electro. et al 2004 Reimers et al 2001 By utilizing different photosynthetic chemically active bacteria 0 07 0 16 gVSS gCOD is much less than the. organisms for solar energy capturing people have developed plant activated sludge 0 35 0 45 gVSS gCOD so it can reduce sludge pro. MFCs phototrophic MFCs and algae MFCs Deng et al 2012 He duction by 50 70 Fan et al 2012 Huggins et al which in turn. et al 2009 Strik et al 2011 By integrating other technologies with may reduce 20 30 of the plant operation cost Other bene ts may in. the MES platform new systems with superior performance can be de clude nutrient removal and the production of value added products. veloped For instance by incorporating reverse electrodialysis RED such as caustic solutions for disinfection or H2 and biogas for energy. with an MEC the microbial reverse electrodialysis electrolysis cell which will be discussed more extensively in the following sections. MREC can produce H2 without any external power supply Kim and. Logan 2011a By integrating capacitive deionization CDI with an 4 2 Benthic microbial fuel cells benthic MFCs. MDC the microbial capacitive desalination cell MCDC could improve. desalination ef ciency by 7 25 times compared to traditional CDI pro Benthic MFCs BMFCs also known as sediment MFCs SMFCs are. cesses Forrestal et al 2012b Other names may come from the systems that utilize the naturally occurring potential difference. H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807 1801. between the anoxic sediment and oxic seawater to produce electricity a maximum power density of 294 mW m2 Zhang and Angelidaki. Lovley 2006 Microorganisms oxidize the substrates in the sediment 2012b. and transfer electrons to the anode either embedded in or rested on. top of the sediment and then the electrons are transferred to the 4 3 Microbial remediation cells MRCs. cathode suspended in the overlying seawater where dissolved oxygen. is reduced to water Fig 3B Donovan et al 2011 The abundant avail Another emerging application of the MES platform is using the. ability of substrates in the sediment makes BMFC a very promising electrodes to serve as inexhaustible electron acceptors anode or do. power source for autonomous marine sensors and underwater vehicles nors cathode for underground contaminant remediation Huang. because they provide consistent and maintenance free power supply et al 2011 Morris and Jin 2008 Yuan et al 2010 Like sediment. for a long period of time without using batteries This is a huge advan MFCs MRCs used in groundwater or soil remediation can be a single. tage compared to batteries because batteries are limited in service life or an array of electrodes without using enclosed containers Such. for about 2 4 years and the replacement can be very expensive espe bioelectrochemically enhanced approach can stimulate microbes to. cially in deep water It was estimated that the initial organic matter in concurrently degrade underground pollutants and produce additional. 1L marine sediment could generate an average current of 0 3mA contin electricity Such process is considered sustainable because it eliminates. uously for 22 years Malik et al 2009 While the concept of BMFC was the injection of expensive chemicals and reduces operational energy. only introduced in 2001 by Reimers et al 2001 it is a type of MES de cost as compared to other technologies. vice that is closest toward commercialization The rst demonstration of Microbial electrochemical remediation of petroleum contaminants. BMFC as a viable power source was reported by Tender et al in 2008 was demonstrated by using electrode as a channel linking underground. where an 18mW meteorological buoy was powered for nearly 7months hydrocarbon oxidation and upground O2 reduction One study showed. Tender et al 2008 Another study showed a chambered BMFC was that the active MRC increased the degradation of diesel range organics. used to power an acoustic modem interfaced with an oceanographic DRO by 164 as compared to open circuit potential Morris et al. sensor for over 50 days with an average power density of 44 mW m2 2009 and another study using a U tube MFC showed crude oil degrada. Gong et al 2011 So far the longest eld demonstration of BMFCs tion can be increased by 120 at the location near the electrode X Wang. has been reported continually operated for at least 2 years without de et al 2012 The dramatic increase in contaminant oxidation rate is. pletion in power Tender et al 2008 Different con gurations of hypothesized due to the faster electron transfer by more conductive elec. BMFCs have been developed and deployed Initial designs include sim trode as compared with electron shuttles It is also possible that the. ple graphite plates buried in the sediment with suspended cathode in competition between microbes to access and deliver electrons to the. water but such designs are fragile and the power output is very low electrodes triggered higher metabolic activities and the immediate re. Tender et al 2002 Nielsen et al developed a chamber based BMFC moval of electrons via the electrode eliminated the potential feedback in. that incorporates a suspended and semi enclosed anode which reduced habitation Similar remediation studies on other reduced pollutants. system footprint and increased power output to a range of 380 mW m2 including diesel ethanol 1 2 dichloroethane pyridine and other con. 3 8 W m3 Nielsen et al 2007 A self stacked submersible microbial taminants were also reported Luo et al 2009 Pham et al 2009. fuel cell SSMFC showed an open circuit voltage OCV of 1 12 V and Zhang et al 2009 Conversely oxidized contaminants such as. Organic H2O Organic H2,CO2 O2 CO2 H,Membrane Membrane. optional optional,H2O Organics Organic H2O,O2 CO2 CO2 O2. Membrane AEM CEM, Anode Bacteria Cathode Bacteria H2 O2 CO2 Organics.
Fig 2 Basic principles in four typical MESs left chamber anode right chamber cathode A Electricity generation in air cathode microbial fuel cells MFCs B hydrogen generation. with external power supply in microbial electrolysis cells MECs C chemical production by microbial electrosynthesis MES D middle chamber desalination in microbial desalina. tion cells MDCs, 1802 H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807. chlorinated solvents perchlorate chromium and uranium can be re 4 4 Microbial solar cells MSCs. duced using the electrode as the electron donor Aulenta et al 2008. Butler et al 2010 Gregory and Lovley 2009 Wang et al 2008 For in Microbial solar cells are collective names for different MESs that. stance studies showed that a negatively polarized electrode could act as integrate the photosynthetic reaction with microbial electricity or. an electron donor for the dechlorination of trichloroethene TCE to eth chemical production using synergistic relationships between photosyn. ene by a mixed culture of microorganisms Aulenta et al 2008 The thetic organisms and EAB Strik et al 2011 While EAB are generally the. similar approach was also used in both lab and eld tests for U VI reduc same bacterial groups in other MESs the organisms that are responsible. tion where the horizontally distributed anodes and cathodes enabled di for converting solar energy to organic matter may include higher plants. rect correlation between acetate injection and uranium reduction and photoautotrophic bacteria and algae A very wide variety of names. current production may be an effective proxy for monitoring in situ mi and systems related to MSCs have appeared in literature such as. crobial activity and remediation performance Fig 3C Williams et al photo microbial fuel cell p MFC Thorne et al 2011 microbial. 2010 photoelectrochemical solar cell Malik et al 2009 solar powered. Fig 3 MFC based systems for electricity generation A wastewater microbial fuel cells B benthic microbial fuel cells C microbial remediation cells and D microbial solar cells. Reproduced with permission from refs Donovan et al 2011 Liu and Logan 2004 Strik et al 2011 Williams et al 2010. H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807 1803. microbial fuel cell Strik et al 2010 photobioelectrochemical fuel cell evolution which was much lower than the 1 8 2 0 V used in traditional. Rosenbaum et al 2005 photosynthetic microbial fuel cells PMFCs water electrolysis Liu et al 2005b Logan et al 2008 Another advan. Zou et al 2009 photosynthetic electrochemical cell Yagishita et al tage was that the substrates can be from renewable and waste materials. 1997 and solar driven microbial photoelectrochemical cell solar rather than fossil fuels and the H2 production rate can be more than. MPC Qian et al 2010 Despite the variations in system designs the 1 m3 day m3 reactor with a yield up to 11 mol H2 mol glucose which. basic principle of MSCs usually include 4 steps as described by Strik is more than 3 times higher than dark fermentation Liu et al 2010. et al 2011 and illustrated in Fig 3D i photosynthesis of organic mat Logan et al 2008 Several excellent reviews summarized the material. ter ii transport of organic matter to the anode compartment iii an and system development of the MECs for H2 production Lee et al. odic oxidation of organic matter by EAB and iv cathodic reduction of 2010 Liu et al 2010 Logan et al 2008. oxygen or other electron acceptors Here we categorize the MSCs into 3 The elimination of membranes or separators converted dual cham. groups based on the organisms responsible for photosynthesis plant ber MECs to single chamber reactors and signi cantly increased H2 gen. MSCs phototrophic MSCs and algae MSCs More detailed information eration rate but the produced H2 was more likely consumed by. can be found in other reviews Deng et al 2012 He et al 2009 Strik methanogenesis to generate CH4 Liu et al 2010 Logan et al 2008. et al 2011 Researchers have tried different inhibition approaches such as adding. The most popular MSCs are plant MSCs which use the organic expensive methanogen inhibitors periodically expose solution in aero. rhizodeposits excreted from living higher plants to feed EAB for electric bic environment and control the pH and redox potentials but the CH4. ity production Reed mannagrass and rice plants were used rst to dem contamination of H2 in single chamber MECs still remains a major ob. onstrate the syntrophic relations with maximal power outputs of stacle Hu et al 2008 Liu et al 2010 Logan et al 2008 The small ex. 67 mW m2 and 26 mW m2 respectively Schamphelaire et al 2008 ternal voltage can be supplied by MFC stacks or other renewable power. Strik et al 2008a Other plants such as Spartina anglica Arundinella sources such as solar and wind Chae et al 2009 Sun et al 2008 Re. anomala and Arundo donax were also investigated for concurrent elec cently reverse electrodialysis RED was added into MECs generating a. tricity and biomass production A donax failed Helder et al 2010 but new system called microbial reverse electrodialysis electrolysis cells. S anglica was able to generate current for up to 119 days Timmers MRECs with spontaneous H2 production by combining together the. et al 2010 Despite the low power output at the current stage a driving forces from anode organic oxidation and salinity gradient ener. European research consortium estimated that the power production gy Fig 4A and salt solutions could be continuously regenerated with. from plant MSCs could reach 1000 GJ ha year 3 2 W m2 Strik et al waste heat 40 C Cusick et al 2012 Kim and Logan 2011a. 2011 Unlike plant MSCs the phototrophic MSCs do not require the co By using similar strategies in MECs other inorganic chemicals have. operation between the two groups of microbes because studies showed been produced in the cathode chamber Cusick and Logan discovered. that strains of photosynthetic bacteria such as Rhodobacter sphaeroides that phosphate can be recovered as struvite MgNH4PO4 6H2O in a. can generate electricity through the metabolic activity of in situ oxidation modi ed microbial electrolysis struvite precipitation cell MESC. of photobiological hydrogen Rosenbaum et al 2005 and the power Cusick and Logan 2012 Rozendal et al reported that hydrogen perox. density can be comparable with nonphotosynthetic MFCs Cao et al ide can be produced by reducing oxygen through the two electron reduc. 2008 A self assembling self repairing marine sediment system with tion and the proof of concept study showed that at an applied voltage of. photosynthetic microbes was reported to generate electricity from sun 0 5 V H2O2 can be generated at a rate of 1 9 0 2 kg H2O2 m3 day with a. light without the need of providing constant ux of glucose and oxygen concentration of 0 13 0 01 wt and an overall ef ciency of 83 1 4 8. Malik et al 2009 The algae MSC is an emerging system because the Rozendal et al 2009 The same group later used a similar approach to. functions of algae and EAB are complementary The consortium not produce alkaline solutions as they found that by using acetate as the. only can convert solar energy to electric energy it can also remove nutri electron donor in the anode the MEC generated up to 1 05A in current. ents and produce value added chemicals such as protein and biodiesel at an applied voltage of 1 77 V which allowed for the production of. Both microalgae e g Chlorella vulgaris and macroalgae e g Ulva caustic to 3 4 wt Rabaey et al 2010 Such chemicals can be produced. lactuca have been used in algae MSCs to provide substrates for EAB during wastewater treatment process and then used as low cost disin. Velasquez Orta et al 2009 In addition to traditional batch reactors fectants for many industries. Strik et al developed a ow through photosynthetic algal microbial. fuel cell PAMFC to automatically feed algae to MFCs Strik et al 6 MES based systems for chemical production. 2008b Another study integrated photobioreactor anaerobic digester. and MFC reactors together to recover both biogas and electricity Microbial electrosynthesis also shortened as MES in literature is an. Schamphelaire and Verstraete 2009 Other systems include recycling emerging area in microbial electrochemical research and development. anode off gas CO2 into an algae grown cathode for additional carbon and it uses the electrons derived from the cathode to reduce carbon di. capture Wang et al 2010 and an integrated photobioelectrochemical oxide and other chemicals into a variety of organic compounds espe. system with an MFC enclosed inside an algal bioreactor Xiao et al cially those with multiple carbons that are precursors for desirable. 2012 Utilizing the algae cyanobacteria and protozoa Strik et al report value added chemicals or liquid transportation fuels Lovley and. ed an MSC with a reversible bioelectrode which can function as a Nevin 2011 Rabaey and Rozendal 2010 Rabaey et al 2011 The po. biocathode during illumination for photosynthesis reaction and can tential of MES not only comes from the double bene ts of carbon se. then switch to the anode in the dark for organic degradation Strik questration and organic production but may also address the. et al 2010 MSCs are the only MESs that do not rely on external electron harvesting storage and distribution problems associated with energy. donors but convert inexhaustible solar energy into electrical energy and crops solar and wind farms and natural gas exploration because the. chemicals so they carry great potential if current challenges such as low electrons can be from any renewable source and microbes may harvest. power output are addressed solar energy in a 100 fold higher ef ciency than biomass based chemi. cal production Lovley and Nevin 2011, 5 MEC based systems for chemical production The concept of microbial electrosynthesis was only introduced in. 2009 2010 with the initial ndings associated with methane generation. The concept of microbial electrolysis cell was originated in 2005 from a reactor with an abiotic anode and a biocathode acclimated with. with the key feature of using an external voltage on top of the MFC po Methanobacterium palustre Cheng et al 2009 Another early study dem. tential to enable hydrogen gas evolution at the cathode through the re onstrated that bio lms of Sporomusa ovata could use the electrons sup. duction of protons Liu et al 2005b Rozendal et al 2006 Early studies plied by the cathode to reduce carbon dioxide into acetate and small. used external power supplies ranged from 0 6 to 1 0 V to catalyze H2 amounts of 2 oxobutyrate Electrons appearing in these products. 1804 H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807. Fig 4 Some advanced MESs A a microbial reverse electrodialysis electrolysis cell MREC B a microbial electrosynthesis MES and C a microbial capacitive desalination cell. Reproduced with permission from refs Forrestal et al 2012b Kim and Logan 2011a Nevin et al 2010. accounted for over 85 of the electrons consumed Fig 4B Nevin et al top technology paper by Environmental Science Technology Cao. 2010 In general acetogenic bacteria use hydrogen as the electron donor et al 2009 The basic principle of MDC is to utilize the electric potential. for carbon dioxide reduction but it was found that many acetogenic bac generated across the anode and cathode to drive desalination in situ. teria such as Clostridium ljungdahlii Clostridium aceticum Sporomusa Compare to other MESs MDCs have a third chamber for desalination. sphaeroides and Moorella thermoacetica were all able to consume electri by inserting an anion exchange membrane AEM and a cation ex. cal current and produce organic acids Nevin et al 2011 Studies also change membrane CEM in between the anode and cathode chambers. showed that ethanol can be produced by reducing acetate at the cathode When bacteria in the anode chamber oxidize biodegradable substrates. but some processes required addition of mediators such as methyl and produce current and protons the anions e g Cl in the middle. viologen MV Steinbusch et al 2010 The mixed culture originated chamber migrate to the anode and the cations e g Na are drawn to. from brewery wastewater was reported to generate methane acetate the cathode for charge balance thus the middle chamber solution is de. and hydrogen gas from a biocathode poised at 590 mV vs SHE with salinated Cao et al 2009 Luo et al 2012c Recently other approaches. CO2 as the only carbon source Marshall et al 2012 and research on ge were developed to achieve desalination as well For example by. netically modi ed microorganisms may signi cantly facilitate electron switching the CEM to the anode side and AEM to the cathode side a mi. uptake and organic synthesis As discussed in several conceptual review crobial saline wastewater electrolysis cell MSC desalinates anolyte. articles the microbial electrosynthesis carries great potential but there and catholyte by driving salts into the middle chamber Kim and. are also many technological and economic challenges to be solved before Logan 2013b Osmotic microbial fuel cells OsMFCs or osmotic. it can be implemented in large scale Lovley and Nevin 2011 Rabaey and MDCs OsMDCs MODCs use a forward osmosis membrane to replace. Rozendal 2010 Rabaey et al 2011 the AEM and withdraw pure water from wastewater to the draw solu. tion and then water can be recovered during draw solution regenera. 7 MDC based systems for water desalination and bene cial reuse tion Kim and Logan 2013a Zhang et al 2011 A capacitive. microbial desalination cell cMDC incorporates capacitive deionization. Water desalination using the MDC process was rst introduced in into an MDC to improve desalination ef ciency Forrestal et al 2012a. 2009 by Cao et al and the proof of concept study was selected as the 2012b Yuan et al 2012 In addition to desalination acid HCl and. H Wang Z J Ren Biotechnology Advances 31 2013 1796 1807 1805. base NaOH solutions can be produced if a bipolar membrane is placed Ren 2012 H Wang et al 2012 Multiple reviews have summarized. into the MDC next to the anode chamber creating a four chamber sys the progresses of MFC system development and provided insights in. tem called a microbial electrolysis desalination and chemical further directions Logan 2010 Lovley 2011 Rozendal et al 2008. production cell MEDCC Chen et al 2012 Wei et al 2011. The MDC can be used as either a stand alone for simultaneous Compared to electricity generation in MFCs chemical production. organic and salt removal with energy production or a pretreatment for and desalination from MESs have been considered technically and eco. conventional desalination processes such as reverse osmosis RO to re nomically more feasible due to the higher price of chemicals and rela. duce the salt concentration in feed solution and minimize energy con tively simple collection process But such processes are relatively new. sumption and membrane fouling Compared with current technologies and mainly in lab scale and there have been few reports in scale ups. that use 6 68 kWh to desalinate 1 m3 of seawater MDC studies showed Cusick et al 2011 Logan 2010 Among the many different functions. that 180 231 more energy can be recovered as H2 than the reactor en developed using this MES platform technology as discussed across. ergy input when desalinating 5 20 g L NaCl solutions Luo et al 2011 this article it is not clear where the MES can contribute the most to. Mehanna et al 2010 and it was estimated that an MDC may produce the current environmental infrastructure and chemical industries. up to 58 of the electrical energy required by downstream RO systems There have been very limited evaluations of different systems regarding. Jacobson et al 2011 Higher desalination ef ciency and current output to their life cycles in terms of function selections or comparisons with. can be achieved through membrane stacks Chen et al 2011 Kim and established technologies which they may complement Foley et al. Logan 2011c and electrolyte recirculation was shown effective in stabi 2010 Pant et al 2011 It has been assumed that the most environmen. lizing electrolyte pH Luo et al 2012a Qu et al 2012 Traditional MDC tal bene ts from MESs come from the displacement of fossil fuel depen. designs accomplish desalination by transporting ions from the middle dent resources i e grid electricity or chemical manufacture through. chamber to the anode and cathode chambers which increases the con co product production i e electricity chemicals from renewable. ductivity of the anolyte and catholyte This change has been shown ben sources but the energy and environmental footprints of different sys. e cial to electricity generation due to improved mass transfer but the tems have to be clearly quanti ed before implementing large scale ap. increased salinity may also affect ef uent water quality and prevent plications In addition fundamental understandings on the unique. subsequent bene cial use of treated wastewater Luo et al 2012c electron transfer mechanisms between bacterial cells and electrodes. One solution for complete salt removal from all the liquids may involve as well as among different microbial species are crucial for further. the physical and electrical adsorption of ions onto high surface area system development Such characterizations should be performed on. membrane electrode assemblies such as microbial capacitive desalina both pure cultures at different growth stages as well as microbial. tion cells MCDCs which showed up to 25 times of increase in salt re consortiums that are present in the environment Overall despite the. moval and complete salt recovery Fig 4C Forrestal et al 2012b remaining challenges if MES keeps its pace in research and develop. Similar as many membrane based technologies one challenge for ment it is reasonable to believe that in the near future this platform. MDCs may come from membrane fouling due to bio lm growth and technology will provide viable solutions to address many energy and. scaling due to the deposition of hardness causing cations but studies environmental problems. on understanding and addressing such problems are just getting started. and solutions remain to be found Luo et al 2012a 2012b. Acknowledgment, This work was supported by the US National Science Foundation. under Award CBET 1235848 and the Of ce of Naval Research under. In about one decade of research and development the functionality. Award N000141310901, of MESs has expanded dramatically and the performance has improved. exponentially However despite the many different functions discov. ered there are many remaining challenges before this technology can References. be implemented in larger scale Taking MFCs as an example the Aelterman P Rabaey K Pham HT Boon N Verstraete W Continuous electricity generation. power density has increased by orders of magnitude from less than at high voltages and currents using stacked microbial fuel cells Environ Sci Technol. 1 mW m3 to 2 87 kW m3 or 10 9 kA m3 Fan et al 2012 primarily 2006 40 3388 94. 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ChemSusChem 2012 5 959 61 Zhang B He Z Integrated salinity reduction and water recovery in an osmotic microbial. Scott K Murano C Microbial fuel cells utilising carbohydrates J Chem Technol Biotechnol desalination cell RSC Adv 2012 2 3265 9. 2007 82 92 100 Zhang C Li M Liu G Luo H Zhang R Pyridine degradation in the microbial fuel cells J. Sleutels THJA Heijne AT Buisman CJN Hamelers HVM Bioelectrochemical systems an Hazard Mater 2009 172 465 71. outlook for practical applications ChemSusChem 2012 5 1012 9 Zhang T Gannon SM Nevin KP Franks AE Lovley DR Stimulating the anaerobic degrada. Steinbusch KJJ Hamelers HVM Schaap JD Kampman C Buisman CJN Bioelectrochemical tion of aromatic hydrocarbons in contaminated sediments by providing an electrode. ethanol production through mediated acetate reduction by mixed cultures Environ as the electron acceptor Environ Microbiol 2010 12 1011 20. Sci Technol 2010 44 513 7 Zhang X Cheng S Huang X Logan BE The use of nylon and glass ber lter separators. Strik DPBTB Terlouw H Hamelers HVM Buisman CJN Renewable sustainable with different pore sizes in air cathode single chamber microbial fuel cells Energy. biocatalyzed electricity production in a photosynthetic algal microbial fuel cell Environ Sci 2010 3 659 64. PAMFC Appl Microbiol Biotechnol 2008a 81 659 68 Zhang F Brastad KS He Z Integrating forward osmosis into microbial fuel cells for waste. Strik DPBTB Bert HVMH Snel JFH Buisman CJN Green electricity production with living water treatment water extraction ad bioelectricity generation Environ Sci Technol. plants and bacteria in a fuel cell Int J Energy Res 2008b 32 870 6 2011 45 6690 6. Strik DPBTB Hamelers HVM Buisman CJN Solar energy powered microbial fuel cell with Zhang B Zhang J Yang Q Feng C Zhu Y Ye Z et al Investigation and optimization of the. a reversible bioelectrode Environ Sci Technol 2010 44 532 7 novel UASB MFC integrated system for sulfate removal and bioelectricity generation. Strik DPBTB Timmers RA Helder M Steinbusch KJJ Hamelers HVM Buisman CJN Micro using the response surface methodology RSM Bioresour Technol 2012 124 1 7. bial solar cells applying photosynthetic and electrochemically active organisms Zhu X Hatzell MC Cusick RD Logan BE Microbial reverse electrodialysis. Trends Biotechnol 2011 29 41 9 chemical production cell for acid and alkali production Electrochem Commun. Summers ZM Fogarty HE Leang C Franks AE Malvankar NS Lovley DR Direct exchange 2013 31 52 5. of electrons within aggregates of an evolved syntrophic coculture of anaerobic bacte Zou Y Pisciotta J Billmyre RB Baskakov IV Photosynthetic microbial fuel cells with pos. ria Science 2010 330 1413 5 itive light response Biotechnol Bioeng 2009 104 939 46.

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