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Critical Review pubs.acs.org/est Practical Energy Harvesting for Microbial Fuel Cells: A Review Heming Wang,† Jae-Do Park,‡ and Zhiyong Jason Ren*,† † Department of Civil, Environmental, and Architectural Engineering, University of Colorado Boulder, Boulder, Colorado 80309, United States ‡ Department of Electrical Engineering, University of Colorado Denver, Denver, Colorado 80204, United States ABSTRACT: The microbial fuel cell (MFC) technology offers sustainable solutions for distributed power systems and energy positive wastewater treatment, but the generation of practically usable power from MFCs remains a major challenge for system scale up and application. Commonly used external resistors will not harvest any usable energy, so energy-harvesting circuits are needed for real world applications. This review summarizes, explains, and discusses the different energy harvesting methods, components, and systems that can extract and condition the MFC energy for direct utilization. This study aims to assist environmental scientists and engineers to gain fundamental understandings of these electronic systems and algorithms, and it also offers research directions and insights on how to overcome the barriers, so the technology can be further advanced and applied in larger scale. 1. INTRODUCTION The microbial fuel cell (MFC) technology has been intensively researched in the recent decade, because it offers a solution for environmental sustainability by simultaneously performing pollutant removal and energy production. MFCs use exoelectrogenic microorganisms to convert the chemical energy stored in biodegradable substances to direct electricity. Furthermore, the electrical current can be utilized for many other functions, including producing value-added chemicals such as H2 in microbial electrolysis cells (MECs) or driving water desalination in microbial desalination cells (MDCs).1,2 The advancements in reactor architecture, material, and operation optimization of these bioelectrochemical systems (BES) have remarkably relieved the physical and chemical constraints of reactor systems,3,4 leading to orders of magnitude increase in power output. However, one main challenge for MFCs or BESs to be used in real-world applications is the low energy output, and to overcome this, one key element that has been largely neglected is how to harvest and practically utilize the MFC energy based on the true potential of the system rather than simply reporting the measured power density using external resistors. Compared to other alternative energy systems such as solar and wind, MFC is a low power system due to its thermodynamic limitation. The theoretical anode and cathode potentials calculated by Nernst equation are −0.3 V (vs NHE) and 0.8 V (vs NHE), respectively, when acetate servers as the electron donor and oxygen serves as the electron acceptor. Therefore, the theoretical voltage across the two electrodes is 0.8 V to −0.3 V = 1.1 V.5−7 However, the experimentally observed open circuit voltage is only around 0.7−0.8 V (Figure 1) due to the losses on the electrode potential, such as activation polarization, concentration polarization and ohmic losses.6 The potential also varies when different electron © 2015 American Chemical Society Figure 1. Ideal operation conditions for different BESs, including microbial fuel cells (MFCs) and microbial desalination cells (MDCs). The typical polarization (red) and power density curves (blue) were generated using a lab scale recirculation-flow MFC. Microbial electrolysis cells (MECs) are not shown in the figure because their operation points are beyond this range. donors, electron acceptors, or microbial inocula are used in the system. Traditionally, MFC power output is reported by changing the external resistance (Rext) at a 5−30 min interval or conducting a voltammetry sweep.7−10 Figure 1 shows typical polarization and power density curves obtained from a lab scale MFC. The curves demonstrate that MFC voltage is inversely proportional to the output current, and there exists a pair of voltage and current that delivers the maximum power, when Received: Revised: Accepted: Published: 3267 September 29, 2014 February 6, 2015 February 11, 2015 February 11, 2015 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology Rext is equal to the system internal resistance (Rint). This peak point is called the maximum power point (MPP), which is the ideal operating point for MFCs and reported by most studies as the top power output.7,11,12 However, top power may not be the goal of all systems. For MFCs used in wastewater treatment, the primary goal may not be high power output but rather more efficient organic removal, so a balance in operation during different phases needs to be considered whether to operate the system at the MPP for maximum power output or at the high current condition for the fastest substrate oxidation rate.8 Similarly, for H2 production in an MEC, the ideal operating point is not MPP but rather the high current region, because H2 production directly correlates with electron flow (current) in the circuit and proton reduction at the cathode. Because an additional voltage is required for MECs, the operation point of MEC is beyond the limiting current of the polarization curve at negative voltages, and the external energy input, as well as energy content of the produced H2 should be considered in addition to the amount of H2 produced, so the actual energy efficiency and energy recovery can be quantified.13 In contrast, the operation of MDCs depends on different needs, because if high energy is desired, the MPP will be the ideal point, but if high salt removal is the primary goal, then high current will be needed (Figure 1).14 Furthermore, the different operational points identified on the power density curve only represent the potential of power output rather than usable energy, as the electricity generated is dissipated into heat through resistors instead of being utilized by electronics. In addition, the fixed Rext cannot always match the system Rint and extract energy at the MPP, because the Rint of an MFC varies constantly with changes in microbial activities and operational parameters. Studies showed that MFCs may lose more than 50% of produced power across the Rint if the operating voltage is not at the MPP.15 To harvest usable MFC or BES energy, resistors have to be replaced with devices that can capture and store energy and boost voltage for practical usage. The direct outputs of a single MFC are primarily in the level of 700−800 mV and 100−2000 mW/m2, which generally cannot directly power common electronics.16 For example, a single light emitting diode (LED) requires a minimum voltage of 2 V and consumes 30 mW,17,18 and many wireless sensors need a voltage of 3.3 V and wattlevel power for temperature, pressure, and humidity monitoring.19−22 While higher power using single or multiple MFCs has been researched, it was reported that larger power production cannot be easily achieved by just building larger MFCs or simply connecting MFCs in series or in parallel due to the nonlinear nature of MFCs.23,24 Therefore, developing tailored energy harvesting systems including MPP tracking and power management systems (PMS) are crucial for MFC and BES scale-up and real-world application. Such systems generally composed of multiple electronics, such as off-the-shelf capacitors, rechargeable batteries, charge pumps, and boost converters, but these devices are not designed for MFC conditions so the efficiency was low and initial voltage boosts were needed. Customized harvesting systems have been reported by several groups, including our group, but there is very limited knowledge base for this important area, because it requires understanding of power electronics, circuitry, and programing, which are not provided in traditional environmental science and engineering education. In this paper, we therefore offer a first comprehensive review of energy harvesting strategies and systems for MFCs to assist researchers gain fundamental understandings of such methods. We also provide discussions and our insights on the challenges and research needs of this field, so researchers and engineers can help advance the technology development and finally overcome these barriers of MFC application. 2. ENERGY HARVESTING TECHNOLOGIES Since the direct energy production from MFCs is generally not sufficient for practical applications, various circuit topologies have been developed to interface MFCs with electronic loads. Figure 2A shows a concise flowchart of energy harvesting Figure 2. Schematics of energy harvesting processes: (A) a concise process from MFCs (energy generator) to electronic devices (energy consumer); (B) a classic and widely adopted PMS circuit composed of a charge pump and a boost converter with accessary components; (C) a two-layer energy-harvesting scheme, which is operated in alternative CHARGE and DISCHARGE phases. process from MFCs (energy generator) to electronic devices (energy consumer), where PMS (e.g., capacitor-based systems, charge pump-based systems, boost converter-based systems, and unreported systems) as the central command aims to control the MFC at its optimal condition and extracts and stores the energy for the uses by external loads. A PMS is an electronic circuit that is composed of electronic components such as capacitors, charge pumps, boost converters, diodes, inductors, power switches, and potentiometers, with the function of harvesting MFC energy and shaping it to a usable form.25 This is different from external resistances, which have been used in most MFC/BES studies to represent the energy output potential but not capture any usable energy, because the current passed through the resistor is dissipated into heat. Table 1 lists all the commercially available parts that have been used in PMS designs for MFCs including the information on manufacturer/model number and the function of each component. Additionally, Table 2 summarizes the energy harvesting performances that have been reported so far and as well the main electronic components utilized in each study. 3268 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology Table 1. Key Electronic Components Used in Energy Harvesting Systems electronic components capacitor rechargeable battery charge pump boost converter inductor transformer diode metaleoxideesemiconductor feld-effect transistor (MOSFET) junction gate field-effect transistor (JFET) Comparator oscillators energy harvesting board manufacturer and model number functions Duracell (DC2400 NiMH rechargeable AAA battery) Seiko Instruments (S-882Z) STMicroelectronics (L6920DB) Linear Technologies (LTC3108) Linear Technologies (LTC3429) Texas Instruments (TPS61200) Texas Instruments (TPS61201) Maxim Semiconductor (max1797evkit) AMI Electronics (T3005P) Triad Magnetics (RC-7) Triad Magnetics (CST206−1A) Triad Magnetics (CST206−3A) Coilcraft (LPR6235−253PML) Coilcraft (LPR6235−752SML) Würth Elektronik (WE749197301) Micro Commercial Components (1N5711) Fairchild Semiconductor (1N755A) Fairchild Semiconductor (BAT54) Avago Technologies (HSMS-286x) Vishay (Si3460BDV) Vishay (Si3499DV) Advanced Linear Device (ALD110800) ON Semiconductor (4906NG) Diodes Incorporated (DMG6968) Vishay (2N4338) Energy storage in a magnetic field Energy transfer through electromagnetic induction A switch that blocks reverse current flow A transistor that switches electronic signals A transistor that amplifies electronic signals Compare a voltage/current against a reference and output a digital signal indicating whether the voltage/current reaches the set level Produces a periodic and oscillating signal, such as square waves Linear Technologies (LTC6906) Advanced Linear Devices (ALD1502) Advanced Linear Devices (EH4295) An integrated circuit ready for energy harvesting 1 C(Ve2 − Vb2) 2 46 21,22,40,43,45,47 21,43,45 20,21,50 48 42,46 47 19 74 66 61 20 65,69 40,66 59 65 65 21,45,66 21,45 20 59 65 61 57 68 outputs of current, voltage, and power from MFCs. To date five charging/discharging techniques have been reported: direct charging, intermittent energy harvesting (IEH, a.k.a. intermittent charging (IC)), alternate charging and discharging (ACD), charging capacitors in parallel while discharging in series and charging capacitive electrodes (Figure 2A and Table 2).17,27−30 A capacitor circuit can be a simplest PMS, which charges one or more capacitors until enough energy is accumulated for discharging to power electronic devices. The amount of power extracted and system efficiency vary along with the power curve. Capacitor operation is simple and straightforward, but the output voltage is limited at the open circuit potential (OCP) of the MFC because the capacitor stops charging when its voltage reaches the OCP.21 Therefore, MFC stacks with multiple units can be used to charge capacitors and obtain higher voltage outputs. A successful demonstration of such circuitry is the energetically autonomous robot called EcoBot.31 From 2003 to 2013, four generations of EcoBots were developed using MFC stack as the power source and capacitors as the harvesting system.31,32 By using a similar energy harvesting strategy, other studies have been conducted to pulse an artificial heartbeat,33 power a mobile phone,34 and create a self-sustainable MFC stack system.35 The IEH or IC approach cumulates energy extracted from MFCs in a capacitor and discharges it to a load. This mode Each study is also labeled whether or not its PMS needs an external power supply and whether or not the external power is included in the reported efficiency. The tables may serve the readers as an index for necessary information needed for PMS components and functions, and in the following sections we elaborate on each specific energy-harvesting regime for MFCs. 2.1. Capacitor-Based Systems. A capacitor is composed of two conductive terminals separated by a dielectric material, and energy is stored in the electrostatic field. When a capacitor is directly connected to an MFC, it is charged by the reactor and acts like a variable resistor, because the charging current changes as the capacitor voltage varies.26,27 The required time for a full charge is determined by the charging potential and capacitance.27 The amount of energy W (J) stored in a capacitor when the capacitor is charged from Vb (V) to Ve (V) can be calculated by W= ref energy storage in an electric field energy storage through electrochemical reactions A DC/DC converter to step the voltage up or down A DC/DC converter to step up the voltage (1) where Vb and Ve are the voltage across the capacitor at the beginning and end of charging, respectively, and C (F) is the capacitance. In energy harvesting systems, capacitors are widely used as either final energy storage before utilization or transitional energy storage during energy extraction. Different arrangements of multiple capacitors in the circuit can manipulate 3269 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 3270 25 0.5 3 sediment MFC 12 two-chamber MFCstack 12 two-chamber MFCstack 3−5 3−10.4 72 1800 3.3 3.3 3.3 2.85 3.6 9 1800 3.3 72 3.25 2.5 0.48 output voltage (V) 1.0 0.73−0.78 input power (mW) 0.633 0.7 0.3 4.2−4.55 input voltage (V) 23 24 main electronic components 2.1 3.25 0.7 0.7 BES Capacitor-Based Systems Direct Charging 1 40 single-chamber MFC- capacitor stack 2 8 single-chamber MFCstack 3 8 single-chamber MFCstack 4 8 single-chamber MFCstack 5 24 single-chamber MFCstack 6 24 single-chamber MFCstack 7 24 single-chamber MFC- rechargeable battery stack Intermittent Energy Harvesting (IEH, a.k.a. Intermittent Charging (IC)) 8 two-chamber MFC capacitor 9 single-chamber MFC 10 single-chamber MFC Alternate Charging and Discharging (ACD) 11 two-chamber MFC/MEC capacitor Charging Capacitors in Parallel and Discharging in Series 12 single-chamber MFC capacitor 13 single-chamber MFC 14 single-chamber MFC Charging Capacitive Electrodes 15 two-chamber MFC quasi-capacitor (capacitive electrode) Charge Pump-Based Systems 16 two-chamber MFC charge pump, capacitor 17 three-chamber MCDC Boost Converter-Based Systems Capacitor -Boost Converter Systems 18 upflow MDC (UMDC) rechargeable battery, DC/DC boost converter 19 benthic MFC capacitor, DC/DC boost converter 20 upflow MDC (UMDC) 21 benthic MFC 22 sediment MFC no. Table 2. Summary of Studies Reported Energy Harvesting Systems for BESs 3.52 36.97 0.73−0.78 0.152 output power (mW) N N N N N N N N N N 41.8a 79b 75.3b Y N Y N Y N N Y 86.6a N N N N N N N N N N N N N N N N N N Y Y Y Y N N N N N Y Y Y N maximum power point (Y/N) N need external power (Y/N) 4.3b 0.94b 100a 90a >90b 95.2b efficiency (%) 79 48 74 19 46 47 49 46 40 41 30 17 38 39 29 27 36 37 34 33 32 78 76,77 75 35 ref Environmental Science & Technology Critical Review DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 BES main electronic components 3271 two-chamber miniaturized MFC 0.06−0.17 0.36 0.4 0.6−0.7 0.328 0.512 0.9−1.2 >3 2.5 6 0.6−2 0.3 0.3 0.3 0.35 >3 2.5 2.2 5 0.174 3.3 3.3 3.3 3.3 7 3.3 0.316−0.372 0.3 0.28−0.33 0.2−0.4 0.052−0.32 0.6 0.5 1.12−1.44 0.4 0.3 2−7.5 3.3 3.3 1.7−3.3 0.475 0.79 0.18 0.6 output voltage (V) 4 0.37 input power (mW) 0.4 input voltage (V) 85 18 95 95 2500 95 95 output power (mW) 17b 30b <85b N N N Y Y Y Y N N N N 36.0a 46.1a 75.9a 73b 66.5−80.6b 74b 85b Y Y 3−13a <67.7a 60b 22.54−37.80b <70b 5.33b N N N N N N N N N N N N 58b 4.29b N need external power (Y/N) 55b efficiency (%) N N Y Y Y Y Y Y Y Y Y N N N N N N N N N N N N N N N maximum power point (Y/N) 67 68 16 40 59 60 12 65 69 70 51 57 66 21 22 44 45 42 43 73 71 61 20 21 50 72 ref a The efficiency presents the circuit efficiency (η1) only. External power was provided but not included in the calculation. bThe efficiency presents both the circuit efficiency (η1) and the overall system efficiency (η2). No external power was provided or external power is included in the calculation. 51 33 sediment MFC 34 benthic MFC 35 sediment MFC 36 benthic MFC 37 benthic MFC 38 sediment-MFC Custom-Designed Systems 39 two-chamber MFC capacitor, inductor, diode 40 two-chamber MFC Maximum Power Point-Based Systems 41 two-chamber MFC capacitor, inductor, diode 42 two-chamber MFC capacitor, transformer 43 two-chamber MFC capacitor, inductor 44 two-chamber MFC 45 single-chamber MFC capacitor, transformer, diode 46 single-chamber MFC 47 single-chamber MFC 48 benthic MFC unknown Integrated Circuit-Based Systems 49 single-chamber MFC commercial IC, capacitors 50 two-chamber MFC custom-designed IC Capacitor -Boost Converter Systems 26 sediment-MFC Capacitor-Transformer-Boost Converter Systems 27 single-chamber MFC capacitor, transformer 28 single-chamber MFC capacitor, transformer, DC/DC boost converter 29 single-chamber MFC 30 sediment MFC Capacitor-Charge Pump-Boost Converter Systems 31 single-chamber MFC capacitor, charge pump, DC/DC boost converter 32 sediment MFC no. Table 2. continued Environmental Science & Technology Critical Review DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology pump circuit are first charged by the power source and then connected in different combinations to generate various voltages for different applications. The S-882Z series charge pump from Seiko Instruments has been widely used in BES studies, and it requires a minimum input voltage of 0.3 V in order to generate a discharge voltage of 1.8−2.4 V (Figure 2A). The charge pump consumes a minimum 0.1−0.5 mA current during operation when the input voltage is 0.3−0.6 V, which may limit its charging speed when the current is low and leads to long charging/discharging cycles and low energy harvesting efficiency.20,40 For example, using a 316 mL air−cathode MFC as the power source, it took 22 h for the charge pump-based circuit to output a voltage of 3.3 V during the start-up phase, but a transformer-based circuit only took 2.5 h to output the same voltage,21 suggesting that the energy extraction rate of the charge pump was much slower compared to the transformer. Similar performance was observed by Wang et al., who found that due to charge pump’s input current limitation, its operating point was maintained at the low current region of the power curve which was far away from the MPP (Table 2).40 When using a charge pump to conduct capacitive discharge from a microbial capacitive desalination cell for energy production, Forrestal et al., found the Coulombic efficiency was only 0.94%, indicating that the charge pump is not sufficient for energy harvesting during desalination regeneration (Table 2).41 Therefore, charge pumps can accommodate low-voltage MFC sources and be used for intermittent energy harvesting when low charging rate is acceptable, such as for remote sensors. The performance of the charge pump can be greatly improved when input current increases. Furthermore, charge pumps can also be used as dynamic switches in the circuit to automatically control on/off and prevent reverse current flows.42,43 S-882Z (Seiko Instruments) has been the most commonly used commercially available charge pump in BES studies, and because its maximum output voltage 2.4 V, sometimes it is not sufficient to power common electronic devices. To further increase the output voltage, another layer of power converter may be placed after the charge pump for voltage boost. 2.3. Boost Converter-Based Systems. A DC/DC converter is an electric circuit to convert direct current (DC) power from one voltage level to another level, so an unregulated DC input can be converted to a controlled output. The input voltage can be stepped down (buck converter), stepped up (boost converter) or inverted. Boost converters are widely used in MFC research (Figure 2A), and the circuit of a boost converter includes both semiconductors, such as diodes and transistors, and energy storage components, such as capacitors and inductors, with a more complex structure than that in the charge pump. While the commonly used charge pump can step up the voltage from 0.3 V to 1.8−2.4 V, the output may still be low for many electronics such as marine sensors (3.3 V)19,44 In such cases, DC/DC boost converters can be used to boost the output voltage further. For example, several studies used a boost converter (L6920DB, STMicroelectronics) to obtain an output voltage of 3.3 V with a minimum start up input voltage of 0.8 V.21,43,45 Most commercially available low input voltage boost converters require a minimum input voltage of 0.7 V (max1797evkit, Maxim Semiconductor) or 0.8 V (L6920DB, STMicroelectronics), which are practically beyond the voltage capability of a single air-cathode MFC or a parallel-linked MFC stack. There are two off-the-shelf boost converters that require delivers power in intermittent pulses when the source is not capable of supplying continuous power to the load. Compared with the conventional continuous energy harvesting (CEH) in which current is continuously passing through the load, one study showed that the IEH approach harvested 152 μW from a 500 mL two-chamber MFC which is 111% higher than that in the CEH mode (72 μW).27 The results were explained by using an analogy that plug flow reactors (PFR) are more efficient than continuous stirred tank reactors (CSTR). In the IEH mode, the electrical current decreases slowly as the process progresses, similar as a PFR operation, so within a given period of time more electrical charges can be harvested than CEH, in which the reaction rate keeps stable like a CSTR. The effect of charging and discharging frequency during the IC mode can affect system performance, and it was suggested that lower frequency led to higher current output and chemical oxygen demand (COD) removal, though an optimum frequency should also consider charge recovery efficiency.36 Similarly, progressively switching MFC units from parallel to serial connection in the stack reduced capacitor charging time in half and increased current generation by 35% when comparing with MFC stack with serial connections.37 In the ACD mode, an MFC charges capacitors first for energy collection, and then the charged capacitors discharge the energy back to the system for MEC operation. Liang et al. showed that the ACD mode could increase the current by 22− 32% compared to the IC mode, which was attributed to the shorter discharging time than the charging time, as well as the higher anode potential caused by discharging the capacitor.29 However, power densities in the ACD mode were lower than those in the IC mode. The voltage output can be increased when charging an array of capacitors connected in parallel and then discharging them in series. By using two groups of capacitors with alternative charging and discharging sequence, Kim et al. found the output voltage was constantly enhanced from 0.7 V to as high as 2.5 V.17 Moreover, this approach does not require a minimum input voltage threshold, so voltage can be increased without using initial boost. It also effectively alleviated voltage reversal problem with negligible energy losses in the circuit. However, external energy supplied to control relay switches was not considered in the energy calculation. Another study used the same array to harvest energy from multiple MFCs and power an MEC, and it was found that energy recovery improved from 9% to 13%, and H2 production rate doubled from 0.31 to 0.72 m3/m3/day.38 A similar study used three capacitors separately charged by three MFCs and then linked them in series to power an electrochemical deposition system (ECD), which obtained a sulfur recovery efficiency up to 46.5 ± 1.5%.39 Another new capacitor-based energy harvesting is quasicapacitor-based method. In such systems, a capacitive bioanode was constructed by coating a capacitive layer consisted of a mixture of activated carbon and polymer, and then the anode can be used as an internal capacitor.30 The MFC equipped with the capacitive bioanode produced a peak current density up to 1.7 A/m2, which almost doubled the output of a control noncapacitive anode (0.9 A/m2). Future studies are needed to investigate the longevity of the capacitive electrodes. 2.2. Charge Pump-Based Systems. Charge pumps are low cost devices with simple circuit topologies. In general, a charge pump is an inductor-less DC/DC converter that uses capacitors to store and transfer energy in order to generate either higher or lower voltages. The capacitors in the charge 3272 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology requires a much longer charging time (11.3 h vs 1.06 h) and a higher minimum input voltage (0.3 V vs 0.18 V).21 To obtain high energy efficiencies, a classic PMS circuit composed of a charge pump, a boost converter, and the load with accessary components, such as capacitors and switches, has been widely adopted by benthic MFCs (BMFCs) (Figure 2B).22,42−45,47 BMFCs utilize naturally occurring potential difference between the anoxic sediment and oxic water to generate electricity and therefore provide long-term power source for remote sensors.51−54 One challenge of BMFCs is the low power output due to poor ion transfer between the sediment anode and the air cathode in the natural water body.55,56 This classic PMS first uses charge pumps to harvest energy from the low voltage/current BMFCs and then boosts the voltage via a boost converter to provide intermittent power for wireless sensors, telemetry systems or hydrophones.44,45 The intermittent energy harvesting is a practical approach for BMFC operation, as it allows a small power source such as BMFC to power larger electronic devices with higher energy demand, and the energy efficiency is higher than continuous operation. When coupling the PMS with a two-cathode BMFC (one floating and one settling), Zhang et al. found that continuous sensor charging was possible, but the charging rate was faster when only using the floating cathode.42 A multianode decoupling circuit could be used to separately connect charge pumps with different anodes, so interactions among anodes with different performances could be avoided.43 2.4. Maximum Power Point Tracking and Active Energy Harvesting. In addition to commercially available devices such as capacitors, charge pumps, and boost converters, customized energy harvesting systems with maximum power point tracking (MPPT) capability have been developed to increase power harvesting. While different systems have been reported with various performances, Table 1 shows the common components used in such systems, and each unit has a specific function. For example, inductor stores energy in the magnetic field; transformer transfers and amplifies energy through electromagnetic induction; diode, metal-oxide-semiconductor field-effect transistor (MOSFET), and junction gate field-effect transistor (JFET) are utilized as switches to prevent current reverse flow. Figure 2C shows a two-layer energyharvesting scheme, which can be used in conjunction with various converters such as a boost converter or flyback converter to further increase the output voltage. The energyharvesting scheme was operated in alternative CHARGE and DISCHARGE phases.40,57,58 During the CHARGE phase (the first half of the circuit in Figure 2C), the controller extracts energy from MFCs and temporarily stores it in the inductor; during the DISCHARGE phase (the second half of the circuit in Figure 2C), the controller discharges the energy from the inductor to the capacitor for storage. To increase the harvesting efficiency, the inductor was replaced with a transformer, and the diode was replaced by a MOSFET.59,60 Adami et al. developed a flyback converter by using a step-up transformer and a normally on N-channel JFET transistor, and they obtained an output voltage up to 7.5 V, which was much higher than the 3.3−5.0 V obtained from commercial boost converters.61 An MFC is a dynamic system that its internal resistance and power density curve vary constantly with changes of microbial activities and operational parameters, such as substrate concentration, pH, and temperature. This means that static energy harvesting without adaptation to MFC real time condition cannot capture the peak energy all the time, and very low operating input voltages, for example, LTC3108 (0.02 V, Linear Technologies) and TPS61200/TPS61201 (0.3 V, Texas Instruments), but their low input voltages can also limit the output voltages, making it hard to be used for real world applications. Although the OCP of MFCs could be around 0.7−0.8 V, the output voltage of a single MFC or parallelconnected MFCs decrease rapidly during current extraction by the boost converter, which is likely the reason for system failure when connecting a boost converter directly with three parallelconnected upflow MDCs (UMDCs).46 Hence the coordination between MFC outputs and electronic components must be carefully controlled to avoid system collapse. Series-connected MFCs could provide a higher input voltage, but it is at the risk of voltage reversal and performance is not stable due to changes in environmental conditions. To bridge the gap between the MFCs and the boost converter, electronic components like capacitors/rechargeable batteries, transformers, charge pumps, etc. are placed before boost converters to cumulate energy and jumpstart the converter. Table 2 summarizes different adopted components in related studies. Capacitors/rechargeable batteries are the most commonly used for storing energy. For example, Bo et al. used three serial-connected UMDCs as a predesalination process and harvested their energy into a rechargeable battery or a capacitor, then boosted the voltage via a boost converter to power a electrodialysis (ED) cell for further desalination.46 Compared with ED, this two-step desalination process can effectively reduce both energy consumption and desalination time. A similar approach was used by a benthic MFC with a biocathode and a sacrificial anode, which first charged a capacitor to 1.2 V and then boosted the voltage by a boost converter to 3.3 V, the minimum requirement as an intermittent power source for a wireless sensor.19 A higher efficiency was reported when two capacitors were charged by two MFCs individually, and then linked them in series and further boosted the voltage by the boost converter for higher voltage/current output.47 This method was used to develop a bulk energy storage for more efficient power conversion. By implementing two groups of supercapacitors with one group (12 supercapacitors) charged in parallel and the other switched in series, the harvesting approach was able to boost output voltage to 9 V.48 To provide a continuous power supply to sensors such as a submersible ultrasonic receiver (SUR) that listens and records time and signals, Donovan et al. developed a novel SMFC PMS composed of two boost converters to continuously power a real-time clock (RTC) in a sensor system.49 The second option is using transformers coupled with boost converter to amplify the voltage by transferring energy through electromagnetic induction. The advantage of transformers is that they extract energy much faster and can take lower input voltage than charge pumps. Yang et al. reported that by connecting an MFC with a capacitor and a transformer, the PMS worked well under a low input voltage of 0.18 V and successfully boosted output to 3.3 V.20 Without using capacitors, Thomas et al. connected an MFC directly with a transformer and boosted output voltage to 1.7−3.3 V.50 As discussed in section 2.2, charge pumps can also be used to connect low-voltage MFCs/BESs and the boost converter. A comparative study showed that a charge pump-capacitorconverter PMS had a higher energy efficiency (5.33%) than a capacitor-transformer-converter PMS (4.29%), but it also 3273 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology therefore the efficiency is low. Great efforts have been made in the MPPT techniques which can successfully track the maximum power production of MFCs in real-time, such as perturb and observe (P&O) method, partial OCP method, and multiunit method, etc.11,15,62 An MPPT technique not only maximizes the power production of MFCs, but also reduces the start-up time and increases exoelectrogenic activity and Coulombic efficiency.63 Moreover, the control of MPPT can be applied on each MFC separately to achieve a high stack voltage without the issue of voltage reversal.64 However, traditional MPPT techniques still adjust external resistances to demonstrate the power production potential with no actual energy harvested. To actually use the MPPT real time tracking and produce usable energy, Park and Ren built a hysteresis controller based MPPT energy harvesting system, which can track the MPP and maintain the energy harvesting at the peak level in real-time.12 Degrenne et al. developed an original converter system which contains a voltage controller for maintaining the input voltage at the maximum power production stage.65 Based on the real-time MPPT, a maximum power point circuit (MPPC) was developed to control a BES at any operation point along the power density curve, especially at the MPP for MFC operation.40 This is a new energy harvesting approach that not only can capture the maximum power from an MFC, but also harvest energy actively without using any external resistance. Compared with traditional circuits using capacitors or charge pumps, which passively receiving electrons from the reactor, this controller can actively extract energy from the MFC at any operating point, especially at the peak power point to maximize energy production. Using this active approach, the MPPC extracted 76 times more energy than the commonly used Seiko charge pump, and the Coulombic efficiency increased by 21 times.40 Despite this dramatic improvement, the efficiency of this diode-based boost converter was only about 36% with nearly 60% of energy lost, which means much more potential can be tapped. Follow-up studies showed that by replacing the diode with a P-channel MOSFET or using a newly designed synchronous flyback converter, the efficiencies were improved by 37.6% and 73.0%, respectively.15,59,60 The effects of inductance, duty ratio, and switching frequency on these power electronic converters for MFC energy extraction have also been investigated, and results indicated that these factors play important roles for the performance of MFC and energy harvesting, and their effects can be cross-linked. While current and voltage are generally proportional and inversely proportional to the inductance, respectively, the total harvested energy and efficiency vary significantly by combinations of duty ratio and switching frequency.66 perspective and stimulate more interests and research activities, we think the following areas will require more investigations: 1. The main challenge for MFC harvesting circuit or PMS design is to build an efficient system that can operate at the low-level voltage/energy supplied by MFCs yet support high-level voltage/energy electronic devices. Energy loss inevitably happens during each conversion process, so it is imperative to develop a circuit with an acceptable complexity but with high efficiency. This is especially critical for long distance distributed power applications such as benthic MFCs, because the transmission loss can be significant. So far, almost all PMSs developed for MFCs are discrete circuits that are built with various electric components, which lead to low efficiency. Integrated circuits (ICs) or chips have been commonly used in all common electronic devices nowadays due to their small volume, low cost, low energy consumption, and quick switch among components, so developing ICs for MFC energy harvesting should be a primary task. This would inevitably need interdisciplinary collaboration, and some groups have already started creating the high efficiency and high performance ICs for MFCs16,67 or adopting commercially available IC energy harvesters.68 2. Another main challenge for many developed PMS circuits is that they are not autonomous, which means that they require an external power source to either jumpstart or operate the circuit for energy extraction from MFCs. Although the circuit has a better controllability when supplied by an external power, this is not considered sustainable especially for stand-alone sensor-type systems. SMFC-powered PMSs for monitoring environmental parameters can become autonomous when intermittent operation is possible, which allows long energy harvesting time. Reactor type MFCs used in wastewater treatment and other applications are generally capable of maintaining the PMS operation due to their scale, but the direct voltage or current from the MFC may not always meet the minimum requirements of the circuits to carry out tasks continuously, and inverters requiring grid frequency or voltage maybe needed for practical applications. To solve this problem, the MFC energy output and the PMS operational requirement should be carefully evaluated, and more importantly, self-starting and self-powering systems need to be developed. Several recent studies have reported such systems, which require either a small jump start57 or no extra power16,61,65,67,69,70 for self-sustaining operation. The two key factors to develop self-sustaining PMSs are effective energy harvesting strategies and low-power consuming circuits. On one hand, MPPT function might be integrated in the PMSs to dynamically maximize the energy harvesting in real time; on the other hand, the PMSs should be managed effectively with minimum power consumed. Further studies are still required to improve the system efficiency, lower the start-up voltage, shorten the start-up time, investigate long-time performance and robustness, implement pilot-scale and full-scale studies on field, etc. 3. More on the evaluation of energy harvesting efficiency, we think quantitative methods need to be developed similar as general MFC parameters like Coulombic 3. CHALLENGES AND PERSPECTIVES The generation of practically usable power is a critical milestone for further MFC development and application, and how to effectively and efficiently harvest and utilize MFC’s energy remains a key challenge. This review discusses the different methods and systems that have been developed for MFC energy extraction and conditions for practical use, but it is very clear that more work needs to be done to optimize the design, improve harvesting efficiency, and reduce the cost. We consider this is a main bottleneck for MFC application and should be a new frontier of MFC research. To put it into 3274 DOI: 10.1021/es5047765 Environ. Sci. Technol. 2015, 49, 3267−3277 Critical Review Environmental Science & Technology efficiency. To optimize capacitor charging, an MFC tester (MFCT) was developed to determine the optimum capacitor sizes, charging/discharging potentials, the frequency of charging, the limiting electrode and even the optimum size of the electrodes required to power a particular sensor.26 It is also necessary to optimize each component in the circuit to accommodate different MFC capabilities. Wu et al. explained how to determine the value of each component for a voltage boost circuit design.57 In literature, there are two ways to calculate energy harvesting efficiency (η) (eqs 2 and 3). η1 = η2 = Eoutput EMFC Eoutput E input × 100% (2) × 100% (3) where Eoutput is the energy applied on the electronic devices or the energy output at the final step of PMS; EMFC is the energy produced by MFC only; Einput is the total energy input into the system including energy produced by BES and the extra energy added on the circuit; Many studies used eq 2 to calculate energy harvesting efficiency, but it actually presents the energy loss through the PMS or harvesting circuit, so η1 cannot reflect the overall energy harvesting efficiency when extra power is supplied. Instead, eq 3 is suggested to replace EMFC with Einput to present the total energy added on the whole system. If no extra energy is supplied on the circuit, the two calculations can be the same, that is η1 = η2. Therefore, η1 focuses on the efficiency of the energy harvesting circuit, while η 2 is to emphasize the importance of net energy harvesting. 4. The scale up of MFC/BES technology has been largely focused on the reactor itself, while current PMS has primarily focused on benthic MFCs and sediment MFCs because such devices could meet the lower demand of remote sensors in practical operations.22,48,49,71−73 Though the efficiency can be low and a long charging time is required, it is still acceptable since most sensors do not need to work continuously. However, for wastewater treatment and bioremediation, multiple MFC units have to be connected as stacks in order to obtain a higher treatment efficiency and applicable power output, which requires high efficiency power harvesting systems. The development of MFC stacks has been very challenging, because the efficiency of MFC stacks was low and the performance was not stable due to the nonlinear nature of MFCs. Unlike traditional fuel cell stacks, which depend on stable chemical reactions in each unit to provide a higher system voltage output, MFCs rely on relatively unstable microbial activity to provide potential and current outputs. The microbial activity and resulted voltage output are very sensitive to environmental and operation condition changes and can fluctuate significantly. Moreover, the overall performance of an MFC-stack is generally limited by the worst performing unit(s), resulting in a reduced efficiency.23 One solution for obtaining and maintaining power output from MFC stacks is to connect each MFC unit with a separate energy harvesting controller and then make different combinations of these pairs as needed.71 ■ Each active harvester stores the captured energy in a common reservoir. Once enough energy is captured in the reservoir, a separate boost converter can readily generate an appropriate voltage for the load. Connecting MFCs through controllers allows real-time tracking and harvesting capability, and the power output can avoid the issue of voltage reversal. If necessary, individual units can be simply removed from the stack without affecting other units and the overall system performance. 5. While most research focuses on system development, little is known that how energy harvesting will change microbial activity and community. While passive harvesting using charge pumps or capacitors may not affect such parameters much because these devices just receive whatever amount of power provided by the MFC without controllability, power electronics converters use pulse-shaped power extraction in high frequency may lead to microbial community shifts and electron transfer mechanism changes. Our preliminary results support the hypothesis that microbial activity, biofilm viability, and mix culture community may shift and evolve during active power extraction. Such process creates a selective pressure on the microbial community to regulate respiratory pathways for more efficient electron transfer and ATP synthesis. Specifically, cells with multiple extracellular electron transfer mechanisms may shift their mechanisms to more efficient pathways, such as from mediated indirect transfer to direct transfer, while bacteria with more efficient electron transfer mechanisms in a mixed culture may outcompete less efficient species as they are more likely able to meet the requirements of high rate electron delivery. This will be a very interesting topic to investigate. AUTHOR INFORMATION Corresponding Author *Phone: (303) 492-4137; fax: (303) 492-7317; e-mail: jason. [email protected]. Notes The authors declare no competing financial interest. ■ ACKNOWLEDGMENTS We thank the financial support from Dr. Linda Chrisey at the Office of Naval Research (ONR) under Award N000141310901. ■ REFERENCES (1) Wang, H.; Ren, Z. J. 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