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Renewable Energy: Jianjun Hu, Quanguo Zhang, Duu-Jong Lee, Huu Hao Ngo
Renewable Energy: Jianjun Hu, Quanguo Zhang, Duu-Jong Lee, Huu Hao Ngo
Renewable Energy
journal homepage: www.elsevier.com/locate/renene
a r t i c l e i n f o a b s t r a c t
Article history: The microbial fuel cells (MFC) can directly transform chemical energy in feed substance to electricity by
Received 30 December 2016 anodic aspiration pathways. This mini review provides an order-of-magnitude argument that MFC has
Received in revised form much lower catalyst density at electrode surface and much higher diffusional resistance for substrates
28 January 2017
than the chemical fuel cell, the former should not be used as an energy generation unit; rather, it should
Accepted 1 February 2017
Available online 4 February 2017
be applied in low power density level applications such as biofilm wastewater treatment. The literature
studies using MFC for pollution treatment are discussed.
© 2017 Elsevier Ltd. All rights reserved.
Keywords:
Microbial fuel cell
Environmental applications
Review
Technical obstacle
http://dx.doi.org/10.1016/j.renene.2017.02.001
0960-1481/© 2017 Elsevier Ltd. All rights reserved.
J. Hu et al. / Renewable Energy 129 (2018) 824e829 825
without internal resistance to be 17e19 W/m3. By assuming full without external irreversibilities as stated above, the inherent
loading of 20-layer bacterial biofilm with compact packing and a transport/reaction resistances in biofilm [19] and the biological
specific surface area of 100 m2/m3 at all electrodes, Zhang et al. [11] limit set by proton accumulation within cell membrane at high
estimated the ultimate volumetric energy generation and the po- electricity current [20,21] yields the power level “ceiling” of an
wer density as 5360 W/m3 and 53.6 W/m2, respectively. Song et al. MFC. All these natural constraints lead to the inconvenient truth
[12] applied a logic-based maximum power point tracking algo- that the MFC can only work under low energy density level
rithm for controlling the resistive load for a continuous-flow flat- applications.
plate MFC. These authors showed that by the optimal controlling
strategy the maximum power density can reach 88 W/m3. 2.2. MFC versus PEM FC for power generation
To reduce operational cost, the use of MFC to harvest energy
from waste or wastewater is recommended for future practice [13]. As an energy generation unit, however, the market competitor
An estimation of the energy contents in the wastewaters can be for MFC is the PEM FC, whose power density by its commercial
made by assuming a typical US city of population of one million version can easily reach 140 kW/m3, at a surface power density of
population equivalent with each generating 380 L sewage per day 105 W/m2. Restated, the ultimate power level by Refs. [9,10] and by
[14]. The wastewater stream has energy content of 7500 ± 100 kJ/ Ref. [11] are only 3e4 orders of magnitude lower than those pro-
m3 when all COD is converted to CO2 and H2O [9,15]. Then the total vided by commercial FC unit [2]. In this section, the PEM fuel cells
energy content in the city's wastewater is 2.8 109 kJ/d. Taking are selected as the market competitor as power generation unit
household energy consumption rate of 1 kW, this potential can which needs sufficiently high power output in use. Other low
power about (10 h/d) 79,000 houses in the city. Since the waste- power-density level applications such as the use as power sources
water is assume free of charge, then why the wastewater power is in certain sensors are not regarded “power generation unit” herein.
still not in the market? Table 1 lists an order-of-magnitude comparison between the
To make MFC a practical energy generation unit, large reactor PEM FC and MFC. The essential differences between PEM FC and
with sufficient energy output should be developed. Following the MFC are the nature of electrode catalyst: (noble) metal catalysts for
proposal by Ref. [9], numerous efforts were made to improve MFC the former and biocatalyst with exoelectrogens (or also with
performances [16]. Zhang et al. [11] demonstrated in their Fig. 2 endoelectrogens) in biofilms. The anodic catalyst in PEM FC is in the
that the power densities for liter-MFC were generally less than 1 W/ form of metal clusters of size nm2. Conversely, the catalyst in MFC is
m2. Considering a compact electrode configuration with surface counted in the unit of biological cells, whose sizes are of order mm2.
area up to 100 m2/m3, the power generation rate would be about Consider compact packings of cells (20-layers with 50 (say) cata-
100 W/m3. Fig. 1 shows the power density data versus reactor lytic sites on individual cell) in anodic biofilm or of clusters on
volume data collected from papers published in 2016 (red sym- electrode surface, the maximum catalyst concentration ratio for
bols). Those presented in Ref. [11] being shown as grey symbols for PEM FC to MFC is or order 103 (¼(mm2/nm2)/20/50). The anodic
comparison. It is clear that the studies updated to 2016 still rarely substrate for PEM FC is pure H2 and O2 gas, with product in the form
provided power density exceeding 1 W/m2 for the liter-scale MFC. of water; while that for MFC is organic matters dissolved in water.
The energy available for use is different from those existing in Therefore, there is no transport resistance for pure hydrogen gas to
the substrate [17]. Restated, the total energy (represented by free anode but the transport resistance of substrates to anode of MFC
energy) of a wastewater stream is often much smaller than the depends on the bulk mixing and the structure of biofilm consid-
available energy (represented by exergy) of the stream since to use ering the diffusivities of the dissolved organic compounds are of
the energy for powering an external device needs extraction of order 109 m2/s. Therefore, the substrate from bulk anodic solution
involved energy to a portable form, that is limited by the potential to be reacted on anode surface would experience at least 104 times
differences and all the losses by each conversion stages [18]. Even higher resistance for the MFC than for the PEM FC. On the cathode
side, if both PEM FC and MFC utilized metal catalyst on cathode, the
product of PEM FC is liquid water to be discharged directly from
cathode surface to the drains, while that of MFC is various oxidized
compound that needs to be transported to bulk cathodic solution
across a liquid film (in case of using biocathode, the transport
resistance of product across the biofilm would also come into play).
Restated, the transport resistance at PEM FC cathodic chamber for
oxidized products is principally contributed by the pressure drop in
channel with two-phase flow [22] and that for MFC is by diffusional
transport. With appropriate flow channel design for both cells,
these two resistances can be assumed of the same order of
magnitude. The proton transport resistances across the PEM should
be greater in the PEM FC than that in MFC since the former is in
partial saturation in moisture; however, the higher operational
temperature for the former compensates part of the adverse effects
by the excess resistance with partial saturated medium. The
membrane-less MFC can be operated without PEM resistance. Since
the microbes in MFC needs time to adapt to a new eco-environment
[23] while the metal catalyst in PEM FC needs no pre-adaption, the
startup time for the former (in days) is much longer than the latter
(in mins). Moreover, since the biofilm composition and architecture
Fig. 1. Power density versus anodic chamber volume data. Grey symbols: data from are very sensitive to the near-electrode environment [24,25], the
references cited in Zhang et al. (2016). Red symbols: data from studies published in
2016. Volume indicates either anodic chamber volume or total volume. (For inter-
consistency of the electrochemical characteristics of the MFC bio-
pretation of the references to colour in this figure legend, the reader is referred to the film would be much poorer than that for the electrodes in PEM FC.
web version of this article.) This concern also confines the applicability for the MFC as energy
826 J. Hu et al. / Renewable Energy 129 (2018) 824e829
Table 1
Comparisons of characteristics of MFC, PEM FC and anaerobic film reactor.
Catalyst biological cell (mm2) noble metal cluster (nm2) biological cell (mm2)
Bulk transport organics/ions in water (Ac in Pure hydrogen and oxygen. organics/ions in water (Ac in
water 25 C ¼ 1.2 109 m2/s) (O2 in air 60 C ¼ 3.4 105 m2/s) water 25 C ¼ 1.2 109 m2/s)
Substrate saturation ca. 5 A/m2 @ 0.6 V >107 A/m2 ca. 5 A/m2 @ 0.6 V
Key parameter biofilm control water management biofilm control
Consistency poor nice mediate
Substrate adaptability good poor good
Operation condition room temperature/pressure 60e90 C and 3e5 atms room temperature/pressure
Cost mediate high low
Startup slow fast slow
cathode using simple rolling-press method with activated carbon and MFC systems were proposed and tested. In general, the ad-
powders and PTFE (6:1 w/w) being rolled on the stainless steel vantages of MFC and X should be highlighted in the integrating
mesh for MFC applications. system so the proposed can have the niche to use [63]. For instance,
The novel designs proposed are majorly to make MFC of prac- the integrating reactors with anoxic/aerobic batch reactor followed
tical sizes. For instance, the MFC was made by sandwich form for by a BES are applied to efficiently treat pharmaceutical wastewaters
easy scale-up [47]. Khaifbadam et al. [48] used 9.64-L MFC to treat [64]. These authors found that the power production was 536 mV
municipal wastewaters with the anode carbon felt being used as a and 1.21 mA. Integrating membrane filtration module and 345-mL
filter to remove particulates in wastewaters. Oliot et al. [49] regu- MFC was applied with granular activated carbon being fluidized
larly replaced the air-cathode of the 1.8-L MFC so the maximum across the membrane to reduce membrane fouling [65]. Sugnaux
projected power density (on cathode area) reached 1.96 W/m2 with et al. [66] used 10-L MFC followed by a 33-L microbial electrolysis
50 cm2 bioanode. Four-air-cathode MFC of 938-mL volume was cell (MEC) to cogenerate ethanol and biohydrogen. The MFC can be
applied to treat synthetic wastewater and municipal wastewater embedded into existing conventional wastewater treatment plants
[50]. for enhancing COD removal [67]. Qin et al. [68] investigated the
Appropriately designed stacks can lead to practical MFC with combined forward osmosis (FO) and MFC for treating wastewaters.
minimum engineering efforts. An et al. [51] used dual anode/ These authors measured the reverse salt flux over the FO mem-
cathode stacks (1 L each) connected in series to enlarge the MFC for brane during the treatment. A novel integrating system even
ethanolamine wastewater treatment. He et al. [52] used a 4.5-L combined two MFCs, one for short-cut nitrification and the other
MFC stack with four anodes and three two-sided cathodes to for autotrophic denitrification to remove 99.9% nitrogen at
treat domestic wastewater fed in parallel to individual anode or in 0.0125 kg-N/m3-d with energy-positive scenario. The integrating
sequence to anodes. Kim et al. [53] proposed a new design on constructed wetland reactor and an MFC (total liquid volume of
stackable MFC modules for treating synthetic wastewaters of 1.2 L) were used for removing COD from oil sewage streams (Yang
160 mg/L COD. The tested tank of 30-L volume was used for et al., 2016 [69]). With a total of 95.7% oil removed, the maximum
generating up to 41.5 mW/m2 power. Wu et al. [54] applied a 72-L power density was 102 mW/m2, higher than those using MFC alone.
MFC stacks with large PEM surface to reactor ratio, high surface However, the integrating systems may also suffer the disad-
area and enhanced adsorption by packed granular activated carbon vantages of both MFC and X if not properly designed and operated.
electrodes to treat synthetic wastewaters at 200e1200 mg/L COD. For instance, the MFC with photobioreactor for microalgal culti-
Ge and He [27] proposed the use of a 200-L modularized MFC with vation can be an option to zero-emission integrating system
96 MFC modules for removing over 75% COD in primary effluent. Ni [70,71]. Uggetti and Puigagut [72] applied an anaerobic digestion
et al. [55] tested the use of 1.5-L two-chambered MFC for treating reactor as anode and a microalgal photoreactor as cathode to
inorganic sulfur compound wastewaters. These authors noted a constitute an MFC. With coupling of these two reactors the oxygen
power density ranging 0.23e4.8 mW/m2 using different reactor/ and CO2 demand for the fuel cell can be mutually supplied, which
PEM configurations. Hiegemann et al. [56] integrated four single- enhanced microalgal biomass production rates and anaerobic
chambered membrane-less MFCs to a 45-L pilot system for treat- digestion rates. Possible applications of using photobioreactor with
ing municipal wastewaters. These authors can reach 82 mW/m2 MFC are of potential to reach aerobic wastewater treatment
(based on cathode) at 22 h HRT and at 20e30 C. Also, energy without aeration. Integrating 5.65-L single-chambered MFC and
balance calculations revealed that the addition of MFC is an energy- granular activated carbon adsorption column was proposed to treat
gain step since the excess sludge production rate and oxygen de- palm oil mill effluent at >90% COD removal with power density
mand rate were both largely reduced. 55 mW/m3 (¼2.75 mW/m2) [73]. However, the large difference in
The membrane-less MFC's are widely studied owing to the growth rates and the need of large surface to volume ratio for
lower construction costs than the conventional two-chambered photobioreactor can lead to difficulty to stable MFC operation [74].
MFC [57,58]. However, owing to the absence of an ionic mem-
brane barrier, it is difficult to hold all fed organic matters in the 4. Ways forward
anodic chamber without crossover. Kim et al. [59] employed dual
anodes in membrane-less MFC for providing additional reaction As discussed in Sec. 2, MFC should be used in applications of
surface for the pollutant to reduce its crossover. Multiple electrodes without the need of very high electrical current fluxes, such as in
in individual chambers may be a design for minimizing the in- environmental pollution control units. Nonetheless, the current
homogeneity of flow and concentration fields in large-scale MFC power density levels in pollution control units ranged
[60]. 100e1000 mW/m2 (Fig. 1), suggesting that there is still large room
Adding chemicals to mitigating the pollutant levels for regu- for performance improvements by novel design as a pollution
lating microbial activities in MFC is an active control mode for treatment unit to the “ceiling” 17 W/m3 by Ref. [10] or 88 W/m3 by
enhanced cell performance. For instance, since high levels of Ref. [12]. Efforts should be devoted to novel MFC design and
ammonium and nitrate can inhibit activities of exoelectrogens in operation strategies so the reactor performance can be further
MFC [61], the addition of 300 g/L Fe/MnO catalyst and 1000 mL/min improved in low power level applications.
O2 microbubbles can reduce ammonium and nitrate levels so the One of current trend for MFC studies is noted to apply it for
MFC can yield 2.14 mA current in operation. handling different substrate-containing wastewaters or waste
Novel operational strategy design was also proposed in MFC streams. Principally any substrate has sufficient reducing power can
studies. Wang et al. [62] proposed a novel strategy to enhance be oxidized at anode and that has oxidizing power can be reduced
heavy metal ion recovery from wastewaters. Two MFC of volume at cathode. The studies reporting not only reactor performance but
28 mL each were used and connected in parallel first for charging. also with detailed mechanism discussion should be encouraged.
Afterward, the MFC was linked to external load for discharging with Conversely, the wastewater treatment with resource recovery can
heavy metal ion recovery. be a niche approach. for instance, You et al. [75] employed the MFC
to accelerate human urine to NHþ 4 , which can be precipitated with
3.3. Integrating systems magnesium and phosphate ions to form struvite for recovery.
Liter-scale MFC has been studied. The practical version of tonne-
As reviewed by Ref. [11], the MFC þ X and X þ MFC or parallel X scale MFC should be proposed and tested with real wastewaters.
828 J. Hu et al. / Renewable Energy 129 (2018) 824e829
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