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Article
Renewable Coffee-Waste-Derived Porous Carbons as Anode
Materials for High-Performance Sustainable Microbial Fuel Cells
Yu-Hsuan Hung, Tzu-Yin Liu, and Han-Yi Chen
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.9b02405 • Publication Date (Web): 07 Aug 2019
Downloaded from pubs.acs.org on August 20, 2019

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Renewable Coffee-Waste-Derived Porous Carbons
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as Anode Materials for High-Performance
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Sustainable Microbial Fuel Cells
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21 Yu-Hsuan Hung †, Tzu-Yin Liu,* ‡ and Han-Yi Chen* †
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24 Department of Material Science and Engineering, National Tsing Hua University, 101, Sec. 2,
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26 Kuang-Fu Road, Hsinchu 30013, Taiwan.
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30 Institute of Bioinformatics and Structural Biology & Department of Life Science, National
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32 Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan.
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35 *Corresponding author. E-mail: hanyi.chen@mx.nthu.edu.tw (Prof. Han-Yi Chen);
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38 tzliu@life.nthu.edu.tw (Prof. Tzu-Yin Liu).
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41 KEYWORDS: Microbial fuel cell, Activated carbon, Porous structure, Coffee waste, High power
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43 density
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47 ABSTRACT
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51 Microbial fuel cell (MFC) is a sustainable technology that can produce electrons using microbes.
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53 However, low power density and high cost are the two major issues that hamper the development
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55 of MFCs. In this study, we demonstrated that renewable coffee-waste-derived activated carbons
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3 (CWACs) can serve as anode materials in Escherichia coli system-based MFCs. By modifying the
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6 CWAC pore size, we achieved a power density of 3927 mW m−2, which was higher than that of
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8 commercial activated carbon (975 mW m−2). The enhanced power density of the CWAC was
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10 attributed to its high conductivity and suitable pore size distribution, which led to fast electron
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transfer and bacterial adhesion. Furthermore, the long-term performance of the MFC with the
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15 CWAC anode was investigated; it continuously functioned for more than 100 h at a power density
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17 of 2000 mW m−2 without any further nutrient resupply. These results indicate that CWAC is a
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promising anode material for renewable and sustainable energy systems that could significantly
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22 reduce the device cost.
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INTRODUCTION
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28 Microbial fuel cell (MFC) is a promising sustainable technology that can directly transform
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30 chemical energy into bioelectricity.1 The applications of MFCs in wastewater treatment,2 hydrogen
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production,3 and small electronic devices4 have drew widespread attention. However, their low
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35 power densities have been a major bottleneck that need to be addressed to meet the rapidly growing
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37 energy demands. In an MFC, active microorganisms in the anode compartment oxidize organic
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39 substrates and produce electrons. Oxygen is then reduced into water by electrons and protons at
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42 the cathode.5 Therefore, the electron transfer abilities of the electrodes significantly affect the
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44 power output as shown in Figure 1 (a).
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46 The main types of anode materials developed for MFCs are commercial carbon materials, such
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as carbon cloth, carbon paper, and graphite felt.5-6 Recently, researchers have attempted to improve
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51 the performances of MFCs by modifying the anodes (Table 1). For instance, Fan et al. reported
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53 an MFC with a maximum power density of 560 mW m−2 by utilizing functionalized multi-walled
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carbon nanotubes (MWCNTs) on carbon cloth, which enhanced biofilm formation and electron
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3 transfer.7 Furthermore, nanocomposites consisting of CNTs and metal oxides have been
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6 demonstrated to be beneficial. Mehdinia et al. showed that addition of SnO2 into MWCNTs on
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8 glassy carbon enhanced the power density to 1421 mW m−2.8 Another method of modification
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10 involves the use of conductive polymers. For example, Kumar et al. synthesized a reduced
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graphene oxide (rGO)/polypyrrole (PPy) composite catalyst for a carbon cloth electrode; the
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15 maximum power density achieved was almost three times higher than that of the unmodified
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17 carbon cloth electrode.9 In addition, Li et al. achieved an excellent power density output of 3800
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mW m−2 by using CNTs with poly(bisphenol A-co-epichlorohydrin) (PBE) as the anode.10
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22 However, the high costs of CNT and rGO anode materials, and the Pt cathode catalyst for oxygen
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24 reduction limit their commercial viability.
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26 Activated carbon (AC) is a cheaper alternative anode material for MFCs because of its high
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29 surface area (500 − 3000 m2 g−1) and electrical conductivity, low-cost characteristics, and high
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31 performance. An anode fabricated by rolling Fe3O4 into AC on stainless steel mesh (SSM)
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33 increased the maximum power density by 22% compared to that with only AC on a SSM. 11 The
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power density of an acid-treated AC fiber felt has been reported to be 2066 mW m−2.12 Notably,
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38 the predominant pores in those commercial ACs are micropores (< 2 nm) or mesopores (2 − 50
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40 nm). According to Jiang et al., macroporous (> 50 nm) materials can increase the bacterial loading
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capacity, resulting in high power density.13 Therefore, here we propose a new sustainable anode
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45 material, coffee-waste-derived AC (CWAC), for MFCs. The consumption of coffee has
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47 skyrocketed as the population of coffee drinkers has been continuously growing all over the world.
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49 Because of high coffee consumption, six million tons of spent coffee grounds are generated per
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52 year.14 Therefore, utilization of coffee-waste-derived porous carbons as renewable electrode
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54 materials not only lowers the MFC cost but also reduces the waste. In this study, we tuned the pore
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3 size of the CWAC by varying the ratio of coffee waste to activating agent to increase the bacterial
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6 loading capacity. The Escherichia coli (E. coli) system-based MFCs with CWAC electrodes
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8 exhibited significantly enhanced electrochemical performances after activation compared to those
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10 before activation and commercial AC anode. Moreover, instead of using the expensive Pt cathode
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catalyst, we utilized a low-cost and high-surface-area commercial AC (832.06 m2 g−1) as a catalyst.
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15 Many studies have pointed out that AC can be used not only as the catalyst support but also as the
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and the performance of AC is even better than Pt as the cathode material for
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MFC.17-18 AC provides high porosity and specific surface area, and the defects or functional groups
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22 on AC generated from the activation and carbonization processes can be the catalyst reaction sites
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24 at which facilitate the oxygen reduction reaction.15, 19
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40 Figure 1. Schematics of (a) MFC functionality and (b) CWAC synthesis.
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3 Table 1 Comparison of Escherichia coli (E. coli) system-based MFCs fabricated in this study and
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those reported in the literature.
6 Power
Electrode Bacterial
7 Anode Cathode Device Density Ref.
Area Strains
8 (mW m-2)
9 100 mL single
CNT/PBEa carbon felt Pt/carbon paper 9 cm2 E. coli DH5α 3800 10
10 chamber
11 PPy/ SrFe12O19 200 mL two
Carbon cloth 2 cm2 E. coli 3317 20
12 nanofibers/nonwoven chamber
13 Al-alloy mesh/carbon Al-alloy 155 mL two
31.5 cm2 E. coli 51534 2966 21
14 cloth mesh/carbon cloth chamber
15 E. coli ATCC 127 mL two
Graphene/SSM Carbon paper 1 cm2 2688 22
16 25922 chamber
17 N-doped Ni/carbon 40 mL two
N-doped Ni/carbon fiber 4 cm2 E. coli K12 2496 23
18 fiber chamber
19 Sn/Pt/MWNT/carbon Sn/Pt/MWNT/carbo 250 mL two 24
/ E. coli DH5α 2470
20 paper n paper chamber
rGO/PANIb/Pt/carbon E. coli ATCC 10 mL two
21 Pt/carbon cloth 1.5 cm2 2059 25
cloth 27325 chamber
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candle soot derived candle soot derived 50 mL two
23 0.78 cm2 E. coli K12 1650 26
AC/SSM AC/SSM chamber
24 E. coli 75 mL two
25 rGO/ SnO2/carbon cloth Pt rod 6 cm2 1624 27
ATCC11775 chamber
26 100 mL single
27 SiO2 spheres/carbon felt Pt/air cathode 9 cm2 E. coli 1606 28
chamber
28 MWCNTs/SnO2/glassy E. coli 120 mL two
29 Pt rod / 1421 8
carbon ATCC11775 chamber
30 E. coli ATCC 10 mL two
31 rGO/PPy/carbon cloth Pt/carbon cloth 1.5 cm2 1068 9
27325 chamber
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Fe3O4/CNT/carbon paper Pt/carbon cloth 1 cm2 E. coli K12 830 29
33 chamber
34 MWCNT-COOH/carbon 120 mL single
Pt/air cathode 19.6 cm2 E. coli K12 560 7
35 cloth chamber
36 18 mL single
PANc/graphite Pt/carbon paper 2 cm2 E. coli 30.7 30
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38 Coffee waste derived Commercial 40 mL single This
1 cm2 E. coli DH5α 3927
39 AC/carbon cloth AC/carbon cloth chamber work
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40 PBE: Poly(bisphenol A-co-epichlorohydrin), bPANI: polyaniline, cPAN: polyacrylonitrile
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44 EXPERIMENTAL SECTION
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Preparation and Characterization of CWACs
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49 Coffee waste was collected from a coffee shop in Taiwan. First, as shown in Figure 1 (b), the
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51 collected coffee waste was washed with distilled water, filtered, and dried to remove impurities.
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Next, the dried coffee waste was mixed with a saturated KOH solution for one day with different
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3 performed at 900 °C for 1 h under a nitrogen atmosphere. Eventually, the obtained products were
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6 washed with distilled water to remove the residual KOH (until pH 7) and ball milled for 24 h to
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8 obtain powders. The obtained powder samples were accordingly labelled CWAC0 (coffee waste :
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10 KOH = 1:0), CWAC1 (coffee waste : KOH = 1:1), CWAC5 (coffee waste : KOH = 1:5), and
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CWAC10 (coffee waste : KOH = 1:10).
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15 The surface areas and pore size distributions of the CWAC samples were determined by
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17 the Brunauer–Emmett–Teller (BET) analysis from the N2 adsorption–desorption isotherms
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obtained at 77 K using an ASAP 2020 instrument (Micrometric Corp.). Field-emission scanning
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22 electron microscopy (FE-SEM, SU-8010) was performed to observe the morphologies of the
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24 CWAC samples. The crystallinity and degree of carbonization of the samples were determined by
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26 X-ray diffraction (XRD, D2 Phaser diffractometer) with the Cu Kα radiation (wavelength = 0.154
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29 nm) and Raman spectroscopy with a 532 nm laser excitation source (Micro Raman Spectromete,
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31 RAMaker, PTT), respectively. High-resolution X-ray photoelectron spectroscopy (HR-XPS,
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33 ULVAC-PHI PHI 5000 Versaprobe II) with an Al Kα source was employed to characterize the
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elemental contents and bonding states.
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38 MFC Set-up
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40 A single-chamber air-cathode MFC with an inner volume of 40 mL was constructed as shown in
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Figure 1 (b). The anode was 1 cm2 carbon cloth substrate coated with a 10 mg CWAC active layer.
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45 The coated layer was prepared by mixing CWAC, conductive carbon black (Super P, Alfa Aesar),
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47 and polyvinylidene difluoride (PVDF, Arkema, Kynar HSV 900) binder in n-methyl-2-pyrrolidone
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49 (NMP, 6 wt%, ACROS Organics, ≥ 99.5%) solvent with a weight ratio of 80:10:10. The resulting
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52 slurry was then coated onto a carbon cloth and dried at 80 °C overnight. The air cathode comprised
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54 a carbon cloth substrate and commercial AC catalyst (HOMYTECH CO., LTD., G03-Y200-1K,
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3 BET surface area = 832.06 m2 g−1, see Figure S2, 10 mg cm−2). The catalyst was coated by the
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6 same method used for anode fabrication. The two electrodes were separated with a Nafion 117
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8 membrane. Carbon clothes were purchased from CoTech Co., Ltd., and Nafion 117 membranes
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10 (Alfa, 0.18 mm thick, 1.5 cm2) were bought from ECHO Chemical Co., Ltd. The Luria-Bertani
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(LB) medium (10 g L−1 yeast extract, 5 g L−1 Bacto Peptone, and 10 g L−1 NaCl, adjusted to pH
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15 7.) is used for the growth of E. coli DH5α . A 20-μL overnight bacterial preculture was added to
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17 40-mL LB medium (OD600 = 2~3) in a 50-mL Erlenmeyer flask and incubated at 37 °C for 16 h
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with shaking at 200 rpm. The anodes were also incubated together with the cell culture. After
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22 incubation, the anodes and the cell culture medium were transferred to the single-chambered MFC
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24 devices as shown in Figure 1(a). For microbe fixation on the CWACs, the anodes were first
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26 washed with distilled water and then immersed in 25% glutaraldehyde (Alfa, A17876) at 4 °C for
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29 3 h. After fixation, the samples were dehydrated using ethanol solutions with increasing
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31 concentrations: 30, 50, 70, 80, 90, and 99.5% for 15 min each.31 Subsequently, the samples were
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dried with supercritical CO2 using a semi-automatic critical point dryer (Tousimis, SAMDRI® -
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36 795). Finally, the dried samples were coated with platinum. The surface morphologies of the
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43 Electrochemical Measurements on MFC
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45 Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were
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47 performed using a three-electrode cell system. The CWAC anode, Ag/AgCl in saturated KCl
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50 (0.197 V vs. SHE), and a Pt wire were used as the working, reference, and the counter electrodes,
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52 respectively. The CV curves were recorded from −0.9 V to 0.9 V at a scan rate of 10 mV s−1, and
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54 the EIS profiles were recorded in the frequency range from 100 kHz to 100 mHz with a sinusoidal
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3 excitation signal of 10 mV. The polarization curves and power density (P) data were obtained by
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6 linear sweep voltammetry (LSV) at a scan rate of 1 mV s−1 from open circuit voltage (OCV) to 0
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8 mV with a two-electrode cell system where the anode was CWAC and cathode was commercial
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10 AC; the power density was calculated as cell voltage (V) × current density (I). Both I and P were
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13 normalized to the working area of the anode. In addition, the long-term performance was also
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15 evaluated in the same construction. After the first discharging, the MFC was rested for 2 h to
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17 restore the electricity and then discharged again. This step was repeated several times up to 5 days
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without nutrient refreshment. The electrochemical tests and data acquisition were performed with
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26 RESULTS AND DISCUSSION
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29 Material Characterization of CWACs
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31 CWACs with different ratios of coffee waste to KOH weight were successfully prepared by the
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33 KOH-activated process, and their morphologies were observed by SEM. The SEM images in
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36 Figure 2 shows several micropores on the surface of the particles, which were activated by KOH.
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38 For CWAC5, some mesopores with diameters ~50 nm are observed on the particle surface. In the
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40 case of CWAC10, micropores on the particle surfaces are not distinct; however, the particles
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appear to be curved, indicating that the macropores were formed during ball milling when the
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45 particles were crushed into small pieces. The BET analysis results in Figure 3 show that the
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47 amount and the size of pores can be modified by adjusting the amount of KOH used. The pore size
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49 increases following the increased amount of KOH. CWAC1 and CWAC5 show steep slopes at
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52 low relative pressures, corresponding to narrow micropores. In addition, these samples exhibit
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54 obvious H4-type (IUPAC classification) hysteresis loops , which are often observed for micro-
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3 mesoporous carbon materials.32 The specific surface areas and pore volumes of the CWAC
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6 samples are listed in Table 2. Among the samples, CWAC1 exhibits the highest surface area (428
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(c), the pore size and the quantity of macropores for CWAC5 are higher than those for CWAC1.
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CWAC10, the addition of large amounts of KOH causes corrosion of most of the carbon surface,
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22 resulting in a low specific surface area.
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25 (a) CWAC0 (b) CWAC1
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500 nm 500 nm
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(c) CWAC5 (d) CWAC10
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32 Figure 3. (a) Nitrogen adsorption/desorption isotherms, (b) micropore distribution, (c)
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34 meso/macropore distribution, and (d) pore volume distribution plots of coffee-waste derived
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37 activated carbon.
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40 Table 2. BET surface area and pore parameters of coffee-waste derived activated carbons
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42 SBET (m2 Daverage pore Vmicro (cm3 Vmeso (cm3 Vmacro Vtotal (cm3
43 g-1) (nm) g-1) g-1) (cm3 g-1) g-1)
44 CWAC0 18.97 23.21 0.00663 0.00734 0.00796 0.02193
45 CWAC1 428.00 7.95 0.14388 0.02239 0.01110 0.17737
46 CWAC5 164.33 16.94 0.05861 0.01042 0.01118 0.08021
47 CWAC10 3.58 15.43 0.00000 0.00516 0.00572 0.01088
48 SBET: BET specific surface area, Daverage pore: average pore diameter, Vmicro: micropore volume,
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Vmeso: mesopore volume, Vmacro: macropore volume, Vtotal: total pore volume
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The CWAC samples show similar XRD patterns (see Figure 4 (a)). The patterns contain two
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3 defects. The carbonization degrees of CWACs were analyzed by Raman spectroscopy, as shown
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6 in Figure 4 (b). The ratio of D-band to G-band intensity (ID/IG) indicates the carbonization degree
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8 of a carbon material. The higher the ID/IG value, the higher the distortion of sp2 rings in the carbon
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10 material.35 The calculated ID/IG ratios for all CWAC samples are close to 1. Moreover, the ID/IG
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ratios for CWAC5 and CWAC10 are smaller than those for CWAC0 and CWAC1, indicating that
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36 Figure 4. (a) XRD pattern and (b) Raman spectra of coffee-waste derived activated carbons.
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39 The chemical states of functional groups and carbon bonding characteristics were analyzed by
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41 XPS. As seen in Figure 5, the C 1s peak can be considered a contribution of several peaks. The
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43 dominant peaks at 284.4 ± 0.1 eV and 285 ± 0.2 eV can be attributed to the graphitic structure (sp2
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46 C=C) and hybridized carbon (sp3 C-C), respectively.36-37 The small peaks centered at 286 ± 0.2,
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48 287.4 ± 0.2, and 288.8 ± 0.2 eV are assigned to the phenolic groups (C-O), carbonyl groups (C=O),
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50 and carboxyl or ester groups (O-C=O), respectively.38 From Table 3, sp2 percentages for CWAC5
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(68.19%) and CWAC10 (68.61%) are higher than those for CWAC0 (55.00%) and CWAC1
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3 (48.39%), indicating that CWAC5 and CWAC10 possess higher proportions of the graphitic
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6 structure. This is consistent with the Raman result discussed earlier.
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37 Figure 5. XPS C 1s profiles of (a) CWAC0, (b) CWAC1, (c) CWAC5, and (d) CWAC10.
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40 Table 3. Surface components of coffee-waste-derived activated carbon.
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42 C 1s (at%) O 1s (at%) N 1s (at%) C-C (%) C=C (%) C-O (%) C=O (%) O-C=O (%)
43 CWAC0 80.41 16.59 3.01 18.32 55.00 16.97 7.83 1.87
44 CWAC1 82.24 15.52 2.24 22.88 48.39 15.73 8.14 4.85
45 CWAC5 87.54 10.10 2.36 17.61 63.19 8.74 6.03 4.42
46 CWAC10 80.94 16.10 2.96 12.97 68.61 9.10 5.48 3.84
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Electrochemical Performances of CWACs in MFCs
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52 CV was performed to determine the electrochemical activities of the CWAC electrodes before and
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54 after inoculation with E. coli, as shown in Figure 6. The CV curves before inoculation are nearly
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3 rectangular, implying double layer capacitive properties of the CWACs.39 After inoculation,
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6 CWAC5 and CWAC10 exhibit oxidation peaks; however CWAC0 and CWAC1 do not show any
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8 apparently differences. To further investigate the contribution of the colonization of E. coli to the
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10 MFC, the integrated areas of each CV curves were used to calculate the capacitance.40 The
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increased amounts of integrated area in different CWAC electrodes were also shown in Figure 6.
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15 The integrated curve areas of CWAC5 and CWAC10 were increased by 53.9% and 41.7% after
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in CWAC5, and the semi-curved surfaces of CWAC10 particles, providing a better surface
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22 environment for bacterial adhesion.13 SEM was performed on the CWAC anodes after bacterial
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24 inoculation to confirm this notion. The rod-like E. coli bacteria attached onto the CWAC particle
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26 surfaces form biofilms on the CWAC anodes as shown in Figure 7. For comparison, the SEM
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29 image of E. coli on the surface of a plain carbon cloth anode is shown in Figure 7 (a); the surface
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31 area of the plain carbon cloth is much smaller than those of the CWACs, thus limiting the bacterial
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33 load. As observed in Figure 7, the numerous evenly distributed E. coli can be observed in yellow
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on the surface of the CWAC5 anode. By comparison, less amount of microbes, which are
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38 aggregated in certain areas, are observed on the surfaces of CWAC1 and CWAC10 anodes. Fewer
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40 microbes are observed on the CWAC0 anode surface compared to those on the surfaces of the
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other anodes. The low-magnification SEM images of the anodes are shown in Figure S1. The
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45 presence of numerous microbes on the surface of CWAC5 can be explained on the basis of the
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47 pore size distribution. CWAC5 consists of numerous macropores and meso/micro pores, providing
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49 suitable surface roughness for bacterial attachment. Moreover, CWAC5 exhibits the highest
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52 oxidation current among all the CWAC anodes, as shown in Figure 6 (b). This indicates that the
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54 electron transfer ability of microbes on the CWAC5 anode is higher than those on the other CWAC
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36 Figure 6. Cyclic voltammograms obtained at 10 mV s−1 for (a) CWAC0, (b) CWAC1, (c)
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38 CWAC5, and (d) CWAC10 electrodes before and after inoculation in the potential range from −0.9
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40 V to 0.9 V versus Ag/AgCl reference electrode.
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23 Figure 7. SEM images of E. coli on (a) carbon cloth, (b) CWAC0, (c) CWAC1, (d) CWAC5, (e)
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25 CWAC5 (enlarged), and (f) CWAC10 anode surfaces.
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28 To investigate the electron transfer ability for the different CWAC anodes, EIS was performed
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30 in the three-electrode mode after incubation. The Nyquist plots are shown in Figure 8 and the
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33 equivalent circuit model is given as an inset in Figure 8 (a), where Rs, Rct, C and Zw represent the
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35 equivalent series resistance, the charge transfer resistance, the capacitance, and the Warburg
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37 diffusion impedance, respectively.41 The fitted results were simulated using the Zview software.
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40 The Rs values—the combined electrolyte, substrate, and contact resistances42—are 21.25, 19,
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42 12.22, and 9.57 Ω for CWAC0, CWAC1, CWAC5, and CWAC10, respectively (Table 4),
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44 indicating that CWAC5 and CWAC10 have lower electrode resistances than CWAC0 and
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CWAC1. These results can be attributed to the presence of higher fractions of graphitic structure
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49 in CWAC5 and CWAC10, as revealed by Raman and XPS analyses. In addition, CWAC5 exhibits
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51 a significantly lower Rct value (0.19 Ω) than CWAC0, CWAC1, and CWAC10 (1.53, 0.67, and
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53 1.08 Ω, respectively). This indicates that the anodes with sufficient active biofilms exhibit
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20 Figure 8. Electrochemical impedance spectroscopy results: (a) Nyquist plots for CWAC anodes
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22 after inoculation and (b) magnified plots for CWAC1, CWAC5, and CWAC10.
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25 Table 4. Internal resistance components of MFCs with different CWAC anodes
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27 CWAC0 CWAC1 CWAC5 CWAC10
28 Rs (Ω) 21.25 19.00 12.22 9.57
29 Rct (Ω) 1.53 0.67 0.19 1.08
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33 Performances of MFCs with Various CWAC Anodes
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35 The polarization curves and power density data for single-chamber MFCs with different CWAC
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37 anodes and commercial AC air cathode were obtained by LSV at a scan rate of 1 mV s −1 from
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40 OCV to 0 mV, as displayed in Figure 9 (a) and (b), respectively. For comparison, a commercial
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42 AC was utilized as the anode control group. As observed, the MFC with the CWAC5 anode
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44 exhibits a maximum power density of 3927 mW m−2, which is 4 and 2.5 times higher than those
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47 of the MFCs with the commercial AC anode (975 mW m−2) and inactivated CWAC0 anode (1568
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49 mW m−2), respectively. In addition, the maximum power densities for MFCs with CWAC1 and
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51 CWAC10 anodes are 3445 mW m−2 and 3399 mW m−2, respectively, which are higher than that
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for the MFC with the CWAC0 anode. This demonstrates the importance of porous structures for
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3 that ACs with mostly macropores as well as some meso/micropores are ideal for bacterial
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6 adsorption.43 Unlike the high-surface-area commercial AC (Figure S2) and CWAC1 with
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8 predominant microporous structures, and low-surface-area CWAC0 and CWAC10 with smooth
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10 surfaces, CWAC5 consists of mostly macropores and some meso/micropores, thus exhibits
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suitable surface roughness for bacterial attachment, as discussed above. Furthermore, CWAC5 has
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15 a higher proportion of the sp2 graphitic structure with lesser defects than CWAC0 and CWAC1,
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17 leading to higher electrical conductivity. The superior bacterial attachment ability and the higher
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electrical conductivity of the CWAC5 anode compared to those of the other CWAC anodes lead
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22 to a better electron transfer ability, contributing to larger power and current output. Notably, the
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24 MFC fabricated with the CWAC5 anode and a commercial AC cathode in this study exhibits
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26 higher power density than the previously reported MFCs based on E. coli bacterial systems (Table
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29 1). These results demonstrate that the low-cost, environmentally-friendly biowaste-derived
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31 CWAC is a promising anode material for the high-power-generating MFC system, which is
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33 compatible with the strategies of circular economy for sustainable energy production.
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In addition, the long-term performance of the MFC with the CWAC5 anode was evaluated as
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38 shown in Figure 9 (c) and (d). The MFC with the CWAC5 anode was discharged after inoculation
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40 followed by a 2-hour rest without nutrient-solution refreshment.44 After inoculation, the OCV
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reaches 945 mV and then stabilizes at about 600 mV after operation for one day. The maximum
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45 power density also exhibits the same tendency; it reaches 3927 mW m−2 and remains constant at
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47 about 2000 mW m−2. Notably, the MFC with the CWAC5 anode can operate for additional 4 days
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49 without further nutrient supplement and stabilize at 2000 mW m−2. The observation that both the
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52 OCV and the power density gradually decreased but not completely vanished may result from a
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54 certain population of E. coli able to survive the stationary phase under the nutrient-limiting
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3 environment before entering death phase.45 Usually after 24 hours of incubation, most of the
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6 bacterial cells die; however, the survivors can undergo adaptive evolution during long-term
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8 stationary phase45 and the turnover rate of E. coli eventually reaches a balance and can maintain a
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10 number of the living cells for several weeks.45-46 This reveals that E. coli-based MFC with the
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CWAC5 anode is a promising self-rechargeable system.
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45 Figure 9. Performances of MFCs with various CWAC anodes: (a) polarization curves and (b)
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47 power densities. Long-term test results of MFC with CWAC5 anode: (c) cell voltage and (d)
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49 maximum power density profiles.
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54 CONCLUSIONS
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3 In this study, the MFC fabricated with the coffee-waste-derived anode (CWAC5) exhibited
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6 considerably higher performance than previous reported E. coli-based MFCs with modified anode
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8 materials. We optimized the MFC performance by varying the weight ratio of coffee waste to the
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10 activation agent (KOH) in the anode precursor. The CWAC5 anode with a large amount of
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macropores and some mixed meso/micropores exhibited the highest power density of 3927 mW
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15 m−2 among the CWAC anodes. The surface area and pore size distribution of CWAC5 were
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17 suitable for biofilm formation, thus enhancing the electron transfer ability. In addition, a higher
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proportion of the graphitic structure in CWAC5, resulting from the carbonization process, led to
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22 improvement in the electronic conductivity. Furthermore, the MFC with CWAC5 anode exhibited
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24 a self-powering/self-recharging ability. Overall, the high performances of MFCs with CWAC
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26 anodes demonstrate the potential of CWAC for sustainable energy applications as well as the
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29 development of a green and circular economy.
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33 ASSOCIATED CONTENT
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Supporting information
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39 The supporting information is available free of charge on the ACS, including the low-
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41 magnification SEM images of E.coli on anode surface as well as the BET surface area and pore
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43 size distribution of commercial activated carbon.
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AUTHOR INFORMANTION
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49 *Corresponding author. E-mail: hanyi.chen@mx.nthu.edu.tw (Prof. Han-Yi Chen);
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51 tzliu@life.nthu.edu.tw (Prof. Tzu-Yin Liu).
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54 ACKNOWLEDGMENTS
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3 This work was financially supported by the Young Scholar Fellowship Program of the Ministry of
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6 Science and Technology (MOST) in Taiwan under grant no. MOST107-2636-E-007-007 to Dr.
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8 Han Yi-Chen and by the grant no. MOST 105-2621-M-007-001-MY3 to Dr. Tzu-Yin Liu.
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10
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24 The microbial fuel cells (MFCs) fabricated with the coffee-waste-derived activated carbon anode
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