Comparative bioelectricity generation from waste citrus

fruit using a galvanic cell, fuel cell and microbial fuel cell

Abdul Majeed Khan

Muhammad Obaid
Department of Chemistry, Federal Urdu University, Gulshan-e-Iqbal Campus, Karachi, Pakistan

Abstract 1. Introduction
This article demonstrates the new approaches for Energy is the prime requirement of all sectors
the generation of bioelectricity from waste citrus including industry, transportation, agriculture and
fruit using direct a galvanic cell (DGC), an indirect domestic use without which advancement of tech-
galvanic cell (IDGC), a conventional fuel cell (CFC) nology and survival of life is not possible (Carvalho
and a microbial fuel cell (MFC). The citrus fruit was et al., 2011). Most of the energy around the world
used as whole for the preparation of DGC and their comes from non-renewable sources including:
juices for the preparation of IDGC, CFC and MFC. petroleum, coal, oil and natural gas which are being
The performance and bioelectrical parameters depleting at a high rate (Larhum, 2010). Fossil fuels
obtained were compared. The voltage found to be are the major source of global warming and pollu-
increased by increasing the number of cells in a tion due to increase in greenhouse gases, volatile
series while, the current remains constant. Whereas matter and particles in the atmosphere (Khan et al.,
the voltage remains constant and the current found 2011). However, technologies of renewable energy
to be increased with increasing the number of cells are growing worldwide that can overcome these
in parallel sequence. The power output of three drawbacks (Christi, 2007; Goff et al., 2004; Ha et
units of citrus fruit connected together in a series al., 2010). Biomass, which includes agricultural
found to be sufficient to turn on the LED light bulb crops, seeds, algae and biowastes are major sources
in all cases. The result showed that lemons have the of renewable energy that replenish themselves
maximum power output by the DGC and MFC through natural processes (Hossain and Mekhled,
method, whereas grapefruit showed the maximum 2010; Mata et al., 2010; Dincer, 2000).
power output by IDGC, and thus considered as the Bioelectricity generation is reported from waste-
best citrus fruit. Addition of NaCl solution in DGC water using a microbial fuel cell (Khan 2009, Khan
and IDGC slightly increased the values of power et al., 2010, Khan et al., 2011, Khan and Naz,
output. The power output of citrus fruit was also 2014). Lemon, orange and grapefruit are examples
determined by CFC and MFC before and after the of biomass and commonly known as citrus fruit
inoculation of Escherichia coli. The detailed micro- (Randhawa et al., 2014). They contain citric acid,
scopic analysis of all the samples was carried out. It sugar and other ingredients with sufficient chemical
is found that all MFCs have higher power output as energy that can be converted into electrical energy
compared to their counterpart CFCs. However, by means of redox reaction with a specific condition
maximum power output was displayed by DGCs. and thus be utilized as batteries to light up LEDs
Moreover, a lemon fuel cell has the higher power and power up a clock or a calculator etc. (Kelter and
output as compared to the fuel cells of other citrus Morgan, 1996; Goodisman, 2001; Swartling et al.,
fruit. This approach can be used to overcome the 1998). Under certain conditions, the citric acid con-
disadvantages of many non-renewable and conven- tained in citrus fruit may act as an electrolyte, which
tional sources of energy including burning of fossil enables the generation of electricity just the same
fuels to mitigate the major source of global warming way as a galvanic battery (Oon, 2007).
and pollution by using such biodegradable and The population around the globe is continuous-
renewable sources. ly increasing, which is demanding not only more
food but also the energy to fulfil the requirement of
Keywords: citrus fruit, bioelectricity, direct method, the latest needs and technology. Some crops may
indirect method, galvanic cell, microbial fuel cell, E. be produced and consumed for both purposes like
coli corn, sugarcane, fruit and vegetable oils. Therefore,

90 Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015

there is an urgent need to develop the food vs. fruit. A copper wire was connected to the zinc elec-
energy priority for a sustainable future. However, trode on one end and the other end was connected
the increase in crop yield with the passage of time is to one end of the electric socket. Similarly, a copper
not as per the desired level, which may increase the wire was connected to the copper electrode on one
price of food grain but on the other hand, hectors of end and the other end was connected to another
arable land is available for additional harvesting of end of the electric socket to complete the circuit.
crops for both food and fuel (energy). This manu- The voltage, current and other parameters of
script demonstrates the conversion of waste to ener- this electric circuit were determined with a digital
gy using waste citrus fruit as a source of biofeed- multimeter with a positive terminal connected to the
stock. Large quantities of waste citrus fruit are gen- zinc electrode and a negative terminal connected
erated from agricultural processes and in the retail with copper electrode. The LED was connected to
markets worldwide. This waste is often simply the circuit with zinc electrode to its short leg and
dumped into landfills or the ocean. Therefore, there copper electrode to its long leg. Then the numbers
is no doubt in easy availability and cheap prices of of citrus fruit were increased in series by connecting
such waste biofeedstock. Waste citrus fruit has suffi- the zinc electrode of one fruit to the copper elec-
cient content of acid and sugar that can be used for trode of the next fruit via copper wire using alligator
the production of bioelectricity using a galvanic cell clips. In addition to the above series combination,
and microbial fuel cell technology at a laboratory the cells were also connected in parallel sequence
scale. This will not only reduce the disposal cost of by connecting the anode electrodes (zinc) of all cells
waste but also increase a total of the production of together and the cathode electrodes (copper) of all
bioenergy with nominal investment. Moreover, the cells together. The electrical parameters were deter-
production of citrus fruit is increasing gradually and mined using the same multimeter. Afterwards, 1%
there is no evidence that the supply of citrus fruit solution (1 ml) of NaCl was injected into each fruit
will face a shortage in the near future. Therefore, and the electrical parameters were measured (see
there is no significant impact of food vs energy due Figure 1).
to the generation of bioelectricity from waste citrus
fruit. 2.3. Indirect galvanic cell (IDGC)
During this experiment, the juice of waste citrus fruit
2. Experimental (lemon, orange, grapefruit and mixed fruit), were
2.1. Materials and instruments collected into a separate glass vessel. The parame-
The materials and instruments applied during this ters of the fruit juices including pH, total dissolved
research included analytical weighing balance TE solids (TDS), water content (Karl Fisher), acid con-
3135-DS (Sartoris, Germany), digital multimeter, tent, salinity were determined and compared. The
CD771 (Sanawa, Japan), pH meter, Hi-9810 juices of citrus fruit were transferred into 1 to 4 glass
(Hanna, Rhode Island), TDS/ conductivity meter, vessels. One electrode of each metal (zinc and cop-
LF12 (Schott, Germany), Karl Fisher (Mettler, per) of dimension 5 cm x 1 cm was inserted into the
USA), Binocular Microscope, 107BN (Jinhua fruit juice distant (2 to 4 cm) to each other. A cop-
Huiyou Equipment and Instrument Co. Ltd.), incu- per wire was connected to the zinc electrode on one
bator (MMM Medcenter Einrich-tungen, Germany), end and the other end was connected to an electric
autoclave YX 280B (China), Cumber test kit socket. Similarly, a copper wire was connected to
(Roche), copper electrode, zinc electrode, LED the copper electrode on one end and the other end
(light bulb), copper electrical wire, connector, alliga- was connected to the electric socket to complete the
tor clip, fruit (lemons, oranges, grapefruit), sodium circuit. The voltage and current were noted by con-
chloride solution (1%), distilled water, potassium necting a digital multimeter. The positive terminal
chloride (KCl), volumetric flask, beaker, glass vessel, was connected to the zinc electrode and negative
container, PVC pipe and microorganism (E. coli), terminal to the copper electrode. The LED was con-
glass slide, crystal violet, Gram’s stain, safranin, nected to the zinc electrode to its short leg and the
ethanol, and a wire loop. copper electrode to the long leg of the LED bulb.
The cell units were also connected in a series and
2.2. Direct galvanic cell (DGC) parallel combination and the electrical parameters
In this experiment, four series of fruit were studied were determined using the same multimeter.
for the generation of bioelectricity. The three series Afterwards, 1% solution (1 ml) of NaCl was inject-
contain a single type of either of the waste fruit ed into each fruit juice and the electrical parameters
(lemon, orange and grapefruit) and the fourth series were measured.
contain mixed fruit arranged in alternate arrange-
ment in a successive manner. A zinc electrode of 2.4. Conventional fuel cell
dimension 5 cm x 1 cm was inserted into one side The construction of a conventional fuel cell (CFC)
of the fruit and a copper electrode of the same consists of two chambers. One is the Anodic cham-
dimension was inserted into another side of the ber containing either of the fruit juice of waste

Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015 91

 Figure 1: Bioelectricity generation by galvanic cell

lemon, orange, grapefruit and mixed fruits. The connection chambers as of CFC however, the
other is a cathodic chamber containing water in microorganism (E. coli) was added to either of the
which air was continuously pumped by an aquari- fruit juice of lemon, orange, grapefruit and mixed
um pump. The two chambers were connected with fruits filled in the anodic chamber, which was sealed
a salt bridge (25% NaCl: 75% sand). One zinc elec- to prevent the entrance of air and thus forced the
trode was submerged in the fruit juice of the anod- microorganism to aid the fermentation of the sugar
ic chamber and another electrode of copper metal contents of the fruit juice. The cell units were also
was submerged in water. The two metal electrodes connected in a series and parallel combination and
were connected together with a copper wire to com- the electrical parameters were determined using the
pete the one unit of CFC. Then the numbers of the digital multimeter for each sample.
CFC unit were increased from one to four in a series
by connecting the zinc electrode of one CFC to the 3. Results and discussion
copper electrode of the next CFC via copper wire. The drawbacks of conventional technologies of
The electrical parameters with increasing number of energy like fossil fuels which are non-renewable,
CFC units were determined using the digital multi- being depleted and also considered as the major
meter for each fruit juice (see Figure 2). source of global warming and pollution stimulated
us to conduct this research in which some basic
2.5 Microbial fuel cell (MFC) parameters to generate the electricity from citrus
2.5.1 Microscopic examination fruit including lemon, orange, grapefruit and mixed
The apparatus and glass wares used were sterilized fruit were investigated. Experiments were carried
either by autoclaving or a flame (wire loop) where out using a galvanic cell (with two approaches
required. The extract of fruit juices were subjected namely direct method and indirect method), a fuel
to microscopic examination before and after inocu- cell and a microbial fuel cell. In the direct method,
lation of microorganism. A reference slide with E. whole fruit was used as a unit for the construction
coli culture was prepared for comparison. The sam- of a direct galvanic cell (DGC), whereas in the indi-
ples were incubated at 37°C for 7 days and the rect method, fruit juices were used for the prepara-
smears on glass slides were stained with standard tion of an indirect galvanic cell (IDGC, CFC and
procedure of gram’s staining technique (Khan and MFC). The galvanic cells (DGC and IDGC) were
Naz, 2014). The slides were examined through a tested with and without the addition of NaCl solu-
lens having a resolution of 10/ 0.25 (160/0.17). tion as electrolyte. Furthermore, a conventional fuel
cell (CFC) and a microbial fuel cell (MFC) were test-
2.5.2. MFC construction ed before and after the addition of microorganism
The MFC was constructed with the same electrical (E. coli).

92 Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015

 Figure 2: Bioelectricity generation by fuel cell

3.1 Galvanic cell In the indirect method, the fruit juices were
In a galvanic cell, proton (H+) of citric acid dissolves extracted and analysed for the determination of
the zinc electrode of the anodic chamber to produce acid content, sugar, pH, total dissolved solids
zinc ions (Zn2+) along with the liberated electrons (TDS), salinity, water content, refractive index, con-
which travel via copper wire to the copper electrode ductivity etc. (see Table 1). The value of voltage and
at the cathodic chamber and reacted with H+ ions current in the indirect method was found to be
from the citrus fruit that generated bio-H2 gas. This lower but more stable than the direct method. This
supply of electron generates electric current due to may be due to better homogeneity and less hin-
the potential difference of the two electrodes (Oon, drance faced by ions in free flowing liquid medium
2007; Naidu and Kamakshiaih, 1995; Franco, as compared to the pulp of the whole fruit in the
2005) (see Figure 3). direct method. In the indirect method, the voltage
and current does not get altered by increasing the
Zn → Zn2+ + 2e- (Anodic reaction) amount (volume) of fruit juices in a glass container.
When the same juices were divided up into four
2H+ + 2e- → H2 (Cathodic reaction) separate glass containers (galvanic cells) connected
in a series, the voltage and power output were
Zn + 2H+ → Zn2+ + H2 (Overall reaction) increased in a typical manner with an increasing
number of cells and thus the LED light turn on.

Table 1: Physiochemical parameters of the juices of citrus fruit*

Testing parameters Units Lemon Orange Grapefruit Mixed fruit
Acid content % w/w 4.60 0.80 1.20 2.30
Carbohydrates % w/w 10.62 12.20 8.33 10.57
Sugar content % w/w 2.95 9.15 5.30 5.42
pH - 2.31 3.77 3.18 3.37
TDS µg L-1 1.80 1.28 1.34 1.37
Salinity µg L-1 1.90 1.30 1.40 1.40
Water content % w/w 39.30 51.2 47.80 44.5
Refractive index - 1.37 1.39 1.33 1.34
Conductivity µS 3.38 2.37 2.49 2.54
* All the data is replicated three times and mean values are included in the table

Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015 93

 fruit) and the cathodic chamber contains tap water
with continuous flushing of air. The electrical
parameters were measured before and after the
inoculation of the microorganism in a closed anod-
ic chamber to prevent the entrance of air oxygen.

3.3. Microbial fuel cell

The reference slide was prepared by E. coli cul-
ture that displayed the rod shaped bacilli. The slide
prepared by the fruit juice extract does not show the
presence of E. coli instead random particles were
observed. The slides of fruit juices prepared after
the inoculation of E. coli showed few rod shaped E.
coli (see Figure 4).

Figure 3: Circuit diagram of galvanic cells connected In a microbial fuel cell, microorganism uses carbo-
in a series hydrates of the citrus fruit juices as food and con-
verts them to biogas, which is finally converted
3.2. Conventional fuel cell into H+, with the loss of electrons via a fermenta-
In a conventional fuel cell, carbohydrates of the cit- tion pathway in the absence of air oxygen in the
rus fruit juices in the anodic chamber were to sealed anodic chamber. The electrons move from
undergo the self-fermentation by environmental the zinc electrode of the anodic chamber via cop-
microorganisms to produce biogases (CH4, H2, per wire and reach the copper electrode at the
CO2, N2 etc.), where CH4 and H2 were utilized as cathodic chamber in the form of current and the
fuel along with liberation of H+ ions and electrons protons librated at the anodic chamber were trans-
at the anodic chamber. The electrons moves from ferred via the salt bridge to the cathodic chamber
zinc electrode of the anodic chamber via copper containing tap water where it reacted with O2 to
wire and reach the copper electrode at the cathod- produce extra ordinary pure water (Bennetto,
ic chamber in the form of current and the protons 1990; Moawad, 2013; Delaney et al., 1984) (see
librated at the anodic chamber were transferred via Figure 5). The values obtained for voltage, current
a salt bridge to the cathodic chamber containing tap and power output by DGC, IDGC, CFC and MFC
water, where it reacted with the air oxygen to pro- are displayed in Table 2.
duce water (John, 1983; Leon and Mugrwa, 1993;
Badwal et al, 2015). CH4 + 2H2O4 → H2 + CO2 (Anodic reaction)

Anodic reactions: 4H2 → 8H+ + 8e- (Oxidation at anode)

C6H12O6 → 3CH3COOH + H2 2O2 + 8H+ + 8e- → 4H2O (Reduction at cathode)

3CH3COOH → 3CH4 + 3CO2 CH4 + 2O2 → CO2 + 2H2O (Overall reaction)

3CH4 + 6H2O → 12H2 + 3CO2

3.5. Comparative study
12H2 → 24H+ + 24e- (Oxidation) The voltage of the circuit was increased with the
increase in the number of galvanic or fuel cells in
C6H12O6 + 6H2O → H2 + 6CO2 + 24H+ series. Thus, the values of power output were also
+ 24e- (Overall anodic reaction) increased accordingly and the current of the circuit
remains almost constant. The procedure was
Cathodic reactions: repeated with DGC and IDGC after the addition of
NaCl (1ml of 1% solution) to lemon, orange, grape-
6O2 + 24H+ + 24e- → 12H2O (Reduction) fruit and mixed fruit, which showed a slight increase
in the values of the power output (see Figure 6).
C6H12O6 + 6O2 → H2 + 6CO2 + 6H2O MFCs showed higher values of power output in
(Overall reaction) all cases (lemon, orange, grapefruit and mixed fruit)
as compared to their counterpart CFCs. Moreover,
The conventional fuel cell (CFC) and microbial the MFC of lemon showed highest values of power
fuel cells (MFCs) were arranged in series. The anod- output among the MFCs of citrus fruit (orange,
ic chamber of each fuel cell contain either of the grapefruit and mixed fruit series). However, the
fruit juice (lemon, orange, grapefruit and mixed power outputs by MFCs are still lower as compared

94 Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015

 Figure 4: Microscopic pictorial representation

Figure 5: Circuit diagram of microbial fuels connected in a series

to their counterpart galvanic cells (DGC and trons) in the circuit and thus produced the highest
IDGC). The difference in power output before and power output difference. Therefore, it suggested
after the addition of microorganism is observed that orange is a better choice for MFC in this exper-
highest in the orange series. This is due to the fer- iment (see Figure 7).
mentation of carbohydrates and acid contents (cit- In addition to above experimentation, a com-
ric acid) present in oranges in the highest quantity parison of series and parallel sequence were made
as compared to other fruit and convert them into with lemon fruit and electrical parameters were
simpler compounds with the liberation of electrons used using DGC, IDGC and MFC methods. The
and protons, which leads to surplus current (elec- results showed that, in parallel sequence, voltage

Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015 95

 Table 2: Parameters obtained from citrus fruit by using different bioelectrical cells*

Souce No. of DGC° IDGC° CFC¤ MFC ø

unit cells
V (v) I (mA) P (mW) V (v) I (mA) P (mW) V (v) I (mA) P (mW) V (v) I (mA) P (mW)
Lemon 1 0.97 2.53 2.45 0.91 1.25 1.14 0.77 0.88 0.68 0.78 1.02 0.80
2 1.94 2.45 4.75 1.89 1.24 2.34 1.51 0.83 1.25 1.55 1.00 1.55
3^ 2.84 2.25 6.39 2.72 1.25 3.40 2.33 0.79 1.84 2.36 0.99 2.34
4^ 3.76 2.24 8.42 3.66 1.29 4.72 3.02 0.75 2.27 3.07 0.95 2.92
Orange 1 0.86 0.98 0.85 0.82 0.82 0.67 0.72 0.48 0.35 0.74 0.89 0.66
2 1.56 0.95 1.48 1.57 0.85 1.33 1.35 0.47 0.63 1.55 0.85 1.32
3^ 2.62 0.91 2.38 2.43 0.72 1.75 1.91 0.45 0.86 2.39 0.82 1.96
4^ 3.12 0.89 2.78 3.02 0.84 2.54 2.87 0.40 1.15 3.43 0.77 2.64
Grapefruit
1 0.91 1.21 1.10 0.88 1.82 1.60 0.78 0.68 0.53 0.83 0.79 0.66
2 1.75 1.25 2.19 1.65 1.75 2.89 1.52 0.65 0.99 1.58 0.77 1.22
3^ 2.70 1.23 3.32 2.29 1.87 4.28 2.21 0.62 1.37 2.35 0.74 1.74
4^ 3.31 1.20 3.97 3.17 1.79 5.68 2.99 0.61 1.82 3.13 0.72 2.25
Mixed fruit1
0.94 2.28 2.14 0.85 1.32 1.12 0.74 0.65 0.48 0.80 0.73 0.58
2 1.81 2.12 3.84 1.61 1.35 2.17 1.35 0.61 0.82 1.57 0.69 1.08
3^ 2.69 1.76 4.74 2.32 1.39 3.22 1.96 0.59 1.16 2.34 0.65 1.52
4^ 3.52 1.89 6.65 3.29 1.34 4.41 2.67 0.54 1.44 3.15 0.64 2.02
* All the data is replicated three times and the mean values were included in the table.
° Before addition of NaCl, ¤ Before addition of microorganism, ø After inoculation of microorganism, ^ LED light up

remain constant nearly at a value obtained with a output found less in IDGC, CFC and MFC respec-
single unit however, the current increased with tively. Orange has the lowest value of voltage in
increasing the number of galvanic or fuel cells in DGC and thus showed the lowest value of power
contrast to the series circuit, where the voltage was output. However, the orange showed competitive
increased with the increase in the number of gal- value of power output by MFC as compared to
vanic or fuel cells and the current in the circuit other fruit. Grapefruit has the highest power out in
remains almost constant (Table 3). IDGC and thus considered as most suitable for this
Furthermore, comparison of power output method. Mixed fruit showed the average values of
showed that the lemon has displayed the highest other fruits and thus no benefit or loss is considered
values of power output by DGC among the other with this series (see Figure 8). The merits and
citrus fruit, followed by mixed fruit, grapefruit and demerits of different fuel cells (DGC, IDGC, CFC
orange respectively. However, the values of power and MFC) have been summarized in Table 4.

Figure 6: Comparison of power output of four units by DGC

96 Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015

 Figure 7: Comparison of power output of four units obtained by MFC and CFC

Table 3: Comparison of series circuit and parallel circuit of lemon cell*

Methods No. of Series circuit Parallel circuit
unit cells V (v) I (mA) P (mW) V (v) I (mA) P (mW)
¤DGC 1 0.97 2.53 2.45 0.97 2.43 2.36
2 1.94 2.45 4.75 0.95 4.69 4.46
3 2.84 2.25 6.39 0.96 6.93 6.63
4 3.76 2.24 8.42 0.90 9.16 8.24
¤IDGC 1 0.91 1.25 1.14 0.92 1.33 1.22
2 1.89 1.24 2.34 0.91 2.51 2.28
3 2.72 1.25 3.40 0.93 3.63 3.38
4 3.66 1.29 4.72 0.90 4.76 4.28
CFC 1 0.77 0.88 0.68 0.75 0.82 0.62
2 1.51 0.83 1.25 0.73 1.54 1.12
3 2.33 0.79 1.84 0.78 2.25 1.76
4 3.02 0.75 2.27 0.76 3.08 2.34
MFC 1 0.78 1.02 0.80 0.77 0.99 0.76
2 1.55 1.00 1.55 0.76 1.87 1.42
3 2.36 0.99 2.34 0.73 2.79 2.04
4 3.07 0.95 2.92 0.77 4.61 3.55
* All the data is replicated three times and the mean values were included in the table
¤ Without addition of NaCl

Figure 8: Comparison of power output of four units by different methods

Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015 97

 Table 4: Merits and demerits of different types of cells

4. Conclusions the galvanic cells. The power output by the MFC

The physiochemical analysis of fruit juices showed method is found higher due to the addition of
that lemon has the lowest pH value (highest acid microorganism as compared to their counterpart
contents/ citric acid) which make this most prefer- CFC method. Finally, the results showed that lemon
able to utilized lemon for bioelectricity generation generates the highest power output by the DGC
among the other fruit (orange, grapefruit and mixed method, and grapefruit showed the highest power
fruit). The voltage of the circuit found to be output by IDGC. However, orange showed signifi-
increased with increasing the number of cells con- cant increase in power output by MFC as compared
nected in series in all cases and the current remains to CFC, which is considered due to highest sugar
almost constant. The current of the circuit was content in orange among the other fruit included in
found to be increased with increasing the number of this article. The shortage of non-renewable fossil
cells connected in parallel sequence in all cases and fuels will increase the cost of conventional electrici-
the voltage remains constant. The power output by ty with time, and the advancement in the field of
DGC is found higher as compared to the IDGC, genetic engineering and bioelectricity technology
CFC and MFC method. The power output after the will certainly result in the development of renew-
addition of the NaCl solution in all cases showed able, environmental friendly and a convenient
slightly higher values as compared to the values source of energy around the globe.
obtained before the addition of the NaCl solution in

98 Journal of Energy in Southern Africa • Vol 26 No 3 • August 2015

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Commission of Pakistan for financial support. In addition,
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