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(GRAM) 5. Chap7-8+Ref
(GRAM) 5. Chap7-8+Ref
CHAPTER 7
RESULT AND DISCUSSION
7.1. The study of the change of cyclic voltammogram and the relationship between scan
rate and peak current.
When the ferricyanide solution is used as the electrolyte, the anodic and cathodic currents are
given at specific potential value because the redox couples are defined as ferricyanide and
ferrocyanide. The changes in the cyclic voltammograms would reflect the diffusion coefficient
between the solution and the surface of the electrode by using the cyclic voltammetric
measurement. For this, the cyclic voltammetric analysis was performed with the various types
of electrodes for the changes in cyclic voltammograms determination including the anodic peak
current, cathodic peak current and the diffusion coefficient in each type of electrodes.
7.1.1. Carbon fiber electrode
A) B)
C) D)
28
E)
Figure19: The changes in the cyclic voltammograms of carbon fiber as a working electrode
for (A) 5, (B) 10, (C) 50, (D)75, and (E) 100 mV/s with the potential between -1 to 1 V vs.
the Ag/AgCl reference electrode, pH = 7
A) B)
29
C) D)
E) F)
30
G)
Figure20: The anodic and cathodic peak currents vs. square root of the scan rate that were
caused by the bacteria adhesion on the carbon fiber electrode for (A) 1 hr.,(B) 5 hrs., (C) 9 hrs.,
(D) 13 hrs., (E) 17 hrs., (F) 21 hrs., and (G) 25 hrs. with the potential between -1 to 1 V vs. the
Ag/AgCl reference electrode, pH = 7
Fig19 Indicates that the current increase in the range of -1 to 1 V with time, this change of
current indicates the ability of the bacteria to digest the organic matters in the electrolyte and
the electrons participated in the redox reaction. (S. Kurissery, N. Kanavillil, K. Leung, A. Chen,
L. Davey, H. Schraft, Biofouling 26 (2010) 799.)One interpretation for the current increase
shown in fig.19 is that an electrochemical interaction like the electron transfer between the
bacterial that has its ability to digest the organic matters in the synthesis wastewater and gives
out the electron to the surface of electrodes, which considered as oxidized layer, enhanced the
electrons to the surface and generated the desorption current as known as anodic current The
glucose molecule acts as the electron donor, and appears as oxidation reaction while the
ferricyanide as the electron acceptor received the electrons from the surface electrode that acts
as reduced layer which leads to the adsorption current, as known as cathodic current, the
ferricyanide as the electron acceptor so Fe3+ accept electron and undergoes to Fe2+, which leads
to the solution that turns blue (Prussian blue) in the presence of Fe2+ ions of ferrocyanide ions.
31
A) B)
Figure21: A) Initial solution for carbon fiber without modification and B) Final solution for
carbon fiber without modification
Figure 19 (a) to (e) presents the changes in the cyclic voltammograms by the bacteria that digest
organic matters (glucose) in synthesis wastewater, which acts as electron donor in the
ferricyanide solution as an electron acceptor together with the anodic and cathodic peak
currents with respect to time clearly demonstrates that the longer time, the ability of the bacteria
to digest the glucose molecule was increased, which leads to the absolute values of anodic and
cathodic currents increase as shown in Fig.20 (a) to (g).
Figure22: The anodic and cathodic peak currents vs. Time at the various scan rates
5,10,50,75,100 mV/s for carbon fiber electrodes as the working electrode( with the potential
between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7).
Fig.22 shows that the current is proportional to the scan rate, according to the Randles-Sevcik
equation (eq.1), the current was increased as well as the scan rate that was increased. Moreover
the current was increased until the specific time that it was stable and eventually decreased.
The current was decreased since the changes of cyclic voltammograms were induced not only
by the enhanced electron transfers but also the decrease of the surface area. The previous
studies (R.A. Illsley, S.G. Roscoe, E.D. Jackson, T.J. Hughes, Biofouling 11 (1997) 191.), S.
Kurissery, N. Kanavillil, K. Leung, A. Chen, L. Davey, H. Schraft, Biofouling 26(2010) 799.
Which reported that microbial adsorption on the electrode contributed to the current decrease
in cyclic voltammogram as a result of the diminishing of the surface coverage by bacterial
adhesion.
32
Additionally, the difference between the anodic and cathodic peak potential, which indicated
the reversibility of the electrochemical reaction, increased with time as shown in Fig.23
For the peak potential, which is anodic peak potential (Epa) indicates the adsorption of the
electron for the carbon fiber working electrode that undergoes the oxidation reaction, which
has glucose in the solution as the electron donor. Also, the cathodic peak potential (Epc)
indicates the desorption of electron for the carbon fiber working electrode, which undergoes
the reduction reaction, which has ferricyanide ions in the solution as the electron acceptor.
Desorption current is relevant to the reductive process of oxidized layer, whereas the adsorption
current is relevant to the oxidative process of the reduced layer. These currents are familiar
patterns in typical cyclic voltammograms of working electrodes in aqueous electrolytes.(A.J.
Bard, L.R. Faulkner, Electrochemical Methods, Wiley, 2001.)
The relationship between the current and potential for the changes in cyclic voltammograms
for 1, 5, 9, 13, 17, 21, and 25 hrs. With scan rate 5,10,50,75,100 mV/s as shown in the table
below, corresponded to the adsorption (Eq.1) and desorption (Eq.2) of the electron for the
carbon fiber working electrode that leads to the adsorption and desorption currents (ipa, ipc) and
potentials (Epa, Epc).
A) B)
C) D)
E) F)
Figure24: the changes in the cyclic voltammograms of carbon fiber modified with Nitric acid
as a working electrode for A) 1, B) 3, C) 6, D)9, E) 12, and F) 24 hrs. with the potential between
-1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7
35
A) B)
C) D)
E) F)
G)
H)
36
I)
Figure25: The anodic and cathodic peak
currents vs. square root of the scan rate that was caused by the bacteria adhesion on the carbon
fiber modified with Nitric acid electrode for (a) 1 hr. (b) 3 hrs. (c) 6 hrs. (d) 9 hrs. (e) 12 hrs.
(f) 15 hrs. (g) 18 hrs.(h) 21 hrs. (i) 24 hrs. with the potential between -1 to 1 V vs. the Ag/AgCl
reference electrode, pH = 7
Figure 24(a) to (f) presents the changes in the cyclic voltammograms by the bacteria that digest
organic matters (glucose) in synthesis wastewater, which acts as electron donor in the
ferricyanide solution as an electron acceptor together with the anodic and cathodic peak
currents with respect to time clearly demonstrates that the longer time, the ability of the bacteria
to digest the glucose molecule was increased, which leads to the absolute values of anodic and
cathodic currents increase. For the anodic peak current, it was observed to disappear after 12
hrs. operation whereas the cathodic peak current still increased concerning time as shown in
Fig.25 (a) to (i). Moreover, Fig.20 shows that from 6 hrs. , the higher scan rate cannot detect
the anodic peak current, while at low scan rate still able to detect. The assumption is that at low
scan rate the current response to the electrode is almost at the steady-state condition since the
electrons have sufficient time to penetrate the pores of the material, whereas, for higher scan
rates, only the electrons accumulate on the outer surface. Therefore, it is considered as transient
steady state condition, which leads to the low detection. Also, it shows that the
electrochemical reaction has a low reaction rate. Then, when applying low scan rates the
reaction has a higher time to occur and, consequently, the peak associated with it grows.
37
One assumption for the disappearing of the anodic current is the glucose in the solution was
used up. Therefore the electrons were no more enhanced to the surface of carbon fiber modified
with the nitric acid electrode. Another assumption is the treatment for nitric acid to the carbon
fiber electrode was practically incorrect. Since the nitric acid causes the formation of oxygen
surface complex at the edge sites of carbon structures, which also can hinder the electron
enhancement during oxidation process in case of the wrong treatment was applied.
Figure26: The anodic and cathodic peak currents vs. Time at the various scan rates 3,5,7,10
mV/s for carbon fiber modified with Nitric acid electrodes as the working electrode( with the
potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7)
Fig.26 shows that the current is proportional to the scan rate, according to the Randles-Sevcik
equation (eq.1). The current was increased as well as the scan rate that was increased. For the
anodic peak current, the current was increased until 10 hrs. Then it was decreased, whereas the
cathodic peak current, was observed that the current was decreased until 10 hrs. That it was
started to increase according to the redox couple reaction.
Additionally, the difference between the anodic and cathodic peak potential, which indicated
the reversibility of the electrochemical reaction, increased with time as shown in Fig.27
The relationship between the current and potential for the changes in cyclic voltammograms
for 1, 3, 6, 9, 12, 15, 18, 21, and 24 hrs. With scan rate 3,5,7,10 mV/s as shown in the table
below, corresponded to the adsorption (Eq.1) and desorption (Eq.2) of the electron for the
carbon fiber working electrode that leads to the adsorption and desorption currents (ipa, ipc) and
potentials (Epa, Epc).
38
A) B)
C) D)
E)
F)
Figure28: The changes in the cyclic voltammograms of carbon fiber as a working electrode for
A) 3, B) 5, C) 7, D)10, E) 30 and F) 50 mV/s with the potential between -1 to 1 V vs. the
Ag/AgCl reference electrode, pH = 7
40
A) B)
C)
Figure29: The anodic and cathodic peak currents vs. square root of the scan rate that was caused
by the bacteria adhesion on the carbon fiber electrode for A) 1 hr. B) 12hrs. moreover, C) 24
hrs. with the potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7
Figure30: Carbon fiber with Teflon treatment solution for an initial and final period
41
Figure 28(a) to (f) presents the changes in the cyclic voltammograms by the bacteria that digest
organic matters (glucose) in synthesis wastewater, which acts as electron donor in the
ferricyanide solution as an electron acceptor together with the anodic and cathodic peak
currents with respect to time clearly demonstrates that the longer time, the ability of the bacteria
to digest the glucose molecule was increased, which leads to the absolute values of anodic and
cathodic currents increase as shown in Fig.29(a) to (c).
Figure31: The anodic and cathodic peak currents vs. Time at the various scan rates 3, 5, 7, 10,
30, and 50 mV/s for carbon fiber electrodes as the working electrode( with the potential
between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7)
Fig.31 shows that the current is proportional to the scan rate, according to the Randles-Sevcik
equation (eq.1), the current was increased as well as the scan rate that was increased. Moreover
the current was increased until the specific time that it was stable and eventually decreased.
Additionally, the difference between the anodic and cathodic peak potential, which indicated
the reversibility of the electrochemical reaction, increased with time as shown in Fig.32.
42
The relationship between the current and potential for the changes in cyclic voltammograms
for 1,12,24 hrs. With scan rate 3, 5, 7, 10, 30, and 50 mV/s as shown in the table below,
corresponded to the adsorption (Eq.1) and desorption (Eq.2) of electron for the carbon fiber
working electrode that leads to the adsorption and desorption currents (ipa, ipc) and potentials
(Epa, Epc).
A)
B)
43
C) D)
E) F)
G) H)
Figure33: the changes in the cyclic voltammograms of carbon fiber modified with PTFE as a
working electrode for A) 1, B) 3, C) 6, D)9, E) 12, F) 18, G)21, and H)24 hrs. with the potential
between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7.
A) B)
44
C) D)
E) F)
H)
I)
Figure34: The anodic and cathodic peak currents vs. square root of the scan rate that were
caused by the bacteria adhesion on the carbon fiber modified with Nitric acid and PTFE
electrode for (a) 1 hr. (b) 3 hrs. (c) 6 hrs. (d) 9 hrs. (e) 12 hrs. (f) 15 hrs. (g) 18 hrs. (h) 21 hrs.
(i) 24 hrs. with the potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7.
15 -0.0078
18 -0.0081
21 -0.0086
24 -0.0085
Table12: Peak slope of carbon fiber with nitric and Teflon treatment condition
A) B)
Figure35: A) Final solution for carbon fiber with nitric and Teflon treatment, B) Electrode
after the experiment for carbon fiber with nitric and Teflon treatment
Figure 33(a) to (h) presents the changes in the cyclic voltammograms by the bacteria that digest
organic matters (glucose) in synthesis wastewater, which acts as electron donor in the
ferricyanide solution as an electron acceptor together with the anodic and cathodic peak
currents with respect to time clearly demonstrates that the longer time, the ability of the bacteria
to digest the glucose molecule was increased, which leads to the absolute values of anodic and
cathodic currents increase as shown in Fig.34 (a) to (i).
Figure36: The anodic and cathodic peak currents vs. Time at the various scan rates 3,5,7,10
mV/s for carbon fiber modified with Nitric acid and PTFE electrodes as the working electrode(
with the potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7).
Fig.36 shows that the current is proportional to the scan rate, according to the Randles-Sevcik
equation (eq.1), the current was increased as well as the scan rate that was increased. For the
anodic peak current the current was increased. Eventually it was decreased, whereas the
46
cathodic peak current, was observed that the current was decreased, eventually it was started
to stable according to the redox couple reactions.
Additionally, the difference between the anodic and cathodic peak potential, which indicated
the reversibility of the electrochemical reaction, increased with time as shown in Fig.37
The relationship between the current and potential for the changes in cyclic voltammograms
for 1, 3, 6, 9, 12, 15, 18, 21, and 24 hrs. With scan rate 3,5,7,10 mV/s as shown in the table
below, corresponded to the adsorption (Eq.1) and desorption (Eq.2) of the electron for the
carbon fiber working electrode that leads to the adsorption and desorption currents (ipa, ipc) and
potentials (Epa, Epc).
A) B)
C) D)
48
E) F)
G) H)
Figure38: the changes in the cyclic voltammograms of carbon fiber with grinded sludge as a
working electrode for (a) 1 (b) 3 (c) 6 (d)9 (e) 12 (f) 18 (g)21 (h)24 hrs. with the potential
between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7.
A) B)
C) D)
49
E)
F)
G) H)
Figure39: The anodic and cathodic peak currents vs. square root of the scan rate that was
caused by the bacteria adhesion on the carbon fiber with grinded sludge electrode for (a) 1 hr.
(b) 3 hrs. (c) 6 hrs. (d) 9 hrs. (e) 12 hrs. (f) 18 hrs. (g) 21 hrs.(h) 24 hrs. with the potential
between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7
15 -0.0078
18 -0.0081
21 -0.0086
24 -0.0085
Table14: Peak slope of carbon fiber with nitric and Teflon treatment condition
A) B)
Figure40: A) Final solution of carbon fiber electrode with grinded sludge, B) Electrode of
carbon fiber with grinded sludge experiment
Figure 38(a) to (h) presents the changes in the cyclic voltammograms by the bacteria that digest
organic matters (glucose) in synthesis wastewater, which acts as electron donor in the
ferricyanide solution as an electron acceptor together with the anodic and cathodic peak
currents with respect to time clearly demonstrates that the longer time, the ability of the bacteria
to digest the glucose molecule was increased, which leads to the absolute values of anodic and
cathodic currents increase. For the anodic peak current, it was observed to disappears after 18
hrs. Operation whereas the cathodic peak current still increased concerning time as shown in
Fig.38 (a) to (h).Fig.39shows that from 18 hrs. , the higher scan rate cannot detect the anodic
peak current, while at low scan rate still able to detect, so it shows that the electrochemical
reaction has a low reaction rate. Then, when applying low scan rates the reaction has a higher
time to occur and, consequently, the peak associated with it grows.
Figure41: The anodic and cathodic peak currents vs. Time at the various scan rates 3,5,7
mV/s for carbon fiber with grinded sludge electrodes as the working electrode( with the
potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7).
51
Figure42: The difference between the anodic and cathodic peak potential (Epa-Epc) ( with the
potential between -1 to 1 V vs. the Ag/AgCl reference electrode, pH = 7).
The relationship between the current and potential for the changes in cyclic voltammograms
for 1, 3, 6, 9, 12, 15, 18, 21, and 24 hrs. with scan rate 3, 5, 7 mV/s as shown in the table below,
corresponded to the adsorption (Eq.1) and desorption (Eq.2) of the electron for the carbon fiber
working electrode that leads to the adsorption and desorption currents (ipa, ipc) and potentials
(Epa, Epc).
The diffusion coefficient can be calculated from the Randles-Sevcik equation. The Randle-
Sevcik equation expresses that the current of the cyclic voltammograms is proportional to the
square root of the scan rate.
ip = (2.69x105)n3/2AactD1/2C0v1/2 (1)
Where, ip : peak current (A) ; n:number of electron (l) ; Aact: active surface area (cm2); D:
diffusion coefficient (cm2/s) ; C0: bulk concentration (mol/cm3) ; v: scan rate (mV/s)
From eq. (1) the diffusion coefficient can be calculated using the slope of curves representing
the relationship between the peak current (ip) and the square root of various scan rate (v1/2)
To obtain the diffusion coefficient, the active surface area was fixed at 6 cm2. Since the
diffusion coefficient is mainly dependent on temperature which operates at room’s temperature
at 25 C. Thus, the influence of Aact affecting on diffusion coefficient is thought to be minimal
at the condition of fixed temperature. Therefore, the diffusion coefficient of the electrode was
calculated.
Peak
Bulk Diffusion
Time current Number of Active surface
concentration coefficient
(hours) slope, ip electrons, n area (cm2)
(mol/cm3) (cm2/s)
(A)
1 0.0162 2.732E-16
5 0.0156 2.534E-16
9 0.0157 2.566E-16
13 0.0195 24 6 0.005164 3.959E-16
17 0.0191 3.798E-16
21 0.0183 3.487E-16
25 0.0179 3.336E-16
53
Table16: Diffusion coefficient of oxidation reaction for carbon fiber working electrode
Peak
Bulk Diffusion
Time current Number of Active surface
concentration coefficient
(hours) slope, ip electrons, n area (cm2)
(mol/cm3) (cm2/s)
(A)
1 0.0103 1.105E-16
5 0.0098 9.999E-17
9 0.0106 1.170E-16
13 0.0107 24 6 0.005164 1.192E-16
17 0.0097 9.796E-17
21 0.0095 9.396E-17
25 0.0091 8.622E-17
Table17: Diffusion coefficient of reduction reaction for carbon fiber working electrode
A) B)
Figure43: Shows the change in the diffusion coefficient calculated from the results of cyclic
voltammograms in A) cathodic and B) anodic diffusion coefficient that indicates how fast the
electrons transfer to the surface of the carbon fiber electrodes.
During the experiment, Fig.43 (b) shows the diffusion coefficient rate for reduction process,
which has ferricyanide as the electron acceptor, increased until 9 hrs. At the rate 1.1958x10-
16
cm2/s, which indicates the maximum value that was occurred, eventually, the rate was
decreased. For the diffusion coefficient rate for oxidation process, which has the glucose as the
electron donor, Fig.43(a) shows the rate was increased until 13 hrs, which is 3.98x10 - 16cm2/s,
which indicates the maximum value that was occurred, eventually the rate was also decreased
similar to the reduction reaction.
1 0.0111 1.29E-16
3 0.0104 1.12E-16
6 0.0089 8.21E-17
9 0.0065 4.43E-17
12 24 6 0.005164
15
18
21
24
Table18: Diffusion coefficient of oxidation reaction for carbon fiber with the nitric acid
treatment working electrode
Bulk Diffusion
Time Peak current Number of Active surface
concentration coefficient
(hours) slope, ip (A) electrons, n area (cm2)
(mol/cm3) (cm2/s)
1 -0.00949 9.38E-17
3 -0.00913 8.68E-17
6 -0.00387 1.56E-17
9 -0.00417 1.81E-17
12 -0.00795 24 6 0.005164 6.58E-17
15 -0.00776 6.27E-17
18 -0.00809 6.81E-17
21 -0.00863 7.75E-17
24 -0.00854 7.59E-17
Table19: Diffusion coefficient of reduction reaction for carbon fiber with the nitric acid
treatment working electrode
Figure43 shows the change in the diffusion coefficient calculated from the results of cyclic
voltammograms in (a) cathodic and (b) anodic diffusion coefficient, that indicates how fast the
electrons transfer to the surface of the carbon fiber modified with Nitric acid and Teflon
electrodes
During the experiment, Fig.31vshows the diffusion coefficient rate for reduction process,
which has ferricyanide as the electron acceptor, increased until 3 hrs. At the rate 8.68x10-17
cm2/s, which indicates the maximum value that was occurred, eventually, the rate was
decreased. For the diffusion coefficient rate for oxidation process, which has the glucose as the
electron donor, Fig.31 shows the rate was increased until 1 hrs, which is 1.29x10-16cm2/s, which
55
indicates the maximum value that was occurred. Eventually the rate was also decreased
similarly to the reduction reaction.
1 0.00848 7.487E-17
3 12 0.00868 24 6 0.005164 7.844E-17
24 0.00824 7.069E-17
Table20: Diffusion coefficient of reduction-oxidation for carbon fiber with Teflon treatment
working electrode
1 -0.00721 5.412E-17
3 12 -0.00722 24 6 0.005164 5.427E-17
24 -0.00775 6.253E-17
Table21: Diffusion coefficient of reduction for carbon fiber with Teflon treatment working
electrode
Figure44: shows the change in the diffusion coefficient calculated from the results of cyclic
voltammograms in (a) cathodic and (b) anodic diffusion coefficient that indicates how fast
the electrons transfer to the surface of the carbon fiber modified with Teflon electrodes.
During the experiment, Fig.15shows the diffusion coefficient rate for reduction process, which
has ferricyanide as the electron acceptor, increased until 12 hrs. at the rate 5.427x10-17 cm2/s,
which indicates the maximum value that was occurred. Eventually the rate was decreased. For
the diffusion coefficient rate for oxidation process, which has the glucose as the electron donor,
56
Fig.15 shows the rate was increased until 12 hrs, which is 7.844x10 -17cm2/s, which indicates
the maximum value that was occurred, eventually the rate was also decreased similar to the
reduction reaction.
7.2.4. Carbon fiber electrode modified with nitric acid and Teflon
The diffusion coefficient of this experiment as shown in the table below;
Bulk Diffusion
Time Peak current Number of Active surface
concentration coefficient
(hours) slope, ip (A) electrons, n area (cm2)
(mol/cm3) (cm2/s)
1 0.01114 1.29E-16
3 0.01038 1.12E-16
6 0.00888 8.21E-17
9 0.00652 4.43E-17
12 24 6 0.005164
15
18
21
24
Table22: Diffusion coefficient of reduction-oxidation for carbon fiber with Teflon treatment
working electrode
1 -0.00949 9.38E-17
3 -0.00913 8.68E-17
6 -0.00387 1.56E-17
9 -0.00417 1.81E-17
12 -0.00795 24 6 0.005164 6.58E-17
15 -0.00776 6.27E-17
18 -0.00809 6.81E-17
21 -0.00863 7.75E-17
24 -0.00845 7.43E-17
Table23: Diffusion coefficient of reduction for carbon fiber with Teflon treatment working
electrode
\
57
During the experiment, Fig.30vshows the diffusion coefficient rate for reduction process,
which has ferricyanide as the electron acceptor, increased until 18 hrs. At the rate 9.47x10-17
cm2/s, which indicates the maximum value that was occurred, eventually, the rate was
decreased. For the diffusion coefficient rate for oxidation process, which has the glucose as the
electron donor, Fig.30 shows the rate was increased until 6 hrs, which is 2.65x10-16cm2/s, which
indicates the maximum value that was occurred, eventually the rate was also decreased similar
to the reduction reaction.
Bulk Diffusion
Time Peak current Number of Active surface
concentration coefficient
(hours) slope, ip (A) electrons, n area (cm2)
(mol/cm3) (cm2/s)
1 0.01114 1.29E-16
3 0.01038 1.12E-16
6 0.00888 8.21E-17
9 0.00652 4.43E-17
12 24 6 0.005164
15
18
21
24
Table24: Diffusion coefficient of reduction-oxidation for carbon fiber with the grinded sludge
working electrode
1 -0.00949 9.38E-17
3 -0.00913 8.68E-17
24 6 0.005164
6 -0.00387 1.56E-17
9 -0.00417 1.81E-17
58
12 -0.00795 6.58E-17
15 -0.00776 6.27E-17
18 -0.00809 6.81E-17
21 -0.00863 7.75E-17
24 -0.00845 7.43E-17
Table25: Diffusion coefficient of reduction for carbon fiber with the grinded sludge working
electrode
During the experiment, Fig.32 shows the diffusion coefficient rate for reduction process, which
has ferricyanide as the electron acceptor, increased until 3 hrs. At the rate 8.68x10-17 cm2/s,
which indicates the maximum value that was occurred, eventually, the rate was decreased. For
the diffusion coefficient rate for oxidation process, which has the glucose as the electron donor,
Fig.32 shows the rate was increased until 1 hrs, which is 1.29x10-16cm2/s, which indicates the
maximum value that was occurred. Eventually, the rate was also decreased similarly to the
reduction reaction.
7.3. The study of the early and later stage of the bacteria and its roles in current
generation by the change in diffusion coefficient and current.
One interpretation for the diffusion coefficient and the current that was decreased after a while
of the experiment that obtained from the result is related to the diminishment of the active
surface area of the electrodes as more bacterial cells cover wider surface, which interferes with
the electrochemical reaction of the electrode. Since the limited amount of the organic matters
(COD ca. 2000 mgO2/L) was added to this experiment, the ability of bacteria to digest the
organic matters was decreased as time passed by. Although, the surface area decreases with
some bacteria growth on the electrode.
Then, there may be two putative actions in opposite directions that change the current in the
cyclic voltammogram with the bacteria roles and attachment; the enhanced electrochemical
reaction like electron transfer between bacteria and electrode surface due to its ability to digest
the organic matters (glucose) in the synthesized wastewater and gives out the electron then it
was enhanced to the electrode surface that increases the current.
Another action is the surface covering action to diminish the area available for the
electrochemical interaction that lowers the current. Moreover, the organic matters (glucose)
that present in the synthesis wastewater also decreased from being digested by the bacteria and
the electrons were less being generated. Therefore, the enhancement of electron to the electrode
surface was decreased, which also leads lowers the current.
59
A)
B)
Figure47: The anodic and cathodic peak currents vs. Time for the carbon fiber-based
electrode with various treatment includes nitric acid, PTFE, nitric acid and PTFE, grided
sludge, as the working electrode( with the potential between -1 to 1 V vs. the Ag/AgCl
reference electrode, scan rate 5 mV/s and pH = 7).
From Fig.47(a), For the anodic peak current it shows that the current was increased concerning
time, eventually stable and decreased as the pattern of an electrochemical redox reaction as
mentioned in eq.(1,2) which has glucose as electron donor and ferricyanide as an electron
acceptor. For carbon fiber electrode, which represents as the material that gives the highest
anodic peak current (0.0478A, 17 hrs) > carbon fiber with Nitric acid and PTFE electrode
(0.0314A, 6 hrs.) > carbon fiber electrode with grinded sludge (0.0237, 9 hrs.) > carbon fiber
with Nitric electrode (0.0215A, 3 hrs.)> carbon fiber with PTFE electrode (0.0185 A,24 hrs.)
as shown in the table below.
From Fig.47(b), For the cathodic peak current, it shows that the current was decreased in the
beginning concerning time, eventually stable as the pattern of an electrochemical redox
reaction as mentioned in eq.(1,2) which has glucose as electron donor and ferricyanide as an
electron acceptor. For carbon fiber electrode, which represents as the material that gives the
maximum cathodic peak current (0.043A, 13 hrs) > carbon fiber with Nitric acid electrode
(0.0325A, 1 hrs.) > carbon fiber electrode with grinded sludge (0.0316, 1 hrs.) > carbon fiber
with Nitric and PTFE electrode (0.0309A, 1 hrs.)> carbon fiber with PTFE electrode (0.0174
A,1 hrs.) as shown in the table below.
60
Anodic Cathodic
Material Peak Peak
Time Time
current current
(hour) (hour)
(A) (A)
From Figs.47(a) and (b), it shows that the carbon fiber electrode gives the highest for both
anodic and cathodic peak current compares to other types of electrode. In the other hands, the
carbon-based electrode with PTFE appears to give the lowest for both anodic and cathodic peak
current compares to other types of electrode. For the carbon-based electrode with Nitric acid,
grinded sludge, nitric acid PTFE do not give a vastly difference from each other.
A) B)
Figure48: The anodic and cathodic diffusion coefficient vs. Time for the carbon fiber-based
electrode with various treatment includes nitric acid, PTFE, nitric acid and PTFE, grided
sludge, as the working electrode( with the potential between -1 to 1 V vs. the Ag/AgCl
reference electrode, scan rate 5 mV/s and pH = 7).
From Fig.48(a), For the anodic diffusion coefficient, it shows that the diffusion coefficient was
increased concerning time, eventually stable and decreased as the pattern of an electrochemical
redox reaction as mentioned in eq.(1,2) which has glucose as electron donor and ferricyanide
as an electron acceptor. For carbon fiber electrode, which represents as the material that gives
the highest anodic diffusion coefficient (6.868x10-16 cm2/s, 9 hrs) > carbon fiber with Nitric
61
acid and PTFE electrode (2.65x10-16 cm2/s, 6 hrs.) > carbon fiber electrode with nitric acid
(1.325x10-16 cm2/s, 1 hrs.) > carbon fiber electrode with grinded sludge(1.056x10-16 cm2/s,
6hrs.)> Carbon fiber with PTFE electrode (7.48x10-17 cm2/s,24 hrs.) as shown in the table
below.
From Fig.48(b), For the cathodic diffusion coefficient, it shows that the diffusion coefficient
was decreased concerning time, eventually stable as the pattern of an electrochemical redox
reaction as mentioned in eq.(1,2) which has glucose as electron donor and ferricyanide as an
electron acceptor. For carbon fiber electrode, this represents as the material that gives the
highest anodic diffusion coefficient (1.2x10-16 cm2/s, 9 hrs) > carbon fiber with Nitric acid
and PTFE electrode (1.028x10-16 cm2/s, 12 hrs.) > carbon fiber electrode with nitric acid
(9.35x10-17 cm2/s, 1 hrs.) > carbon fiber electrode with grinded sludge(8.62x10-17 cm2/s,
12hrs.)> Carbon fiber with PTFE electrode (6.22x10-17 cm2/s,24 hrs.) as shown in the table
below.
Anodic Cathodic
Material
Time Diffusion Time Diffusion
(hour) coefficient (hour) coefficient
From Figs.48(a) and (b), it shows that the carbon fiber electrode gives the highest for both
anodic and cathodic diffusion coefficient compares to other types of electrode. In the other
hands, the carbon-based electrode with PTFE appears to give the lowest for both anodic and
cathodic peak current compares to other types of electrode. For the carbon-based electrode with
Nitric acid, grinded sludge, nitric acid PTFE do not give a vast difference from each other.
The assumption for this phenomena, that the carbon fiber gives the highest for both current
generation and diffusion coefficient in anodic (oxidation reaction) and cathodic (reduction
reaction) is the impractical treatment. Since the treatment for carbon-based with nitric acid
0.3M then dried in an oven at 50 C for 2 hrs. Whereas, the previous studies (G. M. JENKINS
and K. KAWAMURA, “Polymeric Carbon-Carbon Fibre, Glass and Char” (Cambridge
University Press, London, 1976).) used carbon fiber electrode treated with 3M, 2x10-4 m3 Nitric
acid then dried in oven for a few hours and it shows that the ability for adsorption and electrical
properties increase more than 40%, As a result of treating with nitric acid, can lower the surface
resistance for ion migration. For carbon-based with PTFE electrode, during the experiment 40
62
%wt. PTFE was used with carbon fiber, then dried with 100 C in the oven to get rid of the
moisture. Whereas, the previous studies, suggested the optimum amount of PTFE was 20 %wt.
For activated carbon material. Also, adding more than 30 %wt of binder resulted in pore
blockage and reduced the available site on the activated carbon electrode. For carbon-based
with Nitric acid + PTFE electrode, during the experiment 0.3M nitric acid and 30 %wt. PTFE
was used with carbon fiber, then dried with 100 C in the oven to get rid of the moisture. For
carbon-based electrode with grinded sludge, since all the previous batches were varied the
types of electrode and the granular sludge was used, but this batch was focused on the bacteria
which considered as the digestion matters that digested the glucose in the solution, were
grinded. The assumption for this batch is the grinded bacteria has more active surface area
compared to the granular sludge, this means that the effect by the diminished of electrode
surface area is predominant due to the grinded sludge was attached on the surface of the
electrode, which leads to the current and diffusion coefficient were also decreased.
In conclusion, in early stage of the experiment, the effect by the enhanced electron to the
electrode surface interaction is superior to the counter effect by the diminished surface area of
electrode due to the presence of the organic matters (glucose) in the synthesis wastewater, but
in the later stage, the effect by the diminished surface area is predominant due to the decreased
amount of the organic matters (glucose) in the synthesis wastewater.
This means that the change of cyclic voltammogram is dependent on the amount of the organic
matters that present in the synthesis wastewater, the degree of biofilm development, and the
type of electrodes due to its ability of an enhanced electron to the surface of electrodes.
The coulombic efficiency describes the efficiency with which electrons are transferred in a
system facilitating a reaction. It is a fraction of electrons, after the organic matters (glucose)
that present in the synthesis wastewater and were digested by the bacteria then gives out the
electrons, eventually converted to electricity. The coulombic efficiency was calculated by using
CS − CO
CE = × 100
CS
Where,
CE = Coulombic Efficiency
CS = Initial COD
CO = Final COD
The percentage of COD removal and coulombic efficiency (CE) parameters are not available.
Lately, there is the chemical which added as a mediator to the system to increase the electrons
transferring performance, potassium ferricyanide. Besides oxygen which is an electron
acceptor due to its high oxidation potential, potassium ferricyanide is another electron donor
used in MFC studies since its concentration is no limited to solubility like in the case of oxygen
and the result is not only a faster reaction but also get a high power output. From the previous
reasons, potassium ferricyanide was added to the system and later was found that the previous
process of COD measurement may not suit for the solution contains potassium ferricyanide.
Another discussion is glucose left in the solution might too less to use the previous process of
measurement.
63
The table below shows the %COD removal for 24 hours without adding potassium
ferricyanide;
7.5. pH of the synthesis wastewater at the early and later stage of the experiment
pH
Condition
Before After
Carbon fiber without
7 7
modification
Carbon fiber with
7 7
nitric treatment
Carbon fiber with
7 7
Teflon treatment
Carbon fiber with
nitric and Teflon 7 7
treatment
Carbon fiber with
7 7
grinded sludge
Table28: Initial and final pH for all conditions
Table28 shows that pH of the solution in the system did not change along the operating time
which is possible because in the solution there is a buffer which is added in order to stabilize
the pH of the solution in order to avoid the acidic or basic change which can affect the
performance and reaction of chemicals in the system and too basic or acidic condition might
affect or cause toxic to the bacteria also.
64
CHAPTER 8
CONCLUSION
The objectives of this study are to compare the performance in current generation and the
diffusion coefficient, which are a critical physical parameters of the species involved in an
electrochemical reaction that describes diffusion transport, which indicates the performance of
electrons migration between the solution and the electrode surface, for various types of carbon
fiber based electrode and its modification. The result shows that the carbon fiber electrode
gives the highest anodic current is 0.0478A at time 17 hours for operation and also the highest
cathodic peak current is 0.043A at 13 hours for operation. For the effects of the electrode
materials on diffusion coefficient, the carbon fiber electrode gives the highest anodic diffusion
coefficient which is 6.868x10-16 cm2/s with 9 hours of operation and also the highest cathodic
diffusion coefficient is 1.2x10-16 cm2/s with 9 hours operation.
In conclusion, in the early stage of the experiment, the effect by the enhanced electron to the
electrode surface interaction is superior to the counter effect by the diminished surface area of
electrode due to the presence of the organic matters (glucose) in the synthesis wastewater, but
in the later stage, the effect by the diminished surface area is predominant due to the decreased
amount of the organic matters (glucose) in the synthesis wastewater. This means that the
change of cyclic voltammogram is dependent on the amount of the organic matters that present
in the synthesis wastewater, the degree of biofilm development, the type of electrodes due to
its ability of an enhanced electron to the surface of electrodes, and the optimum electrode
treatment condition.
65
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