Synthesis, Structural, and Morphological Characterizations of
Reduced Graphene Oxide-Supported Polypyrrole Anode Catalysts
for Improved Microbial Fuel Cell Performances
G. Gnana kumar,*
,†
C. Joseph Kirubaharan,
†
S. Udhayakumar,
†
K. Ramachandran,
†
C. Karthikeyan,
†
R. Renganathan,
‡
and Kee Suk Nahm*
,§
†
Department of Physical Chemistry, Madurai Kamaraj University, Madurai-625 021, Tamilnadu, India
‡
School of Chemistry, Bharadhidasan University, Trichy-620 024, India
§
School of Chemical Engineering and Department of Hydrogen Fuel Cell Engineering, Chonbuk National University,
Jeonju-561-756, Republic of Korea
ABSTRACT: The conductive polypyrrole (PPy)/reduced graphene oxide (rGO) composites
were synthesized through simple, environmentally benign, time and cost efficient, in situ
polymerization and bioreduction techniques. The pyrrole monomer effectively adsorbed over
the negatively charged GO sheets through electrostatic and π-π interactions was polymerized
into polypyrrole in its adsorbed state. The obtained morphological images of the rGO/PPy
composite ensured that the entire surface of the active carbon support was covered by PPy. The
removal of oxygen functionalities from GO with the aid of Ocimum tenuiflorum extract was
ascertained through FT-IR and UV-vis absorption spectroscopic studies. The rGO/PPy
composite exhibited higher electrocatalytic oxidation current as evidenced from the cyclic
voltammetric analysis. The number of actives sites and continuous carrier channels of the rGO/
PPy composite exhibited a maximum MFC power density of 1068 mW/m
2
, which is almost
two-fold higher than that of bare PPy. The strong active carbon support prohibited the swelling
and shrinkage of the conductive polymer PPy and provided the strong physico and
electrochemical robustness of the rGO/PPy composite, which increased the MFC durability
performances up to 300 h. These findings have not only provided fundamental knowledge on the preparation rGO-based
composites through a green approach but also have found possible applications in large-scale green energy devices.
KEYWORDS: Carbon support, Conduction paths, Electrical conductivity, Oxidation current
■
INTRODUCTION
Microbial fuel cells (MFCs) are emerging green energy devices
that can use bacterial metabolism for the generation of electrical
current from a broad range of organic substrates.
1-3
In MFCs,
biomass energy is directly converted into electrical energy via
an electron transfer process under an ambient temperature. The
development of efficient anode catalysts that could improve the
power production of MFCs is highly significant.
4,2
An MFC
anode amendment has been extensively developed to increase
the bacterial adhesion and electron transfer from bacteria to the
electrode surface.
5
A number of electrode materials such as
carbon cloth, carbon paper, carbon felt, carbon mesh, stainless
steel, graphite, titanium, silver, stainless steel, aluminum, and
nickel have been exploited for the green power generation of
MFCs.
6-10
Among the studied electrode materials, carbon
cloth is well known for its elevated chemical and physical
stabilities under an aqueous environment, prompt electrical
conductivity, stability, high specific surface area, and porosity.
However, the improvement of electron transfer efficiency of
carbon cloth is essential in which electrode modification by the
conducting polymers is significant.
2
Conducting polymers such
as polypyrrole (PPy),
11
polyaniline,
12
polythiophene,
13
poly-
(aniline-co-o-aminophenol),
14
PPy/anthraquinone-2,6-disul-
fonic disodium salt,
15
poly(3-hydroxy butyrate-co-3-hydroxyval-
erate),
16
etc. have been exploited for the anode modification
process for effectual MFC performances. Among the studied
conducting polymers, PPy has been specifically preferred for
anode modi fication, owing to its easier synthesis and
processability, elevated electrical conductivity, redox properties,
high specific capacitance, low charge transfer resistance,
chemical stability, and biocompatibility.
11,15
The high electrical
conductivity and electrocatalytic activity of PPy even under
neutral solution favors the entrapment of biocatalysts, which
increases its viable applications in MFCs.
Hence, few research efforts have been devoted to the
modification of anodes by PPy for the application of
MFCs.
11,15,17
The conductive polymer PPy-equipped photo-
synthetic MFC exhibited a power density of 3.4 mW/m
2
, and
the obtained performance was ascribed to the physical
interaction or intercalation of PPy chains into the cell
membranes, enabling direct and fast transfer of electrons.
11
The conductive PPy modified with anthraquinone-2,6-disul-
Received: April 10, 2014
Revised: August 18, 2014
Published: September 5, 2014
Research Article
pubs.acs.org/journal/ascecg
© 2014 American Chemical Society 2283 dx.doi.org/10.1021/sc500244f | ACS Sustainable Chem. Eng. 2014, 2, 2283-2290