Nanostructured Pt/MnO2 Catalysts and Their Performance for Oxygen Reduction Reaction in Air Cathode Microbial Fuel Cell

Microbial fuel cells (MFCs) represent a promising
technology for simultaneous bioelectricity generation and wastewater
treatment. Catalysts are significant portions of the cost of microbial
fuel cell cathodes. Many materials have been tested as aqueous
cathodes, but air-cathodes are needed to avoid energy demands for
water aeration. The sluggish oxygen reduction reaction (ORR) rate at
air cathode necessitates efficient electrocatalyst such as carbon
supported platinum catalyst (Pt/C) which is very costly. Manganese
oxide (MnO2) was a representative metal oxide which has been
studied as a promising alternative electrocatalyst for ORR and has
been tested in air-cathode MFCs. However the single MnO2 has poor
electric conductivity and low stability. In the present work, the MnO2
catalyst has been modified by doping Pt nanoparticle. The goal of the
work was to improve the performance of the MFC with minimum Pt
loading. MnO2 and Pt nanoparticles were prepared by hydrothermal
and sol gel methods, respectively. Wet impregnation method was
used to synthesize Pt/MnO2 catalyst. The catalysts were further used
as cathode catalysts in air-cathode cubic MFCs, in which anaerobic
sludge was inoculated as biocatalysts and palm oil mill effluent
(POME) was used as the substrate in the anode chamber. The asprepared
Pt/MnO2 was characterized comprehensively through field
emission scanning electron microscope (FESEM), X-Ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), and cyclic
voltammetry (CV) where its surface morphology, crystallinity,
oxidation state and electrochemical activity were examined,
respectively. XPS revealed Mn (IV) oxidation state and Pt (0)
nanoparticle metal, indicating the presence of MnO2 and Pt.
Morphology of Pt/MnO2 observed from FESEM shows that the
doping of Pt did not cause change in needle-like shape of MnO2
which provides large contacting surface area. The electrochemical
active area of the Pt/MnO2 catalysts has been increased from 276 to
617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The
CV results in O2 saturated neutral Na2SO4 solution showed that
MnO2 and Pt/MnO2 catalysts could catalyze ORR with different
catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode
catalyst generates a maximum power density of 165 mW/m3, which
is higher than that of MFC with MnO2 catalyst (95 mW/m3). The
open circuit voltage (OCV) of the MFC operated with MnO2 cathode
gradually decreased during 14 days of operation, whereas the MFC
with Pt/MnO2 cathode remained almost constant throughout the
operation suggesting the higher stability of the Pt/MnO2 catalyst.
Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an
efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced
performance.





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