Physiochemical
Investigation of Shape-Designed MnO<sub>2</sub> Nanostructures and
Their Influence on Oxygen Reduction Reaction
Activity in Alkaline Solution
- Publication date
- Publisher
Abstract
In this work, five
types of MnO<sub>2</sub> nanostructres (nanowires,
nanotubes, nanoparticles, nanorods, and nanoflowers) were synthesized
with a fine control over their α-crystallographic form by hydrothermal
method. The electrocatalytic activities of these materials were examined
toward oxygen reduction reaction (ORR) in alkaline medium. Numerous
characterizations were correlated with the observed activity by analyzing
their crystal structure (TGA, XRD, TEM), material morphology (FE-SEM),
porosity (BET), inherent structural nature (IR, Raman, ESR), surfaces
(XPS), and electrochemical properties (Tafel, Koutecky–Levich
plots and % of H<sub>2</sub>O<sub>2</sub> produced). Moreover, X-ray
absorption near-edge structure (XANES) and the extended X-ray absorption
fine structure (EXAFS) analysis were employed to study the structural
information on the MnO<sub>2</sub> coordination number as well as
interatomic distance. These combined results show that the electrocatalytic
activities are significantly dependent on the nanoshapes and follow
an order nanowire > nanorod > nanotube > nanoparticle >
nanoflower.
α-MnO<sub>2</sub> nanowires possess enhanced electrocatalytic
activity compared to other shapes, even though the nanotubes possess
a much higher BET surface area. In the ORR studies, α-MnO<sub>2</sub> nanowires displayed Tafel slope of 65 mV/decade, n-value
of 3.5 and 3.6% of hydrogen peroxide production. The superior ORR
activity was attributed to the fact that it possesses active sites
composed with two shortened Mn–O bonds along with a Mn–Mn
distance of 2.824 Å, which provides an optimum requirement for
the adsorbed oxygen in a bridge mode favoring the direct 4 electron
reduction. In accordance with the first principles based density functional
theory (DFT), the enhancement in ORR activity is due to the less activation
energy needed for the reaction by the (211) surface than all other
surfaces