Novel Synthesis of LaFeO
3
Nanostructure Dendrites: A Systematic
Investigation of Growth Mechanism, Properties, and Biosensing for
Highly Selective Determination of Neurotransmitter Compounds
S. Thirumalairajan,
†
K. Girija,
†
V. Ganesh,
‡
D. Mangalaraj,
†
C. Viswanathan,
†
and N. Ponpandian*
,†
†
Department of Nanoscience and Technology, Bharathiar University, Coimbatore - 641 046, India
‡
Electrodics and Electro Catalysis Division, Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi - 630 006, India
ABSTRACT: Single-crystalline novel LaFeO
3
dendritic nano-
structures are synthesized by a well-controlled, surfactant-
assisted facile hydrothermal process. The morphology of the
material is investigated by high-resolution transmission and
scanning electron microscopy. The crystal nature and chemical
composition of LaFeO
3
dendritic nanostructures are revealed
from the X-ray diffraction, Raman spectroscopy, and X-ray
photoelectron spectroscopy. Structural characterizations imply
the preferential growth along the [121] direction by oriented
attachment of LaFeO
3
nanoparticles in the diffusion limit,
leading to the formation of LaFeO
3
dendrites. The microscopic studies confirm the formation of dendrites with a length of 3-4
μm, a branch diameter of 80 nm, and a length of 1-1.5 μm. The possible growth mechanism of the dendritic morphology is
discussed from the aspect of diffusion and oriented attachment based on experimental results. Further, the electrochemical
measurements performed on LaFeO
3
dendritic nanostructures deposited on the surface of a glassy carbon electrode exhibit a
strong promoting effect. The oxidation current is proportional to concentration in the linear range of 8.2 × 10
-8
to 1.6 × 10
-7
M
with a detection limit of 62 nM at S/N = 3. Meanwhile, the sensor effectively avoids the interference of ascorbic acid and uric
acid, and it is successfully applied to determine the dopamine formulations with high selectivity and sensitivity.
1. INTRODUCTION
Shape- and size-controlled synthesis of functional nanostruc-
tures, such as nanoparticles, nanocubes, nanospheres, nano-
wires, and nanorods, has gained importance as they exhibit
unique electronic, optic, magnetic, and catalytic properties.
1-4
Especially, substantial attention has been focused on dendritic
structures that can be applied in scientific and technological
applications due to their large surface area and continuous
networks.
5,6
In addition, the dendritic structures provide
fundamental scientific opportunities for investigating the
influence of size and dimensionality with respect to their
collective novel properties and applications resulting from the
spatial orientation and arrangement of nanoparticles. Generally,
dendrite structures of metal oxide exhibit nonequilibrium
growth processes that provide a natural framework for the
study of disordered systems. Numerous theoretical and
experimental results were reported, which contain information
about the structure and growth mechanism of dendrites
possessing promising complex functions, and their properties
are highly dependent on the morphology.
7,8
The perovskite
oxide with dendrite nanostructures also have many special
characteristics, such as a large surface area composed of major
trunks and branches. The preparation of dendritic structures
with well-defined shapes may open new opportunities for wide
applications in nanodevices.
9
Recently, a variety of dendrite
crystals of metals,
10-12
metal oxides,
13
and chalcogenides
14
have been extensively studied theoretically and experimentally.
Despite intensive experimental efforts, the dendritic structures
of perovskite oxides have not been successfully obtained until
now, which has hindered detailed experimental investigation of
the morphology-dependent properties of these oxides. It is
well-known that the properties of nanoparticles are dependent
not only on their chemical composition but also on their
structure, shape, and size. Therefore, the ability to tune the size
and shape of LaFeO
3
nanostructures with tailored properties is
significant for various investigations.
Over the past decade, many chemical methods, such as sol-
gel, coprecipitation, combined polymerization, pyrolysis of
metallo-organic precursors, and hydrothermal routes,
15-19
have
been developed to prepare LaFeO
3
nanostructures with
controlled physical and chemical characteristics. Among the
various conventional techniques, the hydrothermal technique is
an aqueous-based precipitation route allowing control over the
nucleation, growth, and aging process. Surfactants as soft
templates are involved in the formation of di fferent
morphologies by the self-assembly process. The combination
of surfactant-assisted self-assembly under hydrothermal con-
ditions has been used by many researchers to synthesize
different morphologies.
20
The hexadecyltrimethyl ammonium
bromide (CTAB) is used as a surfactant in the synthesis of
Received: September 28, 2012
Revised: November 15, 2012
Published: November 21, 2012
Article
pubs.acs.org/crystal
© 2012 American Chemical Society 291 dx.doi.org/10.1021/cg3014305 | Cryst. Growth Des. 2013, 13, 291-302