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2 PAVITHRA and DEY
1 INTRODUCTION
The development of nanoscale materials has been the
main focus in materials science and technology research
for the past several decades. Moreover, this endeavor
has become innovatory in terms of morphology and
composition, whereby these aspects significantly control
the physiochemical properties of the materials at the
nanoscale. The general morphology of these nanoscale
materials can be zero- (0D), one- (1D), two- (2D), and three-
(3D) dimensional, and these differently designed nano-
materials can often outperform their bulk counterparts
owing to their high surface-to-volume ratio and low bulk
density.[1] In addition, the quantum effect and high surface
area energy can affect the chemical properties, reactiv-
ity, electrical, optical, and magnetic properties, and the
catalytic performance.[1,2] In this direction, although sev-
eral inorganic and organic materials have been explored,[3]
nanometals have attracted significant interest in identi-
fying several applications, spanning from the fields of
biomedical, catalysis, and electronics to energy conversion
[4] This progress in metallic systems has extended toward
the mixing of elements as bimetallic nanoalloys, thereby
providing flexibility in enhancing specific properties to
further improve their diversity through composition and
structure.[5] Owing to their synergistic effects, the bimetal-
lic nanoalloys show better stability over that of the pure
single elements, which makes them an interesting class of
materials for potential applications such as catalysis, mag-
netism, optics, and energy.[5,6] Shape anisotropy becomes
influential in performance of nanomaterials, and has ini-
tiated the synthesis of nanoalloys of various shapes.[4c,7]
The shape anisotropy provides unique physio-chemical
properties owing to their special confinement of phonons,
electrons and electric fields in addition to their surface
to volume ratio. More precisely, anisotropy offers fea-
tures and functions which provide significant change in
their chemical, magnetic and opto-electronic properties
for instance, the optical properties mainly depend on size,
shape, surface charge, and composition, etc. Similarly,
surface area, number of edges, crystallographic facets,
faces, etc. plays an important role in catalytic activity and
chemical reactivity. Indeed, the shape anisotropy behav-
ior in nanoalloys such as nanorods,[8] nanowires (NWs),[9]
platelets,[10] nanostars,[11] and rings,[12] in addition to
nanoparticles (NPs), makes them promising functional
materials. This control over morphology and size, along
with the elemental composition of the alloys, has pro-
gressively evolved into downsizing bulk materials into
complex multi-component nanomaterials with new prop-
erties. Therefore, single-(unary), two- (binary), and three-
(ternary) element alloy nanostructures have been devel-
oped using a variety of techniques, to combine the diverse
properties of the employed elements through a single-
alloy nanostructure.[5a,13] This has led to the exploration
of multi-metal nanostructures at the nanoscale. Indeed,
the incorporation of multiple elements into a single nanos-
tructure alloy (solid-solution) form is an effective way to
go beyond the capabilities of single-element nanostruc-
tures. However, research on these multi-metal nanoalloys
could not go beyond ternary alloy nanostructures, owing
to the complexities involved in accommodating multiple
elements as a solid solution in a single nanostructure.
Recently, with the discovery of a new class of alloys—high-
entropy alloys (HEAs)/multi-component alloys (MCAs)—
scientific research interest has been quickly diverted to the
synthesis of alloys with multiple metals.[14] HEAs/MCAs
are alloys containing five or more elements in high con-
centrations. Based on their compositional range, these
alloys are categorized as HEAs (5–35 at.%) and MCAs.
However, HEAs are considered as special alloys as they
contain several elements unlike in the conventional alloys.
Concept of HEAs initially was introduced by Brian Can-
tor and Jien-Wei Yeh independently, where new alloy
design has begun to explore novel alloys with excep-
tional properties. Soon this exploration of new alloy design
was not just limited to producing bulk structural HEAs
through various processing techniques but for various
functional applications including new magnetic alloys.[15]
This controlled range of the multiple-element composi-
tion as a solid-solution offers promising properties that
are not observed in conventional alloys. Therefore, if these
HEAs/MCAs are explored in the form of multi-metallic
nanostructures, they can act as multi-functional materials
with exceptional properties for diverse new-age applica-
tions in fields spanning from biomedical and catalysis to
energy conversion.[16] The nanostructuring of HEAs are
expected to further enable the tunability in performance of
the material and selectivity through their electronic struc-
ture and surface properties. In addition, the presence of
multiple elements offers structural stability even in harsh
environments.[17] On the other hand, the symmetry break
of surface atoms often offers various adsorption sites in
bulk shape single element materials especially known for
their catalytic performance. However, in case of HEAs, it is
still unclear as they already have large heterogeneities and
big compositional space arising from multiple atoms. Nev-
ertheless, it is expected that the HEAs can offer unique and
synergistically enhanced functionalities, notably in catal-
ysis, resulting from the symmetry break of surface atoms
of multiple elements of dissimilar sizes and characteris-
tics. This further offers more opportunities of tunability
in electronic structure and surface energies that can aug-
ment the adsorption, desorption, stability and reactivity
outputs. However, to date, research on HEAs has been
limited to bulk materials, thin films, and powders,[18] and