By Younan Xia
ESI Special Topics,
March 2004
Citing URL - http://www.esi-topics.com/nhp/2004/march-04-YounanXia.html
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Younan Xia answers a few questions about this month's
new hot paper in the field of Chemistry.
From
•>>March 2004
Field:
Chemistry
Article Title: Shape-controlled synthesis of gold and silver nanoparticles
Authors: Sun, YG;Xia, YN
Journal: SCIENCE
Volume: 298
Page: 2176-2179
Year: DEC 13 2002
* Univ Washington, Dept Chem, Seattle, WA 98195 USA.
* Univ Washington, Dept Chem, Seattle, WA 98195 USA.
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Why
do you think your paper is highly cited?
Our paper provides an intellectual framework—including both
rationale and methodology—for the synthesis of metal
nanostructures with well-controlled shapes and facets. It has
quickly triggered an exponential growth of research activities in
this field by allowing many groups to synthesize these
nanostructures and to explore their fascinating properties and
unique applications.
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“We believe that shape control provides one of the most powerful means to tailor the properties of metal nanostructures.”
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Nanostructures—a class of materials having at least one
dimension in the range of 1 to 100 nm—exhibit distinctive
properties that have substantially deviated from those of bulk
materials. There are a large number of opportunities that can be
realized by making new types of nanostructures or by down-sizing
currently existing structures to the nanoscale. Metal nanostructures,
such as those described in our paper, have already found use in many
applications that include catalysis, photography, photonics,
surface-enhanced Raman scattering (SERS), and health care (sensing,
biological labeling, and image contrast enhancement). The intrinsic
properties of these structures—and thus their performance in
applications—are determined by a number of physical parameters
that include size, shape, composition, crystallinity, and structure
(solid vs. hollow). In principle, one can tailor the properties by
controlling any one of these parameters, albeit the flexibility and
scope of tuning may strongly depend on the specific parameter.
We believe that shape control provides one of the most powerful
means to tailor the properties of metal nanostructures. For example,
theoretical work has indicated that the number and position of
surface plasmon resonance (SPR) modes—as well as the spectral
range for SERS—of silver nanostructures have a strong correlation
with their shapes. The longitudinal SPR peak of gold (or silver)
nanorods has also been shown to display a considerable dependence on
the aspect-ratio. In the case of catalysis, it is well-known that
platinum nanoparticles selectively catalyze different types of
reactions depending on the crystallographic planes exposed by their
surfaces: for example, with {100} and {210} facets promoting
reactions that involve hydrogen and carbon monoxide, respectively.
In spite of its technological importance, the challenge to
synthetically and systematically control the shape of metal
nanostructures has been met with limited success. Recently, we and
many other groups (e.g., Mostafa El-Sayed at Georgia Tech, Paul
Alivisatos at UC Berkeley, Chad Mirkin at Northwestern, Cathy Murphy
at South Carolina, Naomi Halas at Rice, Peidong Yang at UC Berkeley,
David Carroll at Clemson, and Liz-Marzán at University de Vigo of
Spain) just started to tackle this synthetic problem. Our paper
"Shape-controlled synthesis of gold and silver nanoparticles"
might represent a timely breakthrough in this field. Although this
paper only reported a case study on gold and silver, the
methodologies seem to be extendable to many other metals. As a
result, this paper has stimulated an exponential growth of research
in this field by enabling a range of exciting new demonstrations.
Does
it describe a new discovery or new methodology that's useful to
others?
Yes, our paper describes two different approaches to the
synthesis of metal nanostructures with well-controlled shapes and
facets. In the first approach, poly(vinyl pyrrolidone) (PVP) was
used as a capping reagent to control both nucleation and growth of
silver atoms, and thus to obtain silver nanocubes of controllable
sizes as monodispersed samples and in large quantities. These
nanocubes were single crystals and were characterized by slightly
truncated corners and edges. They were mainly enclosed by {100}
facets. The key to the success of this synthesis was PVP, a polymer
capable of selectively capping the {100} rather than {111} or {110}
facets. In a related demonstration, we also showed that uniform
silver nanowires (with five-fold twined, pentagonal cross-sections)
could be synthesized by controlling the amount of PVP added to the
reaction medium in the nucleation step (see, for example, Y. Sun, B.
Mayers, T. Herricks and Y. Xia, "Polyol synthesis of uniform
silver nanowires: A plausible mechanism and the supporting
evidence," Nano Letters 3: 955, 2003). In the second
approach, the silver nanocubes served as sacrificial templates for a
galvanic replacement reaction between silver and chloroauric acid to
generate single crystalline nanoboxes—truncated, hollow cubes
bounded by six {100} and eight {111} facets—of gold (as well as
its alloys with silver). More recently, we further demonstrated that
the second approach could be readily extended to fabricate metal
(e.g., gold, palladium, and platinum) nanostructures characterized
by hollow interiors and a wide variety of morphologies (e.g.,
nanoscale boxes or tubes with highly porous walls). For those
interested in this work, please refer to the following publications:
Y. Sun, B. Mayers and Y. Xia, "Metal nanostructures with hollow
interiors," Advanced Materials 15: 641, 2003; Y. Sun and
Y. Xia, "Alloying and dealloying processes involved in the
preparation of metal nanoshells through a galvanic replacement
reaction," Nano Letters 3: 1569, 2003; Y. Sun and Y. Xia,
"Mechanistic study on the replacement reaction between silver
nanostructures and chloroauric acid in the aqueous medium," Journal
of the American Chemical Society, 2004, in press; Y. Sun
and Y. Xia, "Multiple-walled nanotubes made of metals," Advanced
Materials, 2004, in press. These studies fully
demonstrated the capability and feasibility of the synthetic
strategies as outlined in our Science paper. More
importantly, these metal nanostructures are immediately useful in
applications such as surface plasmonics, SERS detection,
optoelectronics, biomedical imaging, catalysis, and hydrogen
storage.
What
were some of the circumstances that led you to do this research?
I worked with Professor George
M. Whitesides as a Ph.D. student and then a postdoctoral
fellow at Harvard University. My thesis work involved the
development of soft lithography (see, for example, Y. Xia and G. M.
Whitesides, Angewandte
Chemie International Edition in English 37: 551, 1998),
which represents a top-down approach to the fabrication of
nanostructures. When I launched my own research at the University of
Washington, I wanted to explore different routes to nanostructures,
in particular, the bottom-up approach that involves the formation of
nanostructures from building blocks with smaller dimensions. I asked
my student (Byron Gates) to begin with trigonal selenium and
tellurium, two solids well-known for their highly anisotropic
crystallographic structures (both of them are constructed from
helical chains of atoms) and interesting photoconductive properties.
By taking advantage of the anisotropy in structure, we were able to
grow uniform nanowires with diameters in the range of 10-100 nm and
lengths up to hundreds of micrometers (a recent review: B. Mayers,
B. Gates and Y. Xia, "One-dimensional nanostructures of
chalcogens and chalcogenides," International Journal of
Nanotechnology 1/2: 86, 2004). While working on this system, I
also asked myself if a similar chemical approach could be applied to
the synthesis of metal nanowires. It was soon realized that most of
metals crystallize in the face-centered cubic lattice (which is a
highly symmetric structure), and one has to introduce a capping
reagent to help control the shape and structure of seeds formed in
the nucleation process. I asked Dr. Yugang Sun, a postdoc who just
joined my group at that time, to conduct some survey experiments
with silver by using the well-known polyol process (see, for
example, F. Fievet, J. P. Lagier and M. Figlarz, Materials
Research Society Bulletin 14[12]: 29, 1989). In a typical polyol
synthesis, PVP is often added as a surfactant to stabilize the
silver colloids. After we had completed a number of syntheses, we
realized that the silver nanostructures obtained using the polyol
method were extremely rich in terms of morphological variation. The
product of each synthesis usually contained a mixture of many types
of structures such as cubes, tetrahedrons, rods, quasi-spheres, and
irregular particles. After analyzing the possible function of each
component in this system, we concluded that PVP not only served as a
stabilizer for the product but also played a critical role in
dictating the nucleation and growth of silver atoms. By controlling
how the PVP was added and how much of it was added (through the use
of syringe pumps), we finally succeeded in directing the product of
each synthesis solely to one particular morphology or shape.
Could you summarize the significance of your paper in layman's
terms?
Our paper provides two chemical methods for the synthesis of
metal nanostructures having well-controlled shapes and facets. It
has allowed many research groups to enter this field and to explore
fascinating properties and applications associated with this new
class of nanostructured materials. It is also expected that this
work will have significant impact on a range of areas that include
microelectronics, photonics, spectroscopy, sensing, biotechnology,
medical diagnostics, catalysis, and energy conversion/storage.
Younan Xia
Associate Professor of Chemistry
Department of Chemistry
University of Washington
Seattle, Washington, USA
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ESI Special Topics,
March 2004
Citing URL - http://www.esi-topics.com/nhp/2004/march-04-YounanXia.html
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