Advanced Materials - 2023 - He

Recent Advances of Seed-Mediated Growth of Metal Nanoparticles: from Growth to Applications
Meng-Qi He, Yongjian Ai*, Wanting Hu, Liandi Guan, Mingyu Ding and Qionglin Liang*
Dr. M.-Q. He, Dr. Y. J. Ai, W. T. Hu, L. D. Guan, Prof. M. Y. Ding, Prof. Q. L. Liang
MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology,
Department of Chemistry,
Laboratory of Flexible Electronics Technology,
Center for Synthetic and Systems Biology,
Tsinghua University-Peking University Joint Centre for Life Sciences,
Tsinghua University, Beijing 100084, P.R. China
E-mail: ayj@tsinghua.edu.cn, Liangql@tsinghua.edu.cn
Keywords: metal nanoparticles, seed-mediated growth, growth influencing factors,

morphology control, influencing factors
Abstract
Unprecedented advances in metal nanoparticle synthesis have paved the way for broad
applications in sensing, imaging, catalysis, diagnosis and therapy by tuning optical properties,
enhancing catalytic performance, and improving chemical and biological properties of metal
nanoparticles. The central guiding concept for regulating the size and morphology of metal
nanoparticles has been identified as the precise manipulation of nucleation and subsequent
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growth, often known as seed-mediated growth methods. However, since the growth process
is sensitive not only to the metal seeds but also to capping agents, metal precursors, growth
solution, growth/incubation time, reductant and other influencing factors, the precise control
of metal nanoparticle morphology is multifactorial. Further, multiple reaction parameters are
entangled with each other, so it is necessary to clarify the mechanism by which each factor
precisely regulates the morphology of metal nanoparticles. In this review, to exploit the
generality and extendibility of metal nanoparticle synthesis, we systematically summarized
the mechanism of growth influencing factors in seed-mediated growth methods. Second, we
focus on a variety of critical properties and applications enabled by grown metal
nanoparticles. Finally, we review the current progress and offer insights on the challenges,
opportunities, and future directions for the growth and applications of grown metal
nanoparticles.
1. Introduction
In 1916, the seed-mediated growth was initially proposed for the synthesis of bulk single
crystals, also known as the Czochralski (Cz) method.[1] Since the Cz method and seed-
mediated growth of metal nanoparticle (NPs) follow the same general principles, seed-
mediated growth of NPs could be thought of as a nanoscale equivalent of Cz methods.
Murphy was some of the first to show in 2001 that a nanoscale equivalent of the Cz methods
might be utilized to regulate gold nanoparticles (GNPs) seeds to generate gold nanorods
(GNRs).[2, 3] In a normal seed-mediated growth method, preformed metal NPs were used as
seeds, and they were then introduced to a growth solution containing metal precursors,
reductants, or capping agents, and so on, to commence secondary growth on the seeds.[4-6]
The second growth process mainly consists of two parts: (1) metal precursors reduction; (2)
metal atoms deposition on pre-existing metal seeds. Thus, seed-mediated growth is a
powerful and versatile method for preparing metal NPs with well-defined size, composition,
morphology and structure (Figure 1).[7, 8] The great appeal of this approach over the one-step
approach is that the nucleation and growth steps are separate, making it easier to regulate

both the size and shape of a product by simply focusing on the growth step.[9, 10] Actually,
there is a special seed-mediated growth method where there is no seed at the beginning, but
after mixing capping agents, metal precursors, reductants, etc., the reaction goes through two
steps in the same solution: first a nucleation reaction and then a growth reaction. This means
that it is a process of self-seeding growth of metal NPs. Moreover, the grown shell can
protect metal NPs from aggregation, sintering or interference from other reagents. Therefore,
the seeded growth method has generally been utilized to increase the size of the metal NPs or
produce core-shell metal NPs with different morphologies.[11, 12]
Figure 1. Mechanisms of seed-mediated growth of metal NPs.
The morphology of metal NPs affects numerous of their relevant physical, chemical and
physiological properties, and thus influences the performance of metal NPs in terms of
physicochemical (such as optical and catalytic), biomedical and biological performance.[13]
Although many different NPs can now be produced using traditional synthesis techniques, it
remains difficult to rationally construct the required structures in a highly predictable way.[14]
As described above, the seed-mediated growth method relies on the conversion of existing
NPs into desired ones, allowing direct prediction products and independent control over
response parameters.[15, 16] In fact, by adjusting the thickness, shape, and composition of the
shell material as well as the size, shape, and composition of the core, it is simple and effective
to alter the morphology and structure of metal NPs.[17, 18] However, the effects of
experimental parameters in seeded growth methods are not systematically summarized and
discussed, and are often entangled with each other. Therefore, systematic comprehension of
the growth mechanism of shape-dependent influencing factors (such as seeds, capping agents,
metal precursors, growth solution, reductants and other impact factors) during the growth of
metal NPs is necessary to foresee their characteristics and investigate their applications (such
as optical, catalytic and biomedical applications).[19, 20]
Figure 2. An outline of seed-mediated growth of metal NPs: from growth influencing factors
to applications.
Additionally, in the past two decades, metal NPs with various morphologies synthesized
by seeded growth method have also been rapidly developed and used for various
applications.[21, 22] In this article, we review the last two decades of researches on metal NPs
with different morphologies and structures synthesized by seed-mediated growth method for
physicochemical and biomedical applications such as sensing, imaging, catalysis or therapy,
especially focus on factors and mechanisms that influence the morphology and structure of
metal NPs. In a word, we have systematically elaborated the growth, mechanism, properties
and applications of metal NPs synthesized by seed-mediated growth method. In detail, we
intend to discuss our understanding of the effect of (I) metal seeds (size, shape and faceting);
(II) capping agents (functional group, concentration, and size; DNA, amino acid, peptide,
protein and non-biomolecules as capping agents); (III) metal precursors (reduction potential,
concentration, injection rate and the extent of lattice mismatch with seeds); (IV) growth
solution (pH and temperature); (V) growth/incubation time; (VI) reductants (concentration,
reduction pathway and structural characteristics); (VII) external factors (light, chelating
agents and templates) as growth influencing factors in the seed-mediated growth methods
based on the relevant results obtained in our research (Table 1). We then focus on a variety
of critical properties and applications enabled by the core-shell metal NPs, including those
related to optics (Raman, fluorescence, scattered light, chirality and absorption), catalysis
(photocatalysis and electrocatalysis), and biomedical applications (photoacoustic imaging and
photothermal therapy) (Figure 2). It is worth mentioning that novel metal NPs show unique
localized surface plasmon resonances (LSPR, a phenomenon in which the optical property
change are induced by manipulating the collective oscillation of free electrons on metal NPs'
surface by incident light).[23-25] This greatly expands the range of applications for metal NPs.
Finally, we summarize the current progress and provide insights on the challenges,
opportunities, and potential future directions for the growth of metal NPs and applications of
grown metal NPs.
Table 1. Summarize the growth influencing factors of metal nanoparticles by seed-mediated

growth methods.
Influencing factors Specific classification Morphology of seed Type of metal Application Ref.
Size and shape Nanorods CdSe-Au / 38

Metal seeds
Faceting Nanorods Au Chirality 44

Nanocubes / / 45
Decahedras Au-Ag / 49
Bipyramids Au-Ag / 50
Nanospheres Au / 51
Biomolecules Octahedrons Au Chirality 58
Photoacoustic
imaging
Nanospheres Co, Ni, Cu-Tc 59
/Photothermal
therapy
Capping agents
Nanorods Au-Ag / 63
Photothermal
Nanorods Au 66
therapy
Non-biomolecules
Concave pentagonal
Au-Cu Scattering spectra 67
nanoparticles
Nanorods Au Absorption 69
Inherent properties
Nanorods Au Absorption 70
Cuboctahedral
Reduction potential Pd / 71
nanoparticles
Metal precursors Concentration Nanospheres Au-Cu / 74
Injection rate Nanocubes Rh / 75
Lattice mismatch Nanospheres Au / 76
pH Nanocubes Ag-Au / 85
Growth solution
Temperature Nanocubes Pd / 92
Growth time / Nanoplates Ag / 94
Incubation time / Nanospheres Au Absorption 93
Decahedral
Concentration Au / 105
nanoparticles
Reductants
Reduction pathway Nanospheres Au-Ag / 106
Structure characteristics Nanowires Cu Raman 107
External factors Light Nanoplate Au / 112

Chelating agents Nanospheres Au / 113
Template Nanorods Au Chirality 114
2. Influencing Factors of Seed-Mediated Growth of Metal Nanoparticles
In the typical seed-mediated growth method, there are two processes: seed pre-synthesis
and seed growth.[26, 27] Obviously, if the morphology of NPs needs to be significantly
regulated, it is usually necessary to understand the mechanism of seeded growth method.
Although great efforts have been made to develop NPs with different morphologies, research
has thus far mostly been focused on specific materials or synthetic techniques, and there is a
lack of systematic summarization and discussion of which factors affect and how to affect the
morphology of NPs. Subsequently, we draw the conclude that the diversity of metal NPs
synthesized by the seed-mediated methods is affected by an array of growth influencing
factors based on extensive experimental work, including seeds, capping agents, metal
precursors, growth solution, growth/incubation time, reductants, and external factors. More
importantly, we also analyzed the mechanisms by which these factors affect the growth
morphology of metal NPs and the relationship between thermodynamic and kinetic
parameters and key growth influencing factors in seed-mediated growth methods. In fact,
thermodynamics focuses with the force that propels a system from its beginning state to its
final state, whereas kinetics is focused on the energy barriers of the particular pathways in
this process. The primary procedure in thermodynamic and kinetic analysis is comparing the
relative stability of the initial, intermediate, and product states. In other words, the former
focuses on the result of the reaction, while the latter focuses on the process of the reaction.
Identification of these influencing factors and comprehension of their mechanism give useful
directions for growth of metal NPs with high-quality. Therefore, we will pay special attention
to key principles and methodologies to ensure directional seed growth in this article.
2.1 The Influence of Seeds
Seed-mediated growth methods generally refer to atom deposition using metal NPs as
seeds. The metal seeds can be utilized or collected in the initial reaction medium before being
distributed to another medium.[28, 29] It is worth pointing out, however, that the specific
function performed by the seeds in those early researches was rather ambiguous. It was not
until a few years later that scientist realized there was a direct connection between the
crystallinity or internal structure of a seed and the prospective of a metal NP. In fact, when
defining a seed, two factors must be considered: the internal structure (or crystallinity) and
the surface structure (or faceting).[30] Several review articles have comprehensively
summarized the effects of seeds with different internal structures on the morphology and
structure of grown NPs; therefore, this review will no longer use this classification as a
basis.[31, 32] Crystal faceting is a characteristic that may be more precisely determined later in
the seed synthesis procedure. In addition, the size and morphology of the seeds also have an
effect on the grown NPs.[33, 34] Therefore, regarding the classification of seeds, we mainly
study the effect of seed size, shape and faceting on grown NPs synthesized by seed-mediated
growth methods.
2.1.1 Size and Shape of the Seeds
The size and shape of the NP seed can have a range of effects on growth of metal NPs.
First, according to the Gibbs–Thompson effect, chemical potential of NPs has inversely
proportional to its radius. Smaller NPs have a greater radius of curvature than larger NPs and
are accompanied by a higher chemical potential and more reactive. For example, Dabbousi
and colleagues found that the temperature needed to form a ZnS shell onto a CdSe core rose
with the diameter of the core, implying that smaller NPs were more reactive.[35] Similarly, a
similar phenomenon is observed for differences in seed shape. For anisotropic NP seeds,
growth should be faster where the radius of curvature is high.[26, 36] In contrast to the sides of
NRs are faceted and generally flat, the ends are often rounded, meaning there is a larger
surface energy and a higher reactivity. Previous research has shown that GNPs develop more
preferentially at the ends of CdSe and CdS NRs than on their sidewalls.[37] For example,
Figure 3A shows the selective growth of gold onto the ends of CdSe NRs via a simple
reaction at ambient temperature, resulting in “nanodumbbells.”[38] In a typical gold growth
reaction of Au onto CdSe rods, a growth solution prepared containing AuCl3 (the metal
precursor), dodecyldimethylammonium bromide and dodecylamine (the capping agent) in
toluene (the reductant) and sonicated for 5 min at room temperature. CdSe quantum rods
(metal seeds) of required dimensions were dissolved in toluene in a three-neck flask under
argon. The growth solution was added drop-wise over a period of 3 min. During the addition,
carried out room temperature, the quantum rods were precipitated by addition of methanol
and separated by centrifugation. And the authors have proposed that the ends of rods are
more reactive due to increased surface energy, which also contributes to preferential growth
along ends of CdSe rods. In fact, the NRs synthesized by the seed growth method also grow
anisotropic. Generally, in order to start and maintain anisotropic growth from a highly
symmetric seed, the synthesis must be placed under a kinetic control. This can be obtained by
adjusting the formation or deposition rate of metal atoms as well as the surface diffusion rate
of adatoms. For example, the initial stage of nanosphere generation is kinetically controlled.
At the second stage, a slower reaction rate and the dissolving/deposition dynamic would aid
in establishing the stable facets.
In addition, the time gap between the preparation of seeds and their introduction into the
growth solution is another crucial factor of how seeds affect the growth of metal NPs. This
means that the final shape of the seed varies with the time interval. Although it is though that
seeds are formed practically immediately after reduction begins with NaBH4, the excess
reductant must be removed by aging the seeds. Two steps operate during this time: (1) the
decomposition of excess NaBH4, (2) the ripening of metal seeds. The final metal seeds can
often be utilized after being stored at 27 °C for a few hours.[39] As the seeds continue to age,
more NPs rather than NRs start to develop in the growth solution.[40, 41] This also brings some
implications for improving the yield of NRs. In short, these results show that the size and
shape of the metal seeds, which are controlled by a number of factors, have an impact on the
structure and morphology of the resulting metal NPs.
2.1.2 Faceting of the Seeds
When the seed size exceeds a few nanometers, the emergence of well-defined surface
facets may have a significant impact on predicting the growth trend of seeds.[42, 43] The
presence of facets may allow for selective growth owing to changes in chemical reactivity,
which may be another factor influencing the reported gold growth behavior on CdS and CdSe

NRs.[37] Cadmium chalcogenide NRs has an atomic structure that is not centrosymmetric: one
end facet is often enriched in cadmium, while the other end is usually richer in chalcogenide.
Because the metal-chalcogenide bond enthalpy is often high, metal growth should be easier at
such a location. This means that gold preferentially grows at the chalcogenide-rich end,
followed by growth onto other sites at longer reaction times. The difference in affinity
between the capping agent and facets of the seed is another critical element for selective
development. For example, Wong and co-authors found that multiple tips developed on the
end of the GNRs as the CYS concentration increased, accompanied by an increase in the
anisotropy factor (Figure 3B).[44] Before synthesizing functional NRs, GNRs were pre-
synthesized as seeds. The GNRs were also synthesized by seed-mediated growth method, and
the synthesis process was as follows: a seed solution was firstly prepared in which 10 mL
solution of CTAB containing HAuCl4 was mixed with NaBH4. The solution was stored at
room temperature for 2 h before use. A growth solution was prepared by adding HAuCl4 (the
precursor), AgNO3 (the capping agent), ascorbic acid (AA, the reductant), and HCl into 40 ml
of CTAB solution. Then synthesized seed solution was added to the growth solution, mixed
thoroughly and placed at 25 °C for 6 h. To fabricate functional NRs, different concentrations
of CYS (the capping agent) were added into the solution which was prepared by mixing
CTAC, AA (the reductant) and HAuCl4 (the metal precursor). Subsequently, 1 mL of gold
NRs (the seeds) were added into the CYS containing solution and the mixture was gently
shaken for several seconds, and then allowed to stand at room temperature for 90 min. Then,
HAuCl4 solution (the precursor) was added to the mixture. After 2 h, the overgrown NRs
were obtained. In fact, CTAB can form a bilayer around GNR. The interaction between
CTAB and Au (111) faces (both ends of GNRs) is comparatively weaker than the CTAB-Au
interaction on Au (100) and (110) faces (both sides of GNRs), with the (111) end face having
a lower packing density than the (100) and (110) side face. Thus, GNR's exposed (111) end
face, which has many active sites, shows a strong preference for CYS molecules.
Furthermore, CYS molecules selectively replaced CTAB at the ends of GNRs by forming
strong Au-thiol bonds because CTAB is more weakly bound at the ends. It can be seen that
the morphology of metal NPs is sometimes not controlled by a single factor. In this study,

both the faceting of the seed and the capping agent influence the morphology of the metal
NPs.
Common isotropic NPs such as nanospheres. Due to the isotropic characteristics of gold
nanospheres (GNSs), the GNSs' surface is adsorbing the precursors without discrimination.
At this time, the size of GNSs becomes larger and the surface becomes rough. Nanocubes are
a bit more complex than nanospheres. Freshly produced atoms should be deposited into the
corners of a cubic seed during shape-controlled development due to the high energy of these
locations. In fact, adatoms can not only be deposited in corner sites, but also diffuse to
various surfaces.[45] The rate of atom deposition and surface diffusion (i.e., Vdep/Vdiff) has a
substantial influence on the development pathway and hence the shape of the NPs, leading to
four different geometrical shapes at the end. Figure 3C(a) shows that when Vdep/Vdiff << 1,
the majority of the adatoms in the corners will move to the side faces and edges, and growth
will prefer the (100) and (110) directions, resulting in the development of thermodynamically
favorable cuboctahedrons. In contrast, Figure 3C(d) shows that when Vdep/Vdiff >> 1, growth
will be shifted to the (111) directions as surface diffusion can be neglected, supporting the
creation of a kinetically favorable octapod as the end result. In circumstances where the ratios
of Vdep to Vdiff are halfway between the two extremes, similar arguments can be used. For
example, when Vdep/Vdiff is slightly less than 1, some adatoms remain at the corners while the
remainder migrate to the side faces and edges, resulting in an expanded cube with slightly
truncated corners (Figure 3C(b)). Thermodynamics favor this shape as long as the reaction
solution contains enough capping agent to sufficiently passivate and stabilize the expanded
side faces. When Vdep/Vdiff is significantly larger than 1, adatoms near the corners can diffuse
to the edges in modest numbers (there are relatively more active sites at the edges than at the
sides due to the lower coverage density of the capping agent). Thus, Figure 3C(c) shows that
the finished object will have a concave shape. The total surface free energy of the four types
of nanocrystals is as follow: cuboctahedron < truncated cube < concave cube < octapod.
Notably, the surface diffusion rate can be used to identify whether the product is being
created under thermodynamic or kinetic control. When Vdep/Vdiff < 1, the growth is under
thermodynamic control, and when Vdep/Vdiff > 1, the synthesis is under kinetic control.

Figure 3. (A) TEM images displaying the regulated growth of gold at the CdSe quantum rod
ends.[38] Copyright 2004, American Association for the Advancement of Science. (B) GNRs
synthesis at various L- or D-Cys concentrations using a seeded growth method.[44] Copyright
2018, WILEY-VCH. (C) Diagram illustrating how a cubic seed with side faces coated by a
capping agent changes in shape under four different kinetic conditions (three-dimensional
model).[45] Copyright 2015, American Chemical Society.
In addition to NRs and nanocubes, the surface energy between the facets of the
nanotriangles (NTs) is also different. For the synthesis of the NTs, citrate ligands serve as the
sole surfactant, essentially blocking outgrowth on the basal {111} facets and allowing only
lateral expansion. Citrate was used to convert the Ag+ precursor to create Ag–citrate
complexes. The complexation slows the reduction reaction and releases the citrate anion,
which contributes in the anisotropic growth of the nanoplates.[46] And surface energy for
different faces of nanotriangles changes in the following order: γ{111}< γ{100} < γ{110}.
Wei employed growth of gold nanotriangles (GNTs) in the presence of chiral ligands to
construct discrete gold propeller-like structures. The three tips of each nanoparticle twist in a
different planar orientation. This is because CYS preferentially binds to the three tips of the
GNTs. Furthermore, the chiroptical property of the as-formed Au propeller-like structures is
very strong. The amount of chiral ligands on the surface of GNTs was shown to be crucial in
determining their chiroptical properties.[33] It can be seen that the difference of the faceting of
the seeds has a great influence on the morphology of metal NPs.
2.2 The Influence of Capping Agents
In the synthesis of the metal NPs using a seed-mediated growth method, the precise
regulation of the further growth using capping agents has been identified as the principal
method for altering the form of the NPs. The capping agent absorbed or bound to the seed
would protect specific facets or significantly reduce the surface energies of facets, resulting in
the confined growth in a specific direction. A variety of different kinds of capping agents
were used to control the morphology of metal NPs. In the following section, we primarily
focus on biomolecules and non-biological molecules as multifunctional modulators that
manipulates the growth mechanism of metal NPs. For example, biomolecules, we mainly
selected DNA (single-stranded DNA, double-stranded and DNA origami), amino acids
(CYS), peptides (GSH) and proteins (BSA), etc; for non-biological molecules, there are gases
(NO2), halides (CTAC), polymer (PVP), oleylamine, halide ions (Cl−, Br−, I−) and small
organic thiol molecules, etc. Moreover, we also investigated the impact of the intrinsic
characteristics of the capping agents on the morphology and properties of the metal NPs.
2.2.1 Biomolecules-Mediated Growth of Metal Nanoparticles
Functional biomolecules including DNA, amino acids, peptide and proteins have been
operated as capping agents with integrated coordination, reduction, and stabilization
functions for the synthesis of metal NPs, providing a variety of predictable NPs with different
morphologies. Common reducing and coordinating functional groups from biomolecules are
hydroxyl, amine, carboxyl, and phenol groups. In fact, great attempts have been undertaken
to create metal NPs during the past ten years by exploiting the specific binding property of
biomolecules as capping agents. Although capping agents can control the morphology of NPs
by binding to metal ions or NP surfaces, they also make the NP growth process more
complex and unpredictable.
The most extensively studied functional biomolecule is by far DNA due to the tunable
sequence, length, conformation, and programmable molecular structure.[47, 48] DNA has a
double helix structure, containing nitrogen- and oxygen-functionalized nucleobase and sugar
units, and the charged phosphate groups on the backbone. The above structural features are
conducive to directional diffusion and deposition of precursor under the modulation of DNA.
Since the molecular structure of DNA and how it binds to metal ions can be precisely
predicted from its sequence, DNA is a star candidate for the precise synthesis and prediction
of NP structure. Lu and co-authors used single-stranded DNA (sequence from 5’ to 3’-
terminal, C20: CCCCC CCCCC CCCCC CCCCC; A20: AAAAA AAAAA AAAAA
AAAAA; T20: TTTTT TTTTT TTTTT TTTTT) to control the synthesis of various colloidal
metal NPs, and systematically studied the effect of different DNA sequences on NP
morphology. On this basis, Lu reported single-stranded DNA-mediated controllable synthesis
of Au-Ag core-shell NPs and a quantitative study of growth mechanism of NPs (Figure
4A).[49] The Au decahedra (the seed) was incubated with single stranded DNA (capping
agent) for 15 min. Then, AA solution (the reductant) and AgOAc (silver acetate) solution (the
metal precursor) were added, followed by vortex of the solution. Then, the reaction was left
to completion. This work quantified the precise regulate of DNA over Ag+ reduction and the
growth mechanism of Au-Ag nanocore-shell structures. The authors calculated the
equilibrium binding constants of DNA and Ag+, the kinetic rate constants of sequence-
specific Ag+ reduction, and the percentage of active surface sites for distinct sequences. The
results revealed that these three influencing factors had a synergistic effect on atom
deposition and diffusion in the growth of NPs from two aspects: kinetics and
thermodynamics respectively. For example, the strong binding between C20 and Ag+
prevented the reduction of free Ag+, whereas a slow solution reduction predominated in C20-
mediated Ag+ reduction pathway. As a result of both conditions, the rate of Ag0 deposition

(Vdep) was slow. Among the three sequences (A20, C20, T20), C20 also has strongest
passivation effect on the surface, which reduces the diffusion rate (Vdif) of atoms on the
nanocrystals. Adatoms migrated to low surface energy sites because the reduced Vdif was still
greater than Vdep. The key thermodynamically advantageous feature of the generated
structures was the presence of {111} facets. Similarly, morphology of NPs with A20 or C20 as
capping ligands can be predicted. Therefore, the capping agent layer influences the
thermodynamic stability of the facets while interacting with the solvent and crystal surface,
which affects the final states of the metal NPs growth. In a word, Lu and co-authors studied
DNA molecules of different sequences as capping agents in synthetic NPs to precisely
control the rate of Ag+ reduction and the growth rate of different crystal planes. Lu further
investigated how different DNA sequences can precisely control the structural parameters
and optical properties of NPs during the growth of Au-Ag-core-shell nanostructures. Lu
systematically analyzed the relationship between the tip angle and aspect ratio of the Au
bipyramid and the optical parameters of the NP. Based on the understanding of how the two
structural (the tip angle and the aspect ratio) change during NP growth, they designed a series
of novel nanostructures with predictable properties by changing the DNA sequence in the
growth of Au-Ag nanostructures (Figure 4B).[50]
In addition to single-stranded DNA as capping agents, double-stranded DNA can also be

used as capping agents. In recent, DNAs have also been used to control the growth of
colloidal metal NPs with either double-strand DNA-modified NPs as cores or DNA-derived
structures (e.g., DNA origami) as templates to generate a variety of specific nanostructures
and multicomponent colloidal metal NPs with tailorable optical properties and controlled
morphologies. Sim et al. achieved well-controlled growth of colloidal metal NPs from a
double-strand DNA-modified GNP seed while using metal precursor and reductant (Figure
4C).[51]. Moreover, they anchored double-stranded DNA onto GNP seeds to control colloidal
metal NPs of Au atoms from NPs surface to the DNA terminus, driven primarily by the
distribution gradient of precursors. They formed colloidal metal NPs with defined topologies
and some topologies are asymmetric. The approach using DNA as a capping agent allows the
synthesis of NPs with controllable three-dimensional structures in the desired orientation.

It is significant that additional DNA-based nanostructures, such as DNA origami, can
function as stiff and active scaffolding to direct the formation of metal NPs. For example, Yin
and co-authors further investigated the formation of defined three-dimensional metallic
nanostructures from DNA templates through seed-mediated growth methods. The inside of
the three-dimensional DNA origami contains a small GNP-seed. The structure is covered
with lids, and either silver or gold ions are used to develop NPs from the seed.[52] Further,
Seidel et al. used rigid and hollow DNA tubes as models for creating NPs.[53]. Because its
structure was not covered, the metal NPs could grow at either end of the DNA tube.
Coincidentally, long and homogeneous growth of gold NWs in the DNA tube models has
become possible.[54] Moreover, not only can DNA origami nanotechnology control the
directed metallization of metal ions (precursors), but it can also be used with nonmetallic
inorganic sources.[55] Also, the seedless growth method using DNA as a capping agent has
also been used to modulate the structure of NPs due to the unique binding ability of DNA to
metal ions. Li and co-authors found that single-stranded DNA can self-fold into
nanostructures with poly-adenine (polyA) loops, and polyA loops can act as particular sites
for seed-free nucleation and growth of NPs.[56] And Liu's lab reported a facile strategy for in
situ growth of near-infrared emitting GNPs with precisely controlled DNA valence using
phosphorothioates (ps)-modified DNA (psDNA) as a template. The particle size could be
fine-tuned in ultra-small ranges from 1.3 to 2.6 nm by adjusting the ps length of psDNA.[57]

Figure 4. (A) Various DNA sequences influence the shape of Au-Ag core-shell NPs and the
mechanism of the silver ions reduction pathway[49] Copyright 2020, American Chemical
Society. (B) Mechanisms for how Au-Ag nanostructures generated using A20 only, C20
only.[50] Copyright 2022, American Chemical Society. (C) Diagram demonstrating the
crystallization of gold nanocrystals using a double-strand DNA as a capping agent.[51]
Copyright 2016, Nature Publishing Group
Peptides, the same as DNA, can also be used to regulate the growth of NPs. The
abundance of amino acids with various functional groups in their side chains and the
availability of both enantiomers for each amino acid are peptides' key advantages over DNA.
For these aspects, researchers have focused heavily on peptides in the creation of metal NPs
with various morphologies. Nam and co-authors have successfully used to guide the bottom-
up synthesis of chiral plasmonic GNPs using amino acids and peptides as the shape
modifiers.[60] The chiral amino acids (CYS) and peptides (GSH) could regulate the reduction
of gold ions, which also allows chirality transfer to modify the optical properties of resultant
GNPs. In the presence of chiral biomolecules (e.g., amino acids), the evolution of GNP from
low- to high-index-plane directed the chiral-selective deposition of gold ions on GNP seeds
and ultimately transmitted the chirality to the resultant GNPs. Recently, Nam and co-authors
further analyzed the growth process and chirality evolution of the dipeptide (γ-

glutamylcysteine, cysteinylglycine)-guided GNPs from a crystallographic characterization.
When γ-glutamylcysteine is present, the NPs synthesized into a cube-like structure. As
opposed to that, the NPs developed with cysteinylglycine presented a rhombic dodecahedron-
like outline. Overall, dipeptides were used as capping agents in 3D geometric models to give
crystallographic insight into the chiral morphology of NPs. (Figure 5A).[58] For this growth
method, gold seed NPs have to be prepared with exposed low-Miller-index facets. First,
octahedron-shaped GNPs with {111} facets were obtained from GNSs by preferentially
attaching iodine to the {111} crystal facets. Subsequently, the octahedron seed NPs were
grown for 2 h in a growth solution. During growth, the CTAB surfactant stabilized the {100}
plane of gold NPs, and AA (the reductant) promoted growth along the {111}. The
competition between the effects of CTAB and AA in the presence of the gold precursor
exposed the high-Miller-index facets on the GNPs surface. A chiral structure was created as a
result of chiral additives (the capping agent) being added to the growing solution.
Asymmetric growth of high-Miller-index facets exposed on the GNPs was caused by the
enantioselective interaction of the chiral molecule with chiral kink sites. The chiral
morphology of the GNPs in three dimensions was created by the surface-level asymmetry
caused by chiral dipeptides.
Compared to amino acids and peptides as capping agents to study the effects on the
morphology and properties of grown metal nanoparticles, proteins as capping agents have
been less studied. For one thing, the structure of proteins is relatively complex, and the
mechanism of influence is also more complicated. Second, the size of the protein is larger
(amino acids form peptides, and peptides form proteins), and the adsorption of the protein to
the seed surface is not conducive to the growth of another metal layer on the seed surface. In
our study, we found that GNRs were seeded with equal concentrations of amino acids,
peptides and proteins as capping agents, AA as a reducing agent and HAuCl4 as precursor.
When amino acids and peptides were used as capping agents, tips grew on the surface of the
GNRs, while when proteins were used as capping agents, the GNRs only became larger in
size without the appearance of tips. However, when we reduced the concentration of the
protein, the tip also appeared on the surface of the GNRs. This indicates that after the high

concentration of protein adsorbed to the GNR seeds, the precursors could only reach the
surface of the GNR through the gaps between the proteins to grow on the GNR seeds and
could not wrap the adsorbed proteins between the seeds and the gold shell due to their large
size (this is described in detail in the subsection on intrinsic properties of capping agents). In
addition to reducing the concentration of protein, some studies have reported that protein can
be added to the synthesis of seeds, which facilitates the formation of seeds (at this point the
protein acts more as a nanoreactors). Proteins having redox characteristics have been used as
multifunctional nanoreactors for the bottom-up synthesis of various protein-conjugated
nanocrystals because of the reduction potential offered by their redox amino acids. However,
early attempts to fabricate nanocrystals generally resulted in clusters with relatively small
size (e.g., several nanometers). This is because the surface topology and residues of proteins
are discontinuous, as is the distribution of reduction potentials. Yang and co-authors solved
this issue by adding a precipitation agent (Na2S) during the formation of Cu-based
nanoclusters. The specific experimental procedure is as follows: the Cu2+ ionic complex was
first created in the alkaline environment by the interaction of metal ions and functional
groups on amino acid residues in the BSA nanoreactor, and then Na2S was added to induce
nucleation through the precipitation reaction between Cu2+ and S2− in the nanoreactor. After
growth, the CuS nanocrystals eventually become larger in size. (Figure 5B).[59] Actually, the
production of CuS nanocrystals in this reaction was shown to be strongly influenced by the
Cu/S ratio. It is worth noting that the approach was rather general because it worked with
more proteins and metal precursors.

Figure 5. (A) Synthesis of dipeptide-directed chiral NPs.[58] Copyright 2020, WILEY-VCH. 15214095, ja, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202211915 by IFW Dresden LBZ Inst for Solid State, Wiley Online Library on [29/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
(B) Transition metal sulfide nanocrystals generated using a protein-nanoreactor method.[59]

Copyright 2016, WILEY-VCH.
2.2.2 Non-Biomolecules-Mediated Growth of Metal Nanoparticles
Besides biomolecules, non-biological molecules have also been used to regulate the
morphology of NPs due to the close correlation between surface coordination and the shape
regulation. The coordination of small molecule ligands on metal surfaces has stimulated a
large number of experimental and theoretical studies on noble metal NPs. We selected typical

non-biomolecules as capping ligands, such as gases (NO2), halides (CTAB), polymer (PVP),
oleylamine, halide ions (Cl−, Br−, I−) and small organic thiol molecules, etc., to explore the
morphology regulation mechanism of non-biomolecules capping agent-mediated seed
growth.
NPs can be modified using gases as capping agents.[61] For example, because NO2 has a
stabilization impact on Pd{111} facets, Yang and co-authors found that NO2 binding
facilitates the formation of NPs with more exposed Pd{111} facets.[62] In detail, they
introduced Pt seeds to synthesize Pt/Pd core–shell nanocubes with AA as the reductant,
K2PdCl4 as the precursor and NO2 as the capping agents. NO2 dissociates on Pd surfaces,
yielding adsorbed NO and adsorbed atomic oxygen. The NO desorbs between 230 and 300 K,
leaving absorbed oxygen, which may interact preferentially with the Pd surfaces of the grown
NPs. The introduce of NO2 changed the growth rates along the {100} and {111} directions,
resulting in Pt/Pd core-shell cuboctahedra and octahedra. So, it follows that epitaxial growth
of cubic Pd shells on cubic Pt seeds proceeds occurs conformally with balanced growth along
the {100} and {111} directions from the {100}-terminated cubic Pt seeds. Moreover, there
are two sources of NO2, one is directly added to gaseous NO2, and the other is obtained by
adding 1:1 volume ratio of HCl (12.1 M) and HNO3 (15.7 M). But one of the most commonly
used non-biological capping agents to modulate NP morphology is CTAC. Qi and co-authors
showed that it is possible to synthesize homogeneous gold nanoarrows by controlling growth
of GNRs, i.e. the combination of CTAC-induced kinetic control and Ag underpotential
deposition-based selective surface passivation (Figure 6A).[63] CTAC served as a weak
binding ligand. Following the growth of GNRs, two pyramidal heads with the exposed {111}
facets and truncated {100} facets grew at the both ends of the NRs. Another surfactant, PVP
(Poly(vinyl pyrrolidone)), can also act as a capping agent. Notably, PVP binds more strongly
to {100} than the {111} facets, thereby slowing the growth rate along the {100} direction.
Finally, nanocubes and nanoplate were produced, where the {111} facets disappearing more
quickly than the {100} facets.[64, 65]
Also, Chen and co-authors discovered that the embedding of small organic thiol
molecules (AMBI) markedly increased the interfacial energy between the growing material
(Au, Ag, Cu2O) and the seeds (GNRs). In this work, an island-growth model, which states
that a growth site would exhaust the growth materials nearby, creating a concentration
gradient and preventing further nucleation sites within a certain radius, can explain the
variance in the number of gold islands on GNRs (Figure 6B).[66] In addition, oleylamine is an
amine-terminated surfactant that selectively passivated the NP surface, driving the geometric
evolution from concave pentagonal NPs to concave “nanostars”. José-Yacamán reported the
regulated selective growth and high-yield formation of AurichCu (concave pentagonal NPs)
and their evolution into branched structures (concave “nanostars”) through a seeded growth
method with oleylamine as capping and self-assembly promoter agents (Figure 6C).[67] Other
capping agents, halide ions' function in regulating the form of metal nanocrystals has recently
attracted a lot of attention. The halide counterion (Cl−, Br−, I−), can serve as synthetic handles
and interact synergistically to drive the shape-controlled growth of NPs.[68] Of course, there
are many other capping agents not listed that play a crucial role in the morphological
regulation of metal NPs.
Figure 6. (A) Kinetic control of controlled growth of gold nanoarrows combined with specific
surface passivation.[63] Copyright 2017, American Association for the Advancement of
Science. (B) The a) usual wetting and b) non-wetting Au-on-GNR homometallic
nanostructures, as well as corresponding TEM images, pictures, and absorption spectra.[66]

Copyright 2020, WILEY-VCH. (C) Structural evolution from concave pentagonal
nanoparticles to concave “nanostars” and their z-direction packing.[67] Copyright 2019,
American Chemical Society.
2.2.3 The Inherent Properties of Capping Agents
Capping agents can bind to the particular interface of NPs, which affects the reduction
and diffusion efficiency of the metal precursor as well as the stability of the whole metal NPs.
As a result, capping agent can be used as one of the primary influencing factors to control the
size and morphology of metal NPs. In other words, most studies have shown that capping
agents modified to the surface of metal NPs will passivate NPs, and therefore precursor will
preferentially grow the unpassivated regions of colloidal metal NPs. Although the surface-
passivated conversion achieved by capping agents is generally considered to be useful in
solution phase reaction. Few research has examined the impact of the capping agent's
inherent properties (such as functional group, concentration and size) between seeds and the
subsequent gold shells (gold shell@capping agent@seed). Exploring the novel functions of
capping agents would help to better comprehend the relationship between intrinsic properties
of capping agents and the structural characteristics of resulting NPs. In fact, the intrinsic
properties of capping agents in the passivated region have a greater effect on NPs
morphology even though precursors grow preferentially in the unpassivated region.
Therefore, our research group studied how the shape and optical properties of GNPs are
affected by the inherent properties of biomolecules.

Figure 7. (A) Mechanism of grown GNRs via seeded growth method with varying peptides or
proteases concentrations.[69] Copyright 2019, American Chemical Society. (B) Mechanism of
preparing Au@gap@GNRs by seeded growth with varying sizes of thiolated molecules or a
DNA/DNA dendrimer nanostructure.[70] Copyright 2020, American Chemical Society.
We used GNRs as seeds, AA as reductant, HAuCl4 as precursor, and thiolated

biomolecular (such as CYS, GSH and BSA) with different affinity to GNRs as capping
agents to study the effects of functional groups, concentration and size of capping agents on
the morphology and optical properties of GNRs. Firstly, GSH is preferentially adsorbed on
both ends of the GNRs through the Au-S bond. After the adsorption is completed, the
precursor is added to growth the GNRs. At this time, tips grow at both ends of the GNR,
which increases the aspect ratio of the GNR. We found that with the increase of the capping
ligand concentration, the number of tips at the end of the GNRs increased, the longitudinal
LSPR peaks also redshifted, and the solution color changed from pink to blue (Figure 7A).[69]
Whether thiol functional group has a role. Moreover, we also selected glycine, lysine,
arginine and proline without thiol group as capping agents for the reaction. The experimental
results showed that the amino acid without thiol group did not have obvious concentration-
dependent phenomenon. Based on this, we designed a cancer-related enzyme cleavage active
site on the peptide to detect the enzyme activity. However, after cleavage, the size of the
peptide changes. Examining the impact of capping agent size on the shape of GNRs, we
selected CYS, GSH and BSA containing thiolated groups as capping agents, respectively
(Figure 7B).[70] Moreover, we found that with the increase of the capping agent size, the
number of tips at the end of the GNRs decreased, the longitudinal LSPR peaks blue shift, and
the color change of the solution becomes less and less obvious. As the size of capping agent
increases, the steric resistance increases, and the concentration of capping agent adsorbed to
the surface of GNRs decreases. As we mentioned above, DNA is also a class of excellent
capping agents because it is easy to modify and its base has different affinities with GNRs.
Also because of the characteristics of the diverse changes in size caused by DNA
programmability, we also used DNA and DNA dendrimers as capping agents to further
examine the impact of capping agent size on the morphology and optical properties of GNRs.
The final results also maintained good consistency. Coincidentally, in Nam's work, in light of
their knowledge of the evolution of chiral morphology, the impact of peptide concentration
and sequence on chirality expression was investigated.[58] The influence of the inherent
characteristics of capping agents on the shape and properties of colloidal metal NPs provides
a new perspective for breaking traditional concepts and lays the foundation for the future
synthesis of diverse functional NPs.
2.3 The Influence of Metal Precursors
In addition to monometallic NPs, seeded growth method can also be used to create
bicomponent nanostructures made up of two different metals. Depending on their
composition, NPs can be classed as pure or composite. Pure NPs are made up of only one
pure material, whereas composites are made up of two or more elements. Composite NPs
have a variety of structures and compositions depending on their atomic arrangement. Next,
we mainly investigated the effect of the metal source with different reduction potentials on
the morphology of monometallic or bimetallic NPs and the effect of the morphology of
grown NPs by varying the concentration of precursors. More importantly, the ultimate
location of the deposited atom is also affected by injection rate of the metal precursor. In
addition to the core-shell structure generated by the traditional lattice-matched seeded growth
method, introducing thin metal layers with significant lattice mismatch can successfully
induce well-defined metal island nucleation on NP seeds. In fact, reducing the precursor
supply will inescapably lead to unequal nucleation and deposition on the multiple equivalent
sites available on a seed’s surface. In other words, when analyzing precursors as growth
influencing factors from the point of view of kinetic and thermodynamic parameters,
assuming that kinetic factors dominate, this can be achieved by reducing the concentration of
precursors. Linking experimental observations to the fundamental thermodynamic and kinetic
parameters that guide atoms to their final positions facilitates the exploration of metal NP
growth. Next, one of the growth influencing factors, metal precursors, is described in detail.
2.3.1 The Reduction Potential of Metal Precursors
The seeds and precursors of monometallic NPs are the same metal source. In order to
obtain NPs with diverse morphologies and functions, capping agents are generally
introduced, or anisotropic NPs are used as seeds. However, some studies have found that the
reduction potential of metal precursors are different, resulting in diverse morphologies of the
final NPs. For example, Xia and co-authors used Pd cubes as seeds, along with PdX42− (X =
Cl− or Br−) as the metal precursor, AA as the reductant and PVP as the capping agent (Figure
8A).[71] In the case of PdCl42−, nanocrystals of two different sizes and forms were found: in
addition to the concave cubes produced by Pd cubic seeds, there were also considerably
smaller particles with an almost spherical shape, which can be ascribed to homogeneous
nucleation. When PdBr42− was utilized as the metal precursor, homogeneous nucleation was
almost completely repressed, resulting in the creation of exclusively Pd concave nanocubes.
Because PdCl42−/Pd has higher positive reduction potential than PdBr42−/Pd, which means
that there is a greater source of metal.
In fact, changing the type of salt precursor could potentially cause kinetically induced
asymmetric development. When Na2PdCl4 or Pd(acac)2 was employed as the precursor, Pd
cuboctahedral seeds could be induced to grow into octahedrons of varying sizes through a

symmetric growth mode or tetrahedrons through an asymmetric growth mode.[72] The
different reduction rates of these two precursors were blamed for the observed disparity in
growth pattern. When Pd(acac)2 was utilized as a precursor, the cuboctahedral seeds were
instructed to grow into octahedrons, truncated tetrahedrons, and finally tetrahedrons. Instead,
when Na2PdCl4 was used as the precursor, the same batch of seeds only grew into
octahedrons of progressively larger sizes. Due to the faster reduction rate of Pd(acac)2, this
discrepancy implies that more Pd2+ ions were reduced to Pd(0) atoms and then integrated into
the Pd octahedrons, inducing a kinetically regulated form of growth. The newly generated Pd
atoms from the reduction of Pd(acac)2 would be insufficient to nucleate on all eight {111}
faces of a Pd octahedron at a later stage. On the contrary, this precursor could be kept at a
relatively high concentration through the gradual reduction of Na2PdCl4 to enable
thermodynamically regulated development. When Na2PdCl4 was utilized as a precursor, the
concentration of Pd2+ permitted nucleation to proceed on all eight sides of the pre-formed Pd
octahedrons.
In addition, the reduction potential of metal precursors is altered by adding chemical

additives that strongly coordinate with metal ions, thereby affecting their reduction kinetics.
For instance, the amine group of hexadecylamine interact with metal precursors such as
Au(III) and Cu(II) ions, reducing reduction potentials of the metal precursors.[73] After
coordination with hexadecylamine, the reduction potentials would decrease. A lower
reduction rate would produce an AuCu alloy shell on a Pd cubic seed as opposed to a phase-
separated Au-Cu shell.
2.3.2 The Concentration of Metal Precursors
Bimetallic NPs refer to nanostructures composed of two different metals. In addition,

NPs containing multiple materials connected by interfaces, often referred to as
heterostructured NPs. Ye and co-authors reported a seeded growth method for Cu NRs
employing GNPs as seeds (Figure 8B).[74] In a typical reaction, CuCl2·2H2O (the precursor)
was mixed with oleylamine (the reductant) in a 50 mL three-neck flask. The mixture was
degassed under vacuum at room temperature and flushed with N2 gas for three times to

remove oxygen. The mixture was then heated at 80 °C for 30 min to fully dissolve CuCl2
forming a blue-colored Cu(II)-oleylamine complex. Subsequently, the solution temperature
was raised to 180 °C when reduction of Cu(II) to Cu(I) occurred resulting in a yellow-colored
solution. Afterward, a certain amount of Au nanocrystals (the seed) solution was injected into
the mixture and the reaction was allowed to proceed at 180 °C for another hour to obtain Cu
NRs. By altering the molar ratio between Au seeds and Cu precursor, the NR aspect ratio
may be easily controlled from 2.8 to 13.1 leading to narrow longitudinal LSPR peaks tunable
from 762 to 2201 nm. According to investigations of reaction intermediates, fast diffusion at
the nanoscale in Au-Cu alloys and the creation of a gold-rich surface encourage symmetry-
breaking.
In addition, the extremely considerable surface curvature and faceting at the ends of
CdSe NRs promotes selective nucleation and growth of gold in such sites. The growth
behavior of this material system is shown to be dependent on the concentration of the gold
precursor. When precursor concentrations are low, there is only surface growth. As the
concentration of gold precursors rises, the growth mechanism shifts from surface growth to a
diffusive process.[77] Due to differences in nucleation time or growth rates, one tip is often
significantly larger than the other. During the ripening process, the smaller tip dissolves while
the larger tip expands, finally resulting in the removal of one tip and the growth of the other.
2.3.3 The Injection Rate of the Metal Precursor
Many synthetic ways for influencing the growth habit and consequently shape of NPs
have been established, however, the majority of them are based on a thermodynamic
approach, such as the introduction of capping agents. Whereas thermodynamic control has
demonstrated its ability to generate metal NPs with different morphologies, it is ultimately
constrained by the need to minimize a system's surface energy. Therefore, using
thermodynamic control to create nanocrystals with high-energy facets and/or a negative
curvature is unfeasible. Xia and co-authors provided an universal approach based on kinetic
control with a syring pump using rhodium as an example, which might possibly be applied to
other noble metals (Figure 8C).[75] By merely regulating the injection rate of the precursor

into the reaction solution, they were able to synthesize concave nanocubes with a
considerable fraction of {110} facets and octapods with a cubic symmetry in excellent yields.
Since Br− can act as a capping agent for {100} facets. This also illustrates that the influencing
factors affecting the size and morphology of metal NPs are mutually constraining and
interacting.
As mentioned above, the ratio of deposition rate to surface diffusion rate dictates which
path the nanostructure will take. When Vdep > Vdiff, the deposited atoms are more likely to
“hit and stick” at the deposition site, allowing for site-selective and kinetically controlled
growth. If Vdep < Vdiff, atoms hit seed's surface, diffuse over it, and this cause the
thermodynamically preferred conformal growth mode. Slowing down the injection rate of the
metal precursor can help establish a conformal shell by reducing deposition rate. For
example, Ag@Au core-shell NWs with a conformal Au shell could be made using a slow
injection rate for the Au(III) precursor because the condition allowed enough time for the Au
atoms to diffuse after deposition to cover the whole surface of the Ag NWs.[78] In a word,
controlling the injection rate of precursors to modulate the morphology of metal NPs is one
of the simple, fast and effective methods. In addition, the ability to perform high throughput
tuning for the synthesis of the required metal NPs is one of its advantages.
2.3.4 The Extent of Lattice Mismatch with Seeds
In typical seeded growth processes, conformal coating is induced by a perfect lattice

match between the deposited metal and seeds, which results in either size increases (such as
Au on Au) or the creation of core–shell NPs (such as Ag on Au) with various morphologies.
For example, because the lattice structure is just the same, Au atoms are deposited on an Au
seed using the layer-by-layer mode.[79] However, recent research demonstrated that the
growth of a thin metal layer with significant lattice mismatch can efficiently promote the
nucleation of well-defined gold islands on GNP seeds. Yin and co-authors were able to
generate complex gold nanostructures by controlling the interfacial energy between the seed
and the deposited material, oxidative ripening, and surface diffusion of metal precursors. The
number of islands on the seed can be controlled, and their structures ranges from core-

satellite to tetramer, trimer and dimer.[76] In fact, by coating Pt on the Au seeds, it is possible
to induce a lattice mismatch interface that causes the metal deposition to transition to an
island-growth mode, resulting in the formation of core satellite structures. Pt, which has a
4.08% lattice mismatch with Au, is deposited on the surface of Au seeds to boost interfacial
energy and stimulate island formation (Figure 8D). During the seeded growth phase, the
interfacial energy can be easily changed by adjusting the molar ratio of Pt/Au. When the
lattice mismatch between the two metal is significant, the inability to perform epitaxial
growth will result in defects, offering another route for symmetry breaking. This unique
technique could be used to create nanostructures with more unusual morphologies using
different metals and inorganic chemicals.[80-82]
Figure 8. (A) Possible involvement of two distinct reduction mechanisms by a seeded growth
method.[71] Copyright 2017, American Chemical Society. (B) Mechanism of grown Cu NRs
with Au nanocrystals as seeds.[74] Copyright 2020, American Chemical Society. (C) Grown
Rh nanocrystals by two different injection modes.[75] Copyright 2011, American Chemical

Society. (D) Relevant characteristic of AuPt-0.1 NPs (a, b, c, d) and AuPt-0.1-Au NPs (e, f,
g, h).[76] Copyright 2021, WILEY-VCH.
2.4 The Influence of the Growth Solution
Physical parameters such as pH and temperature of the growth solution have a

significant impact on the morphologies of NPs since they directly influence crystal nucleus
formation, particle growth and evolution. Then, we mainly investigated the effect of the
growth solution with different pH and temperature on the morphology of metal NPs
synthesized by seed-mediated growth methods. For example, pH of growth solution can
improve growth kinetics; reactivity of reactive oxidants depends on the pH of the growth
solution. For temperature, diffusion barriers often prevent adatoms from moving into
thermodynamically preferred positions, necessitating a considerably high temperature to
supply adequate kinetic energy for adatoms to get past these barriers. Therefore, temperature-
driven growth kinetics and thermodynamic control also caught our attention. Additionally,
the ratio of atom deposition to surface diffusion (Vdep/Vdiff) may be adjusted by modulating
the temperature.
2.4.1 pH of the Growth Solution
Among the most effective ways to produce NPs with different morphologies, especially
high-Miller-index NPs, is to control growth kinetics during the seeded method because
quicker growing circumstances result in tapered regions of high curvature in NPs. Simple
changes in growth conditions, such as growth solution pH, can improve growth kinetics. For
example, pH-dependent variations in growth kinetics and ultimate morphological
modifications of Au-Pd bimetallic NPs were reported by Skrabalak and co-authors.[83] The
addition of HCl inhibits the reduction of precursors (such as Au and Pd), resulting in the
production of a thermodynamically advantageous NP. In contrast to low pH, higher pH
values accelerate the reduction rate of metal precursors, leading to a variety of high-Miller-
index NP morphologies, such as octopods and hopper-like structures. The importance of pH
has recently been recognized, and it has been claimed that pH can be used to manipulate NPs.

Likewise, to synthesize PdNRs, H2PdCl4 was mixed with CTAB and AA, etc. The
reduction was permitted to continue for 1 h at 90 °C.[84] By decreasing the pH of the growth
solution, the resulting structures' diameter was mostly fixed at 20 nm, while the length of the
resulting PdNRs could be controlled between 100 and 500 nm. As shown in Figure 9A, a
typical example was used to demonstrate how the pH-dependent reducing ability of AA can
be employed to control the reduction rate of a precursor (Rred) in compassion to the rate of the
galvanic reaction (Rgal).[85] Adding HAuCl4 was reduced by AA before it could take part in
the galvanic reaction with Ag nanocubes by increasing the pH to maximize the reduction
power of AA. Their success is dependent on the use of a strong reducing agent to compete
with and so impede the galvanic replacement between Ag and HAuCl4.
Also, various nanohybrid morphologies were produced by modifying the pH parameters

of the growing solution.[86] While platinum metal was seen to grow on segregated CdSe NRs
at high pH, a CdSe nanonet with platinum metal islands dispersed throughout the
nanostructure was generated at low pH. This pH dependence was explained as the result of
the mercaptocarboxylic acid ligands' dissociation from the rod surfaces under acidic
conditions, which caused the rods to fuse together to form a nanonet structure. Additionally,
the reactivity of reactive oxidants depends on the pH of the solution. For example, Guo
discovered a controllable hydrothermal method for controlling the growth of Ag2S shells on
Au nanotriangles.[87] Through adjusting pH value, two types of Au/Ag2S heteronanostructures
were produced, including shells on the ends and sides, respectively. At this time, the sulfur
source used is NaHS. NaHS is an active oxidant with a high reactivity that is dependent on
the pH value of the solution.[88] Interestingly, when the sulfur source was changed to
thioacetamide, the morphology of the grown NPs changed again. Thus, the morphology and
structure of metal NPs can be changed easily and quickly by changing the pH of the growth
solution.
2.4.2 Temperature of Growth Solution
In addition to modifying growth kinetics with additives (e.g., HCl), Hong and co-authors
synthesized hexoctahedron GNPs encircled by (321) high-Miller-index facets and

emphasized the temperature-driven growth kinetics.[89] Higher reaction temperatures of 35,
70, and 100 °C combined with faster growth rates produce consistently sized hexoctahedron
NPs as opposed to room temperature synthesis, which produces inhomogeneous NPs. The
kinetic controlled synthesis of high-Miller-index NPs offers the benefit of simple reaction
parameter manipulation to yield high-Miller-index facets.
Likewise, the shape of the final NPs changed due to too high or too low temperatures
corresponding to strong or weak reduction power. The finding was that lateral development
was promoted by a high reaction temperature.[90] For example, reducing the temperature can
minimize the diameter of AgNWs. In another study, when the precursor and reductant are the
same, we discovered that the reduction pathway might be altered from surface to solution
reduction according to the reaction temperature, which could impact the reduction kinetics.
For instance, during the reduction of PdBr42− with Pd NPs as seeds, a change from surface to
solution reduction was observed with increasing temperature.[71]
In addition, temperature is a key factor in the thermodynamic control of the solution

phase. This is a simple and efficient strategy that is conveniently accomplished during the
experiment. Thus, thermodynamic control has become frequently used for shape control of
NPs. Guo and co-authors reported the shape-regulate the production. The shapes can be
changed from nanocubes to NRs, and finally to NWs. The authors found that at high
temperatures, the reaction results in rapid creation of thermodynamically advantageous
nanocubes, whereas at low temperature results in elongated NPs. The discrepancy of growth
and shape-controlled is probably caused by difference in interparticle ripening at different
temperatures.[91] In other words, a relatively high temperature is frequently required to
provide adatoms enough kinetic energy to overcome diffusion barriers, which often prevent
them from settling into thermodynamically advantageous sites. However, when studying a
kinetically controlled reaction, lowering the temperature just enough to allow the reaction to
take place will boost the yield.
By modulating the temperature, the Vdep/Vdiff could be adjusted. The adatoms collected
at corners at a low temperature of 0 °C, resulting in the formation of Pd octapods as final

products, because Vdep > Vdiff (Figure 9B).[92] The formation of cuboctahedra was possible
when the temperature was increased to 75 °C because Vdep < Vdiff allowed the adatoms to
move from the corners to the edges and subsequently to the side faces. Products with
intermediate forms were generated when the reaction temperature was kept in the middle of
these two extremes. Moreover, fixing the reaction temperature while adjusting the injection
rate of the Na2PdCl4 solution yielded similar results. The regulation of the temperature of the
growth solution is also one of the simple, fast and efficient methods to regulate metal NPs.
However, most of the present-day studies have focused on high-temperature regulation, and
the growth solution used to regulate the morphology of NPs at 0 °C or even below 0 °C has
rarely been studied. In fact, the introduction of ultra-low temperature may lead to different
reaction results.
Figure 9. (A) Two routes and products possibly involve in a seeded growth at different pH
values.[85] Copyright 2014, American Chemical Society. (B) Effects of different temperatures
on growth modes of Pd cubic seeds.[92] Copyright 2013, National Academy of Sciences. (C)
TEM and HRTEM images of Au “nanomatryoshkas” embedded with nanometer-thick
molecular layers and their corresponding thickness distribution histograms.[93] Copyright
2017, The Royal Society of Chemistry.
2.5 The Influence of Growth and Incubation Time
Seed-mediated growth is generally divided into two stages when the seed is already
present: the first stage is the incubation stage, the second stage is the growth stage. In the first
stage, capping agent are incubated with seeds, and the main factor affecting the morphology
and properties of metal NPs besides the capping agents is incubation time. However, there are
many factors that can be regulated in the second stage, so most studies mainly focus on the
regulation of growth environment in the second stage. In addition to the pH and temperature
of the growth solution, the impact of growth time on the morphology of the grown NPs is the
subject of our next discussion. In fact, the size of NPs was determined by the growth time.
Additionally, the metal layer's deposition was time-dependent, enabling the metal layer's
thickness to be controlled by varying the growth time. For example, a sol-gel method was
used to coat Ag nanoplates with a TiO2 shell.[94] The TiO2 shell's thickness could be directly
adjusted from 1 nm to 15 nm by altering the growth time. In fact, when synthesizing the
thermodynamically controlled NPs, it is important to give the reaction enough time to achieve
equilibrium. However, when studying kinetically controlled reactions, the products should be
isolated immediately after the reaction is completed in order to increase the yield, so that
competing and inverse reactions can be suppressed.
Alternatively, varying the incubation time can also affect the morphology and properties
of metal NPs. For example, the intra-nanogap (nanogap between cores and shells) can be
tuned by adjusting the incubation time. The intra-nanogap distance can be controllable by
utilizing molecules with varying numbers of benzene rings, such as 4,4’,-biphenyldithiol
(BPDT), BDT (1,4,-benzenedithiol), and 4,4’,-terphenyldithiol (TPDT) and reaction
durations of 0.5, 3, and 8 h (Figure 9C).[93] In the case of BDT, the intra-nanogap distance
was 0.71, 0.93, and 1.23 nm for incubation periods of 0.5, 3, and 8 h, respectively. In
contrast, for BPDT and TPDT with incubation durations of 0.5, 3, and 8 h, respectively, the
intra-nanogap distances were 0.83, 0.89, and 1.18 nm and 0.87, 1.04, and 1.22 nm,
respectively. Longer incubation times lead to a wider interior nanogap (nanogap between
cores and shells), resulting in thicker layers.

2.6 The Influence of Reductant
Reductants have a great influence on the successful synthesis of NPs. Generally

speaking, kinetically regulated syntheses that can delay reduction are necessary to attain high
yields.[95-98] The reduction rate can be slowed down by using a weak reductant;[99, 100] slow
injection of metal precursors with a syringe pump; and complexing the metal ion with a
strong ligand.[101-103] Next, we mainly introduce the effect of reductant on seed-mediated
growth, such as the effect of reductant concentration, reduction pathway, and structural
characteristics on the reduction rate, which in turn affects the morphology of NPs. In general,
the thermodynamic and kinetic principles are universal. Reducing the atom supply will
unavoidably lead to uneven nucleation and deposition on the several analogous sites that are
present on a seed's surface. In other words, when kinetic parameters dominate, the rate of
reaction is reduced, that is to say, the rate of reduction is reduced. For example, reducing the
concentration of reducing agent.
2.6.1 The Concentration of Reductant
The ability of reductant to reduce precursors is related to its concentration. The higher
the concentration of reductant, the stronger the ability to reduce the metal precursors, and the
increased particle size of the grown NPs. For example, Xia and co-authors studied the effect
of reductant concentration on the morphology of grown NPs in seed-mediated growth
methods.[104] This study is not the traditional seed-mediated growth method. Common seed-
mediated growth methods involve a two-step process: the first stage is for seeds and capping
agents to be incubated, and the second stage is for seeds to be grown in growth solution.
However, this study added capping agent directly to the growth solution before the seeds
were created, which would first undergo a nucleation reaction and then grow further to obtain
metal NPs. The specific synthesis process is as follows: CuCl2·2H2O (the precursor), glucose
(the reductant) and hexadecylamine (an effective capping agent for Cu with high selectivity
for the {100} faces) were dissolved in 10 mL water in a 22.2-mL vial at room temperature.
After the vial had been capped, the solution was magnetically stirred at room temperature
overnight. Then, the capped vial was transferred into an oil bath and heated at 100 ºC for 6 h

under magnetic stirring. By increasing the glucose concentration from 5 to 10 mg mL−1, they
obtained tadpole-like copper NWs. The experimental results show that the tadpole-shaped
copper NWs are derived from conical nanocrystals. The effect of changing the concentration
of the reducing agent on the morphology of the nanocrystals in the presence of seeds is
described in the work. At relatively low glucose concentrations (5 mg mL−1), the decahedral
seeds formed penta-twinned NWs with uniform diameter due to the anisotropic growth. The
growth rate significantly increased when glucose concentration was raised from 5 to 10 mg
mL−1. Early on, the decahedral seeds continued to favor isotropic growth, resulting in the
formation of decahedra. When glucose is gradually consumed with the reaction, a lower
reduction rate is produced. The pentagonal bipyramids were formed while the isotropic
growth was shifted to an anisotropic mode. Lastly, these pentagonal bipyramids might
develop into tadpole-like NWs.
Likewise, Li et al. provided a general method for producing a family of penta-twinned

gold nanocrystal (Figure 10A).[105] Specially, different penta-twinned nanocrystals with
tunable size and high purity were easily created in a single system by adjusting the deposition
kinetics of adatoms on various decahedral seed sites. First, the obtained Au decahedral seed
was placed in a glass vial and subjected to a conventional synthesis by adding HAuCl4 and
AA. They specifically specified R to be the molar ratio of AA to HAuCl4. The solution
mixture was then placed in an oven set at 50 °C for 2 h to produce a brown colloidal solution.
The controlled deposition kinetics can be achieved by adjusting the ratio of reductant to metal
precursors (R). In addition, it is possible to achieve the selective development of a second
metal (silver) on penta-twinned gold seeds by slightly altering R. This creates a new path for
mechanistic research by enabling the visualization of the seed localization within the final
particles.
2.6.2 Different Reduction Pathway
During the production of metal nanostructures, there are two different pathways to
reduce a metal precursor: solution reduction and surface reduction. As mentioned above, Xia
and co-authors used Pd cubes as seeds, along with PdX42− (X = Cl− or Br−) as metal

precursor, AA as reductant and PVP as capping agent.[71] Once seeds have been formed (or
introduction of preformed seeds), the precursor can be reduced in one of two ways. The
precursor can be reduced to an atom before being deposited on the surface of a growing
nanocrystal in the solution phase. Another option is for the metal precursor to adsorb on a
growing nanocrystal's surface, followed by autocatalytic reduction. Using quantitative
analysis, it was shown that when the reduction rate is slow, the precursor will be reduced by a
self-catalytic procedure on a seed's surface, whereas when the reduction rate is fast, the
precursor will be reduced in the solution phase.
Similarly, due to the different reduction methods, NPs with different structures can also
be generated. For example, core-shell nanostructures with controllable mixed-shell
composition and shell thickness, were successfully prepared by gradual reduction process,
such as Atomic (AT)-layer, Intermediate (IN)-layer, and Thick (TH)-layer. Using a
sonochemical dispersion method, Tsang and co-authors were able to precisely synthesize a
optimally balanced silver-gold atomic layer on a gold seed (Figure 10B).[106] In the
following, the synthesis process of two different metal NPs will be described. The synthesis
of Au-Ag core-shell NPs is based on the gradual reduction of Ag+ ion on the as prepared
citrate-stabilized GNPs through adding the AgNO3 (the precursor) stepwise. For the first
cycle, potassium hydroxide, AA and AgNO3 were added into the as-prepared GNPs at room
temperature respectively, then reaction was stirred constantly for 30 min, namely IN-layer
Au-Ag core-shell sample. Repeat the cycles for three times with reaction time of 30 min for
each cycle, the TH-layer Au-Ag core-shell NP was obtained. For the AT-layer of the Au-Ag
core-shell NPs, as-prepared GNPs was added into a round bottom flask which was then
placed in a sonication bath under ambient conditions. Typically, potassium hydroxide and
AA were added into the flask followed by sonication (120 s). AgNO3 was then added into the
flask and sonicated for another 120 s to obtain a well sonochemical dispersion of Ag. This is
to ensure the reduction of Ag+ onto the Au cores while inhibit the formation of free Ag
nuclei. After that the mixture was stirred constantly for 30 min at room temperature to obtain
the final product. Although the shell thickness is close to that of an atomic layer, there is no

pure sliver atomic shell in the atomic-layer situation, but there is still a combination of silver
and gold atoms on the gold core.
Figure 10. (A) A summary of the experimental R values associated with the formation of
distinctively shaped Au penta-twinned nanocrystals.[105] Copyright 2021, The Royal Society
of Chemistry. (B) Au-Ag core-shell NPs were created via a sonochemical dispersion and
progressive reduction procedure.[106] Copyright 2021, WILEY-VCH. (C) Schematic
illustration of grown five-fold twinned copper NWs.[107] Copyright 2014, American Chemical
Society.
2.6.3 Structural Characteristics of Reductants
Sometimes, reductant can not only play a reducing role, but also can serve as capping
agent in the growth of NP due to the structural characteristics of the reductant. Common
functional groups such as hydroxyl, carboxylic, amine and phenolic groups have both
reduction and coordination functions. Thus, reductant with these functional groups can
simultaneously reduce and coordinate metal precursors to generate corresponding NPs.
Alkylamines (such as oleylamine) can operate as both reducing and capping agents in
specific reaction condition due to their structural characteristics. For instance, Cu NWs were
created by heating CuCl in oleylamine (Figure 10C).[107] The specific synthesis process is as
follows: CuCl (the precursor) and oleylamine (the reducing and capping agent) formed CuCl-
oleylamine mixture in a 20 mL glass vial. The mixture was stirred and heated to 170 °C in an
oil bath. The reaction was carried out at 170 °C for 6 h to obtain the Cu NWs. Based on the
experimental results, the self-seed growth of Cu NWs was determined, through a mechanism
similar to what was proposed by Xia and co-authors.[104] Cu NPs of two different sizes were
created in the earliest stages of reactions. Larger five-twinned Cu NPs acted as seeds for
anisotropic nanocrystal growth. Additionally, Cu atoms obtained from an Ostwald ripening
process or reduction reactions of a Cu(I)-oleylamine mixture continue to deposit and
crystallize on the twin boundaries. The seeds eventually developed into Cu NWs as a result of
the twin boundary's high energy and the oleylamine's capping of the Cu {100} facets.
Another typical example of the influence of the structure of the reductant on the
morphology of the grown metal NPs is when PVP is used as a reductant. PVP has hydroxyl
groups at the chain ends and tertiary amine on the pyrrolidone ring. Nitrogen-containing
functional group (such as the pyrrolidone ring) can absorb a significant quantity of ionic
precursor and confine the ions in the polymer matrix, whereas –OH group at the chain ends
favor the moderate reduction of precursors, allowing for the regulated creation of NPs using a
reactive polymer platform.[108] Also, the oxygen and nitrogen atoms on the backbone of PVP
allow it to securely adsorb on the surface of as-generated NPs, giving them a respectable
level of colloidal stability. For example, Xia and co-authors have proposed that changes in
the concentration of hydroxyl-terminal groups of PVP correlates with reduction kinetics and
affects the evolution of plate morphology.[102] In fact, Pd nanoplates were also obtained by
self-seed growth. The specific synthesis process is as follows: PVP dissolved in water was
added to a 25-mL three-neck flask and heated to 80 °C under magnetic stirring in air. At the
same time, quickly add Na2PdCl4 solution to the flask. The reaction mixture was heated at 80
°C for 5 h to obtain Pd nanoplates. They found that when the reduction kinetics was
accelerated by increasing the concentration of hydroxyl-terminal groups of PVP, the Pd NPs
of evolved from hexagonal to triangular plates. In this instance, the increased concentration
of hydroxyl groups causes faster reduction rates and the development of thermodynamically

advantageous morphology. On the other hand, PVP may easily adsorb onto the surface of
metal NPs thanks to the oxygen and nitrogen atoms of the pyrrolidone unit, making it a useful
stabilizer to prevent NPs from agglomeration. Therefore, the PVP also plays a dual role in
this work. Speaking generally, many proteins have the ability of reduce or stabilize and can
be used to synthesize NPs. In fact, these abilities result from the unique reactivity of
individual amino acid residues inside the protein structure such as tyrosine.[109] This
phenomenon also deserves follow-up attention.
2.7 The Influence of External Factors
In summary, all the typical internal factors that affect the growth morphology of metal
NPs are introduced. Along with the primary synergetic methods of NPs with various shapes
mentioned above, a few alternative strategies have been tried out. In detail, there are
generally seeds, capping agents, reductants, precursors and growth solution in the seed-
mediated growth method, but there are also some reports on the influence of external factors
on the morphology of NPs, such as light, chelators, and templates. Next, we will detail the
light-induced seeded growth method and the modification of NP morphology by adding
chelating agents and templates.
In addition to high temperatures, external energy in the form of light can be used to
remove the energetic barrier to the growth of metal on seeds. For example, Pacholski and co-
authors have shown that single silver NPs may be photodeposition on ZnO NRs at specific
sits; thus light was utilized to create single and distinct metal NPs on NRs.[110] Dukovic and
co-authors utilized light for platinum deposition on CdS NRs and CdSe/CdS NRs.[111] In
contrast to CdS NRs, where the metal island grows close to the CdSe core, CdSe/CdS NRs
exhibit directionality in the light-induced deposition. Coincidentally, Neretina et al. also used
light as an external energy source (Figure 11A).[112] The growth solution is mixed in a
separate beaker and then slowly pipetted into the cuvette, consists of methanol, PVP, and
HAuCl4 (the precursor). Once added, the cuvette is covered with parafilm to prevent the
evaporation of volatile components during the 4 h synthesis. The solution is illuminated with
a broadband light source where the fiber optic cable is positioned 2 inches from the substrate

and directed at an angle that is normal to the substrate surface. In other words, the seeds are
treated to a liquid-phase plasmon-mediated synthesis in which light used as an external
stimulus to trigger a reaction that results in periodic arrays of hexagonal gold nanoplates.
Moreover, nanoimprint lithography and a vapor-phase assembly procedure are used to create
the seeds in periodic arrays. Therefore, the introduction of external energy such as light
provides an alternative pathway for the controlled synthesis of metal NPs. And it is more
convenient and simple compared with the internal growth influencing factors, which can be
properly considered in the future synthesis of metal NPs.
Figure 11. (A) Diagrams illustrate the plasmon-mediated growth method that result in the
formation of Au nanoplates.[112] Copyright 2019, American Chemical Society. (B) The
growth of a spherical seed into a hexagonal star was depicted.[113] Copyright 2019, American
Chemical Society. (C) Molecular dynamics simulations of 1,1′-bi(2-naphthol)-CTAC
micelles and their assembly on GNRs.[114] Copyright 2020, American Association for the
Advancement of Science.
In general, similar to ethylenediaminetetraacetic acid (EDTA), which is generally used

as a capping agent, has recently been shown to be effective as a chelating agent to control the
growth of NPs. For example, gold often exhibits a face-centered cubic (fcc) lattice or crystal
phase in a cubic close-packed structure. Xia and co-authors show that fcc-GNSs can serve as
the metal seeds for the synthesis of gold hexagonal stars.[113] The effectiveness of this

synthesis depends on the use of EDTA to chelate with Au3+ ions as a precursor and the
addition of 2-phospho-L-ascorbic acid trisodium salt as a special reductant to control the
reduction kinetics. HAuCl4 (the precursor) and EDTA·2Na were added sequentially into DI
water. The solution was mixed under vigorous vortex for 2 min, and the chelation of Au3+
with EDTA was allowed to proceed for 2 h at room temperature under gentle shaking. In a
standard protocol, the freshly prepared aqueous suspension of 10-nm GNSs (the seed) was
added into CTAC aqueous solution, followed by the addition of 2-phospho-L-ascorbic acid
trisodium salt aqueous solution (the reductant). Afterward, Au3+-EDTA complex was added
and the reaction was allowed to proceed under gentle shaking for 30 min to obtain gold
hexagonal stars. In fact, the formation of the Au3+-EDTA complex and the rapid decrease of
HAuCl4 presumably took place simultaneously, roughly splitting the growth of nanocrystals
into two stages: firstly, as HAuCl4 was decreased, quasi-spherical nanocrystals appeared;
next, the atoms produced by the reduction of the Au3+-EDTA complex are deposited on the
intermediates as seeds. The further growth on these intermediates then formed teardrop-like
NPs (Figure 11B). The introduction of chelating agents facilitates the slowing down of the
reaction rate and allows a more careful adjustment of the morphology of the metal NPs.
The template-mediated method is a simple and universal approach to synthesizing NPs

because it allows the selection of an appropriate template to control the morphology of the
resultant structure.[115, 116] In fact, we have described the template for seed-mediated growth
method in the review.[52, 57] Combining the seeded growth method and the template-mediated
method can combine the advantages of both methods to open up new avenues for the growth
of metal NPs. For example, Liz-Marzán and co-authors found that anisotropic gold
nanocrystals with high chiroptical activity can be created through surfactant-assisted seeded
growth of metal NPs by using the templating effect of chiral micelles generated in the
presence of dissymmetric cosurfactants (Figure 11C).[114] The mixed micelles were adsorbed
on GNRs to form quasihelical patterns, which guided the seeds to growth into NPs with
distinct morphology and optical handedness. Chiral plasmon modes with high dissymmetry
factors (~0.20) are produced by sharp chiral wrinkles. Moreover, it is possible to extend the

micelle-guided process to other systems, such as the seed-mediated growth of chiral platinum
shells on GNRs.
3. Properties and Applications
Regulating the morphologies of metal NPs is an important step in controlling their

physicochemical characteristics, such as optical and catalytical properties, and more
importantly: derive related applications from these property.[117, 118] Core-shell NPs
synthesized by the seed-mediated growth method consist of an inner core coated with an
outer shell formed of the same or another metal. The introduction of core-shell NPs can have
a number of benefits, including tuning of optical properties, enhancing in catalytic
performance; improving in chemical and biological properties. Next, we will focus on the
optical, catalytic and biological properties of core-shell NPs and their applications in sensing,
imaging, diagnosis and therapy.
3.1 Optical Application
The relationship between the morphologies of metal NPs and their optical characteristics
is well recognized. Regulating the morphologies of metal NPs enables manipulation of their
optical properties and corresponding applications in Raman, fluorescence or scattered light
imaging, chirality and absorption. Seeded growth is an effective and adaptable approach to
modulate morphology of NPs.[7, 119] There are multiple features of using core-shell
nanostructures, such as tuning of optical properties. Therefore, we will focus on the optical
properties and related applications of metal NPs synthesized by seed-mediated growth
method.
3.1.1 Surface-Enhanced Raman Scattering
Since its development in 1997, surface-enhanced Raman scattering (SERS) has been
extensively utilized in the detection of biomolecules. Signal amplification is caused by the
high electromagnetic field of the “hot spot” regions at the rough surface of metal. For
instance, Tian’s group created a general method for expanding SERS from noble metal
surfaces using chemically fabricated NPs composed of Au cores with transition metal
shells.[120, 121] The Au@transition metal shells structures was able to increase SERS signals by
four to five orders of magnitude, allowing for in-depth molecular research. In addition, SERS
imaging has been utilized to image tumors and direct their surgical excision, specifically to
clarify their margins.[122, 123] For example, Song and co-authors reported a novel core
(forming GNR coated with Au shell with nanogap)-satellite (GNPS) gold nanostructure for
dual, ratiometric SERS and photoacoustic imaging to accurately detect inflammation/cancer-
related H2O2.[124] Inflammation and normal tissue can be distinguished with great specificity
using H2O2-activated second near-infrared (NIR-II) photoacoustic and SERS imaging. It's
interesting to note that the Raman signal of 4-mercaptobenzonitrile (2228 cm−1) on the GNPS
significantly decreased in the presence of H2O2, although the Raman signal of 2-
naphthalenethiol (1418 cm−1) inside the nanogap of GNRs remained steady. They employed
the bioprobe to image and detect H2O2 in a 4T1-tumor-bearing mice model. Figure 12A
shows how the ratiometric SERS (I2228/I1418) mapping varied over time in the tumor from
light blue with a higher value to dark blue with a lower ratio, whereas the SERS ratio
mapping of I2228/I1418 hardly changed in the normal tissues.
3.1.2 Fluorescence Imaging
The morphology of metal NPs is extremely important for their application in

fluorescence imaging. Quantum dots (QDs) are one of appropriate choice among all
fluorescent materials due to their narrow fluorescence emission bands, and resistance to
photobleaching.[125, 126] The shape of QDs can be tailored by creating core-shell
nanostructure, which could be classified into three types depending on the band alignment of
their constituent nanomaterials' valence and conduction bands.[127, 128] For example, Cd-based
type II QDs emit near-IR light as a result of electron-hole recombination at the core-shell
contact.[129] And Cd-free type II QDs display photoluminescence color by just changing the
shell thickness.[130] The photoluminescence quantum yield can also be increased by adding a
ZnS shell on the CuInS2 QDs because it could reduce the surface defects from QD
nanocrystals (Figure 12B).[131] And their findings demonstrated that the QD materials might
be used in biological systems.

Figure 12. (A) Confocal Raman imaging at 2228 cm−1 and 1418 cm−1 and the ratio image
(I2228/I1418) of normal and tumor tissues, and photoacoustic imaging at 750 nm and 1250
nm.[124] Copyright 2021, WILEY-VCH. (B) Confocal images of C. elegans treated with
CuInS2/ZnS QDs for different time.[131] Copyright 2015, American Chemical Society. (C)
Individual fractal nanoplasmonic labels covered with protein were tracked intracellularly for
a long time..[132] Copyright 2019, American Chemical Society.
3.1.3 Dark-Field Microscopy Imaging
Dark-field microscopy has a chance to become a powerful optical tool since it was
developed in 1830 because of its balance between the imaging background and visibility.
Dark-field microscopy have intrinsic advantages in reducing the imaging background in
contrast to bright-field microscopy, which is essential for sensitive sensing.[133] We have
described previously that oleylamine can be used as a capping ligand to directionally regulate
the morphology of NPs. José-Yacamán et al. utilized dark-field microscopy to study the
controlled growth from the 5-fold concave morphology into nanostars.[67] They employed the
scattering spectra and morphological characteristics of individual particle to verify the source
of the plasmon bands in the spectra. Likewise, Song et al. monitored and imaged the
underpotential deposition of copper on AgNPs at the single particle level.[134] In addition, Fan
et al. described the development of DNA-engineered fractal nanoplasmonic labels for single-
cell dark-field microscopy imaging with ultrahigh brightness and photostability (Figure
12C).[132] They used GNPs as seeds, DNA as capping ligands, AuCl4− as precursor, and
NH2OH·HCl as reductant to synthesized fractal NPs with extremely controllable tip height to
width aspect ratio. The ability to tune plasmonic colors is enabled through fractal control over
outer shell morphology. The plasmonic labels made it possible to simultaneously dynamically
image various types of endocytosis in single cells by labeling of intracellular proteins.
Figure 13. The mechanism of chiral NPs’ inhibition and protect tumor growth.[141] Copyright
2022, WILEY-VCH.
3.1.4 Chirality
Chair nanostructure have garnered substantial levels of attention over the last decade
due to their potential application in DNA cleavage,[135] drug delivery,[136] chiral sensing,[137]
oxidation prevention[138] and the treatment of Alzheimer's disease,[139] and so on.[140] Among
these chiral nanomaterials, core-shell chiral nanostructures have shown advantageous optical
properties because of their robust optical activity and distinctive surface plasmon resonance.
More importantly, the chiral signal is greatly enhanced when the chiral molecule is between

the core and shell due to the local electromagnetic field, compared to the chiral molecule in
nature. Additionally, the characteristics can be adjusted by altering the size or shape of chair
nanostructures. Recently, it is demonstrated that the chirality of NPs can affect their
interaction with cells and biological system. Kuang and co-authors synthesized chiral GNPs
by a seed-mediated growth method. Prism GNPs were initially created as seeds (Figure
13).[141] Chloroauric acid, reductant, chiral molecule, and polarized light were introduced for
the growth process. After 30 min, the chiral NPs were obtained. Chiral NPs have been shown
to improve both innate and acquired immunity against tumor growth in comparison to achiral
NPs. It discovered that chiral NPs improve the activation of CD8+ T and natural killer cells
(CD69+ NK cells) by activating dendritic cells (DCs). Notably, L-type NPs produce a 1.65-
fold higher proportion of CD8+ T and CD69+ NK cells compared to D-type NPs. It is
discovered that L-type NPs are significantly better than D-type NPs in inducing tumor cells
apoptosis and extending the survival time of model mice.
3.1.5 Colorimetric Assay and LSPR shift
One of the important optical characteristics of GNPs is their distinctive extinction

(absorption and scattering) properties, which result in the bright colors visible to the naked
eye. Therefore, based on their distinctive optical properties, the colorimetric assay and LSPR
shift of GNPs can provide rapid and sensitive sensing performance. Pompa and co-authors
demonstrated the fast and sensitive detection of methylmercury based on colorimetric assay
(Figure 14A)[142]. In the seed-mediated growth method, GNPs are used as seeds, formic acid
is used as reductant (GNPs also act as catalysts), and methylmercury is used as precursor for
growth. The reaction between the weak reductant (such as formic acid) and methylmercury
occurs on the surface of GNPs, resulting in the rapid reduction of methylmercury to Hg0 and
the deposition of metallic mercury on the surface of GNPs. This causes a significant
instability of the GNPs due to the development of large particle aggregates and the
subsequent red-to-violet color change of the solution brought on by plasmonic shift. As a
result, mercury species can be detected colorimetrically in a very short amount of time (1
minute).

We determined that the LSPR peak of GNRs red shifted with the increase of capping
agent concentration, and the LSPR peak blue shifted with the increase of capping agent size
through seeded growth method.[69, 70] Therefore, we took advantage of the concentration
effect, that is, the cleavage of peptides by proteases caused an increase in peptide
concentration and resulted in a red shift of the LSPR peak, to detect cancer-related proteases
(Figure 14B). Using the size effect, that is, combining the seeded growth method with DNA
nanotechnology, with the increase of the target DNA concentration, the LSPR peak gradually
blue-shifts, and the size effect dominates at this time; however, as the target DNA
concentration continues to increase, the concentration effect dominates and the LSPR peaks
are red-shifted again and are used to detect target DNA. We use biomolecules as capping
agents for biosensing through the seeded growth method, which exploits the inherent
properties of biomolecules. However, there are too few studies of this kind, and most of them
focus on the application of metal NPs after synthesis. Thus, there is development space
regarding the application of optical properties of metal nanoparticles due to the inherent
properties of biomolecules.

Figure 14. (A) Red-Ox reaction between formic acid and methylmercury on the surface of 15214095, ja, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202211915 by IFW Dresden LBZ Inst for Solid State, Wiley Online Library on [29/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
GNPs.[142] Copyright 2019, WILEY-VCH. (B) "Peptide-encoded" GNRs produced by

treatment of peptide substrates with different concentrations of trypsin.[69] Copyright 2019,
American Chemical Society.
3.2 Catalytic Application
The field of nanocatalysis is rapidly expanding.[143, 144] In comparison to their bulk

counterparts, nanocatalysts have been found to have striking novel catalytic properties, such
as greatly increased reactivity and selectivity.[145, 146] Numerous researches have clarified the
elements, such as metal NPs' size, shape or interactions with their support, that have a
substantial impact on their catalytic performance.[147] However, the effect of these factors isn't
independent, for example, size and support decide on the most stable shape of NPs,
complicating the research. Among these parameters, the shape-dependent effect in catalysis
has drawn more and more interest recently. It has been demonstrated that the catalytic
behavior is significantly influenced by the exposed crystal faces, which are governed by the
shape of catalyst NPs. The adsorption energy, reaction energy and activation barrier are all
significantly impacted by the surface structure of the exposed crystal face. Nanocatalysts with
various anisotropic shape usually exposed several facts as well as other types of sites, such as
edges or corners.[148] Reactants and products can created other facets or completely new
structures in a reactive environment. Catalysis is especially dependent on undercoordinated
sites at edges and corners. In contrast, the surface structure of facets typically has a
significant impact on the potential energy diagram for the surface reactions. Next, we discuss
the effect of the morphology of the core-shell structures synthesized by the seeded growth
method on photocatalysis and electrocatalysis, and the application of photocatalysis and
electrocatalysis.
3.2.1 Photocatalysts
Light-excited surface plasmons have the potential to decay into highly energetic
electrons and holes.[149, 150] Then, these charge carriers can proceed to chemistry on the
surface of the metal NPs. The LSPR property of NPs can be modulated in the visible and
infrared regions. The rate and effectiveness of photon-to-chemical conversion can be further
increased by combining the plasmonically active NPs with catalytic metals. Additionally,
bimetallic NPs show enhanced catalysis in comparison to their monometallic counterparts
(single-component gold or silver NPs). In bimetallic nanostructure, for example, thin Ag shell
coated on GNPs produces plasmonic properties and increases chemical stabilities.[151] Au/Pd
bimetallic NPs with both strong catalytic activities and LSPR property have been used for
plasmon-enhanced photocatalysis.[152] The grown GNR was added to a growth solution
containing of CTAC, H2PdCl4, and AA to prepare the Au-Pd NPs. Yan and co-authors
demonstrated how to employ plasmonic Au-Pd NPs to directly gather visible-to-near-infrared
light for reactions.[153] The combination of GNRs with Pd NPs via seed-mediated growth
method enable excellent light harvesting for catalytic reactions on the nanostructures (Figure
15A). Both plasmonic photocatalysis and photothermal conversion were used to induce and
speed up catalytic processes after plasmon stimulation. Moreover, to inhibit the transfer of
electron between the gold core and Pd NPs, they created the nanostructures with a 25-nm-
thick TiOx shell between the two metals. Based on the above research background, Pd or Pt-
tipped GNRs have been employed as photocatalysts for Suzuki coupling, formic acid
dehydrogenation and methanol oxidation. Suzuki coupling with Pd-tipped GNRs resulted in
an increase in reaction yield from 55% to 95.8% when the nanostructures were exposed to
laser energy at 809 nm, which coincided to their resonance peak.[154]
Figure 15. (A) The effective light harvesting for catalytic reactions on the Au−Pd
nanostructures through seeded growth.[153] Copyright 2013, American Chemical Society. (B)
When compared to samples that were entirely covered, the Pt-tipped sample showed
significantly more activity.[155] Copyright 2014, American Chemical Society.
However, it is challenging to draw comparisons between various efforts since the degree
of enhancement depends on a variety of variables, such as the illumination wavelengths, the
light intensity and the type of nanostructure. Based on comparisons of the internal quantum
efficiency, the impact of nanostructures on light absorption and photocatalysis can be
deconvolved using the ratio of collected electrons to absorbed photons. For instance, the
quantum efficiency of Pt-tipped and Pt-covered GNRs was compared in the research of the
H2 generation, and it was discovered that the former had a higher internal quantum efficiency
than the latter. (Figure 15B).[155] They attributed this outcome to the Pt-tipped NRs improved
charge separation.
3.2.2 Electrocatalysts
Electrochemistry is crucial in energy conversion since it enables several sustainable

procedures for emerging technology.[156] In the majority of electrochemical processes,
electrocatalysts play a crucial role in lowering energy barriers and speeding up reactions.
Core-shell metal NPs as electrocatalysts in electrocatalytic applications such as oxygen
reduction reaction, methanol oxidation and formic acid oxidation has been investigated.
Although monometallic NPs usually present superb performance, adding a second metal can
increase their activity and cost-effectiveness. Three outcomes can lead to the addition of a
second metal: (i) an ensemble effect, whereby a number of metals create a number of reaction
sites and increase the chances that the reactants or intermediates will bind with the metals; (ii)
a ligand effect, whereby electronic structure and activity of two different surface atoms are
altered by charge transfer; and (iii) a geometric effect, whereby strain, geometric shape and
size have an impact on the spatial arrangement of surface atoms.[157] Numerous
electrocatalysts have been developed as a result of the core-shell nanostructure. For instance,
Pd@Pt core-shell NWs had a mass activity 10 times higher than a commercial Pt/C catalyst
(Figure 16A)[158]. The strain effect generated by the core-shell structure of the Pd@Pt NWs
may be principally responsible for their exceptional activity.
Fast oxidation of methanol to CO and oxidation of CO to CO2 are both steps in the
electrochemical oxidation of methanol. Faster methanol conversion and better CO tolerance
are crucial for achieving superior catalytic activity. PtRu nanotubes and Cu@PtRu core-shell
NWs were investigated as support-free electrocatalysts for the methanol oxidation reaction
among other forms of catalysts.[160] For formic acid oxidation, Most commonly employed as
electrocatalysts are Pd and Pd-based NPs.[161] For instance, the activity of PdNWs supported

on carbon was 5 times more than commercial Pd/C (Figure 16B).[159] The presence of {100}
side faces and the twin boundary-induced increase in surface strain significantly enhanced the
catalytic performance of PdNWs. PdAg NWs shown significantly improved electrocatalytic
activity toward formic acid oxidation with a higher tolerance to CO poisoning, larger
oxidation current density.[162]
Figure 16. (A) Electrochemical activities of Pd@Pt NWs versus Pd NWs and Pt/C.[158]
Copyright 2015, American Chemical Society. (B) Electrocatalytic performance of Pd
NWs/C.[159] Copyright 2017, American Chemical Society.
3.3 Biomedical Applications

The field of nanomedicine has recently witnessed interest and progress in designing and
studying NPs synthesized by seed-mediated growth methods.[163, 164] Due to its tunable and
versatile plasmonic properties, such core-shell NPs has the potential to enable bioimaging
modalities, diagnosis and treatment of numerous diseases. This study analyzes and
emphasizes significant advancements in the growing subject of bioapplication-guided
engineering of core-shell metal NPs, focusing on design considerations and implementation
approaches. In particular, the effects of the morphology of core-shell NPs on their
photothermal and photoacoustic properties are discussed, with emphasis on the biological
applications of core-shell NPs, such as photoacoustic imaging and photothermal therapy.
3.3.1 Photothermal Therapy
Photothermal therapy targets hyperthermia, a situation where cells are subjected to heat
(above 42 °C) for tens of minutes, in order to kill tumor cells. Because the cell membrane
will be destroyed or the proteins will become denaturized, the cells will suffer permanent
damage.[165, 166] Nanomaterials like GNPs can convert electromagnetic energy into heat
through photothermal effect and have excellent tumor selectivity due to their capacity to
concentrate in tumor sites.[167-169] Additionally, shape has a significant impact on GNP-based
photothermal treatment applications. As previously mentioned, Chen and co-authors achieved
precise control of Au-Au hybrid nanostructures by controlling the growth of Au on the
surface of GNR seeds by strong ligands, and obtained a series of Au-on-GNR hybrid
nanostructures.[66] Based on the above structure control, the structural variation made the
LSPR great candidates for plasmonic applications since it allowed for fine-tuning in the full
spectrum range. The nanocorals exhibit outstanding photothermal conversion capability in
NIR-II window and black-body absorption. They were proven to be excellent photothermal
therapy in vitro and in vivo.
It is vital to integrate different mechanisms to maximize photothermal conversion

efficiency, yet it is still difficult to create therapeutic agents for photothermal tumor
treatment.[170] Wang et al. reported a method to create asymmetric Bi2Se3/CdSe-Au
hierarchical NRs with high photothermal conversion (Figure 17A).[171] Sliver wetting is first

generated to compensate the interfacial lattice mismatch and encourage the site-selective
growth of AgCdSe on one end or side surface of GNRs. Then, in the course of the cation
exchange reaction and epitaxial development of the Bi2Se3 shell, Ag+ is seen to be removed
from the lattice. A type-II band aligned Bi2Se3/CdSe heterojunction is created and located at
the plasmonic hotspots of GNRs. With 4.3 times the temperature of pure GNRs, the
matchstick-like Bi2Se3/CdSe-GNRs exhibit outstanding photothermal conversion. They are
excellent photothermal therapeutic agents, as demonstrated by both in vitro and in vivo
investigations. Furthermore, in order to increase the efficacy and applicability of the
photothermal effect, researchers have attempted to combine it with other treatment
modalities. In addition to GNRs, other platform nanomaterials have been utilized to ablate
tumor using imaging-guided photothermal therapy. Xia and co-authors created PdCu@Au
core-shell tripods (Figure 17B, C).[5] A functional peptide that targets the receptor
overexpressed on breast cancer cells allowed some of the injected tripods to collect inside
tumor tissue. The lesion as shown by the PET imaging might be eradicated with laser
irradiation while protecting the healthy and surrounding tissues.

Figure 17 (A) Mechanism of the preparation of Bi2Se3/CdSe-Au NRs for photothermal
therapy.[171] Copyright 2021, WILEY-VCH. (B) Combined PET/CT imaging of mice
intravenously administrated. (C) Thermographs of mice with tumors following photothermal
therapy for varying lengths of time.[5] Copyright 2021, American Chemical Society.
3.3.2 Photoacoustic Imaging
The fundamental principle of photoacoustic imaging is based on the tissue's ability to

absorb light pulses, leading to optical contrast. In comparison to conventional imaging
modalities, it combines the advantages of optical and ultrasonic imaging, including real-time
and dynamic monitoring deeper tissue, higher signal-to-noise ratio, and improved spatial
resolution.[172-176] For example, compared with fluorescence imaging, photoacoustic imaging
is less likely to be affected by external environment, because fluorescence is easily quenched.
The absorption in the second near-infrared (NIR-II, 900−2000 nm) window improves
penetration depth and reduce light scatting, leading to better imaging than that in the first
near-infrared (NIR-I, 680−900 nm) window.[177-179] To improve absorption in the NIR-II
window, several contrast agents are used such as gold-based nanoplates and NRs. For
example, Emelianov et al. described the synthesis of miniature GNRs that absorb in the NIR-
II and are between 5 and 11 times smaller than conventional GNRs while maintaining a
similar aspect ratio (Figure 18A).[180] The type and concentration of the surfactant, the pH of
the growth solution and concentration of the reduction agent must be taken into consideration
at the same time in order to minimize the size of GNRs while maintaining the aspect ratio.
Small NRs are approximately 3 times more thermally stable and provide 3.5 times greater
photoacoustic signal than their absorption-matched larger counterparts under nanosecond
pulsed laser illumination.
Additionally, in order to realize the integration of diagnosis and treatment, the

researchers combined photoacoustic imaging and photothermal therapy. For instance, Liu et
al. demonstrated the use of a photothermal and photoacoustic agent that is triggered by the
tumor microenvironment as an activatable prodrug and probe for accurate cancer diagnosis
and treatment (Figure 18B).[181] Although GNRs are a superb contrast agent for
photoacoustic imaging, coating silver on GNRs reduced their photoacoustic signal. As more

Ag deposited, LSPR of the nanostars gradually blue-shifted. However, H2O2 can etch and
oxidize the Ag shell. In fact, excessive H2O2 is produced in the tumor environment. This
permits monitoring of real-time photothermal and photoacoustic imaging of tumors without
unwanted phototoxicity to normal tissues. Likewise, a novel H2O2-responsive theranostic
nanoplatform comprising Ag shell and GNRs is created. Ag+ are released when the Ag shell
is etched and oxidized by H2O2, killing bacteria in vivo and causing a change in their
absorption at 700 and 1260 nm.[182] The ratiometric photoacoustic imaging at 1260 and 700
nm correctly quantified in a model of bacterial infection and abdomen inflammation. There
are many other studies using gold/silver hybrid NPs for treatment and photoacoustic imaging
of bacterial infection.[183]

Figure 18 (A) In a mice with prostate cancer, photoacoustic imaging of targeted small and
large GNRs was performed.[180] Copyright 2019, Nature Publishing Group (B) Photoacoustic
imaging of tumors and metastatic lymph nodes using Au@Ag@PEG/Apt.[181] Copyright
2010, The Royal Society of Chemistry.
4. Summary and Outlook

In this review, we briefly introduced the mechanisms of the seed-mediated growth of
metal nanoparticles, aimed at outlining the key influencing factors for preparation of these
metal nanoparticles in a highly predictive manner, focusing on the physical, chemical and
biological properties of grown metal nanoparticles. Emphases have been placed on growth
influencing factors such as seeds, capping agents, metal precursors, growth solution,
growth/incubation time, reductant and external factors. Precise regulation of metal
nanoparticle synthesis through seeded growth could be achieved by controlling the property
(size, shape and faceting) of the seeds; using biomolecules/non-biomolecules as capping
agents and tuning the inherent properties of capping agents; changing the reduction potential,
concentration and injection rate of the metal precursors, as well as the extent of lattice
mismatch between metal precursors and seeds; changing the reaction condition such as pH
and temperature of growth solution; adjusting the growth/incubation time; manipulating the
concentration, reduction pathway and structural characteristics of reductant, and introducing
the external factors such as light, chelating agent and templating. More importantly, this
process is governed by both kinetic and thermodynamic parameters, and it can be
manipulated by carefully adjusting the experimental conditions, such as changing the
temperature, the concentration of metal precursor, capping agent and reductant, etc. As a
result, the direct transformation of existing metal seeds into target ones has proven to be an
efficient and reliable method for producing a variety of complicated metal nanoparticles. In
particular, maximizing the efficiency and convenience of deposition of the second metal on
the more reactive seeds by using strong capping agents to effectively stabilize the precursors
of the second metal. Finally, growing metal seeds into specific metal nanoparticles using
seed-mediated growth is a flexible method that has a significant impact on controlling the
properties of the final product, which is desirable for a variety of physicochemical and
biological applications. Therefore, we highlight some significant properties and applications
enabled by the core-shell metal nanoparticles, including those related to optics (Raman,
fluorescence, scattered light, chirality and absorption), catalysis (photocatalysis and
electrocatalysis), and biomedical applications (photoacoustic imaging and photothermal
therapy).

There are both challenges and opportunities in the investigation of seed-mediated
growth of metal nanoparticles. For instance, a greater understanding of the relationship
between the intrinsic properties of functional capping agents and structural parameters (size
and shape) of resultant metal nanoparticles would result from investigating novel and
inherent functionalities of capping agents. Chirality, which is one of DNA's fundamental
structural characteristics, has rarely been used to create highly ordered nanostructures with
distinctive optical features. Particularly, the growth of metal nanoparticles from ionic
precursors directed by DNA origami can exhibit a chiral-optical response. However, the CD
signal was absent in previously produced metal nanoparticles coupled to chiral DNA. This
strategy offers up new avenues for connecting the periodicity and chirality of biomolecules
with the optical characteristics of chiral nanostructures created using DNA as capping agents.
Although proteins, such as enzymes, can exhibit CD in the UV and infrared due to their chiral
secondary structure, there has yet to be a recorded attempt to directly structure chiral metal
nanostructures using proteins as capping agents through seed-mediated growth methods.
Certainly, amino acids and peptides as the components of proteins have recently been used as
capping agents in seed-mediated growth methods to precisely tune the morphology and
properties of metal nanoparticles.
Further, the fundamental building blocks for the synthesis of functional metal
nanoparticles are provided by extensive investigations on the thermodynamic and kinetic
parameters that regulate the nucleation and growth processes of metal nanoparticles in
synthetic methods. There is still no study that can generalize the relationship between
thermodynamics or/and kinetics factors and various key influencing factors of growth in the
seed growth method to facilitate the synthesis of metal nanoparticles in a highly predictable
and facile way. Therefore, we have summarized in the article. We hope that this review will
not only help researchers understand the growth influencing factors during seed-mediated
growth methods, but also provide the necessary insights for designing their own experiments
from the perspective of the relationship between kinetic and thermodynamic parameters and
growth influencing factors. However, the synthesis mechanisms of thermodynamic and
kinetic parameters are complex, interact with each other, and behave differently under

different experimental conditions. This also poses a challenge for researchers to further study
the relationship between thermodynamic and kinetic parameters and growth factors. In
addition, for the creation of metal nanoparticles with complex morphologies, the combination
of seed-mediated growth with the templating method holds great promise. Templated
synthesis will need to address cost efficiency and sustainability challenges. All in all, taking
seed-mediated growth methods to the next level holds great promise, but there is still some
way to go.
Acknowledgements
This work was financially supported by the National Key R&D Program of China
(2022YFA1103403), Tsinghua-Foshan Innovation Special Fund (2022THFS6121),
Innovation Team and Talents Cultivation Program of National Administration of Traditional
Chinese Medicine (ZYYCXTD-D-202208), Postdoctoral Innovative Talent Support Program
(BX20220160), China Postdoctoral Science Foundation Funded Project (2022M711779),
National Natural Science Foundation of China (22074157), Young Elite Scientist
Sponsorship Program of the Beijing Association for Science and Technology, and Tsinghua-
Peking Joint Center for Life Sciences Postdoctoral Foundation Program.
Conflict of Interest
The authors declare no conflict of interest.
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Yongjian Ai received his Ph.D in 2021 from Department of Chemistry, Tsinghua University
under the supervise of Professor Qionglin Liang. Then, he worked as an associate professor at
Nanchang University. Currently he is a research associate (postdoctoral fellow) in Tsinghua
University. His research interests focus on bioanalysis and bioengineering drugs, published
over 60 peer-reviewed papers.

Qionglin Liang received both his Ph.D (2005) and B.Sc. (2000) from Department of
Chemistry, Tsinghua University. Currently he is a chair professor in Department of
Chemistry at Tsinghua University. His research interests focus on the development of bio-
inspired microfluidics techniques and their applications in biomaterials, biofabrication and
organ-on-a-chip, published over 200 peer-reviewed papers.
To highlight these achievements and help researchers to understand the current

investigation status of seed-mediated methods, the state-of-the-art development in seeded
growth methods from key influencing factors of growth and applications of grown metal
nanoparticles are summarized in this review. Furthermore, the challenges faced by seed-
mediated methods are outlined and the future directions for advancing seed-mediated
methods are outlooked.
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Recent Advances of Seed-Mediated Growth of Metal Nanoparticles: from Growth to Applications

MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology,

Laboratory of Flexible Electronics Technology,

Center for Synthetic and Systems Biology,

Tsinghua University-Peking University Joint Centre for Life Sciences,

Tsinghua University, Beijing 100084, P.R. China

E-mail: ayj@tsinghua.edu.cn, Liangql@tsinghua.edu.cn

Keywords: metal nanoparticles, seed-mediated growth, growth influencing factors,

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Figure 1. Mechanisms of seed-mediated growth of metal NPs.

Table 1. Summarize the growth influencing factors of metal nanoparticles by seed-mediated

Size and shape Nanorods CdSe-Au / 38

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Biomolecules Octahedrons Au Chirality 58

Metal precursors Concentration Nanospheres Au-Cu / 74

Injection rate Nanocubes Rh / 75

Lattice mismatch Nanospheres Au / 76

Growth time / Nanoplates Ag / 94

Incubation time / Nanospheres Au Absorption 93

Structure characteristics Nanowires Cu Raman 107

External factors Light Nanoplate Au / 112

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Template Nanorods Au Chirality 114

2. Influencing Factors of Seed-Mediated Growth of Metal Nanoparticles

2.1 The Influence of Seeds

2.1.1 Size and Shape of the Seeds

2.1.2 Faceting of the Seeds

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2.2 The Influence of Capping Agents

2.2.1 Biomolecules-Mediated Growth of Metal Nanoparticles

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In addition to single-stranded DNA as capping agents, double-stranded DNA can also be

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(B) Transition metal sulfide nanocrystals generated using a protein-nanoreactor method.[59]

2.2.2 Non-Biomolecules-Mediated Growth of Metal Nanoparticles

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2.2.3 The Inherent Properties of Capping Agents

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We used GNRs as seeds, AA as reductant, HAuCl4 as precursor, and thiolated

2.3 The Influence of Metal Precursors

2.3.1 The Reduction Potential of Metal Precursors

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In addition, the reduction potential of metal precursors is altered by adding chemical

2.3.2 The Concentration of Metal Precursors

Bimetallic NPs refer to nanostructures composed of two different metals. In addition,

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2.3.3 The Injection Rate of the Metal Precursor

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2.3.4 The Extent of Lattice Mismatch with Seeds

In typical seeded growth processes, conformal coating is induced by a perfect lattice

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2.4 The Influence of the Growth Solution

Physical parameters such as pH and temperature of the growth solution have a

2.4.1 pH of the Growth Solution

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