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A review of the role and mechanism of surfactants

Cite this: Nanoscale, 2021, 13, 3895
in the morphology control of metal nanoparticles
Tongxin Song, Fei Gao, Siyu Guo,* Yangping Zhang, Shujin Li, Huaming You and
Yukou Du *

Received 14th October 2020,
Accepted 29th January 2021
DOI: 10.1039/d0nr07339c
rsc.li/nanoscale
Although great progress has been made in the synthesis of metal nanoparticles, good repeatability and
accurate predictability are still difficult to achieve. This difficulty can be attributed to the synthetic method
based primarily on observation and subjective experience, and the role of many surfactants remains
unclear. It should be noted that surfactants play an important role in the synthetic process. Understanding
their function and mechanism in the synthetic process is a prerequisite for the rational design of nanoca-
talysts with ideal morphology and performance. In this review article, the function of surfactants is intro-
duced first, and then the mechanism of action of surfactants in controlling the morphology of nano-
particles is discussed according to the types of surfactants, and the promoting and sealing effects of sur-
factants on the crystal surface is revealed. The relationship between surfactants and the morphology
structure of nanoparticles is studied. The removal methods of surfactants are discussed, and the existing
problems in the current development strategy are summarized. Finally, the application of surfactants in
controlling the morphology of metal nanocrystals is prospected. It is hoped that the review can open up
new avenues for the synthesis of nanocrystals.

1. Introduction size-dependent PdAg nanoparticles for alcohol oxidation reac-

Inorganic nanoparticles have attracted considerable attention
for their wide application in various fields. Platinum (Pt)/palla-
dium (Pd)-based nanomaterials are used in electrocatalytic oxi-
dation reactions of alcohols1,2 and oxygen reduction reactions
(ORRs).3,4 Ruthenium (Ru)/iridium (Ir) nanocrystals are mainly
applied in hydrogen evolution reactions (HERs)5–7 and oxygen
evolution reactions (OERs).8,9 Gold (Au) and silver (Ag)
elements are mostly used in photocatalysts due to their
plasma effect,10 in particular Au nanoparticles are widely used
in biomedical research.11,12 CO2 reduction reactions (CO2RRs)
are usually catalyzed by non-noble metal particles.13,14 Due to
the impact of the traditional concept of “the performance
depends on the structure”,15–17 researchers concentrated on
the development and design of nanocrystals with unique mor-
phology, and expected that more surface-active sites can be
exposed via fine-modification interface engineering, so as to
improve their catalytic performance.
Many studies have reported that the morphological and
structural characterizations of nanocrystals have a significant
impact on the catalytic performance. Wang et al. reported the
College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, P.R. China. E-mail: syguo@suda.edu.cn,
duyk@suda.edu.cn; Fax: +86-512-6588089; Tel: +86-512-65880089
tions, and proved that nanodots with the smallest diameter
had the best catalytic performance,18 which was also testified
by Gao et al. in nanocubes with different sizes.19 Xia’s group
showed that the mass activity of PtNi nanocages was much
higher than that of PtNi nanospheres,20 which indicated that
the structure of nanomaterials affects the catalytic perform-
ance for ORRs. Other hollow structures also exhibited better
catalytic properties than solid structures.21,22 In another case
of alcohol catalysis, among 3D tremella-like PdM (M = Ag, Pb,
and Au) nanosheets (NSs),23 PdAg nanosheets were proved to
have the best catalytic performance, indicating that the
elemental composition of nanomaterials would have an
impact on the catalytic performance.
From the macro perspective, the crystal growth process is
the transition of the parent phase containing crystal units
from the low-order phase to the high-order phase. From the
micro perspective, the growth of metal nanoparticles can be
described as the birth of a seed, which then evolves into crys-
tals with different shapes. In general, the structural property of
nanomaterials mainly depends on the crystal growth process.
Abundant studies demonstrated that many factors including
metal precursors, reductants, solvents, pH values, ionic
strengths, reaction temperatures, and surfactants could manip-
ulate the crystal structure.24,25 The research of crystal growth
theory is still in a semi-empirical state, so it is challenging to
reveal the crystal growth law in essence, which makes it more

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difficult to synthesize metal nanocrystals with excellent mor-
phology. The surfactants play a very important role in the mor-
phology regulation of nanocrystals, and they can control the
crystal growth to some extent via diffusion and selective
adsorption. Therefore, it is necessary to study the role and
mechanism of surfactants.
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It is conceivable that the introduction of surfactants also
brings other complexities to the reaction system. In addition to
the types of surfactants, the concentration, pH value, and
ionic strength of the surfactant solution also affect the growth
of nanocrystals.24,25 Zheng’s group confirmed that the ionic
strength of surfactants could influence the self-assembly of Au
nanoparticles.25 In addition, various surfactants can form a
mixture in the progress of nanoparticle synthesis.26,27 In a
reported work, a mixture of cationic surfactants (cetyltri-
methylammonium bromide, CTAB) and anionic surfactants
(sodium oleate, NaOL) was used to assist the synthesis of Pd
nanodendrites.27 The introduction of NaOL destroyed the
CTAB bilayer and formed mixed surfactant micelles in the
surface of Pd seeds via electrostatic interaction. The mecha-
nism of active agents is still in the development phase.
Therefore, it is very significant to explore the roles of surfac-
tants in the synthesis of nanocrystals.
In this review, our target is to provide a comprehensive
understanding of the role and mechanism of different types of
surfactants and to provide a theoretical guidance and predic-
tion for the synthesis of nanocrystals. Combined with specific
experimental cases, we qualitatively analyzed the influence of
surfactants on the morphology, crystal plane, components,
defects, and phase structure of nanocrystals during the syn-
thesis process at the atomic/molecular level. In addition, we
summarized the removal methods of surfactants and expect to
further improve the quality and catalytic performance of nano-
materials through post-treatment.
2. Roles of surfactants in nanocrystal
synthesis
Nanocrystals are usually synthesized by wet-chemical methods
including precipitation, hydrothermal, solvent-thermal, sol–
gel, polyol, thermal decomposition, seed-mediated growth,
and galvanic replacement reactions,28 and they always spon-
taneously tend to form a bulk polyhedron with the lowest
surface energy. The surfactant can induce many interesting
effects such as the formation of high-index facets, the gene-
ration of defects and concave structures, and crystal shape
transformation. The role of surfactants depends on the
specific reaction environment. As shown in Fig. 1, the roles of
surfactants are classified and summarized in the following six
categories in detail:
(1) Dispersing agents. Due to the large specific surface area
and high surface energy, nanomaterials tend to be agglomer-
ated. Therefore, for obtaining well-dispersed nanocatalysts, the
surfactant molecules dispersed in the reaction solution cover
the newly formed metal particles, so that the particles are iso-
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Fig. 1 Scheme of the roles of surfactants in the synthesis of metal
nanocrystals.
lated without aggregation.29,30 On the one hand, the dispersive
effect is achieved by electrostatic repulsion of ionic surfactants.
On the other hand, the steric hindrance effect of polymeric
surfactants could construct a highly dispersed system. When
the electrostatic repulsion, steric hindrance and van der Waals
force are balanced on the surface of the newly generated metal
atoms, the nanoparticles disperse stably in the system.31,32
(2) Structure-directing agents. When the concentration of
surfactant molecules in the solution reaches a certain value,
the surfactant molecules begin to assemble themselves into
aggregates. Due to the co-existence of hydrophilic and oleophi-
lic groups, these aggregates take on various shapes in the reac-
tion solution, known as micelles, inducing metal atoms to
grow anisotropically into nanocrystals with specific
morphology.33,34 The self-assembled micelles can induce the
formation of morphology-defined nanocrystals such as nano-
spheres, nanowires, nanosheets, nanocubes, and nanonets.
Some chain-like active agents can provide a soft template for
the evolution of nanostructures.35
(3) Capping agents. The capping effect occurs mainly
during the evolution of crystalline seeds. The surfactants in
the solution easily assemble on the surface of crystal seeds via
physical adsorption, covalent bonding, electrostatic inter-
action, or van der Waals force. Facet controlling is realized by
changing the relative order of energy of different crystal
faces.36–38 On the one hand, the capping agent can be selec-
tively attached to a specific crystal surface to form well-defined
nanostructures, for example, capping the (100) crystal faces
can form (100)-plane-stabilized nanocubes,39 and covering the
(111) crystal faces can yield octahedrons surrounded by the
(111)-planes.40 On the other hand, the capping-specific crystal
facet could promote the overgrowth at a certain site or inhibit
the growth of a certain crystal surface, forming a concave struc-
ture with abundant defects.
(4) Weak reducing agents. Some surfactants contain a
special group (reductive groups), which makes them exhibit
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reductive ability in the reaction system. Different from the
general reducing agent, the quite mild reducing property can
control the crystal synthesis desirably from the dynamics.41,42
When the reduction rate is high, the metal atoms always take
the shape that thermodynamics favors.43,44 When the
reduction capacity of the system is extraordinarily weak, the
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crystal seeds can evolve into a variety of dynamically controlled
nanostructures. For commercial PVP, due to the presence of
water and peroxide, the end group is replaced by a hydroxyl
(–OH) group. Like the common long-chain alcohols, it could
act as a mild reducing agent and induce the dynamic-con-
trolled synthesis. Cationic surfactants of quaternary
ammonium salts can be oxidized into nitrite groups in a
specific system as a weak reductant.
(5) Oxidation etching agents. According to thermo-
dynamics, the concave structure is difficult to exist stably. The
Gibbs free energy of concave structure is always lower than
that of the plane or convex region, leading to the priority and
rapid growth of the concave region, thereby eliminating the
concave region and minimizing the total surface energy.45,46
As an oxidation etching agent, it is beneficial to the concave
structure and defect. The formation of the concave structure
must depend on the oxidation etching agent. Some additives
can combine with the oxygen in the system to form oxidation
etching pairs, which can selectively etch unstable and meta-
stable atoms to form a precise concave structure with abun-
dant defects.
(6) Ion exchange. The ions dissociated from the surfactants
can be exchanged with metal precursors as a ligand to form a
new complex during the synthesis. The newly generated
complex may have a completely different redox potential,
which has a far-reaching impact on the reduction kinetics,
affecting the reduction order of different metal atoms and
resulting in different architecture structures, or the transition
from the alloy structure to the core–shell structure, and then
to heterostructure compounds.28 It is worth noting that halide
ionic additives can also control the growth pattern by changing
the relative rate of deposition and diffusion of metal atoms.
Fig. 2 is the scheme of the effect of surfactants on the
crystal formation. Facet-controlled nanocrystals can be syn-
Fig. 2 Schematic of the effect of surfactants on the facet, shape, size,
and architecture of nanocrystals.
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thesised with the capping effect, as shown in the first column
of Fig. 2. The selective adsorption of capping agents on the
crystal surface can affect the relative area of different facets. By
changing the relative area of the (111)- and (100)-facet,
different products such as octahedrons, nanocubes, truncated
octahedron, and truncated nanocubes can be obtained.
Surfactants assemble themselves into micelles of different
shapes in the solution, which are thermodynamically stable
systems. These micelles induce metal atoms to form the same-
shape nanocrystals as the micelles, as shown in the second
column of Fig. 2. In addition, the diameter of spherical
micelles can affect the size of nanoparticles and generate the
size-control nanocrystals, as shown in the third column in
Fig. 2. The architecture-control column is the atomic arrange-
ment diagram of the three architectures. In a bimetallic reac-
tion system, when the redox potential of two metal ions is
similar, they are almost simultaneously reduced, and the two
atoms are uniformly mixed to form an alloy or intermetallic
compound via metal bonds. The former is arranged randomly,
while the latter is in long-range atomic order. When a kind of
metal ion is first reduced into a nucleus, the other metal ions
tend to encompass it in a shell, thus forming a core–shell
structure. If both metal atoms can form a nucleus indepen-
dently, a heterojunction structure is formed.
In the next section, we will elaborate on how different types
of surfactants work in the synthetic process through specific
cases.
3. Mechanism analysis of surfactants
in morphology regulation
Here, we divide surfactants into three categories on the whole:
polymeric surfactants, cationic surfactants, and anionic surfac-
tants. Table 1 lists the surfactants mentioned and the corres-
ponding structures and abbreviations. We will discuss the
effects of these surfactants in specific cases.
3.1 Effects of polymeric surfactants
For polymeric surfactants, we mainly take polyvinylpyrrolidone
(PVP) and Pluronic F127 as examples. PVP is a non-ionic
polymer compound obtained based on free-radical polymeriz-
ation of N-vinyl pyrrolidone. Because it is nontoxic and easily
dissolved in polar solutions, PVP has received much attention
in the synthesis of nanomaterials. The research focuses not
only on the coordination ability of PVP’s repeating units, but
also on the end groups. Impressively, PVP exhibits hydrophilic
properties due to the high polar lactam group in pyrrolidone.
In addition, the pyrrole ring and long chain of PVP contain
nonpolar methylene, so it is lipophilic.47,48 Therefore, PVP has
different solubilities and adsorption selectivities in diverse
polar solvents. PVP has stable physicochemical properties over
a wide pH range. Similarly, polyether, F127 (PEOaPPObPEOc),
is also a frequently used polymer surfactant. It is a segmented
copolymer formed by polyethylene oxide and polypropylene
oxide, with different oil-hydrophilic equilibrium values. As an
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Table 1 The surfactants mentioned in the following content and their corresponding structures and abbreviations

Category Surfactant Structure Abbreviation

Polymeric Polyvinylpyrrolidone PVP

surfactants
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Pluronic F127 F127

Cationic Cetyl trimethyl ammonium CTAC

surfactants chloride

Cetyl trimethyl ammonium CTAB

bromide

Docosyl trimethyl ammonium C22TAC

chloride

Dimethyl dioctadecyl DDAC

ammonium chloride

Dimethyl dioctadecyl DDAB

ammonium bromide

Hexadecyl dimethyl benzyl HDBAC

ammonium chloride

Octadecyl trimethyl ammonium STAC

chloride

Dodecyl trimethyl ammonium DTAC

chloride

Anionic Sodium dodecyl sulfate SDS

surfactants

Sodium dodecyl benzene SDBS

sulfonate

Sodium dodecyl sulfonate SLS

emulgator, it can form micelles in the solutions and be used
in the synthesis of mesoporous nanoparticles.49,50
3.1.1 Prevention of aggregation. There are usually two che-
misorption modes for PVP: adsorption of only oxygen atoms
and adsorption of both nitrogen and oxygen, as shown in
Fig. 3a.51 The two adsorption modes of PVP provide enough
space for nanocrystals to grow, similar to a protective layer.
Fig. 3b shows the adsorption mode of PVP on the Ag core,
mainly through the interaction of carbonyl oxygen atoms with
Ag atoms. Fig. 3c is the radial distribution function between the
Ag core and the segment of PVP.52 The function g(Ag–N) shows
unstructured peaks, implying weak adsorption. The backbone
of PVP tends to lie flat. The adsorption mode of PVP could
affect the size of final product. The chemisorption mode of
PVP is related to the ratio of the number of repeat unites to the
mole of metal. For PVP with a high molecular weight, more are
coated on metal atoms, and the size of the synthesized nano-
particles is smaller. In this case, PVP is mainly adsorbed onto
metal atoms via oxygen atoms in the ring. PVP with a low mole-
cular weight has a low coverage on the surface of metal atoms,
and this yields nanoparticles with a larger size, where PVP che-
misorbs via nitrogen atoms and oxygen atoms.

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Fig. 3 (a) Molecular structure of PVP, and the adsorption method of
one structural unit on the surface of Pd nanoparticle. (b) Structural
arrangement of the PVP chain adsorbed on the surface of the Ag core
from the top and side views. (c) Radial distribution functions between Ag
and PVP segments (carbonyl oxygen, nitrogen, and water oxygen). (a)
Reproduced with permission from ref. 51 Copyright 2012, American
Chemical Society. (b and c) Reproduced with permission from ref. 52
Copyright 2015, American Chemical Society.
In most cases, PVP is used as a space stabilizer to prevent
nanoparticles from accumulating due to its large steric effect.
Another explanation is that PVP regulates the reaction kinetics
via complex chelation. Feng et al. synthesized PVP-assisted (Mw
= 58 000) PtPb networks (Fig. 4a and b). When PVP is absent in
the reaction system, the products appeared as agglomerates
(Fig. 4c).53 Zhang’s team has synthesized colloidal PtNi clus-
ters with the alloy phase, porous structure and interconnected
frame using PVP (K40) as a colloidal stabilizer and DMF as a
solvent by a one-pot solvothermal method.54 Fig. 4d and e are
the scanning electron microscopic (SEM) and transmission
electron microscopic (TEM) images. The major product of
control experiment for removing PVP is aggregate irregular
nanoparticles (Fig. 4f ). On the one hand, PVP has a strong
binding ability, which can reduce the surface energy of nano-
particles and avoid the accumulation. On the other hand, PVP
can also change the reduction kinetics, promoting the for-
mation of the alloy phase. Under the standard condition
without PVP, the redox potentials of Pt2+/Pt and Ni2+/Ni are
1.19 V and −0.25 V (vs. SHE), respectively. Therefore, Pt can be
reduced preferentially by DMF in the absence of PVP.55
However, in the presence of PVP, Ni particles can also be
detected after half an hour of the reaction, which indicates
that PVP can change the reduction kinetics of Pt2+ and Ni2+.56
Du’s group has also prepared uniform PtAg multi-petal nano-
flowers using PVP (K15-19) as a dispersant (Fig. 4g and h).57
When PVP is absent in the reaction system, an aggregated
block structure is obtained, as shown in Fig. 4i, which fully
demonstrates the role of PVP in dispersing nanoflowers. In
addition, Tang’s group reported a porous nanobowl with the
aid of urea and PVP as a stabilizer.58 Because of the large
molecular weight, PVP can prevent the accumulation of nano-
particles and has a certain capping effect. There are a lot of
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Fig. 4 (a) HAADF-STEM image and (b) TEM image of the PtPb network
with PVP. (c) PtPb network in the absence of PVP. (d) SEM image and (e)
TEM image of PtNi nanoclusters with PVP. (f ) PtNi nanoclusters in the
absence of PVP. (g) TEM image and (h) HR-TEM image of PtAg
nanoflowers with PVP. (i) PtAg nanoflowers in the absence of PVP. (a–c)
Reproduced with permission from ref. 53 Copyright 2016, Wiley-VCH.
(d–f ) Reproduced with permission from ref. 54 Copyright 2018, Wiley-
VCH. (g–i) Reproduced with permission from ref. 57 Copyright 2019,
American Chemical Society.
other works referring the steric effect, using PVP as a
dispersant.59–65
The molecular formula of Pluronic F127 is PEOaPPObPEOc,
the EO segment is an ethoxy group (C2H5O–) and the PO
segment is a propyloxy group (C3H7O–). The PEO segment is
more hydrophilic than the PPO segment, and it can form
hydrogen bonds when combining with metal complexes in
solutions. In a reaction solution, F127 forms micelles with the
PPO segment as the core, dispersing in a solution, which not
only have a guiding effect on the cross-linking of clusters, but
also block the particles. The PPO segment permits assembly
with other hydrophobic building blocks. F127 is not stable
when the temperature is higher than 500 °C during calcina-
tion, which is conducive to the formation of abundant meso-
pores. Therefore, F127 is widely used in the synthesis of meso-
porous materials with small-sized and uniform distribution.
Multi-metallic spheres with mesopores were produced, and
they exhibited outstanding catalytic performance for methanol
oxidation reactions (MORs).66 Fig. 5 illustrated that F127
assisted the synthesis of PdPt, Au@PdPt, and PdPtCu spheres.
Gu’s group synthesized Au@PtPd mesoporous nanorods
(MNRs) with Au nanorods as templates and F127
(PEO100PPO65PEO100) as a colloidal stabilizer.67 When F127
was removed from the reaction system, the product became a
non-uniform aggregate block. The reason for the sharp con-
trast is that the hydrophilic ethoxy group of F127 adsorbs
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Fig. 5 Schematic of mesoporous (a) PdPt spheres, (b) Au@PdPt
spheres, and (c) PdPtCu spheres. (a–c) Reproduced with permission
from ref. 66 Copyright 2015, Wiley-VCH.
metal ions to form complexes, which are reduced on the Au
nanorods to form porous PtPd shells, while also avoiding the
accumulation of metal particles. F127 is used as a surfactant
for many nano/mesoporous materials.23–25 An interesting case
reported by Wang and his coworkers is an urchin nanocrystal,
PdCuIr, with long spines,68 where F127 serves for nucleation,
preventing the nuclei from accumulating and resulting in a
spiny structure.
3.1.2 As capping agents. In addition to being a dispersant,
PVP is also a good capping agent. Studies have shown that
PVP, as a capping agent, can be chemically adsorbed onto the
surface of metal particles, causing the growth of specific
crystal surfaces, and ultimately affecting the electronic struc-
ture of nanomaterials. Many studies have found that PVP
prefers to cover different facets on metal nanoparticles and
metal oxide materials. It is obvious that the atomic density of
the (111) crystal plane is the highest, and the energy sequence
of the low-index crystal facets is γ(111) < γ(100) < γ(110). In the
absence of additives, the (111)-surface is always formed prefer-
entially. Many experimental evidences have shown that PVP
prefers to seal the (100)-face of the metal crystals, facilitating
the formation of the nanocubes. The successful construction
of Ag nanocubes in many studies could be attributed to the
preferential adsorption of the Ag(100) crystal surface by
PVP.69–74
Luo’s group synthesized Ag nanocubes with PVP as the
capping agent and CF3COOAg as the precursor, which was con-
ducted by heating an ethylene glycol (EG) solution containing
NaHS and NaCl, utilizing the reductivity of polyols at high
temperatures.75 Fig. 6a is the TEM image of Ag nanocubes and
Fig. 6b is the atomic model diagram. Subsequently, the PVP-
assisted polyol synthetic method was applied to obtain opti-
mized Pd,76 Pt,77 and Rh78 nanocubes and other nanostructure
enclosed within the (100)-plane.79–81 Fig. 6c–e are the TEM
images of AgIr nanocubes with different amounts of Ir precur-
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Fig. 6 (a) TEM image and (b) atomic model diagram of Ag NCs. (c–e)
TEM images of AgIr NCs with different amounts of Ir precursors and (f )
UV-vis spectra of the reaction suspension solution. Top view of the
binding configurations for the 2-pyrrolidone ring on the (g) Ag(100)-,
and (h) Ag(111)-planes. Red, blue, turquoise, and white spheres represent
O, N, C, and H atoms. (a and b) Reproduced with permission from ref. 75
Copyright 2020, American Chemical Society. (c–f ) Reproduced with
permission from ref. 82 Copyright 2020, Royal Society of Chemistry. (g
and h) Reproduced with permission from ref. 83 Copyright 2012,
American Chemical Society.
sors.82 The UV-vis spectra of the reaction suspension was
measured, as shown in Fig. 6f, and it can be seen that the
major LSPR peak is red-shifted and the intensity decreases. In
addition, density functional theory (DFT) also reveals the
adsorption interaction force of PVP on the Ag(111) and Ag(100)
crystal planes. Al-Saidi et al. calculated from the segment level
and chain level that the monomer bonds more strongly to the
Ag(100) crystal plane than the Ag(111) crystal plane.83 Fig. 6g
and h are the top view of the binding configurations for the
pyrrolidone ring on the Ag(100) and Ag(111) facets. The van
der Waals interaction affects the binding conformations and
flattens the potential energy surface, which makes the energy
of the (100)-plane lower than that of the (111)-plane.
For the synthesis of metal oxide nanoparticles, PVP prefer-
entially adsorbs on the (111)-facet. Zhang et al. adjusted the
amount of PVP (Mw = 30 000) to achieve geometrically fine-con-
trolled Cu2O nanocrystals.84 It was realized by the stable
adsorption on the (111)-facet of Cu2O. As PVP is easier to be
absorbed on the (111)-facet, the vertical growth of the (111)-
plane is inhibited, and the deposition of Cu atoms can only
occur on the uncovered (100)-surface. As the amount of PVP
increases, the crystal surface of (111) is relatively amplified. As
the dosage of PVP increases, the (100)-plane gradually shrinks
and finally forms nanooctahedrons. The specific adsorption of
PVP on the cubic-phase Cu2O (111)-plane is due to the coordi-
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nation between the vacant orbital of the suspended copper
atoms with the lone pair electrons of oxygen atoms in PVP.
The same mechanism is applied to synthesize Ag85 and Au
octahedrons.86
3.1.3 Weak reducibility. For the commonly used PVP, the
end group is usually –OH, since water is involved in the prepa-
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ration process as a polymerization medium. The specific end
group is mildly reductive. The reduction capacity of long-chain
alcohol decreased with the extension of the alkyl chain. Ag
nanocrystals were prepared using PVP as a weak reductant,
and the influences of Mw of PVP and the ratio of PVP to Ag+ on
the synthesized Ag nanostructures were investigated in the
study.87 Fig. 7a and b are the TEM images of Ag nanoplates
synthesized under the condition of Mw = 10 K and 29 K,
PVP : Ag+ = 15. The UV-vis absorption spectra show four peaks
(Fig. 7c). In the range of 420–450 nm, the peak corresponds to
Ag nanospheres, which enhances with the increase in the
PVP : Ag+ ratio. This is attributed to the size of Ag nanoplates.
The concentration of PVP has an impact on the reduction of
Ag+. PVP reduces Ag+ to Ag atoms and aggregates them into a
nucleus. The newly reduced Ag atoms are deposited in layers
to form nanoplates, while other Ag atoms deposited to form
nanospheres. Fig. 7d and e show the number of nanoplates
and nanospheres in different synthetic systems.
Xia’s team synthesized triangular Ag nanoplates in 8 mL of
H2O, which was carried out by –OH from PVP controlling the
reduction kinetics.43 The conversion rate of AgNO3 decreases
with the increasing amount of PVP, which means that the high
concentration of PVP is not conducive to the kinetics of Ag+.
With the increase in Mw, the conversion rate of AgNO3
decreases, which indicates that short-chain PVP has a stronger
Fig. 7 TEM images of Ag nanoplates under the condition of (a) Mw =
10 K, PVP : Ag+ = 15 and (b) Mw = 29 K, PVP : Ag+ = 15. (c) UV-vis absorp-
tion spectra of the reaction solution with different ratios of PVP to Ag+.
(d and e) The number of nanoplates and nanospheres in different syn-
thetic systems. (a–e) Reproduced with permission from ref. 87
Copyright 2018, Royal Society of Chemistry.
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reduction ability. Zheng’s group prepared 5-fold twinned Pd
nanorods using a weak reducibility of PVP (800 mg, Mw =
30 000).88 When the amount of PVP is changed, the products
obtained are uneven shapes. The weak reduction power of PVP
is the main reason that the structure tends toward kinetics
control. The reduction effect is also applied to synthesize
spiral PtNi@Pd nanowires.89
3.2 Cationic surfactants
Cationic surfactants are mainly nitrogenous organic amine
derivatives, which contain hydrophobic alkyl-chain and hydro-
philic ammonium and halogen ions. In controlling the mor-
phology of nanocrystals, cetyltrimethylammonium chloride
(CTAC) and cetyltrimethylammonium bromide (CTAB) are the
most commonly used cationic surfactants. These surfactants
can be ionized into alkyl-chain groups CTA+ and halogen ions
Cl−/Br− in the solution, which have different roles in the syn-
thetic systems. CTA+ is adsorbed onto the crystal facets and it
controlled the morphology by affecting the reduction rate.90,91
Halide ions usually form oxidation etching agents with O2,
which control the morphological evolution by corrosion.92,93
3.2.1 Structural induction. The cationic surfactants in the
reaction system can control the kinetic process of nucleation
and growth of nanoparticles, thereby forming nanocrystals
with different shapes. The long chain of surfactants can selec-
tively be adsorbed onto different metal ions and induce to
form low-dimensional nanostructures via reduction reactions.
As can be seen from Fig. 8, the synthesis of zero-dimensional
(0D) nanospheres,94–97 one-dimensional (1D) nanowires or
Fig. 8 (a, d, and g) Schematic of the structure induction effect for cat-
ionic surfactants. (b and c) TEM images of PtAg nanoparticles. (e and f )
TEM images of Pt3Ni nanorods. (h and i) TEM images of ultrathin PdPtCu
nanosheets. (b and c) Reproduced with permission from ref. 94
Copyright 2018, Royal Society of Chemistry. (e and f ) Reproduced with
permission from ref. 107 Copyright 2019, Elsevier. (h and i) Reproduced
with permission from ref. 105 Copyright 2019, Royal Society of
Chemistry.
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nanorods,98–103 and two-dimensional (2D) nanosheets104–106
can be controlled by alkyl chains. Fig. 8a, d, and g are the
model diagrams of cationic surfactant-assisted synthesis of
nanospheres, nanowires, and nanosheets, respectively.
As displayed in the TEM images of Fig. 8b and c, PtAg nano-
particles prepared by Song et al. in the oleylamine (OAm) solu-
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tion in the presence of CTAB are highly dispersed and homo-
geneous, which also arises from the protective effect of
CTAB.94 A large number of experiments have proved that long-
chain surfactants are beneficial to the formation of 1D struc-
tures. Du’s group reported 1D PtNi alloy nanorods with
dimethyl dioctadecyl ammonium chloride (DDAC) as a struc-
ture-directing agent (Fig. 8e and f ), which showed excellent
catalytic activities and stability towards polyol oxidation reac-
tions.107 In general, when the number of metal atoms is the
same, the 1D nanostructure usually has the largest specific
surface area, which can expose more active catalytic sites.
Nanowires can be divided into many types based on the
surface structure: zigzag-like nanowires,108–112 lavender-like
nanowires,99 smooth nanowires,100,113–116 and networked
nanowires.117,118 In the typical synthesis, the polar head can
adsorb metal precursor ions, under the drive of minimum
entropy, nanoparticles are aggregated into rods. The carried
metal ions are reduced in the system and release free active
agents, which accelerate the generation of reverse
micelles.119,120 When the system reaches a higher temperature,
the alkyl chain loses efficacy, and the vacancy of the original
long chain is replaced by newly reduced metal atoms, thus
instructing the 1D nanostructure to grow. Moreover, hexadecyl
dimethyl benzyl ammonium chloride (HDBAC), octadecyl tri-
methyl ammonium chloride (STAC),121 and dodecyl trimethyl
ammonium chloride (DTAC)116,120 could control the synthesis
of nanorods and short nanowires.
For the synthesis of 2D nanomaterials, the hydrophobic
long chain tail drives the surfactant to self-assemble into
nanosheet structures. The hydrophilic head of the long chain
makes the aggregate more stable and interacts with the metal
precursor via electrostatic or coordination interaction, which
slows down the reduction rate and promotes the anisotropic
growth. When the reduced metal atoms reach the saturation
point in the solution, the newly generated atoms selectively
adsorb each other to form the ideal small crystal planes under
the induction of the alkyl-chain cation.122,123 At this stage, the
anisotropic growth controls the morphology of nanoparticles
tending to be nanosheets. For the structure-oriented action,
the system usually contains chains that are long enough,
which can not only avoid nanocrystal aggregation, but also
eliminate the role of halide ions. Fig. 8h and i are the ultrathin
PdPtCu nanosheets developed by Lv et al. with C22TAC as the
surfactant template and H2O as the solution.105 Hydrophobic
chains motivate the self-assembly to form 2D layered struc-
tures, and Cl− promotes the epitaxial growth on the surface
and stabilizes the sheet structure.
In addition, we found that the effect of cationic surfactants
is related to its carbon chain structure. As shown in Fig. 9a,
Dong’s group reported a series of shape-controlled Pt–Ru
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Fig. 9 (a) Scheme of PtRu nanocrystals with controlled morphology.
TEM images of PtRu (b) nanowires, (c) nanorods, and (d) nanocubes. (a–
d) Reproduced with permission from ref. 114 Copyright 2018, American
Chemical Society.
nanocatalysts, using DDAC, HDBAC, and CTAB as structure-
guiding agents to obtain nanowires (Fig. 9b), nanorods
(Fig. 9c), and nanocubes (Fig. 9d), respectively, and explored
the effect of different structure-guiding agents.114 Gao et al.
found that, as the number of carbon in alkyl chain increases,
the shape of the obtained Au nanocrystals gradually changed
from spherical to rod, and the aspect ratio of the rod
increased.124 The longer alkyl chain and larger concentrations
of surfactants will generate nanowires with a large aspect ratio.
Conversely, the length-to-diameter ratio of nanorods will be
smaller. The double long chains, such as DDAC, are strongly
hydrophobic, which could facilitate the formation of longer
and more stable micelles to wrap the nanocrystals.107 The
double C18 chains from DDAC could also confine the aniso-
tropic growth along the columnar.118 The concentration of sur-
factants would inhibit the anisotropic growth of a
micelle.125,126
CTAB can also direct the generation of nanocubes,127,128
and DTAC can assist in the synthesis of nanomeshes129 and
nanopolyhedron,130–132 or nano-octahedrons.133 The trimetal-
lic core–shell nano-octahedron reported by Kang et al. was syn-
thesized using CTAC as the structural guiding agent.134,135 In
this case, the formation of the core–shell octahedron is related
not only to the structural orientation of the alkyl chain, but
also to the exchange of Cl−. Since the binding capacity of
CTAC to Pd is weaker than that to Pt, the reduction kinetics of
[PdCl4]2− is promoted, which results in the excessive Pd atoms
coated on Pt and the formation of an AuPd@Pt core–shell
structure. A common characterization of these examples is that
CTAC alters the reduction kinetics by binding to metallic ions.
For Au@Pd core–shell nanoparticles enclosed (111)-planes,
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Han’s group found that in addition to being a stabilizer, CTAC
had weaker reduction capacity. During the reaction, it can be
oxidized to form a nitroso group.136 By changing the concen-
tration of metal atoms in the solution, the anisotropic growth
is controlled to become an ideal nanostructure.
3.2.2 Capping agents. In section 3.2.1, we emphasized on
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analyzing the structure guiding effect of alkyl chains, and it is
proved that halide ions also play a vital role in the preparation
of metal nanocrystals. The halide ions from cationic surfac-
tants can be adsorbed on the (100)-, (110)-, or (111)-facets and
regulate the shape evolution of nanocrystals. In general, the
greater the electronegativity of halide ions, the stronger the
binding between them and counterions. The different binding
ability causes a difference in the growth pattern of crystals,
resulting in the change of shape.
In a recent research, halogen ions have been demonstrated
to act as capping agents to induce the formation of Ag nano-
cubes.137 Fig. 10a shows the mechanism of Ag nanocube for-
mation with sharp corners and edges, which is realized using
CTAC as a capping agent. Fig. 10b is the TEM image of Ag
seeds with round corners. CTA+ ions were adsorbed onto the
surface of Ag seeds to form a bilayer, and Cl− ions were selec-
tively adsorbed on the (100)-facet. Ag+ is reduced to an Ag
atom and deposited at the uncovered corners, and selective
deposition promotes the formation of nanocubes, as shown in
Fig. 10c. Subsequently, the Ag atoms began to deposit asym-
metrically and gradually became nanorods (Fig. 10d).
The conclusion was also confirmed during the synthesis of
Pd nanocubes. Xu’s group has proved that CTAB plays a
similar role to halides.138 Br− ions from CTAB have been
shown to facilitate the formation of Pd nanoparticles with the
(100)-facet. Niu et al. synthesized Pd nanocrystallines sur-
rounded by the (200)-facet with the assistance of CTAB.139
Berhault et al. also synthesized the Pd nanocubes using CTAB
as the capping agent and measured its lattice fringes by high-
resolution TEM.140 The lattice fringe of 0.2 nm corresponds to
the (200) crystal surface of Pd. In addition, the selected area
Fig. 10 (a) Scheme of the formation mechanism of Ag nanocubes and
nanorods. (b–d) TEM images of Ag seeds, Ag nanocubes, and Ag nano-
rods. (a–d) Reproduced with permission from ref. 137 Copyright 2018,
Royal Society of Chemistry.
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electron diffraction (SAED) pattern also confirms the presence
of a square lattice corresponding to the (100) reflections. Xu’s
team have reported the truncated cubic Pd nanocrystals,138
which is composed of six (100)-facets and eight (111)-facets,
and the area of the (111)-facet is much smaller than that of the
(100)-facet. It indicates that the stabilizing effect of CTAB on
the (111)-facet is weaker than that on the (100)-facet. The
(110)-facet is not observed at all, manifesting that in the
system where CTAB exists, the (110) facet is the most unstable
one. CTAB can change the energy of the low-index facet in the
following order: γ(100) < γ(111) < γ(110).
The capping effect is also proved in the reaction system of
halides as capping agents.141 Without Br− in the system, the
product is Pd octahedrons. With a shortage of Br−, the trun-
cated Pd nanocubes are obtained; with enough Br−, the
product is a well-defined nanocube. It is worth noting that
when the amount of halogen ions is insufficient and the reac-
tion time is prolonged, the newly reduced metal atoms can
overgrow on the uncapped (111) surface to form a concave
structure.142 It is important to understand the inhibiting and
promoting effects of halogen ions on the crystal surface
growth for the precise synthesis of nanocrystals.
3.2.3 Oxidation etching. It is well known that, in the
process of crystal growth, nanopolyhedrons with a smaller
surface energy and more stable structures are always generated
spontaneously. From the perspective of thermodynamics, the
concave nanoparticles are usually not easy to be synthesized.
However, compared with plain polyhedrons, the concave nano-
catalysts tend to expose more active sites, which is conducive
to the electrocatalytic oxidation reaction. Therefore, more cat-
ionic surfactants are used to synthesize concave and excavated
nanostructures, and such structures have high index facets
and abundant defects.
Deeply excavated Pt3Co nanocubes are fabricated using Pt
(acac)2 and CoSO4·7H2O as metal precursors, and CTAC and
H2O as morphology-controlling agents.143 From the TEM
image (Fig. 11a), the (100)-faces of nanocubes are deeply exca-
vated, like a letter X in the center. The inset in Fig. 11a is the
3D model, which makes it easier to understand the structure.
Fig. 11b shows the atomic arrangement of the high index faces
of (510) and (710), and CTA+ is particularly important for the
formation of high-index facets because of the proper atomic
spacing. Fig. 11c is the growth mechanism of Pt3Co concave
nanocubes. The structural guidance and oxidation etching of
CTAC mainly occurred in morphology evolution, rather than in
nucleation. Due to the introduction of H2O, O2 is contained in
the system, which could combine with Cl− to form Cl−/O2 oxi-
dation etching pairs. At the same time, H2O will break the
original adsorption equilibrium, exposing some metal atomic
sites to Cl−/O2.
In another similar report, excavated and dendritic PtCo
nanocubes were fabricated with CTAC in OAm. In addition to
the concave cubic body, there are eight dendritic vertices.144
The dominating factor for obtaining such nanocrystals is
CTAC (300 mg), which acted as a surfactant. CTAC is ionized
into CTA+ ions and Cl− in oleylamine. Some of CTA+ is
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metal atoms into metal ions. Interestingly, the excavated nano-

crystals can evolve into a hexapod structure with six arms.
Shen’s group illuminated hexapod PtPdCu concave rhombic
dodecahedrons with CTAB working as the surfactant.152 Based
on the similar experimental results, we have an in-depth
understanding of the role of cationic surfactants in the syn-
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thesis process. The surfactant added into the reaction system

can be ionized into an alkyl chain cation and a halogen ion. In
the absence of N2 or inert gas protection, O2 is often present
or even involved in the synthesis. At this time, the halogen
ions and O2 will form a powerful etching agent, thus affecting
the growth process of nanocrystals. Experimental phenomena
have shown that halogen ions/oxygen pairs could etch unstable
metal atoms back into the solution in the form of metal ions,
resulting in a concave structure with defects. Moreover, a
higher concentration of etchant leads to a faster etching rate.
The appropriate concentration of CTAC or homologs will
affect the evolution of the crystal morphology via hydrophobic
alkyl chains and halogen ions. In addition, the adsorption of
long chains and halide ions is competitive and interacts with
each other. Long alkyl chains could maintain the nanocrystals
well dispersed. Two long chains are more conducive to aniso-
tropic growth. On the contrary, more structure-guiding agents

Fig. 11 (a) TEM image of Pt3Co concave nanocubes, and the inset is the
3D model. (b) HRTEM image and the atomic arrangement. (c) Scheme of
the evolution process of Pt3Co concave nanocubes. (d–f ) TEM images
of PtNiCu excavated rhombic dodecahedrons along the [111], [110], and
[100] zone axes. (g–i) The corresponding 3D models. (a–c) Reproduced
with permission from ref. 143 Copyright 2017, American Chemical
Society. (d–i) Reproduced with permission from ref. 151 Copyright 2018,
Springer Nature.

adsorbed on the gas–liquid interface, forming a directional

arrangement. When the interface is filled with a layer of CTA+,
the remaining CTA+ interacts with the reduced Pt/Co atoms in
the liquid phase. The Cl−/O2 oxidative etching pairs are condu-
cive to transform solid nanocrystals into concave nanocrystals.
The more abundant CTAC could inhibit the overgrowth of
branches on the concave surface of nanocubes. The similar
mechanism has been applied to synthesize many concave
nanocrystals such as PtCu3 concave nanocubes,122,145 Au
concave nanocubes,146 and Rh concave nanotetrahedra.147 As
the degree of concave surface increases, the nanostructure is
transformed into excavated nanocrystals148,149 even
150
nanoframes.
Tang et al. reported the excavated PtNiCu rhombic dodeca-
hedrons were achieved using CTAC as the structure-directing
agent.151 Fig. 11d–f are the TEM images along the [111], [110], Fig. 12 (a) TEM and (b) SEM images of MnO2 nanosheets synthesized
with SDS. (c) Scheme for the formation of single-layer MnO2
and [100] axes, and Fig. 11g–i are their corresponding model
nanosheets. SEM images of V2O5 nanocrystals (d) with SDBS and (e) with
diagram. The solid rhombic dodecahedrons eventually evolved SDS. (a–c) Reproduced with permission from ref. 158 Copyright 2015,
into excavated structure that underwent oxidation etching; Wiley-VCH. (d and e) Reproduced with permission from ref. 159
during that process, the Cl−/O2 pairs will oxidize the unstable Copyright 2019, Elsevier.

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will inhibit the growth of a certain crystal surface. In addition
to the structurally induced effect, the halide ions usually
combine with oxygen to perform the role of etching.
3.3 Anionic surfactants
Anionic surfactants have a negative charge as the surface acti-
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of monolayer MnO2. The mechanism diagram is shown in
Fig. 12c. Chen’s group designed turbine-like V2O5 hierarchical
structures via an SDS-assisted hydrothermal process.159 The
SEM images are shown in Fig. 12d and e.
Yan’s team obtained the self-assembled SnO2 nanoflowers
using SDS as the surfactant and cyclohexane as the solvent,
which applied to the principle of reversed micelles.160 The

vation portion, which is a weak acid ion. The role of anionic sur-
factants depends on the pH value. The commonly used anionic
surfactants include sulfonate (R-SO3−), sulfate (RO-SO2−/
RO-SO3−), carboxylate salts (R-COO−), and phosphate salts. The
surfactant molecules can self-assemble into micelles, providing
a stable reaction container for the nanoparticles.153–155 Anionic
surfactants are mainly applied for the synthesis of metal oxide
nanomaterials as a soft template.24,156,157
3.3.1 As a soft template. When the concentration of anionic
surfactants exceeds the critical micelle concentration, ordered
aggregates such as micelles/reverse micelles are formed in the
solution. Nanomaterials with different morphologies and sizes
can be synthesized in the microenvironment, which is the func-
tion of the soft template. Liu et al. demonstrated that SDS can
not only reduce KMnO4 into MnO2 nanosheets in an acidic solu-
tion, but also promote the generation of monolayer nanosheets
acting as a soft template.158 The ultrathin layered structure can
be seen from the TEM and SEM images from Fig. 12a and b,
which show graphene-like wrinkles. In the acidic reaction solu-
tion, SDS self-assembled into a layered structure and slowly
hydrolyzed into dodecyl alcohol. MnO4− ions combine with the
hydrophilic head of anionic surfactants to control the formation
process can be interpreted as follows: Sn(OH)6− is dissolved in
the core of reversed micelles and hydrolyzed to generate SnO2.
Due to the high surface energy of SnO2, the polar groups of
surfactants are adsorbed onto the surface, and the long hydro-
phobic chains are exposed outside. The crystal can only grow
in the gap of long chains because of the steric hindrance, and
the flower clusters formed. Compared with SLS, the presence
of the benzene ring in SDBS leads to an increase in the steric
effect and a slower growth rate along the [001] axis. Table 2
summarized the morphologies that have been reported for syn-
thesized metal nanocrystals with the assistance of surfactants.
4. Removal of surfactants
Although the function of surfactants in managing morphology
is generally accepted, active agents remaining on the surface of
catalysts may occupy the active sites of catalysts and inhibit
their catalytic activity. In most cases, we will carry out the post-
treatment on the nanomaterials synthesized with the assist-
ance of surfactants to remove the residual capping agents.

Table 2 Summary of morphologies that have been reported for synthesized metal nanocrystals with the assistance of surfactants

Concentration of
Surfactant Catalysts Solvent surfactants Morphology Role Ref.

PVP PtPb EG 100 mg per 10 mL Nanowire networks Dispersant 53

PdCuM (Ru, Rh, Ir) DMF 25 mg per 5 mL Nanosheets Dispersant 59
Ag EG 133.2 mg per 25 mL Nanowires Capping agent 81
Pd H2O 105 mg per 11 mL Nanocubes Capping (100) facet 161
PdPt EG 105 mg per 11 mL Nanocubes Capping (100) facet 162

CTAB PdPb OAm 36 mg per 5 mL Nanocubes Structure directing 127

PtAu H2O 288 mg per 8 mL Core–shell concave nanocubes Structure directing 163
Rh DI H2O 360 mg per 10 mL Concave nanotetrahedra Oxidation etching 147
PtCo DMF 30 mg per 12 mL Excavated octahedral Oxidation etching 149
PtPdCu OAm 360 mg per 10 mL Hexapod concave rhombic dodecahedrons Oxidation etching 152

CTAC PtCo OAm 40 mg per 5 mL Zigzag nanowires Structure directing 111

PtNiPd OAm 32 mg per 5 mL Nanorods Structure directing 164
PtFePd OAm 32 mg per 5 mL Core@multi shell nanowires Structure directing 165
Au H2O 63 mg per 12 mL Concave trisoctahedral Oxidation etching 132
Pt–Co OAm 300 mg per 10 mL Excavated and dendritic nanocubes Oxidation etching 144
Au H2O 320 mg per 11 mL Concave nanocubes Oxidation etching 146
PtNiCu OAm 640 mg per 10 mL Excavated rhombic dodecahedrons Oxidation etching 151

C22TAC PdPtCu H2O 15 mg per 10 mL Nanosheets Structure directing 105

HDBAC PtRu OAm 60 mg per 5 mL Nanorods Structure directing 114

PtPd H2O 100 mg per 9 mL Nanosheets Structure directing 123

DTAB PdFePt DMF 39.3 mg per 10 mL Nanosheets Structure directing 129

PdCuPt DMF + OA 105 mg per 12 mL Icosahedrons Structure directing 131

SDS Au H2O 272 mg per 100 mL Nanoparticles Stabilizer 166

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Fig. 13 (a) Surface potential of Au nanorods synthesized using CTAB
with the increase in the number of centrifugation cycles. (b) XRD pattern
of Ir0.9Ni0.1 nanocrystals with subsequent heating. (c) FT-IR spectra of
IrSn and IrNi catalysts before and after different cleaning steps. (d)
Thermogravimetric profile of Pt nanocubes capped with PVP, commer-
cial Pt/C and pure PVP in an oxygen atmosphere. (e) CV curves of the Pt
nanocubes capped with PVP before and after electrochemical cleaning
(200 cycles at 200 mV s−1) in Ar-saturated 0.1 M HClO4, and (f ) 0.1 M
NaOH at a potential of 0.06–1.4 V/RHE. (a) Reproduced with permission
from ref. 168 Copyright 2020, IOP Publishing. (b and c) Reproduced
with permission from ref. 171 Copyright 2020, Royal Society of
Chemistry. (d–f ) Reproduced with permission from ref. 174 Copyright
2017, Elsevier.
The most common method is repeated centrifugation with
poor/good organic solvent mixtures to remove the capping
agents such as ethanol/cyclohexane for the removal of OAm
and acetone/H2O for the removal of PVP. This method is only
suitable for the removal of physically adsorbed surfactants.
Nanocrystals are dispersed in a good solvent, and then the
poor solvent is added to precipitate nanocrystals out. Buratto
et al. detected the amount of PVP that remained on the Pd
nanocubes with repeated washing,167 confirming that with the
increase in the number of cycles of washing, the amount of
remaining PVP decreases gradually. Lee and his workers
detected the surface potential of Au nanorods synthesized
using CTAB.168 As shown in Fig. 13a, the surface potential of
nanorods decreased with the increase in the number of cen-
trifugation cycles, indicating that CTAB was successfully
removed.
The other method is thermal treatment to remove the addi-
tives, which could cause structural collapse.169,170 Fig. 13b
shows the XRD pattern of Ir0.9Ni0.1 catalysts capped with oley-
lamine and oleic acid upon heating in a N2/O2/H2 atmo-
sphere.171 During the thermal treatment, the crystalline size
and lattice spacing change slightly. Fig. 13c is the FT-IR
spectra of InSn and IrNi catalysts before and after the heating
treatment. By comparing the infrared peaks, the content of
oleylamine and oleic acid decreased obviously after heat treat-
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ment. As shown in Fig. 13d, the decomposition curve demon-
strated the adsorption of PVP onto the surface of
nanoparticles.
In addition, there have been reports of surfactant cleaning
under UV/ozone irradiation.172,173 The method is not suitable
for all cases. Liu et al. demonstrated that the thermal method
was effective in removing oleylamine from Pt nanoparticles,
while UV/ozone treatment did not work. Zhong et al. carried
out the experiment by loading PVP-coated Au nanoparticles
onto SiO2 and exposed them to UV/ozone treatment, finally
proving that the method was effective for removing PVP.173
With the extension of UV irradiation time, the PVP-related
infrared bands signal becomes weaker.
The surfactants on the surface of nanocrystals can be
cleaned by an electrochemical protocol. Electro-chemical
cleaning is conducted by 200 cycles of cyclic voltammetry scan-
ning in an Ar-saturated electrolyte solution to oxidize the sur-
factant (Fig. 13e and f ).174 The removal effect is related to the
upper potential and pH value. In addition, we can exchange
the desired ligand with the original one to remove the
surfactant.
5. Concluding remarks
Manipulating the morphology (shape, facet, defect, and phase
structure) of metal nanomaterials can influence their perform-
ance in the corresponding catalytic applications. To date, tre-
mendous progress has been made in the controlled synthesis
and catalytic application of nanomaterials with the aid of sur-
factants. In addition, we believe that the development of nano-
catalysts will not stop there, and there are still some aspects
that need to be improved.
First, the surfactants with long chains can orderly aggre-
gate to form micelles, or reverse micelles, providing a stable
reaction environment or soft template and preventing the
aggregation of nanoparticles. However, the aggregation state
of surfactants in the solution is very complex. Whether
the capping agent is adsorbed on the crystal surface by
lying-down, standing-up vertical adsorption, oblique adsorp-
tion or bending adsorption, it usually requires more necess-
ary and advanced techniques to determine the specific
aggregation form. Binary phase diagrams are worth consid-
ering. In addition, many factors can affect the assembly of
surfactants, especially when there is a chemical reaction
going on.
Second, the quantitative analysis of surfactants is important
for a comprehensive understanding of their roles. In either
one-pot or seed-mediated synthesis, the relative rates of depo-
sition and diffusion of reduced metal atoms induce the gene-
ration of new nanocrystals with different shapes, facets, and
phase structures. Infrared spectroscopy is conducted to detect
the new bands generated on the crystal surface due to adsorp-
tion. Combining with the XPS of specific elements, the adsorp-
tion manner of the capping agent can be determined from the
shift of binding energy. The absorbance of the solution can be
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Nanoscale
detected at different reaction stages by the UV-visible spec-
trum, and the species and concentration in the solution can
be determined from the position of the absorption peak,
which can estimate the metal ion reduction rate to some
extent. Although these methods can qualitatively understand
the capping effect, there are still many problems. Is the
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capping density accurate? How to determine the amount of
surfactant? Hence, in situ tracking technology that can detect
the interfacial adsorption needs to be further exploited and
developed.
Third, the application of surfactant-assisted metal nano-
materials in catalytic reactions has been doubted. The special
post-treatment is usually applied to the cases where the cata-
lytic sites are blocked via centrifugation cleaning, UV/ozone
irradiation, thermal treatment and so on. Thus far, some
experiments have proved that the capping agent can change
the electronic structure of metal atoms, which can improve the
catalytic performance. Many nanocatalysts have been devel-
oped with free surfactants.
Finally, by summarizing the nanocrystals that have been
developed, we expect to find a correspondence between the
specific surfactant and the structure. An appropriate surfactant
can change the energy order of different crystal facets by
adsorption, which can assist in the synthesis of nanocrystals
with an ideal structure. Selecting specific capping agent is the
key to synthesize metal catalysts with controllable crystal
planes. Polymeric surfactants can improve the dispersion of
products. PVP could assist in obtaining the nanocubes sur-
rounded by the (100)-facets. CTAC and its derivatives tend to
produce 1D structures and defective structures in the OAm
solution. Anionic surfactants could be self-assembled into
micelles to provide a microreactor and applied to the synthesis
of flake/sheet/mesoporous materials. Halides generally prefer
to change the growth pattern of particles, and in some cases
as etchants to promote the production of high-index facet and
hollow structures.
How to understand and solve these problems better is the
key to take a significant step forward in nanocrystallography. It
is hoped that this review will provide useful guidance for the
synthesis of surfactant-assisted nanocrystals.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Thanks for the National Natural Science Foundation of China
(grant no. 52073199, 51873136), the National Youth Natural
Science Foundation of China (grant no. 21905189), Natural
Science Foundation of the Jiangsu Higher Education
Institutions of China (18KJA150008), Natural Science
Foundation of Jiangsu Province (BK20181428).
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