mater.scichina.com link.springer.com .................... Published online 25 January 2018 | https://doi.org/10.1007/s40843-018-9213-4
Sci China Mater 2018, 61(8): 1129–1131
Amine facilitates the synthesis of silica-supported
ultrasmall bimetallic nanoparticles
Nanfeng Zheng
*
and Pengxin Liu
Supported catalysts based on metal nanoparticles are a
class of widely used heterogeneous catalysts in industry.
The catalytic performances of supported metal catalysts
are highly determined by many parameters of metal na-
noparticles such as their particle size, composition, sur-
face structure and also interfacial interaction with
supports [1]. Supported metal catalysts are commonly
prepared by depositing metal precursors on high-surface
area supports through various methods such as impreg-
nation (IMP), co-precipitation (CP), and deposition-
precipitation (DP), followed by thermal or chemical re-
duction of the metal precursors deposited thereon to
form supported metal nanoparticles.
The difficulty for conventional methods to prepare
high-quality supported metal nanoparticles with uniform
particle size and composition mainly lies in the following
two aspects: 1) The interaction between metal precursors
and supports is not strong enough to prevent their sin-
tering during the post thermal or chemical reduction
processes; 2) The deposition of metal precursors is not
homogenous so that the phase separation often occurs
after the reducing treatment. By addressing these two
issues, the DP method has been outstanding among other
conventional methods in preparing supported small metal
nanoparticles [2]. However, the DP method has met great
difficulties in preparing high-quality metal nanoparticles
catalysts on many acidic supports (such as silica, WO
x
,
zeolites) due to their relatively low point of zero charge
(PZC) [3]. During the past decade, there has thus been an
emergence of research efforts directed toward the use of
pre-made uniform nanoparticles as precursors to prepare
well-controlled metal nanocatalysts for investigating
complicated interfacial catalytic mechanism [4–6]. In
these colloidal methods, the influence of organic capping
agents is often concerned.
As compared to supported monometallic nanoparticles,
the preparation of high-quality supported alloyed nano-
particles is even more challenging. Alloying has been
well-documented as an effective strategy to tailor the
catalytic performance of supported metal catalysts. On
one hand, alloying provides an avenue to reduce the
usage of expensive scare metal without compromising the
overall catalytic activity. On the other hand, the electronic
density and/or dispersion of catalytically active metal can
be manipulated by the introduction of another metal
species, thus tailoring the reaction pathway and often
optimizing the overall catalytic properties. In order to
obtain high-quality supported alloyed catalysts with uni-
form ultrasmall size and uniform composition, it is es-
sential to have the metal precursors uniformly deposited
onto the surface of supports before being converted into
alloyed nanoparticles.
Recently, Regalbuto and colleagues have developed a
general and simple method to prepare ultrasmall alloyed
metal nanoparticles based on both noble (i.e., Pt, Pd) and
base metals (i.e., Ni, Co, Cu) [7]. The homogeneously
alloyed metal nanoparticles have a narrow size distribu-
tion around 1 nm. In the developed method, positively
charged metal-amine complex precursors were deposited
onto negatively charged surface of silica support through
strong electrostatic adsorption (SEA) [8,9], and then re-
duced by H
2
at an elevated temperature to give supported
uniform ultrasmall alloyed nanoparticles (Fig. 1a). The
key of this work is to use positively charged metal-amine
complexes as metal precursors. Since the surface point of
zero charge of silica (Aerosil 300 silica) is around 3.6, the
surface charge of silica in water is negative in a wide range
of pH value (4–13) before silica is dissolved. The strong
electrostatic interaction can thus promote the homo-
genous deposition, making the method outstanding
conventional preparation methods for the production of
ultrasmall alloyed nanoparticles with different combina-
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of
Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
*
Email: nfzheng@xmu.edu.cn
SCIENCE CHINA Materials ............................. HIGHLIGHTS
August 2018 | Vol. 61 No.8 .................................................................................... 1129 © Science China Press and Springer-Verlag GmbH Germany 2018