Conversion of Sb2Te3 hexagonal nanoplates into three-dimensional porous single-crystal-like network-structured Te plates using oxygen and tartaric acid

Article abstract of DOI:10.1002/anie.201107460

Pore genius: Sb₂Te₃ hexagonal nanoplates can be transformed into 3D porous network-structured Te plates by the dissolution of Sb³⁺ ions induced by tartaric acid (TA), the O₂-assisted oxidation of Te^2-

Full text of DOI:10.1002/anie.201107460

Angewandte
Chemie
DOI: 10.1002/anie.201107460
Mesoporous Materials
Conversion of Sb2Te3 Hexagonal Nanoplates into Three-Dimensional
Porous Single-Crystal-Like Network-Structured Te Plates Using
Oxygen and Tartaric Acid**
Hua Zhang, Huan Wang, You Xu, Sifei Zhuo, Yifu Yu, and Bin Zhang*
Novel applications of nanostructures in catalysis, electronics,
photonics, and bionanotechnology[1] are driving the explora-
tion of synthetic approaches to control and manipulate their
chemical composition, structure, and morphology.[2–5] As well
as the design of synthetic strategies to produce a new class of
nanoscale materials, recent developments have enabled the
chemical transformation of one crystalline material into
another desired target material.[2] Three of the most impor-
tant methods for chemical transformation are the ion-
exchange reaction,[3] the Kikendall effect,[4] and stabilizer-
depleted binary semiconductor nanocrystals.[5] The first two
methods have been shown to produce nanomaterials with a
diverse structure and a controlled composition, but are not
suitable to transform binary materials into unary semicon-
ductors. Interestingly, the third method has been successfully
adopted by Kotov and Tang et al. to convert CdE (E = Se, Te)
into unary E solid nanowires and angled Te nanocrystals.[5]
Among the various materials, porous nanostructures have
received increasing attention owing to their improved chem-
ical and physical performance over solid materials, as well as
their intriguing applications in a variety of fields.[6] In
comparison with their polycrystalline counterparts, single-
crystal-like materials have been found to reduce the number
of defects, and have enhanced electron-transfer and catalytic
properties.[7] However, the development of a facile technique
to transform binary materials into three-dimensional (3D)
porous unary semiconductors, especially with single-crystal-
like structures, remains a great challenge.
of InCl3 during the chemical transformation of Sb2Te3.
Furthermore, the as-prepared porous Te plates can be used
as the template for the highly efficient synthesis of 3D porous
network-structured noble-metal nanoplates with promising
applications.
Firstly, the Sb2Te3 hexagonal nanoplates were synthesized
by using the reported solution–chemical method.[8] Figure 1a
shows a scanning electron microscopy (SEM) image of
hexagonal nanoplates with a thickness of 50–200 nm. The
typical powder X-ray diffraction (XRD) pattern displayed in
Figure 1 f identifies these hexagonal plates as the rhombohe-
Herein we report a facile approach to transform the as-
prepared Sb2Te3 nanoplates into 3D porous Te plates through
the dissolution of Sb3+ ions, the oxidation of Te2À ions to Te0,
and a subsequent Ostwald ripening process induced by
oxygen and tartaric acid (TA). We have demonstrated that
this method can be adopted to convert Sb2Te3 nanoplates into
porous heterogeneous In/Te networks through the reduction
[*] H. Zhang,[+] H. Wang,[+] Y. Xu, S. Zhuo, Y. Yu, Prof. Dr. B. Zhang
Department of Chemistry, School of Science
Tianjin University, Tianjin 300072 (P.R. China)
E-mail: bzhang@tju.edu.cn
[+] These authors contributed equally to this work.
[**] This work was financially supported by the National Natural Science
Foundation of China (20901057 and 11074185), the National Basic
Research Program of China (2009CB939901), the Tianjin Natural
Science Foundation (10JCYBJC01800), the State Key laboratory of
Crystal Material at Shandong University (KF0910) and the Innova-
tion Foundation of Tianjin University.
Figure 1. SEM images of a) the starting Sb2Te3 nanoplates and b) the
3D porous network-structured Te plates, EELS mapping elemental
images of c) the starting Sb2Te3 nanoplates and d) the 3D porous Te
plates, e) EDX image of the 3D porous Te plates, and f) XRD patterns.
g,h) TEM images and i) HRTEM image of the as-prepared 3D porous
network-structured Te nanoplates obtained through the chemical trans-
formation of the Sb2Te3 plates. The inset in Figure 1g is the associated
SAED pattern of one porous network-structured Te plate.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201107460.
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dral phase of Sb2Te3 (JCPDS 15-0874), thus suggesting that
the Sb2Te3 nanoplates can be successfully fabricated. For a
typical transformation of the Sb2Te3 nanoplates, the aqueous
solution containing the as-prepared Sb2Te3 hexagonal nano-
plates (Figure 1a) and TA was hydrothermally treated at
1808C for 6 hours in the presence of a trace amount of
oxygen. Figure 1b and Figure S1 in the Supporting Informa-
tion display scanning electron microscopy (SEM) images of
the as-converted products, and indicate the 3D porous
morphology of the products. The chemical transformations
are further characterized using electron energy loss spectros-
copy (EELS) elemental mapping. As shown in Figure 1c, Sb
and Te elements are uniformly distributed in a solid hexag-
onal plate. However, after the Sb2Te3 nanoplate was hydro-
thermally treated in the presence of TA and oxygen, only the
Te element, with porous distribution, is seen in the EELS
mapping of the porous plate (Figure 1d). This implies that the
Sb3+ ions of the Sb2Te3 nanoplates can be stripped and
dissolved into aqueous solution. The energy-dispersion X-ray
fluorescence (EDX) spectrum (Figure 1e and Figure S2 in the
Supporting Information) also confirms that the as-trans-
formed porous networks are composed of pure tellurium. The
crystal structure and phase composition of the porous net-
work-structured products obtained are characterized using X-
ray powder diffraction (XRD). Figure 1 f shows the XRD
pattern of the porous Te samples, in which all the diffraction
peaks can be indexed to the trigonal phase of Te (JCPDS 36-
1452). This indicates that the Sb2Te3 solid plates can be
completely transformed into porous Te nanoplates with high
purity. These results suggest that the complete conversion of
Sb2Te3 into highly pure 3D porous Te nanoplates can be
achieved in the current approach.
The morphology and structure of the porous network-
structured Te products were further examined by trans-
mission electron microscopy (TEM), selected area electron
diffraction (SAED), and high-resolution TEM (HRTEM).
Figure 1g presents a representative TEM image of the as-
transformed Te nanoplates; this image suggests that the solid
Sb2Te3 hexagonal nanoplates were transformed into the
porous Te hexagonal plates, but the plate-like macroscopic
morphology remained unchanged. The inset of Figure 1g
displays the SAED pattern, which was recorded with the
incident electron beam perpendicular to the wide surface of
the plate, of one porous nanoplate. Interestingly, regular
diffraction spots are observed, thus indicating the single-
crystal-like structure of the porous network-structured Te
disk. Through extensive investigations on individual nano-
plates from the tellurium products with SAED, we found that
the single-crystal-like character of the 3D porous Te plate
were maintained in all of the products. The high-magnifica-
tion TEM image (Figure 1h) clearly shows that the porous
nanoplates are composed of solid nanothreads with a
diameter of 50–100 nm. It can be clearly seen from Figure 1h
that the nanothreads in the porous products are quite flexible.
The clearly observed fringe spacing of 0.32 nm in the HRTEM
image shown in Figure 1i corresponds to the separation of the
(101) lattice plane of Te, therefore further indicating that the
Sb2Te3 plates can be transformed into single-crystal-like
porous Te nanoplates.
To clarify the chemical transformation mechanism, SEM,
EDX, and ICP (inductively coupled plasma emission spec-
troscopy) were used to characterize the intermediates col-
lected at different stages of the reaction. After the reaction
had proceeded for 0.5 hours, the surface of hexagonal plate-
like samples became very rough (Figure 2b). The associated
EDX spectrum and ICP(Figure S3 in the Supporting Infor-
mation) revealed that the intermediatesꢀ atomic ratio of Te to
Figure 2. Typical SEM images and the associated composition of
a) the starting Sb2Te3 nanoplate, and b) the intermediates collected at
0.5 h and c) the intermediates collected at 2 h. The compositions were
determined by EDX spectra and ICP. d) Dependence of the concen-
tration of antimony in aqueous solution on the reaction time. e) XRD
pattern of the intermediates collected at different reaction times.
f) Schematic illustration of the proposed chemical transformation
mechanism of Sb2Te3 solid nanoplates into 3D porous network-
structured Te plates induced by TA and oxygen.
Sb is approximately 2.0, which is higher than the initial ratio
(Te/Sb = 1.5) of the starting Sb2Te3 materials. This indicates
that the Sb composition of the samples is rapid decreasing.
The decreasing ratio in the samples may be attributed to the
appearance of a soluble species (recorded as Sb(TA)x3+) from
the coordination of the Sb3+ ions in Sb2Te3 with TA, as
observed for cadmium ions of CdTe in EDTA.[5a] This
speculation on the dissolution of the Sb3+ ions in the chemical
transformation is further confirmed by the increase of
antimony concentration in the aqueous solution, as shown
in Figure 2d. The XRD patterns of the intermediates (Fig-
ure 2e) show that the intermediates collected at 0.5 hours are
composed of Sb2Te3 and Te, thus confirming that Te2À ions in
the starting materials are partially converted into Te0. When
the reaction proceeds for 2 hours, the porous structure with
the higher ratio of Te to Sb (2.57) appears. A prolonged
transformation reaction time led to a higher composition of
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Te0 and a more obvious porous network (Figure 2c), and
finally generated 3D porous network-structured Te plates
after 6 hours (Figure 1b and Figure S1 in the Supporting
Information). In the corresponding XRD patterns of the
intermediates, the diffraction peaks from Sb2Te3 firstly
decreased and then disappeared after 4 hours (Figure 2e),
but the Te peaks increased during chemical transformation.
This finding testifies that the complete chemical conversion of
Sb2Te3 into porous network-structured Te can be realized
through the solution-phase stripping of Sb3+ ions from Sb2Te3.
To further explore the reaction mechanism, the role of TA
on the chemical and structural transformation was studied. In
the absence of TA, only a slight change to the surface of the
hexagonal nanoplates occurred without an obvious change to
the composition, as displayed in Figure S4 in the Supporting
Information. This implies that TA played an important role in
the chemical transformation of solid Sb2Te3 nanoplates into
porous network-structured Te plates. We also found that the
concentration of TA exerted a remarkable influence on the
final morphology and composition of the products obtained
through such chemical conversion. A high concentration of
TA resulted in a mixture of wire-like Te and porous Te plates
(Figure S5 in the Supporting Information). When citric acid is
used to replace TA and other experimental conditions remain
unchanged, 3D porous network-structured Te plates can also
be obtained (Figure S6 in the Supporting Information), thus
indicating that citric acid can promote the dissolution of
antimony in Sb2Te3. This result suggests that the combination
of organic molecules with Sb3+ ions to form soluble complexes
may be used to treat solid binary semiconductor nanomate-
rials and produce novel materials that cannot be obtained
otherwise. The effect of oxygen on the chemical transforma-
tion reaction was also investigated. When the chemical
conversion reaction was performed under an Ar atmosphere
and other experimental parameters were kept unchanged, the
final products were mainly Sb2Te3 (Figure S7 in the Support-
ing Information). However, excess oxygen gave rise to the
destruction of the plate-like morphology of Te and even
resulted in the formation of white oxides. Additionally, it was
found that the reaction temperature is an important factor to
determine the morphology and composition of the products
(Figure S8 in the Supporting Information).
The continuous dissolution of antimony leads to the appear-
ance of some channels for the release of Sb(TA)x into
3+
solution. When the antimony source of Sb2Te3 is completely
consumed, these channels remain, and become pores in the
final products (Figure 1b and Figure 2). Finally, kinetically
stable 3D nanothread-based porous Te plates with a single-
crystal-like structure, form through an Ostwald ripening
mechanism.[10] Under high concentration of TA, the quick
depletion of the Sb3+ ions, the simultaneous release of Te2À
ions, and their subsequent rapid oxidation to Te, will make the
aqueous solution immediately reach the supersaturation of Te
nuclei. Therefore, the further growth of Te occurs simulta-
neously on the substrate and in the solution, and then gives
rise to the production of a mixture of Te nanoparticles (even
nanowires) and 3D Te porous network-structured plates. Note
that an additional systematic study is necessary to fully
explore fundamental issues of size- and shape-dependent
conversion activity and its generality, for this chemical
transformation strategy.
On the basis of the chemical transformation mechanism,
the synthesis of heterogeneous In/Te porous networks can be
achieved. When InCl3 is added to the initial reaction solution,
In3+ ions are reduced by tartaric acid (Figure S9 in the
Supporting Information) or Te2À ions to form In0, and then In
nucleates and grows on the as-formed Te networks because of
a required lower level of supersaturation on the Te substrate
than that in the solution.[9] This reaction finally generates
heterogeneous In/Te porous networks, as confirmed by SEM
image and EELS mapping images (Figure S10 in the Sup-
porting Information).
The resulting 3D porous network-structured Te nano-
plates can be adopted as templates to produce novel 3D
porous functional nanoplates. Figure 3 gives the SEM and
TEM images of 3D porous Pt plates; these images suggest the
Based on these above-mentioned results, we propose the
following mechanism, involving TA and oxygen, for the
chemical conversion of hexagonal Sb2Te3 nanoplates into 3D
network-structured porous Te nanoplates (Figure 2 f). Firstly,
TA attacks the Sb3+ ions at elevated temperature, and then
removes an antimony ion from Sb2Te3 through the formation
of Sb(TA)x3+. Meanwhile, Te2À ions on the surface are
released into the solution. Then, the Te2À ions are oxidized
by O2 to Te0. The nucleation and growth of Te0 preferentially
takes place on a substrate rather than in an homogeneous
solution because the required level of supersaturation on the
Sb2Te3 substrate is lower than in solution.[9] These as-formed
Te nuclei are used as the seeds for the further growth of Te. A
prolonged chemical transformation time results in the con-
tinuous stripping of the Sb3+ ions from the surface of Sb2Te3
and the oxidation of Te2À ions to Te0. The oxidation of Te2À
ions provides the Te source for further growth of the Te plate.
Figure 3. a) SEM image and b) TEM image of the porous nanothread-
based Pt plates synthesized through the galvanic reaction of metal salt
using porous network-structured Te templates. c,d) TEM images of the
porous nanotube-based Pd plates synthesized through the galvanic
reaction between PdCl2 and porous network-structured Te templates
and the subsequent removal of Te templates.
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large-scale production of porous network-structured Pt
plates. A high-resolution TEM image (Figure S11c in the
Supporting Information) revealed that the porous Pt net-
works are composed of sub-5 nm highly crystalline Pt nano-
particles, which may exhibit improved catalytic properties.
Additionally, porous Au plates can be successfully fabricated
through the galvanic reaction between the as-prepared
porous Te plates and HAuCl4 (Figure S11 in the Supporting
Information). Interestingly, novel porous nanotube-based Pd
plates can be created by the controlled galvanic reaction
between porous network-structured Te plates and PdCl2, and
the subsequent removal of the Te templates (Figure 3c,d and
Figure S12 in the Supporting Information). These novel
porous 3D nanotube-based (or solid-nanothread-based)
noble-metal nanoplates should find promising applications
because noble-metal nanomaterials have been considered to
be one of the most important materials in electrocataly-
sis,[6b,11] plasmonics,[11] fuel cells,[12] sensors,[13] and heteroge-
neous organic catalysis.[14] In addition to the well-known good
photoconductivity of Te nanowires,[15] Te nanowires have
been proved to be ideal templates to create novel one-
dimensional materials, involving Pt, Te-Pt, Pd, Au, Ag2Te,
PbTe and CdTe nanostructures.[2e,16] Thus, the as-prepared
porous network-structured Te plate could possibly be used as
a general template to produce porous nanotube-based (or
solid-nanothread-based) plates of metal tellurides with
potential applications in electronics.[17] Additionally, single-
crystal-like porous network-structured Te plates may exhibit
intriguing optoelectronic properties.[15]
In conclusion, we have developed a new route to induce a
drastic structural and compositional transformation of Sb2Te3
nanoplates into 3D porous network-structured Te nanoplates.
The reaction mechanism involves the dissolution of Sb2Te3 by
the coordination of the Sb3+ ions with tartaric acid, a
subsequent oxygen-assisted oxidation of the Te2À ions to Te0
and subsequent growth of the network at elevated temper-
atures. In the process, the addition of In3+ ions results in the
production of porous heterogeneous In/Te nanoplates. This
chemical transformation strategy from nanotemplates into
derivative porous products with morphological retention can
be considered as a new addition to the growing toolbox of
“conversion chemistry” reactions.[2–5,7d,18] In addition, porous
network-structured Te nanoplates can be used as templates to
prepare high-quality porous nanothread-based noble-metal
nanoplates and porous nanotube-based Pd plates. It is
expected that the porous Te templates will be desirable for
creating other porous functional metal and metal tellurides
(e.g. CdTe, PbTe, Ag2Te). These porous nanostructures can be
of special interest for a variety of applications, including
electrocatalysis, organic catalysis, sensors, separation, photo-
electronics, and nanoelectronics.
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Published online: January 3, 2012
Keywords: chemical transformation · mesoporous materials ·
.
nanostructures · tellurium · template synthesis
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