Communication
Cite This: Chem. Mater. 2017, 29, 9613-9617 pubs.acs.org/cm
High-Quality and Deeply Excavated Pt3Co Nanocubes as Efficient
Catalysts for Liquid Fuel Electrooxidation
Hongyu Du,† Shuiping Luo,† Kai Wang,† Min Tang,† Rinrada Sriphathoorat,† Yanshuo Jin,†
and Pei Kang Shen*,†,§
†
School of Physics, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, P. R. China
§
Collaborative Innovation Center of Sustainable Energy Materials, Guangxi University, Nanning 530004, P. R. China
*
S Supporting Information
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P latinum (Pt) plays an indispensable role in a wide range of
application fields, especially in fuel cells.1 However,
considering the high cost, limited availability, and unsatisfactory
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performance, it has been an urgent need to increase the
utilization efficiency and the catalytic activities of Pt.2 One of
the efficient approaches is alloying Pt with 3d-transition metal
to form Pt−M alloys (M = Fe, Co, Ni, Cu).3−8 Theoretically
speaking, the alloying with a second 3d-transition metal could
downshift the d-band center of Pt, thus leading to the
promotion of the activities.9 Among these Pt−M alloys,
Pt3Co alloys are widely reported to have more obviously
enhanced activities as efficient electrocatalysts in previous
literature.10 Furthermore, Pt3Co alloys have been proved to
have more negative enthalpy than Pt3Ni, which means Pt3Co
alloy could possess better stability during the long-term
test.11,12 Thus, the synthesis of high-quality and efficient
Pt3Co electrocatalysts is of great interest to researchers up to
the present.13−15
Besides the composition, morphology control is another
crucial approach to efficiently influence the catalytic activity of
nanocatalysts, which is attributed to the structure−activity
relationship.16−19 In the past few decades, great efforts have
been made to regulate the structure of nanocatalysts,20−26 and
among these novel structures, excavated structure nanocatalysts
start attracting researchers’ attention recently.27−29 In compar-
ison with convex structure, the nanocatalysts with excavated
structure expose larger accessible surface area and higher
density of low-coordinated atoms (e.g., edges, corners, kinks),
which provide more active catalytic sites that can promote the
activity.30,31 In addition, the deeply excavated nanocubic
structure can be regarded as an assembly of nanosheets side
by side from the geometric structure standpoint.28 It is quite a
stable self-supported structure that can prevent the nano-
catalysts from aggregation, and they rarely collapse or
breakdown, which can promote the durability of the nano-
catalysts.32 Therefore, it is a strong desire to synthesize the
nanocatalysts with a deeply excavated structure. However,
owing to the high exposure of active sites and the migration of
atoms,33 it is still a tough challenge to obtain the deeply
excavated structure in complicated reaction conditions.34,35
Therefore, only a few deeply excavated examples have been
reported.28,36 Herein, we developed a facile one-pot strategy
and successfully synthesized high-quality and deeply excavated
Pt3Co nanocubes (Pt3Co DENCs). This is the first synthesis of
such deeply excavated Pt3Co nanocubes to our knowledge, and
they showed obviously enhanced properties in both methanol
© 2017 American Chemical Society
oxidation reaction and formic acid oxidation reaction compared
with commercial Pt/C. Simultaneously, a simple and effective
strategy was found to tune the structure of the Pt3Co
nanocatalysts from nanocubes with flat surfaces to deeply
excavated nanocubes by just altering the feeding amount of
deionized water. In addition, the electrochemical research
showed that the catalytic activities of cubic nanocrystals were
related to their concavity.
In a typical synthesis, Pt3Co DENCs were obtained in a facile
condition by the one-pot solvothermal method. Pt and Co
precursors were well dissolved in the oleylamine (OAm), which
contains cetyltrimethylammonium chloride (CTAC) and
deionized water (DI water). The solution was sealed in a
Teflon-lined stainless steel autoclave and heated at 150 °C for 3
h with vigorous magnetic stirring (see the Supporting
Information for details).
The final products were then collected and characterized in
detail (Figure 1, Figure S1). A representative transmission
electron microscopy (TEM) image demonstrates that the
nanocrystals are high-quality cubic structure with uniform size
and morphology (Figure 1a). The average edge length of the
nanocubes is 23.2 nm (Figure S2). According to the high angle
annular dark field scanning transmission electron microscopy
(HAADF-STEM) image of the as-obtained products (Figure
1b), the square diagonals are much brighter than other parts of
the nanocrystals, which looks like an X in a square, and the
brightness of the diagonals shows a linear trend to reduce from
the vertex angle to the center of the square. This indicates that
the surfaces of nanocubes were deeply excavated. To further
understand the 3D morphology, TEM images of individual
nanocrystal were recorded along different zone axes, and a
series of TEM images at different rotations of selected
nanocrystals were obtained (Figure 1c1,d1,d2, Figure S3). It
can be seen that the corresponding 3D models can match well
with the TEM figures, which indicates that the six faces of the
nanocubes were all deeply excavated. Moreover, our detailed
analysis shows that the angle between nanosheet (the
nanosheets are slightly thinner than 4.7 nm) and surface of
the ideal nanocube is about 45°, and the nanosheets face-to-
face are approximately at a right angle (90°) to each other
(Figure 1c1). These analyses strongly confirm that the
Received: August 11, 2017
Revised: November 7, 2017
Published: November 8, 2017
9613 DOI: 10.1021/acs.chemmater.7b03406
Chem. Mater. 2017, 29, 9613−9617
Chemistry of Materials
Figure 1. (a) TEM and (b) HAADF-STEM images of Pt3Co DENCs.
(c1, d1, d2) TEM images and schematic models of individual Pt3Co
DENCs in [001], [011], and [111] orientation. (c2) HRTEM image
taken from the red region boxed in (c1). (c3) Corresponding fast
Fourier transform (FFT) pattern of the Pt3Co DENC shown in (c1).
(c4) Enlarged HRTEM image taken from the edge of an individual
Pt3Co DENC and illustration of the atomic arrangement.
nanocubes were deeply excavated. And the nanostructure of a
deeply excavated nanocube can be regarded as an assembly of
12 isosceles right triangle nanosheets side by side.28 High-
resolution TEM (HRTEM) and the corresponding fast Fourier
transform (FFT) pattern were obtained from [001] zone axis
and other orientations (Figure 1c2,c3, Figure S4), which
indicate high crystallinity of the nanocrystals. Simultaneously,
the interplanar spacing of the nanocrystals (1.93 and 1.36 Å) is
slightly shorter than that of the pure Pt (1.96 and 1.39 Å),
which means that the Co was successfully introduced into the
Pt lattice.13 The atomic-resolution TEM image (Figure 1c4)
recorded from the nanocube edge shows an atomic step
composed of (510) and (710), which reveals that the edges of
the nanoparticles are incurved and the 12 edges expose high-
index facets.37
To investigate the composition and element distribution of
as-prepared deeply excavated nanocubes, both energy-dis-
persive X-ray (EDX) spectroscopy elemental mapping and
line scanning were performed. The elemental mapping images
(Figure 2a) clearly indicate that the Pt and Co are uniformly
distributed in the whole nanocube, which is further confirmed
by the line-scanning profile recorded across individual deeply
excavated nanocubes along the red path (Figure 2b). The EDX
spectroscopy analysis (Figure 2c) shows that the atomic ratio of
Pt and Co is 76:24 (approximately equal to 3:1), which can
match pretty well with the result of inductively coupled plasma
atomic emission spectroscopy (ICP-AES). The X-ray diffrac-
tion (XRD) pattern (Figure 2d) of the nanocubes shifted to the
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Communication
Figure 2. (a) HAADF-STEM image and corresponding EDX mapping
images of individual Pt3Co DENC. (b) Line-scanning profiles for Pt
and Co recorded across the red line shown in the inset. (c) EDX
spectrum and (d) XRD pattern of the Pt3Co DENCs.
higher degree compared with the fcc Pt PDF standard card,
which confirms a face-centered-cubic (fcc) structure.15
For further details on how the deeply excavated structures
were formed, the experiments with different feeding amounts of
DI water were made. As shown in Figure 3a−c, in the absence
Figure 3. TEM images of the Pt3Co nanocubes with different
concavity controlled by tuning the feeding amounts of DI water: (a) 0
μL, (b) 80 μL, and (c) 160 μL. (d) Corresponding 3D models of the
Pt3Co nanocubes with different concavity.
of DI water, Pt3Co nanocubes (Pt3Co NCs) with flat surfaces
were obtained (average length of edges is about 22.8 nm).
When the amount of DI water was increased to 80 μL, the final
products were Pt3Co concave nanocubes (Pt3Co CNCs),
whose surfaces were partly excavated (average length of edges is
about 23.5 nm; average concave surface angle is about 145.5 o).
And when 160 μL of DI water was added into the precursor
solution, the Pt3Co DENCs were obtained successfully (Figure
3c, Figures S7 and S8). These results indicate that the concavity
degree of Pt−Co nanocubes was highly sensitive to the amount
of DI water. Thus, the introduction of DI water is critical for
the formation of concave architecture in the present synthesis
system. As is known, the oxidative etching caused by Cl−/O2
DOI: 10.1021/acs.chemmater.7b03406
Chem. Mater. 2017, 29, 9613−9617
Chemistry of Materials
pairs is an efficient method for transforming solid nanocrystals
into concave nanocrystals.4,33,38 Considering the growth-
etching mechanism reported previously,39,40 we propose that
the formation of Pt3Co DENCs may attribute to the
combination of facet-selective capping and oxidative etching.
In the current system, the CTAC uniformly dispersed in the
solution, and the halogen group adsorbs on the side surfaces of
the nanocrystals uniformly and leads the nanocrystals to cubic
structure. In addition, the Cl−/O2 pairs will not work in the
absence of water in the reaction system (Figure S10),41 so the
final products will be the nanocubes. When the DI water is
introduced into the precursor, owing to the presence of the
hydrophilic head, the kinetic equilibrium of some CTAC
capped on the side surface is broken and some sites of surfaces
will be exposed to the Cl−/O2 pairs, which causes the etching
process on the surface. The introduction of DI water could
provide more O2 and increase the amount of Cl−/O2 pairs,
which would enhance the corrosion rate and thus facilitate the
formation of the concave structure. When the feeding amount
of DI water reached a certain level or the O2 was introduced
enough into the precursor, the deeply excavated architecture
would be formed (Figure 3, Figure S11).
The electrochemical studies of methanol and formic acid
oxidation were performed to test the electrocatalytic properties
of Pt3Co DENCs, Pt3Co CNCs, and Pt3Co NCs. Simulta-
neously Pt3Co nanoparticles loaded on carbon (Pt3Co NP/C)
and commercial Pt/C were measured for comparison under the
same conditions (Figure 4, Figures S12−S15). Prior to the
Figure 4. Cyclic voltammetry (CV) curves of three Pt3Co catalysts
with different concavity, Pt3Co NP/C and commercial Pt/C: (a)
methanol oxidation reaction (MOR) in 0.5 M H2SO4 + 1 M CH3OH
solution and (b) formic acid oxidation reaction (FAOR) in 0.5 M
H2SO4 + 0.25 M HCOOH solution (scan rate: 50 mV s−1). (c)
Specific activities and (d) the changes during 1000 potential cycles of
different electrocatalysts for MOR and FAOR. The peak current
densities are all taken at about 0.6 V for MOR and FAOR. The current
densities are normalized to the electrochemical surface area in (a) and
(b). In (c), error bars represent the s.d. (n = 3).
electrochemical measurements, the as-prepared Pt3Co DENCs,
CNCs, and NCs were loaded on commercial carbon (Vulcant-
72). According to the negative scan cyclic voltammetry (CV)
curves measured in N2-saturated 0.5 M H2SO4 solution at a
scan rate of 50 mV s−1 (Figure S16), the ECSA of Pt3Co
DENC/C got the highest rank among these three Pt3Co
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nanocatalysts (Figure S17), and the result is consistent with the
concavity of the nanocrystals. The methanol oxidation reaction
(MOR) and formic acid oxidation reaction (FAOR) were
performed at a scan rate of 50 mV s−1 in 0.5 M H2SO4 + 1 M
CH3OH and 0.5 M H2SO4 + 0.25 M HCOOH, respectively. As
shown in Figure 4a,b, the specific activities of Pt3Co DENC/C
are 4.14 (4.67), 1.71 (1.56), 1.20 (1.15), and 1.27 (1.19) times
higher than those of commercial Pt/C, Pt3Co NP/C, Pt3Co
CNC/C, and Pt3Co NC/C for MOR (FAOR), respectively
(Figure 4c). The peak current densities of Pt3Co DENC/C,
Pt3Co CNC/C, Pt3Co NC/C, Pt3Co NP/C, and commercial
Pt/C are separately taken at 0.63 V, 0.60 V, 0.60 V, 0.61 V, and
0.58 V for MOR and 0.61 V, 0.60 V, 0.60 V, 0.62 V, and 0.61 V
for FAOR. The mass activity of Pt3Co DENC/C is 1.43 and 2
times that of commercial Pt/C for MOR and FAOR,
respectively (Figure S18). Thus, the Pt3Co DENC/C showed
obviously enhanced catalytic activities for both MOR and
FAOR compared with commercial Pt/C. This could be
ascribed to the deeply excavated nanostructure, rich high-
index facets, and the synergistic effects of Pt and Co.42 In
addition, by comparing the electrocatalytic performance of
Pt3Co DENC/C, Pt3Co CNC/C, and Pt3Co NC/C, it is found
that the nanocubes with higher degree of concavity exhibit
higher ECSA and catalytic activities, which may be attributed to
the larger surface area, and their high energy facets and low-
coordinated atoms may also contribute to the performance32,43
(Figure S19).
The durability tests of the catalysts were performed from
−0.2 to 1.0 V vs SCE at a scan rate of 100 mV s−1 (Figure 4d,
Figures S20 and S21). As shown in Figure 4d, the peak current
density of Pt3Co DENC/C remained about 80.4% and 91.8%
of its initial values after 1000 cycles for MOR and FAOR,
respectively. By contrast, the peak current density of
commercial Pt/C only remained 49.9% and 61.2%. This result
shows that the Pt3Co DENC/C had an impressive stability
compared with commercial Pt/C in both methanol and formic
acid solution. The TEM characterization apparently shows
Pt3Co DENCs maintained the morphology after the accelerated
CV durability test, and the EDX results show that the element
ratio of Pt and Co comes to be 4:1 (which matches well with
the result of ICP-AES) (Figure S22). The slight reduction of
Co content could be caused by the electrochemical dealloying
of Co during the electrochemical measurement.35
In summary, we synthesized deeply excavated Pt3Co
nanocubes in a facile one-pot method, and the concavity of
the nanocrystals could be well controlled by just tuning the
feeding amount of DI water. The morphology and composition
of Pt3Co DENCs were characterized in detail. The formation
mechanism of Pt3Co DENCs was studied; CTAC and the
amount of DI water were believed to play the key role in the
synthesis of the deeply excavated structure. The Pt3Co DENCs
showed much enhancement of electrocatalytic activity and
durability for both methanol and formic acid oxidation reaction,
which may owe to the deeply excavated structure, rich high-
index facets, and the synergetic effects between Pt and Co. The
present work provides a simple method to control the
morphology and structure for further Pt-based nanocatalyst
research and gives more possibilities for commercial
applications in the near future.
DOI: 10.1021/acs.chemmater.7b03406
Chem. Mater. 2017, 29, 9613−9617
Chemistry of Materials
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.7b03406.
Experimental details; TEM images and corresponding
3D models of the Pt3Co DENCs; TEM images of
nanocrystals obtained under different conditions; CV
curves of Pt3Co DENC/C, CNC/C, and NC/C; and
TEM images of Pt3Co DENC/C before and after
durability test (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*(P.K.S.) E-mail: stsspk@mail.sysu.edu.cn.
ORCID
Yanshuo Jin: 0000-0001-9614-1454
Pei Kang Shen: 0000-0001-6244-5978
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Funding
This work was supported by the Major International (Region-
al) Joint Research Project (51210002), the National Basic
Research Program of China (2015CB932304), the Natural
Science Foundation of Guangdong Province
(2015A030312007) and Guangxi Science and Technology
Project (AB16380030). P.K.S. acknowledges the support from
the Danish project of Initiative toward Nonprecious Metal
Polymer Fuel Cells (4106-000012B).
Notes
The authors declare no competing financial interest.
■
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9617 DOI: 10.1021/acs.chemmater.7b03406

Chem. Mater. 2017, 29, 9613−9617