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Nanoelectrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan,
Republic of China, and National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan, Republic of China
T
he bulk fabrication of advanced bime-
tallic nanostructures with exceptional ABSTRACT
catalytic,1,2 magnetic,3,4 thermal,5 and
optical6,7 properties is a prerequisite for their
wide applicability in nanotechnology. Bimetal-
lic coreshell nanostructures, made with an
active-metal shell supported on another metal
as a core element, are emerging as one of the
most promising solutions able to address these Although bimetallic core@shell structured nanoparticles (NPs) are achieving prominence due to their
requirements. Such bimetallic coreshell na-
multifunctionalities and exceptional catalytic, magnetic, thermal, and optical properties, the rationale
nostructures with enhanced nanoscale proper-
underlying their design remains unclear. Here we report a kinetically controlled autocatalytic chemical
ties are of interest due to their potential as
highly ecient catalysts,8,9 magnetic compo- process, adaptable for use as a general protocol for the fabrication of bimetallic core@shell structured
nents for ultra-high-density memory devices,8,9 NPs, in which a sacricial Cu ultrathin layer is autocatalytically deposited on a dimensionally stable
and sensors in the biomedical eld.10 noble-metal core under kinetically controlled conditions, which is then displaced to form an active
Among bimetallic coreshell nanostruc- ultrathin metal-layered shell by redoxtransmetalation. Unlike thermodynamically controlled under-
tures, Pt ultrathin layered shells on the sur- potential deposition processes, this general strategy allows for the scaling-up of production of high-
face of a dimensionally stable M metal core
quality coreshell structured NPs, without the need for any additional reducing agents and/or
(McorePtultrathinshell, where M is the noble
electrochemical treatments, some examples being Pd@Pt, Pt@Pd, Ir@Pt, and Ir@Pd. Having immediate
and 3d-transition metals) nanoparticles
(NPs) are achieving prominence due to their and obvious commercial potential, Pd@Pt NPs have been systematically characterized by in situ X-ray
multifunctionalities and enhanced properties absorption, electrochemical-FTIR, transmission electron microscopy, and electrochemical techniques,
that can be broadly exploited for those both during synthesis and subsequently during testing in one particularly important catalytic reaction,
applications.1113 The most widespread role namely, the oxygen reduction reaction, which is pivotal in fuel cell operation. It was found that the
of platinum is as a catalyst, particularly in the bimetallic Pd@Pt NPs exhibited a signicantly enhanced electrocatalytic activity, with respect to this
automobile industry, petrochemical industry,
reaction, in comparison with their monometallic counterparts.
fuel cells, biosensors, etc.14 As Pt is tremen-
dously expensive, it is highly benecial to KEYWORDS: kinetically controlled . autocatalytic . coreshell . Pd@Pt . Pt
reduce the amount of Pt. The McorePtultrathinshell ultrathin layer
NPs comprise a very low Pt content in their
outer ultrathin layer shell and are one of the
best solutions to addressing this issue, an processes and inhomogeneous growth of
approach that can cut back the Pt cost while the heterometallic component on core sur- * Address correspondence to
bjh@mail.ntust.edu.tw.
enhancing catalytic activity. face NPs.15 Thus, it is necessary to develop
Although these bimetallic coreshell na- and couple new NP synthesis methods with Received for review January 21, 2011
nostructures are of signicance, the conven- rst-principles theoretical design, as it gives and accepted November 2, 2011.
tional synthetic approaches have not been mechanistic insight into the atomistic sur-
Published online November 02, 2011
successful in producing high-quality core face chemistry governing the enhanced 10.1021/nn202545a
shell NPs. These diculties are due to sev- properties and provides the groundwork
eral factors including random nucleation for NP fabrication. C 2011 American Chemical Society
PdcoreCuultrathinshell/C NPs. The present method also adsorption (applied potential at 0.00 V), in an electrolyte
allows a Cu ultrathin layer to be deposited on other solution (0.5 M H2SO4) at 30 C; the potential was scanned
highly reactive noble metal surfaces, e.g., Pt and Ir (see at 10 mV 3 s1. The stripping curve for the adsorbed
Figure S2). Utilizing these two reactive metals as the hydrogen shows two distinctive desorption peaks in the
core NPs, various coreshell structured NPs such as potential region between 0 and 0.3 V, associated with the
Pt@Pd, Ir@Pt, and Ir@Pd can be prepared by this oxidation of previously adsorbed hydrogen (2H = 2H
general method. 2e) on dierent Pd crystalline facets.40 This suggests
Finally, the Cu ultrathin layer was sacricially oxi- that the Pd/C NPs have a strong reactivity toward hydro-
dized by the Pt precursor, i.e., K2PtCl4, to form a Pt gen; that is, they absorb, adsorb, split, and oxidize it to
monolayer on the Pd/C NPs via redoxtransmetala- generate electrons22 that can reduce metal ions such as
tion. Using the same argument with a PdcoreCushell Cu2 and in doing so deposit only a Cu ultrathin layer on
structure that was previously conrmed by XAS, we see the Pd/C NP's surface. The existence of this Cu ultrathin
in Figure 2C, right, that the XANES spectrum for the layer correlates well with the stripping voltammogram of
PdcorePtultrathinshell/C NPs at the Pt L3-edge is similar to the PdcoreCuultrathinshell/C NPs (Figure 3A). The stripping
that of Pt foil, indicating a Pt ultrathin layer in a voltammogram was produced as follows: the Pd/C NP's
metallic state (Pt0) had been formed on the Pd/C surface was initially treated with hydrogen in a 0.5 M
surface. The observed parameter relationship in Ta- H2SO4 electrolyte solution. Next CuSO4 (0.01 M) was
ble S1 shows NPdi > NPti and NPdPd > NPtPt > added and the hydrogen purge was continued to ensure
NPdPt and conrms the PdcorePtshell structure of the that sucient hydrogen was adsorbed on the NPs to
PdcorePtultrathinshell/C NPs. reduce the Cu2 ions to form the sacricial Cu ultrathin
We additionally performed an in situ electrochemical layer.
analysis to conrm the formation of Cu ultrathin During the above formation of the sacricial Cu
layered Pd/C NPs. The stripping voltammograms of ultrathin layer, hydrogen is probably absorbed rst,
the adsorbed hydrogen and the Cu ultrathin layer are then spontaneously diuses out to the surface of the
shown in Figure 3A. The striping voltammogram for Pd surface, and subsequently consumed once the Cu2
adsorbed hydrogen on Pd/C was obtained after hydrogen ions are introduced into the solution, as the ratio of the
electron valence of Cu2 to e (from dissociated deposition (Figure S3E)], the peak characteristic of bulk
hydrogen) is 2:1. Thus, it is important to constantly absorbed and subsequent adsorbed hydrogen atoms
purge the hydrogen gas during the synthesis, ensuring (Hads) was suppressed due to the presence of the
a sucient amount of electron ow from the disso- adsorbed Cu ultrathin layer (ca. 0.38 V), whereas a peak
ciated hydrogen atoms to complete the layer deposi- corresponding to additional growth of Cu-bulk layers
tion of Cu atoms and form the Cu ultrathin layer. The was not observed. This Cu ultrathin layer formation was
situation is dierent if the hydrogen is not constantly maintained, and importantly no additional growth of
purged, in which case the generated electrons from Cu bulk was formed, even after the reaction was
the dissociated hydrogen would be insucient to form extended up to 8 h (Figure S3F). On the second sweep,
a complete Cu ultrathin layer. performed after stripping Cu, the voltammograms
The Cu2 ions displaced all the adsorbed hydro- mirrored those observed for Pd/C NPs (i.e., the absence
gen from the NPs' surfaces, which is apparent from of adsorbed Cu). These results emphasize the viability
the suppression of the hydrogen desorption peaks of the present method in achieving only a Cu ultrathin
(Figure 3A). The reduction and deposition of the layer deposition on a Pd core surface.
corresponding Cu2 ions to form a Cu ultrathin layer For comparison we conducted a parallel study in
appear as a strong desorption peak located at ca. 0.38 which the Cu layers were deposited on a Pd/C surface
V.25 In a previous study, Adzic et al.25 located the using an electrochemical (UPD) method, in which
stripping Cu-bulk deposition peak, for agglomerated holding potentials were employed, to deposit Cu layers
Cu, at a much lower onset potential, 0.21 V, which is in a thermodynamically controlled reaction. A Cu mono-
dierent from the value found for the Cu ultrathin layer layer can be formed at a holding potential of 0.28 V
presented here. (Ehold3), as indicated with black arrows (Figure 3B). How-
From Figure 3, we also calculated the ratio between ever, the holding potential associated with this Cu-UPD
the stripping Cu and H charges (QCu/QH). This deter- monolayer must be determined carefully; otherwise it
mines whether, for this present method, it is possible to may form an incomplete Cu-UPD monolayer and/or
form a well-ordered Cu ultrathin layer on the NP's additional bulk Cu deposits.41 For example, a slight
surface, without the three-dimensional (3D) growth change in the holding potential to a lower value, e.g.,
of bulk Cu. To quantify QH and QCu, calculations similar Ehold1 and Ehold2, triggers the growth of additional bulk
to those reported by Green et al.41 have been used. The Cu, as indicated by the strong peak located at ca. 0.28 V.
QCu/QH ratio was found to be about 2, a condition For the reduction reaction of Cu2 2e f Cu(s) at
where the copper atoms adsorb on the Pd metal standard conditions, the bulk Cu(s) will be deposited at
surface at the same sites as hydrogen to form a well- the equilibrium potential (EbulkCu) of 0.3402 V, in
ordered Cu ultrathin layer,41,42 accordance with the Nernst equation:
The cyclic voltammograms (CVs) for the Cu ultrathin
RT
layer stripping as a function of deposition time are Ebulk-Cu ECu
0
ln[CCu2 ] (1)
shown in the supplementary Figure S3. For each strip- nF
ping, the rst CV cycle depicts the stripping curve of where E0Cu = 0.3402 V, R = 8.31441 J 3 mol1 3 K1, F =
the adsorbed Cu atoms on the Pd/C NPs. During the 96484.6 C 3 mol1, CCu2 = 1 M, and n = 2, at a temperature
forward step in this rst CV cycle [typically after 6 h of (T) of 298 K. In general, when the Cu2 concentration is
has also been employed in the surface-sensitive-based powder-XRD measurements for both the spherical-
techniques, i.e., cyclic voltammograms measurements. and cubic-shaped Pd@Pt NPs (Figure S10) and found
From these cyclic voltammograms (Figure S7A), we did a size similarity to that from TEM measurements. To
not nd any trace of Cu residues, since the anodic and be specic, the particle size of the spherical and
cathodic peak currents, at a potential range of approxi- cubic Pd@Pt NPs, estimated by the Scherrer's equa-
mately 0.30.6 V, corresponding to the presence of tion, is found to be 10.6 and 4.3 nm, respectively.
Cu were not observed. These ndings indicate that Additionally in particular with the cubic-shaped
the redoxtransmetalation process with subsequent Pd@Pt NPs, we found two important main peaks
minor electrochemical treatments is exceptionally located at 39 and 46, which represent the
eective in replacing the Cu layer to form a Pt layer (111) and (100) facets, respectively. The presence of
on the Pd core. A similar observation was also made a strong (100) facet in addition to the (111) facet
by Adzic et al.,24 who also employed an electroche- indicates the existence of a cubic shape for this
mical treatment, i.e., a linear potential sweep with a particular Pd@Pt sample.
scan range up to 1.00 VRHE, after the redoxtransme- Figure 6 shows comparisons with carbon-based
talation reaction of Cu by Pt. They also found that the counterparts, i.e., the commercial BASF Pd/C and
Cu layer can be completely displaced by this com- E-tek Pt/C NPs (20 wt %). The data presented in
bined redoxtransmetalation and subsequent elec- Figure 6A have been normalized to the geometric
trochemical processing. To give clear evidence of the area of the rotating disk electrode (0.1964 cm2), where
viability of the present strategy, we strictly per- all the electrochemical measurements used the same
formed TEM-EDX measurements using Cu-free grids weight loading of an active metal, i.e., 0.22 mg 3 cm2.
(i.e., Mo grid) for the sample of the prepared sphe- In particular for PdcorePtultrathinshell/C NPs, the calcula-
rical-shaped Pd@Pt/C NPs and electrochemically tion is based on their active Pt metal shell. Mass and
treated Pd@Pt/C NPs. It is noteworthy that our nd- specic activities at 0.9 VRHE are given as kinetic
ings in EDX analyses are in good agreement with our current density (jk) normalized in reference to the
ndings on XANES and electrochemical measure- weight loading amount and the electrochemically
ments, where the insignicant 2.9% Cu residues active surface area (ECSA) of an active metal,
(Figure S8A) can be completely removed from the respectively.
sample (Figure S8B). The intrinsic ORR activities, both mass and specic
We have also performed TEM measurements with a activities (jk) for the Pd/C, Pt/C, and PdcorePtultrathinshell/
larger area (low-magnication) for the Pd@Pt NPs with C NPs under similar experimental conditions, were
both the spherical and cubic shapes and provided their calculated on the basis of the LSVs curves (Figure 6A).
particle size distributions. The particle size of the In practice the jk value was calculated from the ORR-
spherical and cubic Pd@Pt NPs is found to be uniform LSVs curve by using mass-transport correction and
around 10.7 and 4.5 nm, respectively (Figure S9). In normalized to the weight loading amount and the
addition, the TEM image for the cubic Pd@Pt NPs ECSA of an active metal in order to compare the
shows that the Pd-core surface was uniformly cov- mass and specic activities of the NPs, respectively
ered with a Pt ultrathin layer. We also performed (the detailed steps of the calculation are provided in