pubs.acs.

org/NanoLett Letter

Phase-Controlled Synthesis of Pd−Se Nanocrystals for Phase-

Dependent Oxygen Reduction Catalysis
Zhiyong Yu, Shulin Xu, Yonggang Feng, Chengyong Yang, Qing Yao, Qi Shao, Ya-fei Li,*
and Xiaoqing Huang*
Cite This: Nano Lett. 2021, 21, 3805−3812 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via INDIAN INST OF TECH GUWAHATI on October 30, 2022 at 06:57:46 (UTC).

ABSTRACT: Searching for highly efficient oxygen reduction reaction (ORR)

electrocatalysts for fuel cell technology, in which the crystal structure plays a
powerful role in regulating the electrocatalysis, is urgent yet challenging. Herein,
we have explored the active and stable Pd−Se alloy electrocatalysts with
controlled phase toward alkaline ORR. The phase-controlled Pd−Se nano-
particles (NPs) show interesting phase-dependent electrocatalytic performance,
in which the Pd17Se15 NPs/C exhibits much better ORR performance than its
counterpart, Pd7Se4 NPs/C, and the commercial Pd/C and Pt/C. Based on the
detailed analysis, Pd in Pd17Se15 possesses more Se atom coordination and a
higher valence state, thus providing a stronger capacity for the absorption of
oxygenated species. DFT further reveals more charge transfer from the Pd17Se15
surface to the *OOH intermediate, which is the reason for the activity
enhancement.
KEYWORDS: Phase, Palladium, Chalcogenide, Oxygen Reduction Reaction, Selenium

T he fuel cell is regarded as a promising energy source

because of its high power generation efficiency and low
environmental pollution.1,2 The oxygen reduction reaction
(ORR), a half reaction of a full cell with sluggish kinetics,
directly determines the development of the fuel cell
technology.3−6 Among all the studies, palladium (Pd),
platinum (Pt), and their alloys are the state-of-the-art ORR
catalysts for fuel cells.7−12 Nevertheless, owing to the low
abundance and high price of platinum group metals
(PGM),13−16 it is a prerequisite to develop unique ORR
catalysts with both superior performance and maximized atom
utilization. To this end, the control of Pd-based and Pt-based
electrocatalysts has been deeply explored through various
strategies over the past decades, such as shape, size,
composition, surface strain, electronic structure, and de-
fects.17−20 In fact, the phase and structure of the electrocatalyst
also play a pivotal role in modulating the catalytic activity.21,22
For instance, Cui and co-workers have successfully prepared an
ordered Pd3Fe intermetallic catalyst, in which the ordered
Pd3Fe exhibits significantly enhanced activity and durability for
ORR, outperforming the counterparts of disordered Pd3Fe/C,
Pd/C, and Pt/C.23 Wang and co-workers have described a new
class of Pt−Co nanocatalysts composed of ordered Pt3Co
intermetallic cores with a 2−3 atomic-layer-thick platinum
shell. These nanoparticles are more active and stable than the
disordered Pt3Co/C alloy because of the Pt-rich shell and the
stable intermetallic Pt and Co arrangement in the core.24
Although previous efforts have been directed toward
engineering the crystal structure of bimetallic nanomateri-
als,23−25 the research on modulating the phase of the catalysts
consisting of PGM and nonmetal is very scare. In all the
studies attempting to combine metal-free elements with PGM,
the noble metal-based chalcogenides show the merits of the
comparable catalytic activity and low cost, supporting their
potential applications in electrocatalysis.26,27 More impor-
tantly, this kind of material possesses an extraordinarily rich
structure. In particular, Pd forms a number of stable alloys with
the selenium (Se) under ambient conditions and several stable
phases of Pd8Se, Pd7Se, Pd4Se, Pd3Se, Pd7Se4, PdSe2, and
Pd17Se15 are known to exist.28,29 As the crystal structure plays
an important role in modulating the properties of the
nanocrystals, research on the phase-dependent ORR properties
of Pd−Se nanocrystals will be expected to realize efficient
catalysts, but the relevant reports are scarce.
Herein, we present a wet-chemical method to selectively
synthesize a new class of phase-controlled palladium selenide
(i.e., Pd7Se4, Pd17Se15) nanoparticles (NPs) for enhanced
alkaline ORR. The phase-controlled Pd−Se NPs show the
Received: January 14, 2021
Revised: March 30, 2021
Published: April 20, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.nanolett.1c00147

3805 Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett Letter

Figure 1. (A, D) Local ball-and-stick models, (B, E) the corresponding crystal structures along [001], [010], and [100], and (C, F) the several
atomic arrangements of surface atoms along [100] of the (A−C) Pd17Se15 phase and (D−F) Pd7Se4 phase, respectively. The Pd atoms are in cyan
and Se in purple, respectively.

Figure 2. (A, E) HAADF-STEM images, (B, F) PXRD patterns, (C, D, G, H) HRTEM images, (I, J) HAADF-STEM-EDS mappings, and (K, L)
corresponding line-scan analysis of the (A−D, I, and K) Pd17Se15 NPs and (E−H, J, and L) Pd7Se4 NPs, respectively.

interesting phase-dependent electrocatalytic performance,
where the Pd17Se15 NPs/C exhibit much higher activity and
stability toward ORR than the Pd7Se4 NPs/C. Specifically, the
Pd17Se15 NPs/C shows the ORR mass activity and specific
activity of 0.460 A mgPd−1 and 1.201 mA cm−2 at 0.90 V versus
the reversible hydrogen electrode (RHE), which are 2.47 (2.97
and 8.21) and 1.59 (5.07 and 9.24) times higher than those of
3806
the Pd7Se4 NPs/C (the commercial Pt/C and commercial Pd/
C), respectively. X-ray photoelectron spectroscopy (XPS) and
X-ray absorption spectroscopy (XAS) reveal that the Pd atoms
in the Pd17Se15 crystal structure are in a state of being
positively charged due to the environment of more Se
coordination with respect to the Pd7Se4, thus possessing a
stronger interaction with oxygen intermediates. Density
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett Letter

Figure 3. (A) CV curves of different phase Pd−Se NPs/C and the commercial Pd/C. (B) ORR polarization curves and (C) histogram of the mass
and specific activities of the different catalysts. (D) ORR polarization curves of Pd17Se15 NPs/C before and after various potential cycles. (E)
Normalized mass activity changes of different catalysts before and after various potential cycles.

functional theory (DFT) calculations confirm that the Pd17Se15 T-shaped geometry to three Se atoms. There is a spread of
surfaces can transfer more electrons to the *OOH Pd−Se bond distances ranging from 2.49 to2.55 Å. The last Pd
intermediate, which is the reason for the activity enhancement. is bonded in a distorted linear geometry to two Se atoms. The

■
RESULTS
As shown in Figure 1A, the Pd17Se15 crystallizes cubic
symmetry with the space group Pm3m (No. 221). There are
four crystallographically different Pd atoms. One of the Pd
atoms has a regular octahedron of Se atoms with the Pd−Se
distance of 2.58 Å. The remaining three Pd atoms are
coordinated each with four Se atoms either in a flattened
tetrahedron (one Pd center) with the average Pd−Se distance
of 2.48 Å or square plane (two atoms) with Pd−Se distances of
2.53 and 2.44 Å. The square planar Pd atoms are also
coordinated to Pd atoms with a Pd−Pd distance of 2.78
Å.29−31 According to the local ball-and-stick model of Pd17Se15,
the atomic arrangement of Pd and Se could be viewed along
[001], [010], and [100], respectively (Figure 1B). Figure 1C
clearly shows the arrangement of several layers of surface
atoms along [100], that is, Pd atoms are in the environment of
more Se coordination. In contrary, the Pd7Se4 crystallizes in
the orthorhombic P22121 (No. 18) space group (Figure 1D).
In this structure, there are also four inequivalent Pd sites.
However, two of them are bonded with four Se atoms either in
a distorted square coplanar geometry or 3-coordinate
geometry. In the third Pd atom, Pd is bonded in a distorted
3807
Pd−Pd bond length in this structure ranges from 2.80 to 2.88
Å.31 Figure 1E shows the atomic model along [001], [010],
and [100]. Figure 1F shows the surface atoms along [100],
where the Pd atoms on the surface of this structure are bonded
to fewer Se atoms compared with Pd17Se15.
The Pd−Se NPs were then prepared by a facile wet-chemical
approach (see Materials and Methods for details). As shown by
the high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) and TEM images
(Figures 2A and S1A), the obtained Pd−Se NPs are uniform
with hollow features and an average diameter of 60 nm. The
powder X-ray diffraction (PXRD) pattern (Figure 2B) displays
that all the peaks of Pd−Se NPs can be indexed to an ordered
Pd17Se15 phase (JCPDS No. 29-1437). As shown in the high-
resolution TEM (HRTEM) images taken from an individual
Pd−Se NP, interplanar spacing of 0.258 and 0.320 nm could
be clearly observed, assigned to the (410) and (311) planes of
Pd17Se15 (JCPDS No. 29-1437) (Figure 2C,D). Figure S2A
shows the scanning electron microscopy energy-dispersive X-
ray spectroscopy (SEM-EDS) results of Pd17Se15 NPs. The
measured atomic ratio of Pd:Se is 51.2/48.8, being in good
agreement with the inductively coupled plasma atomic
emission spectrometry (ICP-AES) results of 50.6/49.4 for
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett Letter

Figure 4. (A) Pd 3d XPS spectra and (B) Se 3d XPS spectra of Pd17Se15 NPs/C and Pd7Se4 NPs/C. (C) Pd K-edge XANES profiles of Pd17Se15
NPs/C, Pd7Se4 NPs/C, Pd foil, and PdO. The inset in (C) is shows the magnified near-edge structures of different catalysts. (D) Pd K-edge EXAFS
spectra in R space for different catalysts. (E) Wavelet transform for EXAFS spectra of Pd foil, Pd7Se4 NPs/C, and Pd17Se15 NPs/C.

the Pd17Se15 NPs (Figure S2C). The HAADF-STEM-EDS
mappings (Figure 2I) and line-scan analysis (Figure 2K) reveal
that Pd and Se distribute evenly throughout the entirety of the
Pd17Se15 NPs.
Interestingly, by simply changing the molar ratio of the
Pd:Se precursor to 3.4, a new type of Pd−Se NPs with a
Pd7Se4 crystal structure was obtained. The average diameter of
Pd7Se4 NPs is about 60 nm from the HAADF-STEM and
TEM images (Figures 2E and S1B). The PXRD diffraction
peaks of Pd−Se NPs match well with the Pd7Se4 phase
(JCPDS No. 43-0856) (Figure 2F). The selected parts from
Figure 2E show lattice fringes with an interplanar spacing of
0.290 and 0.259 nm, being consistent with the (210) and
(021) plane of the Pd7Se4 phase (Figure 2G,H). SEM-EDS
and ICP-AES results show that the Pd:Se atomic ratios of
Pd7Se4 NPs are around 63:37 (Figure S2B,C). The elemental
mappings of the Pd7Se4 NPs and line scan show that the Pd
and Se are uniformly distributed (Figure 2J,L). To reveal the
evolutionary process during the synthesis of PdSe NPs, we
have tracked the PdSe NPs intermediates collected from
different reaction times (see Figures S3 and S4 for details).
3808
To gain insight into the electrocatalytic properties of the
various structures, we loaded the two Pd−Se NPs with distinct
phases on commercial carbon black (C, Vulcan XC-72R) by
sonication (Figure S5). Figure S6A shows the typical cyclic
voltammogram (CV) curves for distinct Pd−Se NPs/C and
commercial Pd/C in 1 M KOH solution at a sweep rate of 100
mV s−1.32−34 The electrochemically active surface area (ECSA)
could be calculated from the charge required for desorption
(Figure 3A), where the ECSAs of Pd17Se15 NPs/C, Pd7Se4
NPs/C, and the commercial Pd/C are 38.3, 24.7, and 43.1 m2
gPd−1, respectively.32−34 As a comparison, the ECSA of the
commercial Pt/C is calculated to be 65.3 m2 gPt−1, based on
the CV profile (Figure S6B,C). Figure 3B shows the ORR
polarization curves of the catalysts studied, which are
performed at room temperature in an O2-saturated 0.1 M
KOH solution. We can see that the half-wave potential and the
onset potential of the Pd17Se15 NPs/C shift considerably
compared to those of the other catalysts. Moreover, the mass
and specific activities determined from Figure 3B at 0.9 V
versus RHE for those catalysts are shown in Figure 3C. The
Pd17Se15 NPs/C exhibits the highest mass activity of 0.460 A
mgPd−1, which is 8.21 and 2.97 times better than those of the
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett
commercial Pd/C (0.056 A mgPd−1) and commercial Pt/C
(0.155 A mgPt−1), respectively, and the specific activity of 1.201
mA cm−2 is 9.24 and 5.07 times higher than those of the
commercial Pd/C (0.130 mA cm−2) and commercial Pt/C
(0.237 mA cm−2), respectively. Furthermore, the mass and
specific activities of the Pd17Se15 NPs/C are also better than
those of the Pd7Se4 NPs/C (0.186 A mgPd−1, 0.753 mA cm−2)
investigated. The mass activity and specific activity Tafel plots
for different catalysts also demonstrate the highest ORR
kinetics of the Pd17Se15 NPs/C (Figure S7). Therefore, the
distinct Pd−Se NPs with controlled phases show the
interesting phase-dependent electrocatalytic performance. To
explore how the nanoscale sizes may affect the electrocatalytic
activity, we further investigated the electrocatalytic properties
of bulk-sized PdSe NPs with different phases (Figures S8 and
S9). It could be seen that the bulk-sized Pd17Se15 catalyst also
shows a better ORR activity than that of the Pd7Se4 under the
same conditions, showing the similar phenomenon in the
nanosized catalysts. We pay more attention to the comparison
of the intrinsic activity of the Pd17Se15 NPs and Pd7Se4 NPs in
this work, which is different from the observation of the
previously reported works.31,35
The ORR behaviors of these Pd−Se NPs/C were studied by
using the rotating ring-disk electrode (RRDE) method. Figure
S10 shows that for all Pd−Se NPs/C investigated, the H2O2
selectivity is almost 0% and the number of transferred
electrons is approaching 4 among the applied potentials,
indicating that Pd−Se NPs/C mainly follows a 4-electron
oxygen reduction pathway. The ORR durability of the phase-
controlled Pd−Se NPs/C was also examined through CV
cycling in the range of 0.6 V−1.1 V versus RHE in a N2-
saturated 0.1 M KOH solution at a sweep rate of 100 mV s−1.
After 15 000 cycles of accelerated durability tests (ADTs), the
commercial Pd/C and commercial Pt/C show 46.4% and
44.5% mass activity losses, respectively. In contrast, the
Pd17Se15 NPs/C exhibits excellent ORR durability, as there is
a small negative shift in the polarization curves with 28.2% loss
of mass activity (Figure 3D), whereas the Pd7Se4 NPs/C shows
a relatively larger activity decay of 33.9%. The ORR durability
of different catalysts is summarized in Figure 3E, clearly
showing the best ORR stability of the Pd17Se15 NPs/C. These
catalysts after durability tests were also characterized by TEM,
SEM-EDS, PXRD, XPS, and HAADF-STEM-EDS elemental
mappings. The characterization reveals that there were limited
changes in the shapes, sizes, compositions, and structures of
Pd17Se15 NPs/C and Pd7Se4 NPs/C after 15 000 potential
cycles (Figures S11−16). Specifically, the PXRD pattern of the
studied Pd−Se NPs/C still display typical peaks of the
Pd17Se15 and Pd7Se4 phases (Figure S13). On the sharp
contrary, the commercial Pd/C and commercial Pt/C show
obvious aggregation after the durability tests (Figure S16).
These results reveal that the Pd−Se NPs/C not only owns
superior ORR activity but also possesses excellent ORR
durability compared to the commercial catalysts, in which the
Pd17Se15 NPs/C displays better ORR activity and durability
compared with Pd7Se4 NPs/C. Moreover, the antipoisoning
capability of PdSe NPs in the presence of small molecules was
further investigated in ORR conditions. According to the CO
oxidation peak potential of different catalysts in the CO
stripping experiments and the changes of the polarization
curves when introducing CH3OH in ORR conditions, it could
be concluded that the PdSe NPs/C exhibit a similar
antipoisoning ability compared to Pd/C (Figures S17 and
3809
Letter
S18). Considering that these Pd−Se cathodic catalysts have a
similar component, shape, and size, it is reasonably suggested
that the different phases with various configurations of atoms
and diverse chemical coordination environments are the key
parameters for the ORR enhancement.
■ DISCUSSION
To understand the reason for the enhanced ORR activity of
the phase-controlled Pd−Se NPs, the electronic structures of
the catalysts were initially studied by X-ray photoelectron
spectroscopy. As shown in Figure 4A, the Pd0 3d5/2 and Pd0
3d3/2 peaks of the Pd17Se15 NPs are centered at 336.5 and
341.8 eV, shifting to higher binding energies with respect to
Pd7Se4 NPs at 336.1 and 341.4 eV, suggesting the trans-
formation of the electron from Pd to Se. Figure 4B shows that
the peaks of Se 3d5/2 and Se 3d3/2 shift to lower binding
energies from the Pd7Se4 phase to the Pd17Se15 phase, which is
in accordance with the Pd XPS results and further confirms the
trend of electron transformation. The XPS of PdSe NPs/C
after durability tests also shows the trend of electron
transformation based on the shift of the peaks in the spectrum,
demonstrating that the valence state of the elements and the
trend of the electron migration could be maintained under the
electrochemical conditions (Figure S19). The X-ray absorption
spectroscopy (XAS) technique was also used to further
evaluate the local environment and chemical bonding of
Pd17Se15 NPs/C and Pd7Se4 NPs/C. As revealed by the Pd K-
edge X-ray absorption near-edge structures (XANES) in Figure
4C and the inset in Figure 4C, the valency of Pd for various
Pd−Se NPs are located between the Pd foil and Pd oxides.
This is mainly due to the higher electronegativity of Se atoms
via which the electrons from the Pd atoms are partially shifted
to the neighboring Se atoms. Specifically, Pd in Pd17Se15 NPs/
C has a higher valence state compared to that in Pd7Se4 NPs/
C because of the more coordinated Se atoms, which is in a
good agreement with the XPS results.
Simultaneously, we compared the Fourier transformations of
the Pd K-edge EXAFS for Pd17Se15 NPs/C, Pd7Se4 NPs/C, Pd
foil, and PdO (Figure 4D). The peak at 2.52 Å stands for the
Pd−Pd bond. By obvious contrast, Pd−Se NPs/C displays
negative shifts in comparison with the Pd foil but largely differs
from the profile of PdO. To be specific, Pd17Se15 NPs/C
exhibits a single peak at 2.12 Å in R-space, suggesting the
formation of pure Pd17Se15.36 In the case of Pd7Se4 NPs/C, the
main peak in the spectrum splits to two peaks. These two split
peaks each correspond to Pd−Se and Pd−Pd bonds, which is
caused by the difference of the bond length between the two
kinds of bonds. Apart from that, EXAFS wavelet transform
(WT) analysis was performed to further confirm the difference
of the bonding forms for Pd17Se15 NPs/C, Pd7Se4 NPs/C, and
Pd foil. As shown in Figure 4E, the WT analysis of the Pd foil
reveals only one intensity maximum at about 10.5 Å−1, which is
assigned to the Pd−Pd bond. In comparison, an obvious
negative shift of the intensity maximum to 8.9 Å−1 is observed
for Pd7Se4 NPs/C due to the contribution from the Pd−Se
coordination. The intensity spectrum of Pd17Se15 NPs/C
moves further to the negative direction compared with Pd7Se4
NPs/C, revealing that there is more Pd−Se coordination in
this structure. These results confirm that the Pd atoms in
Pd17Se15 NPs/C bond with more Se atoms compared with
Pd7Se4 NPs/C. Due to the special coordination mode in
Pd17Se15, the Pd atoms in this structure possess an electron-
deficient state, which will inevitably affect the adsorption of
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett Letter

Figure 5. (A, B) Optimized structures of the key intermediates on the (001) facet of Pd17Se15 and Pd7Se4, respectively. (C) Calculated free energy
profiles at 0 and 0.94 V for ORR on Pd17Se15. (D) Calculated free energy profiles at 0 and 0.81 V for ORR on Pd7Se4. Starting from the formation
of *OOH species, the charge density difference of *OOH adsorption on (E) Pd17Se15 and (F) Pd7Se4, respectively. Color code: purple stands for
electron depletion, and pink stands for electron accumulation.

intermediates and then change the activity of the oxygen
reduction reaction. Combined with the performance results, it
could be deduced that electron deficient Pd atoms could
provide a more appropriate binding capacity for adsorption
and activation for intermediates to enhance the catalytic
performance.
We further analyzed the theoretical evidence of ORR
performance enhancement by spin-polarized DFT calculations.
Due to the diverse crystal planes measured in the experiment,
we choose the Pd17Se15 (001) and Pd7Se4 (001) facets to build
the models as shown in Figure S20, of which only the top few
layers were allowed to relax. We studied the ORR steps on the
surfaces of the Pd17Se15 and Pd7Se4. The atomic configurations
at various states along the reaction path are displayed in Figure
5A,B, and the corresponding free energy profiles are
summarized in Figure 5C,D. The adsorption of the second
hydrogen is possible for both O sites, and the ORR can further
proceed following two different pathways: one is the 4e−
reduction pathway, and the other is the 2e− reduction
pathway. Remarkably, for Pd17Se15, the ΔG of this process is
−0.46 eV, which is much less favorable than that of the *OOH
reduction to O* + H2O in the 4e− reduction pathway (ΔG =
−1.95 eV). Similarly, it is also found that the four-electron step
ORR is more advantageous on the Pd7Se4 material, which is
consistent with the experimental results. As for the potential
determination step (PDS), both are the first step (*O2 + H+ +
e− → *OOH). The limiting potentials of Pd17Se15 and Pd7Se4
are 0.94 and 0.81 V, respectively. Compared with Pt (0.79 V),
3810
the ORR activity of Pd17Se15 is much better than that of Pt,
while the activity of Pd7Se4 is equivalent to that of Pt. It could
be concluded that both Pd−Se nanoparticles are excellent
ORR catalysts. To investigate the causes of performance
differences more intuitively, we observe the charge transfer of
these two catalysts. The differential charge densities for *OOH
absorption on Pd sites are shown in Figure 5E,F, revealing that,
in the first step of the protonation process, the surfaces of the
two types of nanoparticles transfer electrons to the *OOH
intermediate. More precisely, the Bader charge analysis (Figure
5E,F) between the surface and the adsorbate presents a charge
transfer of 0.44 e− from the Pd17Se15 surface to the *OOH
intermediate, while for Pd7Se4 it is 0.39 e−. More charge
transfer endows a stronger absorption of the substrate toward
the intermediate. It also explains why the ORR performance of
Pd17Se15 is better than that of Pd7Se4.
■ CONCLUSION
In conclusion, we have successfully developed a facile wet
chemical strategy to selectively prepare Pd−Se NPs with
controlled phases (i.e., Pd17Se15 phase and Pd7Se4 phase) by
simply changing the molar ratio of the precursors. The unique
Pd−Se NPs with controlled phase show the interesting phase-
dependent electrocatalytic performance. Particularly, the
optimized Pd17Se15 NPs/C shows the best ORR performance
with a mass activity of 0.460 A mgPd−1 and specific activity of
1.201 mA cm−2 at 0.9 V versus RHE, which are much higher
than those of the commercial Pd/C, commercial Pt/C, and the
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett
Pd7Se4 NPs/C, and superior ORR durability. Based on the
detailed characterizations, the Pd atoms in the Pd17Se15 phase
could provide a stronger interaction with intermediates
because of the electron deficient state of the Pd atoms. The
DFT simulations further reveal that Pd17Se15 provides more
electrons to the *OOH intermediate in the potential
determination step, which is the reason for the enhancement
of the ORR activity. The present work highlights a new
direction of the phase engineering strategy for designing
efficient electrocatalysts.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.nanolett.1c00147.
Full experimental details and data including TEM
images, SEM-EDS spectra, ICP-AES results, PXRD
patterns, CV curves, ORR mass activities and specific
activities, Tafel plots, ORR polarization curves, H2O2
detection currents at the ring electrode and polarization
curves at the disk electrode, calculated selectivity and
number of transferred electrons of different catalysts,
HRTEM images, and STEM image and STEM-EDS
mappings, CO stripping voltammetry, XPS spectra, and
geometric structures (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Ya-fei Li − School of Chemistry and Materials Science, Nanjing
Normal University, Nanjing 210023, China; orcid.org/
0000-0003-2587-820X; Email: liyafei@njnu.edu.cn
Xiaoqing Huang − State Key Laboratory of Physical
Chemistry of Solid Surfaces, College of Chemistry and
Chemical Engineering, Xiamen University, Xiamen 361005,
China; orcid.org/0000-0003-3219-4316;
Email: hxq006@xmu.edu.cn
Authors
Zhiyong Yu − College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Jiangsu 215123,
China
Shulin Xu − School of Chemistry and Materials Science,
Nanjing Normal University, Nanjing 210023, China
Yonggang Feng − College of Chemistry, Chemical Engineering
and Materials Science, Soochow University, Jiangsu 215123,
China
Chengyong Yang − College of Chemistry, Chemical
Engineering and Materials Science, Soochow University,
Jiangsu 215123, China
Qing Yao − College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Jiangsu 215123,
China
Qi Shao − College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Jiangsu 215123,
China; orcid.org/0000-0002-9858-0458
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.nanolett.1c00147
Author Contributions
X.H. conceived and supervised the research. X.H. and Z.Y.
designed the experiments. X.H., Z.Y., Y.F., C.Y., Q.Y., and Q.S.
performed most of the experiments and data analysis. Y.L. and
3811
Letter
S.X. performed the DFT simulations. X.H. and Z.Y. wrote the
paper. All authors discussed the results and commented on the
manuscript. Z.Y. and S.X. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by Ministry of Science and
Technology (2017YFA0208200, 2016YFA0204100), the Na-
tional Natural Science Foundation of China (22025108),
Natural Science Foundation of Jiangsu Higher Education
Institutions (17KJB150032), the project of scientific and
technologic infrastructure of Suzhou (SZS201708), the
Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD), and the start-up support from
Xiamen University.
■ REFERENCES
(1) Gasteiger, H. A.; Markovic, N. M. Just a dream-or future reality?
Science 2009, 324, 48−49.
(2) Kakati, N.; Maiti, J.; Lee, S. H.; Jee, S. H.; Viswanathan, B.;
Yoon, Y. S. Anode catalysts for direct methanol fuel cells in acidic
media: do we have any alternative for Pt or Pt-Ru? Chem. Rev. 2014,
114, 12397−12429.
(3) Debe, M. K. Electrocatalyst approaches and challenges for
automotive fuel cells. Nature 2012, 486, 43−51.
(4) Steele, B. C. H.; Heinzel, A. Materials for fuel-cell technologies.
Nature 2001, 414, 345−352.
(5) Koenigsmann, C.; Santulli, A. C.; Gong, K.; Vukmirovic, M. B.;
Zhou, W. P.; Sutter, E.; Wong, S. S.; Adzic, R. R. Enhanced
electrocatalytic performance of processed, ultrathin, supported Pd-Pt
core-shell nanowire catalysts for the oxygen reduction reaction. J. Am.
Chem. Soc. 2011, 133, 9783−9795.
(6) Zhu, C.; Du, D.; Eychmuller, A.; Lin, Y. Engineering ordered and
nonordered porous noble metal nanostructures: synthesis, assembly,
and their applications in electrochemistry. Chem. Rev. 2015, 115,
8896−8943.
(7) Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J.;
Lucas, C. A.; Wang, G.; Ross, P. N.; Markovic, N. M. Trends in
electrocatalysis on extended and nanoscale Pt-bimetallic alloy
surfaces. Nat. Mater. 2007, 6, 241−247.
(8) Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G.; Ross, P.
N.; Lucas, C. A.; Marković, N. M. Improved oxygen reduction activity
on Pt3Ni (111) via increased surface site availability. Science 2007,
315, 493−497.
(9) Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T.
P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.;
Nørskov, J. K. Alloys of platinum and early transition metals as oxygen
reduction electrocatalysts. Nat. Chem. 2009, 1, 552−556.
(10) Chen, A.; Ostrom, C. Palladium-based nanomaterials: synthesis
and electrochemical applications. Chem. Rev. 2015, 115, 11999−
12044.
(11) Liu, H.; Manthiram, A. Controlled synthesis and character-
ization of carbon-supported Pd4Co nanoalloy electrocatalysts for
oxygen reduction reaction in fuel cells. Energy Environ. Sci. 2009, 2,
124−132.
(12) Poon, K. C.; Tan, D. C. L.; Vo, T. D.T.; Khezri, B.; Su, H.;
Webster, R. D.; Sato, H. Newly developed stepwise electroless
deposition enables a remarkably facile synthesis of highly active and
stable amorphous Pd nanoparticle electrocatalysts for oxygen
reduction reaction. J. Am. Chem. Soc. 2014, 136, 5217−5220.
(13) Gasteiger, H. A.; Kocha, S. S.; Sompalli, B.; Wagner, F. T.
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt
oxygen reduction catalysts for PEMFCs. Appl. Catal., B 2005, 56, 9−
35.
https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812
Nano Letters pubs.acs.org/NanoLett Letter

(14) Peng, Z.; Yang, H. Designer platinum nanoparticles: Control of non-platinum oxygen reduction electrocatalysts. Sci. Adv. 2018, 4,
shape, composition in alloy, nanostructure and electrocatalytic No. eaap8817.
property. Nano Today 2009, 4, 143−164. (35) Du, C.; Li, P.; Yang, F.; Cheng, G.; Chen, S.; Luo, W.
(15) Wu, G.; More, K. L.; Johnston, C. M.; Zelenay, P. High- Monodisperse palladium sulfide as efficient electrocatalysts for oxygen
performance electrocatalysts for oxygen reduction derived from reduction reaction. ACS Appl. Mater. Interfaces 2018, 10, 753−761.
polyaniline, iron, and cobalt. Science 2011, 332, 443−447. (36) Sarma, S. C.; Vemuri, V.; Mishra, V.; Peter, S. C. Sacrificial
(16) Han, N.; Yang, K. R.; Lu, Z.; Li, Y.; Xu, W.; Gao, T.; Cai, Z.; protection in action!”: ultra-high stability of palladesite mineral
Zhang, Y.; Batista, V. S.; Liu, W.; Sun, X. Nitrogen-doped tungsten towards the oxygen reduction reaction. J. Mater. Chem. A 2019, 7,
carbide nanoarray as an efficient bifunctional electrocatalyst for water 979−984.
splitting in acid. Nat. Commun. 2018, 9, 924.
(17) Tian, N.; Zhou, Z. Y.; Sun, S. G.; Ding, Y.; Wang, Z. L.
Synthesis of tetrahexahedral platinum nanocrystals with high-index
facets and high electro-oxidation activity. Science 2007, 316, 732−735.
(18) Huang, X.; Tang, S.; Mu, X.; Dai, Y.; Chen, G.; Zhou, Z.; Ruan,
F.; Yang, Z.; Zheng, N. Freestanding palladium nanosheets with
plasmonic and catalytic properties. Nat. Nanotechnol. 2011, 6, 28−32.
(19) Chen, M.; Wu, B.; Yang, J.; Zheng, N. Small Adsorbate-Assisted
shape control of Pd and Pt nanocrystals. Adv. Mater. 2012, 24, 862−
879.
(20) Zhang, Z. C.; Xu, B.; Wang, X. Engineering nanointerfaces for
nanocatalysis. Chem. Soc. Rev. 2014, 43, 7870−7886.
(21) Kim, J.; Lee, Y.; Sun, S. Structurally ordered FePt nanoparticles
and their enhanced catalysis for oxygen reduction reaction. J. Am.
Chem. Soc. 2010, 132, 4996−4997.
(22) Sun, S.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A.
Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal
superlattices. Science 2000, 287, 1989−1992.
(23) Cui, Z.; Li, L.; Manthiram, A.; Goodenough, J. B. Enhanced
cycling stability of hybrid Li-air batteries enabled by ordered Pd3Fe
intermetallic electrocatalyst. J. Am. Chem. Soc. 2015, 137, 7278−7281.
(24) Wang, D.; Xin, H. L.; Hovden, R.; Wang, H.; Yu, Y.; Muller, D.
A.; DiSalvo, F. J.; Abruna, H. D. Structurally ordered intermetallic
platinum-cobalt core-shell nanoparticles with enhanced activity and
stability as oxygen reduction electrocatalysts. Nat. Mater. 2013, 12,
81−87.
(25) Wang, D.; Yu, Y.; Xin, H. L.; Hovden, R.; Ercius, P.; Mundy, J.
A.; Chen, H.; Richard, J. H.; Muller, D. A.; DiSalvo, F. J.; Abruna, H.
D. Tuning oxygen reduction reaction activity via controllable
dealloying: a model study of ordered Cu3Pt/C intermetallic
nanocatalysts. Nano Lett. 2012, 12, 5230−5238.
(26) Peng, X.; Peng, L.; Wu, C.; Xie, Y. Two dimensional
nanomaterials for flexible supercapacitors. Chem. Soc. Rev. 2014, 43,
3303−3323.
(27) Hou, Y.; Wang, D.; Yang, X. H.; Fang, W. Q.; Zhang, B.; Wang,
H. F.; Lu, G. Z.; Hu, P.; Zhao, H. J.; Yang, H. G. Rational screening
low-cost counter electrodes for dye-sensitized solar cells. Nat.
Commun. 2013, 4, 1583.
(28) Singh, V. V.; Rao, G. K.; Kumar, A.; Singh, A. K. Palladium (ii)-
selenoether complexes as new single source precursors: First synthesis
of Pd4Se and Pd7Se4 nanoparticles. Dalton Trans. 2012, 41, 1142−
1145.
(29) Dey, S.; Jain, V. K. Platinum Group Metal Chalcogenides.
Platinum Metals Review 2004, 48, 16−28.
(30) Geller, S. The crystal structure of Pd17Se15. Acta Crystallogr.
1962, 15, 713−721.
(31) Kukunuri, S.; Naik, K.; Sampath, S. Effects of composition and
nanostructuring of palladium selenide phases, Pd4Se, Pd7Se4 and
Pd17Se15, on ORR activity and their use in Mg-air batteries. J. Mater.
Chem. A 2017, 5, 4660−4670.
(32) Hong, J. W.; Kim, Y.; Wi, D. H.; Lee, S.; Lee, S. U.; Lee, Y. W.;
Choi, S. I.; Han, S. W. Ultrathin free-standing ternary-alloy
nanosheets. Angew. Chem., Int. Ed. 2016, 55, 2753−2758.
(33) Dai, Y.; Mu, X.; Tan, Y.; Lin, K.; Yang, Z.; Zheng, N.; Fu, G.
Carbon monoxide-assisted synthesis of single-crystalline Pd tetrapod
nanocrystals through hydride formation. J. Am. Chem. Soc. 2012, 134,
7073−7080.
(34) Feng, Y.; Shao, Q.; Ji, Y.; Cui, X.; Li, Y.; Zhu, X.; Huang, X.
Surface-modulated palladium-nickel icosahedra as high-performance

3812 https://doi.org/10.1021/acs.nanolett.1c00147
Nano Lett. 2021, 21, 3805−3812