Article

Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX pubs.acs.org/JACS

Ultrasmall Abundant Metal-Based Clusters as Oxygen-Evolving

Catalysts
Xin-Bao Han,†,# Xing-Yan Tang,†,# Yue Lin,‡,# Eduardo Gracia-Espino,∥ San-Gui Liu,†
Hai-Wei Liang,§ Guang-Zhi Hu,∥,⊥ Xin-Jing Zhao,† Hong-Gang Liao,† Yuan-Zhi Tan,*,†
Thomas Wagberg,*,∥ Su-Yuan Xie,† and Lan-Sun Zheng†
†
State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen, 361005, China
‡
Hefei National Laboratory for Physical Sciences at the Microscale and §Department of Chemistry, University of Science and
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Technology of China, Hefei 230026, P. R. China

∥
Department of Physics, Umeå University, Umeå 90187, Sweden
⊥
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Key Laboratory of Chemistry of Plant Resources in Arid Regions, State Key Laboratory Basis of Xinjiang Indigenous Medicinal
Plants Resource Utilization, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011,
China
*
S Supporting Information

ABSTRACT: The oxygen evolution reaction is a crucial step in water

electrolysis to develop clean and renewable energy. Although noble metal-
based catalysts have demonstrated high activity for the oxygen evolution
reaction, their application is limited by their high cost and low availability.
Here we report the use of a molecule-to-cluster strategy for preparing
ultrasmall trimetallic clusters by using the polyoxometalate molecule as a
precursor. Ultrafine (0.8 nm) transition-metal clusters with controllable
chemical composition are obtained. The transition-metal clusters enable
highly efficient oxygen evolution through water electrolysis in alkaline media,
manifested by an overpotential of 192 mV at 10 mA cm−2, a low Tafel slope of
36 mV dec−1, and long-term stability for 30 h of electrolysis. We note,
however, that besides the excellent performance as an oxygen evolution catalyst, our molecule-to-cluster strategy provides a
means to achieve well-defined transition-metal clusters in the subnanometer regime, which potentially can have an impact on
several other applications.

■ INTRODUCTION
Electrocatalytic water splitting is widely considered to be a
promising and sustainable approach to the production of clean
H2 fuel and O2.1−3 Water oxidation, represented by the half-
reaction 2H2O → 4H+ + 4e− + O2, constitutes a kinetic
bottleneck in water splitting.4,5 Therefore, the development of
highly efficient water oxidation catalysts is crucial in the
renewable energy field.6−8 Noble-metal catalysts such as
iridium and ruthenium oxides are the highly efficient oxygen
evolution reaction (OER) electrocatalysts in acidic media but
suffer from high-cost and relative scarcity9 and also require a
substantial overpotential to reach the desired current density of
≥10 mA cm−2 for OER in alkaline media.10 In alkaline media,
on the other hand, a number of research groups have
demonstrated the use of earth-abundant transition-metal
(TM)-based catalysts, including oxides,11,12 oxyhydroxides,13
borides,14 phosphides,15,16 and molecular complexes,17,18 but
there is still room for significant improvement in OER systems
to obtain good energy efficiency and cost effectiveness in the
alkaline electrolysis systems. More importantly, these studies
suggested that the catalyst size and composition play crucial
roles in governing their OER activities. Small metal clusters,
with controlled composition and size, have, however, proven to
be particularly difficult to synthesize and stabilize. Herein we
report a novel and efficient synthesis of transition-metal
clusters (TMCs) from well-defined polyoxometalate (POM)
molecule precursors via a molecule-to-cluster strategy. The
prepared TMCs are characterized by their ultrafine size (0.8 ±
0.2 nm) and tunable chemical composition, all of which were
inherited from their parent POMs. Our experimental and
theoretical results demonstrate that well-defined Fe-doping of
POMs allow us to precisely modulate the chemical
compositions of the corresponding TMCs, resulting in a
significant enhancement of their OER activities. The best
TMC catalyst exhibited an overpotential of 192 mV at a
current density of 10 mA cm−2, had a low Tafel slope of 36 mV
dec−1, and was shown to remain stable for 6000 cyclic
voltammetry (CV) cycles and 30 h of electrolysis. The
molecule-to-cluster approach applied here could serve as a
Received: August 23, 2018
Published: December 12, 2018

© XXXX American Chemical Society A DOI: 10.1021/jacs.8b09076

J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
general and effective strategy for establishing ultrasmall TM
clusters where practically all atoms reside at the surface and
therefore are tunable for high-efficiency oxygen evolution and
other important electrocatalytic reactions.
■ RESULTS AND DISCUSSION
Synthesis of TMCs. A schematic view of catalyst
preparation is presented in Figure 1a−d. The self-assembly
Figure 1. Schematic illustration of synthesizing the TMCs. (a) Ball
representation of the structure of POMs 1−3. (b) Self-assembly of
POMs and EDA-C60 by electrostatic interaction. (c) Schematic
structure of the POMs/EDA-C60 composites after freeze-drying. (d)
TMC catalysts on a carbonic support. O, gray; Co/Fe, violet; W, red;
and P, yellow.
of [{Co4(OH)3PO4}4(SiW9O34)4]32− (POM 1) (Figure 1a and
Figure S1a,b in Supporting Information (SI)) and ethylenedi-
amine-grafted C60 (EDA-C60), driven by electrostatic inter-
action, resulted in the formation of POM 1/EDA-C60 hybrid
composites (Figure 1b). Images obtained by in situ liquid cell
transmission electron microscopy (TEM)19,20 showed that the
composites contained discrete POMs (Figure 2a), suggesting
that a satisfactory encapsulation of POMs by EDA-C60 is
achieved, ultimately preventing self-aggregation. Similarly,
TEM imaging of freeze-dried hybrid composites provided
additional visual evidence for the embedding of discrete POMs
in the EDA-C60 matrix (Figure S2, Supporting Information).
We speculate that the spatial confinement and single-
molecule dispersion of POMs in the EDA-C60 matrix favor the
formation of TMCs during thermal annealing. Indeed,
annealing of the hybrid composite under a 5% H2/Ar
atmosphere for 3 h at 900 °C led to the transformation of
the embedded POMs into TMCs and the formation of a
carbonic support from EDA-C60 (Figure 1d). The resulting
material was labeled 1-CoW.
The morphology of 1-CoW was studied by scanning
electron microscopy (SEM) and TEM. The SEM image of
1-CoW showed curved sheets with few visible nanoparticles on
the surfaces (Figure 2b) which was consistent with the TEM
image (Figure 2c). In contrast, abundant clusters were
observed to spread over the carbonic supports in images
generated by TEM (Figure 2d) and high-angle annular dark-
field scanning transmission electron microscopy (HAADF-
STEM) (Figure 2e,f and Figure S3 in Supporting Information).
The size distribution of the clusters was in the range of 0.6 to
3.0 nm, with a mean diameter of 0.8 nm (Figure 2f, inset).
B DOI: 10.1021/jacs.8b09076
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Moreover, HAADF-STEM imaging of the clusters demon-
strated a clear speckle pattern (Figure 2e,f). The speckle
pattern is created by the positive correlation of the spot
brightness in HAADF-STEM images and the atomic number
of the visualized atoms,21,22 indicating a well-mixed W−Co
system seen as contiguous brighter and dimmer spots,
respectively. These results are also supported by our theoretical
simulations where W−Co clusters in the range of 0.7−0.9 nm
exhibit a chemical order parameter that is close to zero,
meaning that no significant segregation is observed.23
Furthermore, STEM-coupled energy-dispersive X-ray spectros-
copy (STEM-EDXS) elemental mapping of 1-CoW (Figure
2g) also showed that Co and W were homogeneously
distributed on the carbonic support. It is noteworthy to
indicate that such small TMCs (0.8 nm) have ∼90% of the
atoms located at the surface and are significantly under-
coordinated (Tables S1 and S2), indicating that they are
feasibly surface-passivated by O/OH as suggested by DFT,
discussed later. We therefore suggest that the catalytically
active sites of TMCs are closely related to metal oxy-
hydroxides, in agreement with previous studies,24−26 which is
also confirmed by the X-ray photoelectron spectroscopy (XPS)
analysis of the chemical valence of Co, Fe, W, and O atoms in
TMCs (Figures S4−S7, Supporting Information).
OER Performance of 1-CoW. The OER performance of
the carbon-supported TMCs was compared to that of IrO2 by
using a typical three-electrode system in 1 M KOH solution at
a scan rate of 5 mV s−1. Linear sweep voltammetry (LSV) was
employed to obtain the polarization curves of the electrode. All
potentials were calibrated in reference to the reversible
hydrogen electrode (RHE). Before measurements, the as-
prepared electrodes were repeatedly swept in the electrolyte
until a steady voltammogram curve was obtained, and in this
process, the TMCs would be oxidized. Each catalyst was
coated onto carbon cloth at a density of 0.64 mg cm−2, and the
generated OER currents were measured. As shown in Figure
3a, 1-CoW produced a small overpotential of 240 mV at a
current density of 10 mA cm−2 (Table 1, all current densities
were based on the projected geometric area), which was much
smaller than that of IrO2 (305 mV) under the same conditions.
Enhancing OER Performance by Fe Doping. Doping
additional elements into metallic nanoparticles has proven to
be an effective strategy for enhancing the performance of
metallic catalysts.24,27,28 The molecule-to-cluster protocol
enabled convenient chemical doping of TMCs by modifying
the structure of the POM precursors. By this strategy, we
synthesized POM 2 [{Fe2Co2(OH)3PO4}4(SiW9O34)4]24− and
POM 3 [{FeCo3(OH)3PO4}4(SiW9O34)4]28− (Figure S1,
Supporting Information) by doping POM 1 in situ with
different amounts of Fe. POM 2 and POM 3 were shown by
single-crystal X-ray crystallography to share structures almost
identical to that of POM 1, albeit with different extents of Co
displacement with Fe. We then generated two differently Fe-
doped TMCs on a carbon support, designated as 2-CoFeW
and 3-CoFeW, from POM 2 and POM 3 by the same synthesis
route as that for 1-CoW, respectively. As expected, both 2-
CoFeW and 3-CoFeW were shown by X-ray diffraction (XRD)
patterns, SEM, TEM, and STEM-HAADF characterizations
(Figures S8−S11, Supporting Information) to share morphol-
ogies similar to that of 1-CoW and were confirmed by STEM-
EDXS elemental mapping to be uniformly doped with Fe
(Figure S12, Supporting Information).
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
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Figure 2. Morphology of TMCs on a carbonic support. (a) In-situ liquid cell TEM image of the solution in which POM 1 self-assembles with EDA-
C60. (b) SEM image of 1-CoW. (c and d) TEM images of 1-CoW. (e and f) HAADF-STEM images of 1-CoW showing nanoparticle speckling of
TMCs. The inset image in f illustrates the corresponding size distribution of the TMCs in 1-CoW. (g) HAADF-STEM image and STEM-EDXS
element mapping of 1-CoW.

Both 2-CoFeW and 3-CoFeW showed that the OER
overpotentials decreased by 16 and 35 mV, respectively, at a
current density of 10 mA cm−2 when compared with 1-CoW.
This demonstrated that well-balanced Fe doping could
improve the catalytic performance of the corresponding
TMCs (Figure 3a and Table 1), but it is noteworthy that
the Fe ratio in 2-CoFeW already is “on the down slope” of
OER activity, as manifested by an overpotential of 224 mV at
10 mA cm−2 (19 mV higher than that of 3-CoFeW). This
behavior matches the observations in our DFT studies where
an Fe content that is too high leads to an adsorption energy of
O-intermediates that is too high and thereby an increase in the
overall OER overpotential. In addition, insight into the kinetic
behaviors of all TMC catalysts in OERs was obtained by
analyzing their Tafel slope. As such, the superior OER
performance of 3-CoFeW was supported by its smaller Tafel
slope (38 mV dec−1, Figure 3b) compared to those of 1-CoW
(53 mV dec−1) and 2-CoFeW (43 mV dec−1). The turnover
frequency (TOF) was also calculated at an overpotential of
250 mV in 1 M KOH solution, assuming that all of the Co and
Fe atoms account for the catalytic activity of the OER (Table
S3, Supporting Information). 3-CoFeW has a larger TOF of
0.377 s−1 compared to 0.114 and 0.259 s−1 for 1-CoW and 2-
CoFeW (Table S4, Supporting Information), respectively.
Taken together, these data lent credence to the critical
C DOI: 10.1021/jacs.8b09076
importance of fine tuning the chemical composition of the
TMC to improve its catalytic performance in OERs.
Substrate Influence on OER Performance. To assess
the effect of the substrate on the catalytic efficiency of the
electrode, we loaded the carbon-supported TMC catalysts at a
density of 0.64 mg cm−2 onto gold foam (a nickel foam that
was covered with gold to avoid any spurious effects arising
from the interaction of the catalyst with Ni), which has a
greater conductivity than carbon cloth. This switch in the
substrate significantly boosted the catalytic activities of all
three TMCs without affecting the beneficial impact of Fe
doping (Figure 3c). Specifically, 3-CoFeW had a remarkably
low overpotential of 192 mV at 10 mA cm−2 on the gold foam
(Table 1). The enhanced conductivity of the substrate also led
to a substantial improvement in the OER kinetics, as evidenced
by the decrease in the Tafel slope for all three catalysts (Figure
3d).
In addition, electrochemical impedance spectroscopy (EIS)
of different samples was performed to provide further insight
into the electrode kinetics within the OER process. As shown
in Figure S13 and Table S5 in the Supporting Information, the
solution resistance (Rs) values of 1-CoW, 2-CoFeW, and 3-
CoFeW coated on gold foam are similar, while the charge-
transfer resistance (Rct) of 3-CoFeW coated on gold foam
fitted according to the high-frequency semicircle was only 0.93
Ω, which is smaller than for 1-CoW (2.2 Ω) and 2-CoFeW
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
Figure 3. OER polarization curves of catalysts loaded on (a) carbon cloth or (c) gold foam at a scan rate of 5 mV s−1, without iR correction. Tafel
plots for different catalysts loaded on (b) carbon cloth or (d) gold foam in 1 M KOH solution.
Table 1. Comparison of Electrocatalytic Activity at a
Current Density of 10 mA cm−2
on carbon cloth on gold foam
samples overpotential/mV overpotential/mV
1-CoW 240 (±5) 222 (±3)
2-CoFeW 224 (±3) 205 (±2)
3-CoFeW 205 (±3) 192 (±2)
IrO2 305 (±4)
(1.4 Ω). Such a low Rct value of 3-CoFeW suggested faster
charge transfer kinetics compared to those of 1-CoW and 2-
CoFeW. When 3-CoFeW was coated on carbon cloth, Rs and
Rct skyrocketed from 2.4 to 5.2 Ω and 0.93 to 9.9 Ω,
respectively, which was consistent with the disparity in catalytic
activity on different substrates.
Stability. We next evaluated the electrochemical stability of
the carbon-supported TMC catalysts by long-term cycling. We
first ran water oxidation on the catalyst deposited on carbon
cloth (Figure 4a) and gold foam (Figure 4b) under a long-term
cycling test in 1 M KOH solution. Gratifyingly, the OER
polarization curve of 3-CoFeW remained almost unchanged
throughout the experiment and exhibited a negligible potential
change at 10 mA cm−2 after 6000 CV cycles, despite the
relatively harsh experimental conditions. Chronoamperometric
responses (i−t) of 3-CoFeW coated on carbon cloth (Figure
4c) and gold foam (Figure 4d) retained their activity for 30 h
of long-term electrolysis. The STEM-HAADF and high-
resolution transmission electron microscope (HRTEM)
images of 3-CoFeW after the OER were found to be largely
identical to those of the freshly synthesized catalyst (Figures
S14 and S15, Supporting Information). In addition, XRD
(Figure S16) measurements of catalysts showed almost no
change before and after the long-term OER test. Finally, we
performed the inductively coupled plasma mass spectrometry
D DOI: 10.1021/jacs.8b09076
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(ICP-MS) measurements of the three catalysts to detect the
amount of Co, Fe, or W of the reaction solution after a long-
term cycling test. The data of ICP-MS indicated that there is
less than 0.56% of W; 2.0% of Fe and 1.3% of Co may leach
out of the catalyst (Table S6, Supporting Information). The
enhanced operational stability of such small clusters can be
attributed to the large cohesive energy of tungsten as well as
the strength of the W−C bond probably found at the cluster−
carbonic substrate interface, and similar results have been
observed for PdW/C systems.29 These results revealed the
good electrochemical stability of the TMC catalysts. Although
OER catalysts supported on carbonic supports are widely used
for fundamental study,30−34 it is worth noting that carbonic
supports suffer from carbon corrosion for practical application
under prolonged anodic bias in an alkaline electrolyzer.35,36 We
are continuing our efforts to prepare TMC catalysts supported
on more stable supports for practical applications.
Theoretical Description of the OER. The catalytic
activity of CoFeW clusters was also investigated by DFT.
Three different clusters sizes were prepared by a modified
basin-hopping Monte Carlo (BHMC) method with average
diameters of 0.7, 0.8, and 0.9 nm and chemical compositions of
W13Co16, W23Co16, and W36Co16, respectively (Figures S17
and S18, Supporting Information). The resulting clusters
exhibited an average coordination number of ∼7.2, irrespective
of the particle size. Interestingly, the addition of Fe does not
have a significant effect on the average coordination number.
However, the individual coordination number of Co is
increased in the presence of Fe (Table S2, Supporting
Information), suggesting a Co migration to the cluster core,
which in a 0.8 nm particle corresponds to ∼4 atoms, while Fe
is more often found at the surface. In any case, the severe
undercoordination results in large adsorption energies for OER
intermediates (*O, *OH, and *OOH) degrading the catalytic
activity, but it also indicates the feasibility of forming an
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society Article

Figure 4. Polarization curves of 3-CoFeW loaded on (a) carbon cloth and (b) gold foam before and after 6000 potential cycles in 1 M KOH
solution. Chronoamperometric responses (i−t) of 3-CoFeW coated on (c) carbon cloth and (d) gold foam for 30 h at a constant applied potential
of 1.46 V versus RHE for OER.

oxyhydroxide surface layer and is confirmed by the XPS

analysis of Co, Fe, W, and O atoms in TMCs (Figures S4−S7,
Supporting Information).
The OER activity was investigated only on clusters with an
average diameter of 0.8 nm because these were the most
abundant experimentally. The clusters were initially passivated
with hydroxyl groups until the changes in free energy were
zero. During the passivation process, several water molecules
were formed and removed from the system, resulting in an
OH/O surface passivation (Figure S7, Supporting Informa-
tion) with ratios of 4.2, 4.9, and 6.0 and final compositions of
W23Co16O9(OH)38, W23Co12Fe4O8(OH)39, and
W23Fe16O7(OH)42, respectively. The differences in the OH/ Figure 5. Theoretical catalytic activity for metal oxyhydroxide
O ratio already show the stronger interaction that Fe exhibits clusters. OER activity volcano plot for W23CowFexOy(OH)z clusters.
over the hydroxyl groups compared to a weaker OH
interaction when only Co atoms are present. The catalytic W23Co12Fe4O8(OH)39 cluster. However, we did notice differ-
activity was investigated using the four-electron reaction ences when considering the coordination environment, and
pathway37 and the free-energy difference between the *O those Fe/Co atoms with complete octahedral coordination
and *OH intermediate (ΔGO − ΔGOH) as a universal exhibit the lowest ηOER irrespective of the neighbors’ type.
descriptor.37,38 The latter results in a volcano-like plot such Similar results were observed when using a different set of
as the one seen in Figure 5, where the highest OER activity is atomic models constructed using the γ-FeOOH framework
expected for those materials with a free-energy difference of instead of the BHMC method (W 20 Co 16 O 30 (OH) 51 ,
ΔGO − ΔGOH = 1.6 eV, while those at a lower or higher energy W20Co12Fe4O33(OH)44, and W20Fe16O30(OH)51). See Figures
difference will exhibit a lower OER activity. In our case, the S19 and S20 in Supporting Information for further details. Our
clusters are mostly asymmetric with a large variety of active results are in line with previous publications where CoOOH
sites with diverse OER activity. As seen in Figure 5, all three exhibit a weak interaction with oxygenated species, whereas it
clusters exhibit sites with high activity reflecting the perform- is too strong on FeOOH;24 therefore, a combination of these
ance seen experimentally. However, it can be seen that two ultimately results in a material with an optimal adsorption
W23Co16O9(OH)38 favors weak adsorption energies seen as energy.
ΔGO − ΔGOH > 1.6 eV, with the best site having ηOER = 0.45
V, while W23Fe16O7(OH)42 tends toward a higher adsorption
energy with ΔGO − ΔGOH < 1.6 eV and the lowest is ηOER =
■ CONCLUSIONS
A series of carbon-supported TMCs have been successfully
0.39 V. Trimetallic W23Co12Fe4O8(OH)39 mostly lies around prepared by a molecule-to-cluster strategy and employed as
ΔGO − ΔGOH = 1.6 eV with an optimum ηOER of 0.37 V. It is electrocatalysts for OER in 1 M KOH. These catalysts
noteworthy to mention that we did not observe any significant exhibited high electrocatalytic activity and long-term catalytic
difference between Co and Fe in the mixed stability. In particularly, 3-CoFeW generated a an overpotential
E DOI: 10.1021/jacs.8b09076
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
of 192 mV at a current density of 10 mA cm−2 when loaded on
gold foam as the working electrode, making it one of the most
active OER catalysts reported to date. Even more importantly,
our molecule-to-cluster strategy presented here provides a
unique approach to fine tuning the catalytic properties of
ultrafine clusters by selective and controlled surface doping to
address the adsorption properties of reaction intermediates at
the surface of the TM clusters. We note that our approach has
implications far beyond oxygen evolution reactions.
■
EXPERIMENTAL SECTION
Materials and Methods. All reagents and solvents were used of
commercial grade, without further purification. The SEM images were
obtained on a Hitachi S-4800 scanning electron microscope at an
accelerating voltage of 15 kV. TEM and HAADF-STEM images were
collected on a JEOL ARM-200F field-emission transmission electron
microscope operating at a 200 kV accelerating voltage. STEM-EDXS
images were collected on a Titan Themis transmission electron
microscope (FEI). The in situ TEM observation was carried out using
an FEI Tecnai F20 transmission electron microscopy with a CMOS-
based TemCam-XF416 camera (TVIPS GmbH, Germany).
Synthesis of POM 1. POM 1 was synthesized according to a
previously described method.39 Briefly, CoCl2·6H2O (0.78 g, 3.26
mmol) was dissolved in 40 mL of distilled water, followed by the
addition of Na10[α-SiW9O34]·18H2O40 (1.18 g, 0.40 mmol). The
reaction mixture was stirred until a clear purple solution was obtained.
Na3PO4·12H2O (0.60 g, 1.58 mmol) was then added, and the pH was
maintained in the range of 8.5−9.0 with 1.0 M KOH(aq). The
resultant turbid solution was stirred for 3 h at room temperature, and
the purple precipitate was removed by filtration. The obtained filtrate
was subsequently mixed with 5 mL of 1.0 M KCl solution, stirred for
another 30 min, and filtered into a 50 mL beaker to allow slow
evaporation at room temperature for 1 week, resulting in the
precipitation of 1 as dark-purple crystals. The crystalline product was
collected by filtration, washed with cold water, and air dried.
Synthesis of POM 2. CoCl2·6H2O (0.18 g, 0.75 mmol) and
Fe(NO3)3·9H2O (0.34 g, 0.84 mmol) were dissolved in 50 mL of
distilled water. Na10[α-SiW9O34]·18H2O (1.18 g, 0.40 mmol) was
then added, and the mixture was stirred for 15 min. Next, Na3PO4·
12H2O (0.60 g, 1.58 mmol) was added, and the pH was maintained in
the range of 8.0−8.5 with 1.0 M NaOH(aq). The resultant turbid
solution was stirred for 2 h at 80 °C, and the precipitate was removed
by filtration. The obtained filtrate was subsequently mixed with 5 mL
of 1.0 M NaCl solution, stirred for another 30 min, and transferred to
a 100 mL beaker to allow slow evaporation at room temperature over
1 or 2 weeks. Eventually, product 2 precipitated as light-brown
crystals, which were washed with cold water and air dried. Overall,
239 mg of 2 was obtained, and the yield was calculated to be 19.35%.
Anal. Calcd (%): Na, 4.68; Fe, 3.80; Co, 4.00; W, 56.15. Found: Na,
4.76; Fe,3.73; Co, 3.92; W, 56.41.
Synthesis of POM 3. CoCl2·6H2O (0.36 g, 1.51 mmol) and
Fe(NO3)3·9H2O (0.23 g, 0.57 mmol) were dissolved in 50 mL of
distilled water. Na10[α-SiW9O34]·18H2O (1.18 g, 0.40 mmol) was
then added, and the mixture was stirred for 15 min. Next, Na3PO4·
12H2O (0.60 g, 1.58 mmol) was added, and the pH was maintained in
the range of 8.0−8.5 with 1.0 M NaOH(aq). The resultant turbid
solution was stirred for 2 h at 80 °C, and the precipitate was removed
by filtration. The obtained filtrate was mixed with 5 mL of a 1.0 M
NaCl solution, stirred for another 30 min, and subsequently
transferred to a 100 mL beaker to allow slow evaporation at room
temperature over 1 or 2 weeks. Product 3 precipitated as reddish-
brown crystals, which were washed with cold water and air dried.
Overall, 201 mg of 3 was obtained, and the yield was calculated to be
16.27%. Anal. Calcd (%): Na, 5.38; Fe, 1.87; Co, 5.91; W, 55.24.
Found: Na, 5.45; Fe,1.82; Co, 5.78; W, 55.49.
Synthesis of EDA-C60. EDA-C60 was synthesized by a modified
method.41,42 Typically, C60 (500 mg) and freshly distilled EDA (500
mL) were added to a three-necked flask and stirred in an oil bath for 4
F DOI: 10.1021/jacs.8b09076
Article
days at 80 °C under an Ar atmosphere. The excess EDA was removed
from the crude reaction mixture by rotary evaporation, followed by
the addition of 10 mL of deionized H2O to dissolve the residuals. The
target product was precipitated by adding 500 mL of acetone, washed
several times with acetone, vacuum filtered, and then dried at 60 °C
overnight.
Synthesis of the TMCs Catalysts. EDA-C60 (6 mL, 5 mg·mL−1)
was added to a 150 mL beaker and further diluted with distilled water
to a final concentration of 0.5 mg·mL−1. The solution was vigorously
stirred, and its pH was recorded to be 3.57. Next, POM 1 (20 mL, 0.5
mg·mL−1) was added dropwise. The resultant solution was vigorously
stirred for 1 h at room temperature and further ultrasonicated for 30
min. The 1-CoW catalyst was obtained by freeze drying the reaction
solution and then annealing under a 5% H2/Ar atmosphere for 3 h at
900 °C. The preparation of 2-CoFeW and 3-CoFeW followed a
similar protocol to that of 1-CoW except that different starting
materials were used. Specifically, 20 mL of 0.5 mg·mL−1 POM 2 and
POM 3 was used in place of POM 1 for the syntheses of 2-CoFeW
and 3-CoFeW, respectively.
X-ray Structural Analysis. Single-crystal data sets and unit cells
were collected on an Agilent Super Nova X-ray single-crystal
diffractometer using Cu Kα (λ = 1.54184 Å) microfocus X-ray
sources at 100 K. The structures of POM 2 and POM 3 were solved
by the direct method and refined by the full-matrix least-squares
method on F2 using the SHELX-2014 crystallographic software
package.43,44 The crystal data and structure refinements for POM 2
and POM 3 is shown in Table S7 in Supporting Infromation.
Theoretical Calculations. Ab initio calculations were performed
by means of density functional theory as implemented in the Siesta
code.45 The generalized gradient approximation and the revised
model of Perdew, Burke, and Ernzerhof46 were used to describe the
exchange and correlation functional. The valence electrons are
represented by a linear combination of pseudoatomic numerical
orbitals using a double-ζ polarized basis. An energy cutoff of 250 Ry
was used for the charge and potential integration in real space. The
Co/Fe content of W−Co and W−Fe−Co clusters was selected to
emulate precursors POM 1 and POM 3. Additional W−Fe clusters
were built to study the extreme case where all Co atoms have been
replaced by Fe. The particle size was adjusted by varying the W
content until average diameters of 7, 8, and 9 Å were obtained,
resulting in W13Co16, W23Co16, and W36Co16 clusters, respectively. A
modified BHMC method was used to find an energetically favorable
atomic configuration.47 In brief, an initial structure was randomly
created and geometrically optimized using the conjugate gradient
method, and then the positions of two atoms with different chemical
elements were randomly swapped, followed by a geometrical
optimization. A total of 80 Monte Carlo steps were carried out, and
the lowest-energy configuration was used for the OER study. A
thermal energy kBT of 0.2 eV was used as the criterion for accepting
or rejecting a configuration. Finally, the optimized clusters were
passivated with hydroxyl groups until the change in free energy was
zero, and any created water molecule was removed from the system.
The final OH/O ratio was 4.2, 4.9, and 6.0 for W23Co16, W23Co12Fe4,
and W23Fe16, respectively.
The catalytic activity was studied using the computational
hydrogen-electrode model48 by setting the reference potential equal
to the standard hydrogen electrode. In this way, the chemical
potential of a proton−electron pair (H+ + e−) in solution is equal to
half of the chemical potential of a gas-phase H2 molecule. Under these
conditions, the explicit treatment of solvated protons is avoided. The
adsorption free energy is calculated to be ΔG(i) = ΔE(i) + ΔZPE(i) −
TΔS(i), where ΔE(i) is the adsorption energy of intermediate i
evaluated using H2 and H2O as reference states.49 ΔZPE is the change
in zero-point energies, T is the temperature (298.15 K), and ΔS is the
change in entropy, with values taken from ref 48. The oxygen
adsorption energy was estimated by using the scaling relation for
transition-metal oxides given by ΔEOH = 0.55ΔEO − 0.48 in eV.38
The universal descriptor, (ΔGO − ΔGOH), for transition metals and
OER was used to calculate the theoretical overpotential (ηtheory),
where under standard conditions the overpotential is calculated to be
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
ηtheory = {max[(ΔGO − ΔGOH), 3.2 eV − (ΔGO − ΔGOH)]/e} − 1.23
V.37
■ ASSOCIATED CONTENT
* Supporting Information
S
These materials are available free of charge via the Internet at
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.8b09076.
X-ray crystallography, supplementary figures and tables,
and IR spectra (PDF)
Co8Fe8Na13O233P4Si4W36 (CIF)
C8Co12Fe4Na19O232P4Si4W36 (CIF)
■
AUTHOR INFORMATION
Corresponding Authors
*yuanzhi_tan@xmu.edu.cn.
*thomas.wagberg@physics.umu.se
ORCID
Yue Lin: 0000-0001-5333-511X
Eduardo Gracia-Espino: 0000-0001-9239-0541
Thomas Wagberg: 0000-0002-5080-8273
Author Contributions
# 550−557.
These authors contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21771155, 21721001, and 11874334),
the Ministry of Science and Technology of China
(2014CB845603 and 2017YFA0204902), and Anhui Provin-
cial Natural Science Foundation (1708085MA06). E.G.-E.
acknowledges the Carl Tryggers Foundation (CTS-16-161) for
financial support. The theoretical simulations were performed
on resources provided by the Swedish National Infrastructure
for Computing (SNIC) at the High Performance Computing
Center North (HPC2N). Dr. Dong-Fei Lu, Dr. Yu-Hui Luo,
Prof. Xin-Long Wang, and Prof. Da-Qi Wang are gratefully
acknowledged for their help during the refinement of the X-ray
crystal structures.
■
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H DOI: 10.1021/jacs.8b09076
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX