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Hollow Multivoid Nanocuboids Derived from Ternary

Ni–Co–Fe Prussian Blue Analog for Dual-Electrocatalysis
of Oxygen and Hydrogen Evolution Reactions
Wook Ahn, Moon Gyu Park, Dong Un Lee, Min Ho Seo, Gaopeng Jiang,
Zachary P. Cano, Fathy Mohamed Hassan, and Zhongwei Chen*

1. Introduction
Hydrogen generation from electrochemical water-splitting is an attractive
technology for clean and efficient energy conversion and storage, but it Rapidly increasing international devel-
requires efficient and robust non-noble electrocatalysts for hydrogen and opment of renewable and green energy
sources has drawn widespread atten-
oxygen evolution reactions (HER and OER). Nonprecious transition metal–
tion of researchers to water-splitting
organic frameworks (MOFs) are one of the most promising precursors for oxygen and hydrogen production via the
developing advanced functional catalysts with high porosity and structural electrochemical oxygen evolution reac-
rigidity. Herein, a new transition metal-based hollow multivoid nanocuboidal tion (OER) and hydrogen evolution reac-
catalyst synthesized from a ternary Ni–Co–Fe (NCF)-MOF precursor is tion (HER), respectively.[1–3] To enhance
rationally designed to produce dual-functionality toward OER and HER. these reactions to commercially viable
rates, however, high-performance elec-
Differing ion exchanging rates of the ternary transition metals within the trocatalysts are required to overcome
prussian blue analog MOF precursor are exploited to produce interconnected the activation energies associated with
internal voids, heteroatom doping, and a favorably tuned electronic structure. OER and HER.[4–8] Platinum (Pt) and
This design strategy significantly increases active surface area and pathways iridium (Ir) based materials are cur-
for mass transport, resulting in excellent electroactivities toward OER and rently known to exhibit the highest HER
and OER activities, respectively; however,
HER, which are competitive with recently reported single-function nonprecious
their scarcity and lack of stability have
catalysts. Moreover, outstanding electrochemical durability is realized due made them difficult to be introduced in
to the unique rigid and interconnected porous structure which considerably large-scale energy conversion and storage
retains initial rapid charge transfer and mass transport of active species. The applications. Therefore, development of
MOF-based material design strategy demonstrated here exemplifies a novel non-noble transition metal-based active
and versatile approach to developing non-noble electrocatalysts with high catalysts with tuneable structures and
compositions are currently a major energy
activity and durability for advanced electrochemical water-splitting systems. research focal point for global implemen-
tation of clean and efficient water-splitting
technologies. Recently, catalysts derived
Prof. W. Ahn from metal-organic frameworks (MOFs), typically synthesized
Department of Energy Systems Engineering using precursors consisting of transition metals and organic
Soonchunhyang University linkers, have emerged as promising active and inexpensive elec-
22 Soonchunhyang-ro, Shinchang-myeon, Asan-si, Chungcheongnam-do
trocatalysts due to their intrinsic advantages of high porosity,
31538, South Korea
3D structures, and compositional flexibility. In particular,
Prof. W. Ahn, M. G. Park, Dr. D. U. Lee, Dr. M. H. Seo, Dr. G. Jiang,
Z. P. Cano, Dr. F. M. Hassan, Prof. Z. Chen MOFs with organic ligands containing carbon, nitrogen, and
Department of Chemical Engineering sulfur atoms coordinated to transition metal centers have been
University of Waterloo reported to form 3D and uniformly porous structures, resulting
Waterloo Institute for Nanotechnology in considerably increased active surface area and enhanced
200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada
E-mail: [email protected] physical properties. These MOFs, often composed of transition
Dr. M. H. Seo metal atoms such as nickel, cobalt, and iron, and heteroatoms
Hydrogen & Fuel Cell Center such as nitrogen, sulfur, and phosphorus are characterized by
New & Renewable Energy Research Division strong interactions between them, which can serve as electro-
Korea Institute of Energy Research (KIER) catalytically active sites for HER and OER.[9–17]
20–41 Sinjaesaengeneogi-ro, Haseo-myeon, Buan-gun, Jellabuk-do
The advantages of MOF-derived active materials in
56332, South Korea
advanced energy conversion and storage applications have
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201802129.
been recently applied to efficient electrocatalysts for fuel cells,
metal–air batteries, and electrolyzers.[6,15,17–29] For example,
DOI: 10.1002/adfm.201802129 Gadipelli et al. recently reported a design route for the

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synthesis of MOF-derived electrocatalysts, in which zeolitic imi- These nanocube precursors were subjected to sulfur ion (S2−)
dazolate framework was used as the template.[30] The resulting exchange, and then crystallized via hydrothermal treatment
MOF catalyst containing active Co–N–C species demonstrated followed by postheat treatment (Scheme 1D) to form highly
efficient ORR and OER activities. Yu et al. reported an active crystalline multivoid nanocuboids. This hierarchical hollow
OER electrocatalyst based on porous carbon-coated nickel phos- nanocuboidal MOF structure is very interesting for electroca-
phides (NiP) prepared using Ni-based prussian blue analog talysis of OER and HER due to a possible increased number of
(PBA) nanoplates as a template.[31] The structural advantages active sites from enlarged surface area. The exact morphology
of MOFs allowed the NiP catalyst to demonstrate superior elec- of the MOF catalysts, however, largely depends on the type
trocatalytic activity toward OER compared to NiO and Ni(OH)2 of transition metal centers present in the PBA precursor. For
counterparts. Despite these electrocatalyst developments, how- example, NC-MOF (NC-PBA precursor shown in Figure S1A,B,
ever, bifunctional MOF-derived electrocatalysts active toward Supporting Information) showed nanocuboidal structures with
both HER and OER for water-splitting applications have rarely an average size of 400 nm and relatively large pores on each
been reported to the best of our knowledge. face (Figure 1A,B), while NF-MOF (NF-PBA precursor shown
In this study, we introduce novel MOF-containing Ni–Co–Fe in Figure S1C,D, Supporting Information) showed uniformly
transition metal centers (denoted NCF-MOF) as a dual-function sized cuboidal structures with an average size of 160 nm, main-
water-splitting catalyst for enhancing HER and OER activi- taining the initial PBA precursor morphology (Figure 1D,E).
ties. The morphology of the catalyst is revealed to exhibit a NCF-MOF (NCF-PBA precursor shown in Figure S1E,F,
nanocuboid structure with multiple mesosized and micro- Supporting Information) exhibited general cuboid morphology
sized pores prepared via a facile synthesis procedure. Transi- with an average size of 180 nm and roughened surfaces
tion metal-based PBA nanocubes with a chemical formula (Figure 1G,H). Interestingly, NF-PBA and NCF-PBA precur-
MxII[MyIII(CN)6]z▪H2O, where MII and MIII are divalent and sors were relatively smaller than NC-PBA, probably due to
trivalent transition metal cations, respectively, were selected the presence of Fe ions. Moreover, the large pores observed in
as MOF precursors to obtain unique compositions and multi- NC-MOF possibly formed during the hydrothermal processes
hollow nanocuboid structures.[12,32] Specifically, PBA nanocube due to very rapid ion exchanging between [Co(CN)6]3− and
precursors containing nickel, cobalt, and iron were utilized to S2− ions, resulting in breakage of outer metal ions from the
maintain the general nanocuboidal structure, while optimizing cuboid structures.[34] This led to the formation of NC-MOF with
the composition of transition metal centers for efficient OER considerable shape change from the compact cuboid to porous
and HER activities. This makes NCF-MOF one of the most structures. Unlike the significant morphological changes
promising nonprecious electrocatalysts for water-splitting observed with NC-MOF from its precursor, NF-MOF and NCF-
applications due to several material advantages including MOF largely maintained their nanocuboidal structures. Only a
i) significantly extended active surface area with high porosity slight morphology change observed with NF-MOF (roughening
and robust structure, ii) active nitrogen species formed during of its surface) was likely due to relatively lower ion exchanging
facile synthesis, and iii) favorably tuned electronic structure by power of [Fe(CN)6]3− with S2− anions (compared to that of
combining active transition metals having different number of [Co(CN)6]3− in the case of NC-MOF), resulting in significantly
outer electrons. less ion exchange and minimal morphological change. NCF-
These main electrocatalytic contributors that affect OER and MOF is particularly interesting because of the presence of both
HER were successfully obtained through careful selection of [Co(CN)6]3− and [Fe(CN)6]3− having different ion exchanging
PBA precursors and the facile synthesis procedure. Further- rates which led to partial replacement with S2− ions, resulting
more, the NCF-MOF catalyst exhibited excellent electrochem- in an externally roughened surface, and internally having
ical stability, which is attributed to its highly uniform and rigid multiple voids within a single nanocuboid, which will be
porous nanocuboidal structure that allows rapid charge transfer further discussed in the following section.
and mass transport of active species to be maintained. The Transmission electron microscopy (TEM) analysis was
dual-function of the catalyst and its stability was confirmed by conducted to reveal the internal morphological features of
three-electrode half-cell evaluations, and moreover was inte- the MOF catalysts. NC-MOF under TEM revealed that the
grated onto nickel-foam supports for practical demonstrations large pores observed on all faces of the nanocuboids were in
of efficient and stable water-splitting electrodes. fact interconnected, resulting in a hollow core (Figure 1C).
NF-MOF, on the other hand, maintained the nonporous nano-
cuboidal structure from its precursor (Figure 1F), consistent
2. Results and Discussion with the scanning electron microscopy (SEM) observations.
TEM observations of NCF-MOF revealed spots within a single
A schematic illustration of the synthesis procedure of multi- nanocuboid with different brightness (Figure 1I), indicative
void MOF nanocuboid electrocatalysts using PBA nanocube of multiple void formations during the ion exchanging reac-
precursors is presented in Scheme 1. The PBA precursors tion. These morphological differences again highlight dif-
are composed of transition metal ions (Ni, Fe, and/or Co) ferent ion exchanging rates of each PBA precursor, and how
and cyanide (CN) groups in the face-centered cubic (FCC) they affect the final external and internal structures of the
crystal packing arrangement.[33,34] The PBA precursors used MOF catalysts. In terms of crystal structure, X-ray diffraction
in this study consisted of different combinations of transition (XRD) characterization revealed that the pattern obtained from
metal centers, namely, Ni/Co (NC-PBA, Scheme 1A), Ni/Fe NC-MOF closely matches with that of NiS (JCPDS: 77–1624)
(NF-PBA, Scheme 1B), and Ni/Co/Fe (NCF-PBA, Scheme 1C). (Figure S2A, Supporting Information), indicative of near-complete

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Scheme 1. A–D) Schematic illustration of MOF electrocatalyst synthesis procedure using PBA nanocube precursors to form multivoid hollow nano-
cuboidal MOF catalyst.

exchange of [Co(CN)6]3− with S2− ions, as expected from the compositional characteristics of NC-MOF, as presented in
the above microscopic analyses.[32] The obtained patterns of Figure S3E–J (Supporting Information). The elemental maps
NF-MOF (Figure S2B, Supporting Information) and NCF-MOF indicate that NC-MOF is composed of nickel, nitrogen, sulfur,
(Figure S2C, Supporting Information), on the other hand, carbon, and residual cobalt, which clearly shows that most of
matched the typical characteristic peaks of PBA, due to rela- the [Co(CN)6]3− was in fact exchanged by S2− ions, leading to
tively lower degree of [Fe(CN)6]3− exchanged with S2− anions, the formation of NiS with hollow-core morphology. The inten-
as conjectured based on morphological observations.[34] Scan- sity of each elemental map is in good agreement with the EDS
ning TEM (STEM) of a single NC-MOF nanocuboid was used line-scan measurements.
to obtain energy-dispersive X-ray spectroscopy (EDS) line-scans Meanwhile, NF-MOF exhibited a much denser internal
through the mid-section (Figure S3A, Supporting Information) cuboidal core compared to that of NC-MOF, based on the
and the edge (Figure S3B, Supporting Information). The ele- STEM images shown in Figure S4A,B (Supporting Informa-
ments detected in the nanocuboids, Ni, Co, Fe, C, N, and S, are tion), while SAED patterns obtained at the center (Figure S4C,
indicated by different colors of the line-scan with the respective Supporting Information) and the edge (Figure S4D, Supporting
intensity corresponding to the amount of each element, which Information) of the nanocuboid indicate a polycrystalline FCC
are separately plotted in Figure S5 (Supporting Information). structure. Based on both EDS line-scan (Figures S4A,B and
The plots clearly show that the intensities of all detected ele- S6, Supporting Information) and DFTEM elemental mapping
ments are relatively higher at both ends of the plot compared (Figure S4E–J, Supporting Information) results, relatively larger
to the center, which confirms the internally connected porous amounts of nickel and iron were detected within NF-MOF with
structure with a hollow core. From high-resolution transmis- lower amounts of carbon, sulfur, and nitrogen uniformly dis-
sion electron microscopy (HRTEM) images obtained from tributed along both the center and edge parts. The low amount
NC-MOF (Figure S3C,D, Supporting Information), selected area of sulfur detected is particularly important for verifying that the
electron diffraction (SAED) patterns were also obtained at the rate of ion exchange of [Fe(CN)6]3− with S2− ions was indeed
center and the edge of the nanocuboids, both of which reveal slower than that of [Co(CN)6]3− observed with NC-MOF. Inter-
FCC lattice structures. In terms of composition, dark-field TEM estingly, higher amounts of nitrogen and carbon detected com-
(DFTEM) and elemental mapping were conducted to verify pared to NC-MOF are likely due to the decomposition of the

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Figure 1. A,B,D,E,G,H) SEM and C,F,I) TEM images of various MOF morphologies. A–C) NC-MOF with large face-centered pores, D–F) NF-MOF
nanocuboids, and G–I) NCF-MOF nanocuboids with roughened surface.

cyanide groups in the PBA precursor during the heat-treatment pore size distribution, as presented in Figure S8 (Supporting
process, which will be discussed in more detail later. Information). Based on the N2 isotherms, both NF-MOF and
Based on the above characterizations of NC-MOF and NCF-MOF show a clear hysteresis loop in the high pressure
NF-MOF, it is clear that combining [Co(CN)6]3− and [Fe(CN)6]3− range from 0.6 to 1.0, indicating the presence of mesopores.[21]
anions having different rates of ion exchanging capabilities can However, NCF-MOF adsorbed a much greater volume of N2
lead to a unique morphology and composition for NCF-MOF resulting in a 50.7 m2 g−1 Brunauer–Emmett–Teller (BET) sur-
as observed in microscopic analyses. Compared to NC-MOF face area, compared to only 27.4 m2 g−1 obtained with NF-MOF.
and NF-MOF, the results obtained from EDS line-scans In terms of the pore size distribution, despite both nanocuboids
(Figure 2A,B; Figure S7, Supporting Information) and DFTEM having micropores (under 2 nm) and mesopores (over 2 nm),
elemental mapping (Figure 2E–K) of NCF-MOF show that the NCF-MOF was found to have two times the accumulative pore
three transition metals (nickel, cobalt, and iron) are uniformly volume compared to NF-MOF (0.29 vs 0.14 cc g−1) due to the
distributed along the middle and the edge of nanocuboids, indi- presence of a significantly large number of mesopores. This
cating that [Co(CN)6]3− and [Fe(CN)6]3− anions were only par- direct evidence that NCF-MOF has enhanced specific surface
tially exchanged by S2− ions. This partial ion exchange led to area signifies a potential increase in the number of active sites
the formation of multiple voids within a single nanocuboid, for electrocatalytic processes which can greatly improve OER
where the exchange most likely progressed from the surface and HER activities.
[Co(CN)6]3− anions to the sites in the core. Accordingly, NCF- The composition of the MOF nanocuboid catalysts was fur-
MOF is characterized by having larger interconnected pores in ther analyzed by X-ray photoelectron spectroscopy (XPS). The
the core with smaller pores near the faces of the nanocuboid, survey spectrum of NF-MOF revealed Ni, Fe, O, N, and S,
resulting in a multilevel porous structure. The crystal struc- while that of NCF-MOF revealed Ni, Co, Fe, O, N, C with a low
ture of NCF-MOF confirmed by SAED patterns obtained from intensity S peak (Figure S9A, Supporting Information). By con-
HRTEM images at the face center (Figure 2C) and the edge trast, the spectrum of NC-MOF revealed Ni, O, C with a high
(Figure 2D) reveal [001] and [111] orientations, respectively, intensity S peak, indicating again that most of the [Co(CN)6]3−
as indicated by a series of bright dots from strongly diffracted was ion exchanged with S2− ions leading to the formation of
crystal planes of the nanocuboid, corresponding to a typical hollow-centered NiS nanocuboids, as discussed earlier. The
FCC structure. high-resolution spectrum of selected elements present in the
The observed porosity of NF-MOF and NCF-MOF was quan- nanocuboid catalysts was deconvoluted to verify the oxidation
tified by measuring N2 adsorption/desorption isotherms and states. The high-resolution Ni 2p (Figure S9B, Supporting

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Figure 2. TEM analysis of NCF-MOF. A,B) STEM images with EDS line-scans obtained along the middle and edge of NCF-MOF, C,D) HRTEM
images and SAED patterns obtained at the center and the edge of NCF-MOF, E) DFTEM image of NCF-MOF, and the obtained elemental maps of
F) Ni, G) Co, H) Fe, I) S, J) C, and K) N.

Information) and S 2p (Figure S9C, Supporting Information) (Figure 3C), respectively. Based on the high resolution Ni 2p
spectra of NC-MOF show peaks found at binding energies that peak, it was found that a small quantity of NiS formed (5.4%),
correspond to NiS and Ni3S2.[35] While Ni3S2 was detected from while only low intensity multiplet NiS peaks were observed in
the XPS analysis, no peaks that corresponded to this impurity the high-resolution S 2p spectrum of NCF-MOF (Figure 3D),
in the XRD pattern of NC-MOF were observed, which indicates which are ascribed to the S2− ions partially replacing [Co(CN)6]3−
that its amount may be negligibly small due to a near-complete during ion exchange, consistent with the above XRD and micro-
ion exchange of [Co(CN)6]3− with S2− during the hydrothermal scopic characterization. However, the lack of characteristic NiS
reaction. Based on the analysis of Ni 2p (Figure S9D, Sup- peaks observed in the XRD patterns of NF-MOF and NCF-MOF
porting Information) and Fe 2p (Figure S9E, Supporting Infor- indicate that the small quantities of NiS in these samples were
mation) signals from NF-MOF, it was found to mainly consist amorphous. These oxidation states of the transition metals
of Ni in 2+ states, and Fe with 27% of 3+, and 73% of 2+ states, determined from XPS analysis are related to the number of
leading to a possible chemical formula of NixII[FeyIIFezIII(CN)6]2. valence electrons, which in turn determines the electronic state
NCF-MOF, on the other hand, was found to be composed of and the number of electrons that are involved during elec-
Ni in 2+ states (Figure 3A), Fe in 43% and 57% of 2+ and 3+ trocatalytic reactions.[36–39] Recently, several studies revealed
states (Figure 3B), and Co in 17% and 83% of 2+ and 3+ states that valence electrons of transition metals are highly related

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Figure 3. Deconvoluted high-resolution XPS spectra obtained from NCF-MOF. A) Ni 2p, B) Fe 2p, C) Co 2p, and D) S 2p. Deconvoluted high-resolution
XPS N 1s spectra of E) NF-MOF and F)NCF-MOF.

to the trends in adsorption energies of intermediates of the electrons, it can be implied that the active surface of NF-MOF
OER.[36,38,39] In these works, metals and corresponding metal has relatively high adsorption strength with the oxygen inter-
oxides were studied and the correlation between the number of mediates leading to a lower OER electroactivity. Valence elec-
outer electrons and the adsorption energy of the intermediates trons of NCF-MOF finely tuned by the combination of active Co
such as *OH, *O, and *OOH during oxygen electrocatalysis and Fe metal ions, on the other hand, would render relatively
were systematically investigated. The trends demonstrated the weaker adsorption of the oxygen intermediates, resulting in
higher the number of outer electrons, the larger the adsorption lower overpotential toward OER and more facilitated evolution
energies of the oxygen intermediates leading to higher overpo- of gaseous oxygen. The improved OER performance resulting
tentials toward OER. Furthermore, the trends remained similar from this explanation will be demonstrated by electrochemical
across different structures of metals, metal monoxides, as well evaluation in the next section. The obtained XPS N 1s spectra
as perovskite oxides. In the current study, based on the oxida- of NF-MOF and NCF-MOF were deconvoluted to verify the
tion states determined from the XPS analysis above, the outer type of nitrogen species present in each electrocatalyst, since
electron number of Fe in NF-MOF was found to be 5.73, while N-doping has been reported to facilitate HER. It is noted that
those of Fe and Co in NCF-MOF were found to be 2.71 and the N 1s peak was not detected with NC-MOF, as shown in
2.78, respectively, adding up to 5.49 (detailed calculations in Figure S9A (Supporting Information) due to near-complete
the Supporting Information). Considering the number of outer exchange of [Co(CN)6]3− with S2− ions. The N species found in

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NF-MOF predominantly existed as CN (98.7%), which was This unique N-doping within NCF-MOF which formed during
from the remaining unexchanged [Fe(CN)6]3− anions, and the the decomposition of CN− leads to more favorable HER electro-
rest as oxidized-N (1.9%) formed during the hydrothermal pro- chemical activity due to the synergistic effect with neighboring
cess (Figure 3E). Interestingly, NCF-MOF, in addition to having transition metals, such as Ni, Co, and Fe,[15,18,41,42] which will be
CN (94.7%) and oxidized-N (0.9%), also contained pyri- demonstrated in the next section.
dinic N species (4.24%) (Figure 3F). This unique N-doping of The electrochemical OER and HER activities of the MOF
NCF-MOF is ascribed to the decomposition of free CN− groups electrocatalysts were investigated using a typical three-electrode
generated in solution during the ion exchanging process. In half-cell configuration with conventional glassy carbon rotating
fact, previous studies reported that Fe(CN)6 is effective in disk electrode (RDE) with 0.2 mg cm−2 of catalyst loading
dissociating metal cyanides, decomposing CN− in soil at tem- in N2-saturated 0.1 m KOH electrolyte. Based on the HER
peratures lower than 100 °C.[40] Likewise, Ni3[Fe(CN)6]2 groups polarization curves, NCF-MOF demonstrated the lowest over-
in NCF-MOF most likely facilitated the dissociation of free potential (most positive absolute potential) of 0.27 V (see meas-
[Co(CN)6]3− ions in solution, producing CN− ions which oxi- urement details in the Experimental Section), compared to
dize to CNO− and then further decompose to NH3, a common those of NF-MOF and NC-MOF (0.34 and 0.39 V, respectively)
N-doping source.[40] This N-doping is unique to NCF-MOF at a current density of −10 mA cm−2 (Figure 4A). This excellent
because the remaining Fe(CN)6 groups in the nanocuboid act HER activity of NCF-MOF is comparable to some of the best
as a catalyst to facilitate the decomposition of CN− groups of the known nonprecious HER catalysts in the basic condition (See
[Co(CN)6]3− anions freed into the solution after ion exchanging Table S1 in the Supporting Information), which is attributed to
with S2−. Specifically, 9.85% of [Co(CN)6]3− in NCF-MOF was the reduced energy barrier for HER due to the N-doped spe-
ion exchanged with S2−, and 86% of the freed CN− groups were cies uniquely found in NCF-MOF.[15,40,42] Based on the previous
found to be used as the N source based on the XPS analysis. study, nitrogen doping leads to a decrease in ∆G(H*) by pro-
This result is also consistent with the EDS line-scan analysis viding improved adsorption for H* onto the active sites.[43–46]
presented above, which clearly showed the presence of both Additionally, since the properties of materials are highly sen-
nitrogen and carbon along the middle and edges of NCF-MOF. sitive to their morphology and structure, the unique structure

Figure 4. Electrochemical evaluations of MOF catalysts. A) HER and B) OER curves obtained with MOF catalysts and precious metal-based
benchmark catalysts. C) Chronopotentiometry (v–t) plot obtained with NCF-MOF at a fixed applied current density of −20 mA cm−2 for HER (blue
line) and 20 mA cm−2 for OER (red line). The inset of (C) shows the changes in the overpotentials during chronopotentiometric HER and OER tests
(bar graphs), and the corresponding potential retentions (dot graphs). D) OER polarization curves of NCF-MOF and Ir/C before (solid lines) and after
(dashed lines) 1000 CV cycles.

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as well as the N-doped surface of NCF-MOF probably further of NF-MOF and NC-MOF (157 and 168 mV dec−1, respectively)
contributes to its highly active and durable HER activity.[47] As (Figure 5B), signifying much faster kinetics during the HER.
an effective dual-function catalyst, NCF-MOF also showed the Similarly, the lowest OER overpotential was obtained with the
lowest OER overpotential of 0.32 V obtained at 10 mA cm−2 NCF-MOF catalyst loaded on a NFE, demonstrating 0.48 V
even compared to that of precious-metal benchmark catalyst obtained at 30 mA cm−2, which is 110 and 160 mV lower than
Ir/C (Figure 4B), while it is superior compared to the recently those of NF-MOF and Ir/C, respectively (Figure 5C). The OER
reported nonprecious active OER electrocatalysts (Table S1, Tafel analysis also showed the smallest slope of 49 mV dec−1
Supporting Information). Specifically, NF-MOF, NC-MOF, and for NCF-MOF, compared to those of NF-MOF, NC-MOF, and
Ir/C demonstrated 30, 60, and 20 mV higher overpotentials, Ir/C (119, 99, and 73 mV dec−1, respectively) (Figure 5D), signi-
respectively. The significant OER activity of NCF-MOF is also fying the highest kinetics during the OER on NCF-MOF. As a
comparable to the best reported values of recently developed control, a bare nickel foam without any catalyst loading showed
nonprecious metal-based OER electrocatalysts (see Table S1 current densities associated with HER and OER but at much
in the Supporting Information). The enhanced OER activity of higher overpotentials and with significantly lower magnitudes
NCF-MOF is attributed to the favorably tuned electronic struc- compared to the catalyst-loaded counterparts (Figure S10, Sup-
ture by combining the number of outer electrons of active Co porting Information).
and Fe metal ions, which leads to reduced adsorption strength In addition to the excellent dual OER and HER activities of
with the oxygen intermediates such as *O, *OH, and *OOH, as NCF-MOF, its electrochemical stability was investigated by con-
discussed above. To emphasize excellent OER and HER capabil- ducting chronopotentiometry (CP). When held at −20 mA cm−2,
ities of NCF-MOF, the catalysts were also loaded onto practical the NCF-MOF electrode exhibited an initial HER potential
nickel foam electrodes (NFEs) commonly used in water-splitting of −0.34 V versus reversible hydrogen electrode (RHE), and a
cells (see electrode preparation details in the Experimental Sec- voltage loss of only 0.05 V after 20 000 s (Figure 4C). During
tion). Under HER conditions, NCF-MOF again demonstrated CP under OER conditions, the NCF-MOF electrode held at
the lowest overpotential of 0.16 V obtained at a current density 20 mA cm−2 demonstrated an initial OER potential of 1.53 V
of −30 mA cm−2, compared to those of NF-MOF and NC-MOF versus RHE (0.3 V of OER overpotential). After 20 000 s, only
(0.25 and 0.30 V, respectively) (Figure 5A). Additionally, the a 0.01 V increase in the OER potential was observed, leading to
Tafel plots obtained from the HER curves resulted in the 97% of potential retention, demonstrating very slight degrada-
smallest slope for NCF-MOF (114 mV dec−1) compared to those tion during the durability test (Figure 4C, inset). Conducting

Figure 5. Electrochemical evaluations of MOF catalyst-loaded nickel foam electrodes. A) HER polarization curves, and B) HER Tafel slopes obtained with
NCF-MOF, NF-MOF, NC-MOF, and Pt/C. C) OER polarization curves, and D) OER Tafel slopes obtained with NCF-MOF, NF-MOF, NC-MOF, and Ir/C.

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electrochemical stability via cyclic voltammetry (CV), as com- stability of precious metal-based benchmark catalyst Ir/C, dem-
monly done in the field, further confirmed the considerably onstrating minimal OER potential losses after 1000 CV cycles
high electrochemical stability of NCF-MOF, with Ir/C used in a highly oxidative potential window. Furthermore, the TEM
as the benchmark catalyst for comparison.[22,23,48] Initially, analysis verified the high structural stability of NCF-MOF after
NCF-MOF displayed a significantly lower (superior) OER the long term durability tests conducted in both OER and HER
potential of 1.54 V versus RHE at 10 mA cm−2 in comparison potential regions. This work exemplifies novel electrocatalyst
to 1.57 V obtained with Ir/C (Figure 4D). After 1000 CV cycles development with high activity and durability for next genera-
in the highly oxidative potential window of 1.2 to 1.75 V versus tion energy conversion and liquid-fuel production technologies
RHE, NCF-MOF showed only 1 mV of OER potential loss (99% including electrochemical water-splitting cells.
potential retention), while Ir/C showed a significantly greater
potential loss of 116 mV (66% potential retention). The struc-
tural stability of NCF-MOF after the long term durability tests in
both OER and HER potential regions was verified by performing
4. Experimental Section
TEM characterization in terms of morphology (Figure S11, Sup- Synthesis of Precursor and MOF Materials: The facile preparation
porting Information). The overall nanocuboid morphology of procedure of MOF electrocatalysts is presented in Scheme 1. The PBA
NCF-MOF (A, B are before durability testing) was observed to be nanocubes, which were utilized as precursors, were synthesized by
the coprecipitation method, where the precursors included Ni and Co
maintained after OER (C, D) and HER (E, F) durability tests in
(NC-PBA), Ni and Fe (NF-PBA), or Ni, Fe, and Co (NCF-PBA) ions. For
the alkaline electrolyte. The edges were observed to be somewhat the first precursor, 0.6 mmol of nickel nitrate and 0.9 mmol of sodium
roughened which is likely due to the formation of metal hydrox- citrate were first dissolved in 20 mL of Milli-Q water. Next, 0.4 mmol
ides where the metal sites tend to be undercoordinated, which is of potassium hexacyanoferrate (III) was dissolved in another 20 mL
consistent with the results reported in the literature.[49,50] of Milli-Q water. The two solutions were then mixed and vigorous
The extended electrochemical stability observed with NCF- stirring was conducted for 12 h to synthesize the NF-PBA precursor
with uniformly distributed particle sizes. The NC-PBA and NCF-PBA
MOF during HER and OER is likely attributed to the highly
precursors were synthesized by the same method, except for the use of
rigid porous structure consisting of the robust metal–organic- 0.4 mmol potassium hexacyanocobaltate (III) solution for NC-PBA, and
frameworks, which enables it to mostly retain the initial electro- a mixed solution of 0.2 mmol potassium hexacyanocobaltate (III) and
catalytic activities via retaining the framework during rigorous 0.2 mmol potassium hexacyanoferrate (III) for NCF-PBA. It is well known
H2 and O2 gas bubbling. Additionally, during OER, even lower that the citrate ions prohibit the precipitation reaction from forming
overpotential for NCF-MOF than the precious benchmark large-sized particles. Therefore, a sufficient reaction time was required
to prepare uniformly distributed precursors with small sized particles.[31]
Ir/C catalyst leads to significantly reduced oxidation of active
The MOFs were obtained from the as-prepared PBA precursors through
metals while the catalyst undergoes relatively reduced carbon- a simple hydrothermal reaction with the addition of sodium sulphide
corrosion. It can be concluded that the solid and interconnected (Na2S). 100 mg of PBA precursor and 200 mg of Na2S were mixed in
porous structure via the ternary transition metal-based MOF 100 mL of ethanol and transferred into a Teflon liner and stainless-steel
design as well as the harmonized effects between Co and Fe autoclave. The hydrothermal reaction was carried out at 100 °C for 6 h
metals in the framework achieved synergistic improvements in to induce sufficient ion exchange. Then, the intermediate product was
electrocatalytic activities and durability for both OER and HER. washed, dried, ground, and heat treated at 300 °C in Ar atmosphere for
3 h to form highly crystalline MOFs. The black recrystallized MOFs were
pulverized and dried in a vacuum oven at 70 °C for 12 h. The final MOF
products containing Ni/Co, Ni/Fe, and Ni/Co/Fe centers were denoted
3. Conclusion NC-MOF, NF-MOF, and NCF-MOF, respectively.
Physical Characterization: In order to confirm the crystal structures of
In summary, multivoid nanocuboidal MOF catalysts prepared the synthesized materials, XRD (AXS D8 Advance, Bruker) was carried
by a facile coprecipitation and postheat treatment process were out with Cu Kα radiation (λ = 1.5405 Å) in the 2θ range of 10°–80°
with 0.02° intervals, at a 0.02° min−1 scanning rate. The morphology
found to demonstrate high electrocatalytic activities as well
and elemental distribution of the as-prepared PBA precursors and
as stability toward both OER and HER. The morphology and MOFs were characterized using a SEM (LEO FESEM 1530) and HRTEM
composition of the MOF catalysts were investigated by taking (JEOL 2010F, JEOL Ltd.) with EDS line-scan and mapping analysis. To
advantage of different ion exchanging rates of [Co(CN)6]3− and ascertain each bonding group and verify the oxidation states of the MOF
[Fe(CN)6]3− anions in PBA precursors with S2− ions. The for- materials, XPS was also carried out (K-Alpha XPS spectrometer, Thermal
mation of unique nanocuboid morphology with high internal Scientific). N2 adsorption/desorption isotherm with BET and Barrett-
Joyner-Halenda (BJH) analysis were performed to clarify the specific
porosity of NCF-MOF is attributed to the ion exchanging of
surface area, porosity, and pore volume of the developed catalyst.
[Co(CN)6]3− with S2− ions, while relatively unreactive [Fe(CN)6]3− Electrochemical Characterization RDE Tests: A traditional half-cell system
remains stagnant but facilitates the decomposition of free CN− with three electrodes was utilized to explore the electrochemical activities
groups to induce nitrogen-doping, forming HER active pyridinic of the MOF catalysts, where the three electrodes were a glassy carbon
nitrogen species. Additionally, the unique combination of the electrode (GCE), a saturated calomel electrode (SCE), and a platinum
two precursors containing Co and Fe results in a favorably wire used as the working electrode, reference electrode, and counter
tuned electronic structure, leading to relatively reduced adsorp- electrode, respectively. The electrocatalytic activity toward the OER and
HER was evaluated using catalyst-loaded NFEs or via the RDE technique
tion energy of the oxygen intermediates, which is critical for using catalyst-coated GCEs. A CHI Electrochemical Station (Model 760D)
lowering the overpotential toward OER and facilitating the evo- was used for all electrochemical evaluations. The measurements were
lution of gaseous oxygen. In terms of electrochemical stability, conducted from 0 to 0.85 V versus SCE at 1600 rpm of rotation speed for
after 20 000 s of operation NCF-MOF retained 86% and 97% of OER, and from −0.9 to −1.5 V versus SCE at 1600 rpm of rotation speed
its HER and OER potentials, respectively, and far exceeded the for HER, with a scan rate of 10 mV s−1. Pure nitrogen gas was purged

Adv. Funct. Mater. 2018, 1802129 1802129 (9 of 11) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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for 30 min before OER and HER evaluations and all measurements Keywords
were performed in a 0.1 m KOH solution. All measured potentials were
adjusted to the RHE scale, according to the equation; ERHE = ESCE + 0.241 bifunctional electrocatalysts, hydrogen evolution reaction, metal–
+ 0.059 pH. All measured polarization curves were iR-compensated organic-framework, oxygen evolution reaction, water-splitting
(See details in the Supporting Information) prior to electrochemical testing,
the GCE (diameter: 5 mm) was polished using alumina suspension (size: Received: March 26, 2018
0.05 µm) on a smooth polishing cloth to obtain a uniform and smooth Revised: April 21, 2018
GCE surface, then the polished GCE surface was ultrasonicated in Milli-Q Published online:
water for a few seconds to remove any leftover alumina particles. The
catalyst ink was prepared by combining 2 mg catalyst and 2 mg vulcan
carbon (XC-72, VC) in 1.0 mL of pretreated Nafion solution (mixture of
10 mL IPA and 80 µL of 5 wt% Nafion, Ion Power), followed by
[1] Y. Zheng, Y. Jiao, S. Qiao, A. Vasileff, Angew. Chem., Int. Ed. 2018,
ultrasonication for 60 min to obtain a homogeneous suspension.
57, 2.
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[2] J. Liu, Y. Zheng, Y. Jiao, Z. Wang, Z. Lu, A. Vasileff, S. Z. Qiao, Small
dried in room temperature, achieving a loading of 0.2 mg cm−2catalyst.
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