Communication

1D Nanotubes www.advmat.de

“Wiring” Fe-Nx-Embedded Porous Carbon Framework

onto 1D Nanotubes for Efficient Oxygen Reduction
Reaction in Alkaline and Acidic Media
Sung Hoon Ahn, Xingwen Yu, and Arumugam Manthiram*

system.[16] Consequently, a rational design

This study presents a novel metal-organic-framework-engaged synthesis of M, N-doped carbon catalyst with hierar-
route based on porous tellurium nanotubes as a sacrificial template for chical open pore structure results in a sig-
hierarchically porous 1D carbon nanotubes. Furthermore, an ultrathin Fe-ion- nificantly enhanced ORR activity, owing
containing polydopamine layer has been introduced to generate highly effec- to its advantages in the two crucial factors
described above: (i) number of M-NxC
tive FeNxC active sites into the carbon framework and to induce a high degree active sites that are known to be deter-
of graphitization. The synergistic effects between the hierarchically porous mined by the involved surface nitrogen
1D carbon structure and the embedded FeNxC active sites in the carbon coordination with metal and (ii) enhanced
framework manifest in superior catalytic activity toward oxygen reduction transport properties for the ORR-relevant
reaction (ORR) compared to Pt/C catalyst in both alkaline and acidic media. A molecules via the open pores accessible
to active sites to supply continuously the
rechargeable zinc-air battery assembled in a decoupled configuration with the
reactants. To date, the metal-organic-
nonprecious pCNT@Fe@GL/CNF ORR electrode and Ni-Fe LDH/NiF oxygen framework (MOF)-derived metal/carbon
evolution reaction (OER) electrode exhibits charge–discharge overpotentials synthesis route has attracted tremendous
similar to the counterparts of Pt/C ORR electrode and IrO2 OER electrode. interests for ORR catalysts, attributed to its
high surface area of over 1000 cm2 g−1 and
homogeneous M, N-doped nanoporous
The oxygen reduction reaction (ORR) is a pivotal process for carbon framework after the pyrolysis process, particularly with
electrochemical energy conversion and storage devices such as the zeolitic imidazolium framework (ZIFs), which has transi-
fuel cells and metal-air batteries.[1] Platinum (Pt) based catalyst tion metal ions and nitrogen-containing organic ligands.[17]
is normally used for ORR, but it also suffers from ineluctable With the significantly progressing research on the MOF-derived
problems such as its scarcity, high cost, and poor long-term carbon catalyst, the following issues are regarded as the draw-
stability related to performance degradation during operating backs toward efficient ORR; (i) a self-aggregation and sintering
and poisoning by methanol crossover. Nonprecious transition of microporous MOF nanocrystals during the pyrolysis pro-
metal-based catalysts including metal oxides[2,3] and perovskite- cess, which results in a limited mass transport into the active
type[4,5] and spinel-type[6] mixed-metal oxides have been investi- sites, (ii) the amorphous carbon phase particularly produced
gated to replace Pt-based catalysts. To date, heteroatom doped from the Zn-based ZIF-8, which has relatively lower electronic
carbon materials modified with nonmetallic elements such as conductivity compared to graphitic counterpart, and (iii) the
sulfur,[7] phosphorous,[8,9] boron[10] and dominantly nitrogen,[11] metal species selection is usually restricted to zinc and cobalt
and metallic elements such as nickel, cobalt,[12,13] and iron[14,15] corresponding to, respectively, ZIF-8 and ZIF-67. It is reported
have emerged as the most promising candidates to replace Pt. that a proper ratio of ZIF-8 and ZIF-67 can result in mixed
It should be considered to generate a number of active sites, phases of amorphous and graphitic carbon matrix with a CoNx
e.g., N-C and M-NxC to enhance the electrocatalytic activity moiety after the pyrolysis process.[18] Furthermore, the direct
and the number of active sites is directly associated with the growth approaches of MOFs on low-dimensional templates
specific surface area and the homogeneous distribution of such as 1D ultrathin nanowire,[19] 2D graphene,[20] and layered
the dopant species in the carbon framework. On the other double hydroxides (LDHs)[21] are supposed to greatly reduce
hand, it has recently proven that the catalytic activities of N-C the electrical resistance and loss of electron during the trans-
and M-NxC catalysts are determined not only by maximizing port process through the carbon matrix. It is noteworthy that
the active sites but also by the catalyst kinetics and their pore FeNx moiety is known to have advantages over CoNx in acidic
media.[22–24] Although significant research progress in the iron
Dr. S. H. Ahn, Dr. X. Yu, Prof. A. Manthiram carbide encapsulated by graphene shell has been made for both
Materials Science and Engineering Program & Texas alkaline and acidic media,[23,25–27] it still remains a challenge to
Materials Institute obtain catalytic activity comparable to Pt/C catalyst. The combi-
The University of Texas at Austin nation of the metal-organic framework approach to the FeNxC
Austin, TX 78712, USA
E-mail: rmanth@mail.utexas.edu
catalyst and the post-treatment of ammonia has been reported
to significantly improve the ORR activity in acidic media
DOI: 10.1002/adma.201606534 attributed to the high porosity structure and higher basicity of

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Figure 1. Schematic illustration of the synthetic method for Fe,N embedded interconnected MOF-derived porous carbon nanotubes based on
tellurium nanotubes as a sacrificial template. a) Porous tellurium nanotubes, b) ZIF-8 wired tellurium nanotubes (Te NT@ZIF-8), c) Fe,N embedded,
polydopamine coated Te NT@ZIF-8, and d) Fe,N-embedded, highly graphitic layer coated porous carbon nanotubes after the pyrolysis process at
950 °C for 3 h under argon flow.
the carbon matrix[22] However, the durability of carbon mate-
rials after ammonia treatment is questionable.[5,28,29] Further-
more, since the metal species often leaches out under an acidic
operating environment,[30] it is critical to develop a protection
strategy for avoiding the direct contact of the metal-containing
active sites with the acidic electrolyte and minimizing the deg-
radation in catalytic activity during long-term operation.
Herein, we report a rational design of Fe,N embedded hier-
archical carbon framework wired onto 1D porous carbon nano-
tubes, which is derived from a nucleation and growth of MOF
on the surface of porous tellurium nanotubes (Te NTs). Abun-
dant catalytic active sites toward ORR directly stem from the
MOF-derived high surface area of 1380 cm2 g−1 and homoge-
neous distribution of N,Fe species in the carbon framework.
The mesoscale nanotube structure composed of MOF-derived
microporous framework provides dual-porosity leading to facile
electrolyte transport into the carbon matrix as well as excel-
lent electron transport through the 1D structure. In addition,
a polydopamine(PDA)-derived coating approach[31,32] in the
presence of Fe ions is applied to embed the FeNx moiety into
the carbon framework as well as a uniform highly graphitic
overlayer is used as an electron pathway for further enhanced
electron transport. The active sites are dual-protected by
embedding FeNxC into carbon framework and encapsulation
with graphitic overlayer to prevent degradation and aggregation
during long-term operating conditions. Consequently, the Fe,N
embedded porous 1D carbon catalyst exhibits a superb ORR
activity as well as excellent long-term stability surpassing those
of commercial Pt/C catalyst in both alkaline and acidic media.
The practicality of the application of this carbon catalyst is also
evaluated by using it as an ORR catalyst in a zinc-air battery
(ZAB) with a decoupled configuration[33] with a nonprecious
nickel iron oxyhydroxide as an oxygen evolution reaction (OER)
catalyst. The zinc-air battery assembled with these nonprecious
catalysts exhibits charge–discharge overpotentials similar to the
counterparts of Pt/C (ORR) and IrO2 (OER) electrodes assem-
bled in a decoupled configuration.
The schematic illustration for the preparation of the Fe,N-
doped 1D porous carbon nanotubes with hierarchical structure
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is shown in Figure 1. The porous tellurium nanotubes were
chosen as a starting material, serving as a sacrificial template
providing abundant functionalized surface for nucleation and
growth of ZIF-8 from zinc nitrate hexahydrate and 2-meth-
ylimidazole.[19] First, the porous tellurium nanotubes were
synthesized by an in situ reduction and etching process in the
presence of sodium hydroxide and ammonia from tellurium
oxide nanoparticles.[34] Next, the metal and organic precur-
sors were used to assemble ZIF-8 framework on the surface of
porous tellurium nanotubes, leading to the formation of self-
assembled MOF nanocrystals. Afterward, dopamine was in situ
polymerized at room temperature in the presence of FeCl3, and
FeNxC active sites were embedded into the carbon framework
after the pyrolysis process, which are wrapped by ultrathin
PDA-derived highly graphitic overlayer. During the pyrolysis
process at 950 °C for 3 h under argon atmosphere, zinc oxide
is reduced to zinc in the presence of carbon, and both zinc and
tellurium are evaporated.[19] Consequently, Fe, N-embedded
carbon framework was wired along with 1D carbon nanotubes,
and such a unique structure has many advantages toward
oxygen reduction reaction. First, a homogeneous Fe, N distri-
bution in the hierarchical porous carbon framework generates
abundant FeNxC active sites without the aggregation of the
FeC nanoparticles. Second, the hierarchical open pore struc-
ture consisting of MOF-derived micropores and 1D tubular
structure-derived mesopores results in facile mass transport
and full access to abundant active sites, while the highly gra-
phitic layer prevents direct contact to electrolyte protecting the
catalytic active sites. Those porous 1D carbon nanotubes show
low volumetric density compared to commercial Pt/C catalyst
as shown in Figure S1 (Supporting Information), revealing
another advantage of the template-derived MOF nanostructure
engineering, providing hollow structure and good dispersity
without interparticle agglomeration. Finally, the electron con-
ductivity of carbon catalyst could be enhanced by introduction
of highly conductive pathways composed of PDA-derived gra-
phitic layers and 1D nanotubes.
The porous structure of Te NTs is shown in Figure 2a, which
have a diameter of 150 nm, length of several micrometers,
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Figure 2.  SEM images of a) porous tellurium nanotubes, b) interconnected ZIF-8-derived porous carbon nanotubes (pCNT), and c) Fe,N embedded,
porous carbon nanotubes coated with graphitic overlayer (pCNT@Fe@GL). d) TEM, e) HRTEM, and f) STEM images of pCNT@Fe@GL with EDS
elemental mapping for C, N, and Fe.
and 30–50 nm pores derived from the ammonia treatment.
The porous structure of tellurium nanotubes promotes in situ
nucleation and growth of ZIF-8 nanocrystals along with nano-
tubes in the presence of zinc nitrate hexahydrate and 2 meth-
ylimidazole in methanolic solution at room temperature. The
hierarchical MOF-derived porous N-doped carbon nanotubes
(denoted as pCNT) are obtained after the pyrolysis process at
950 °C for 3 h in Ar flow. As shown in Figure 2b, these ZIF-8
derived porous carbon frameworks are interconnected along
with 1D porous carbon nanotubes. No self-aggregated ZIF-8
is found, revealing the strong interaction between ZIF-8 and
tellurium nanotubes. The overall morphology of pCNT is
maintained after embedding the FeNxC active sites into carbon
framework and deposition of PDA-derived highly graphitic
carbon overlayers, while the porous structure is smoothed by
the deposition of thin graphitic overlayer (Figure 2c). Scan-
ning electron microscopy (SEM) images at a higher resolution
are shown in Figure S2 (Supporting Information). The thick-
ness of PDA-derived graphitic overlayer was systematically
controlled by increasing the concentration of dopamine, the
diameter of 1D nanotubes is tuned up to ≈350 nm without
PDA-derived self-aggregation, and the wired MOF nanocrystals
are completely covered with smooth overlayer (Figure S3, Sup-
porting Information). It is found that such a thick overlayer can
block the diffusion of ORR-reactant to embedded active sites,
resulting in a significant decrease in the ORR activity (Figure
S4a, Supporting Information) and an undesirable electron
transfer compared to a thin overlay layer (Figure S4b, Sup-
porting Information).
The weight ratio of 10:2 is chosen for typical graphitic
layers coated pCNT (pCNT@GL), and this ratio is applied for
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all Fe-embedded, graphitic overlayers coated carbon catalysts
(pCNT@Fe@GL).
The transmission electron microscopy (TEM) image of the
pCNT@Fe@GL displays MOF-derived porous carbon nano-
tubes (Figure 2d). A tubular structure with wired carbon
framework can be clearly observed, and the nanotubes with a
diameter of ≈150 nm show a coincidence with SEM analysis.
In the high-resolution TEM (HRTEM) image (Figure 2e), it is
found that the overall porous carbon framework is success-
fully covered with highly graphitic multiwalls. For the graphitic
carbon overlayer, the typical interplanar distance of 0.35 nm,
corresponding to the (002) planes of carbon, was observed. The
porous structure is more apparently observed in the scanning
transmission electron microscopy (STEM) analysis (Figure 2f),
and a homogeneous distribution of C, N, and Fe in the overall
carbon nanotube structure is confirmed by energy-dispersive
X-ray spectroscopy (EDS) elemental mapping images. The con-
tents of C, N, O, and Fe were determined to be, respectively,
77.9, 8.3, 12.5, and 0.3 wt%, corresponding to the target Fe con-
tents of 0.5 wt% (Figure S5, Supporting Information). The Fe
amount of each carbon catalyst was obtained with the induc-
tively coupled plasma (ICP) analysis, and the amounts were
0.48, 0.81, 1.35, and 1.92 wt%, for the target Fe contents of,
respectively, 0.5, 1.0, 1.5, and 2.5 wt%, while the zinc content
obtained by ICP is in the range of 0.03–0.06 at% for all carbon
samples.
To investigate the effects of deposition of graphitic over-
layer on the surface area and pore structure for porous carbon
nanotubes, N2 adsorption/desorption measurements were per-
formed (Figure 3a). The specific surface area of pCNT was esti-
mated as 1387 m2 g−1 by the Brunauer–Emmett–Teller (BET)
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(a) (b)

Volume Adsorpbed @ STP (cm g )

3 -1
pCNT 0.15 pCNT
pCNT@GL 10 : 2 pCNT@GL 10:2
2500 pCNT@GL 10 : 5 pCNT@GL 10:5

dV / dD (cm g nm )
-1
pCNT@GL 10 : 10 pCNT@GL 10:10
2000

3 -1
0.10
1500

1000 0.05

500

0 0.00
0.0 0.5 1.0 0 5 10 15 20 25 30 35 40 45 50
Relative Pressure (P/Po) Pore width (nm)

(c) (d)
p-CNT N3 N 1s Fe 2p
N1
N2 N4 2+ 3+
Fe ,Fe 2p3/2

Intensity (a.u)
Intensity (a.u)

p-CNT@GL

Fe0
p-CNT@Fe@GL

396 398 400 402 404 705 710 715 720 725 730
Binding Energy (eV) Binding Energy (eV)
Figure 3.  a) N2 sorption isotherms and b) pore-size distribution of pCNT and graphitic overlayer deposited pCNT samples. XPS core level of c) N 1s
spectra of as-prepared carbon catalysts, and d) Fe 2p spectra of pCNT@Fe@GL.

method, and it is reduced to 1112, 977, and 690 m2 g−1 after catalysts were analyzed by X-ray photoelectron spectroscopy
depositing the PDA-derived graphitic carbon overlayer with a (XPS). Although no obvious Fe signal was detected in the survey
TeNT@ZiF-8 to dopamine weight ratio of, respectively, 10:2, spectrum (not shown) attributed to the low content of Fe nano-
10:5, and 10:10. Although the micropore region less than particles, which are covered with graphitic layer,[23,25] the C, N,
2 nm at a relatively low partial pressure is not recorded, all and O signals are obtained with an atomic ratio of, respectively,
the pCNT@GL samples show type IV isotherms, revealing the 81%, 8%, and 11%, indicating the successful nitrogen doping
coexistence of both micropores and mesopores. and complete evaporation of tellurium and zinc species during
Pore-size distribution curves based on quenched solid den- the pyrolysis process. The high-resolution nitrogen 1s spectrum
sity functional theory (QSDFT) model for slit shaped, spher- was de-convoluted into four peaks corresponding to pyridinic
ical, and cylindrical pores (Figure 3b) show the well-developed N (398.5 eV), pyrrolic N (399.7 eV), graphitic N (401.0 eV), and
mesopores broadly distributed up to 50 nm, which mainly oxidized N (402.9 eV) (Figure 3c). It has been reported that both
attributed to MOF-derived porous structure and the tubular pyridinic and graphitic N are essential toward oxygen reduction
structure generated from evaporated tellurium nanotubes used reaction, while the role of pyrrolic and oxidized N is contro-
as sacrificial templates. Because the hysteretic isotherms of versial.[36] Therefore, the relative composition of the N species
our carbon samples showed a sharp desorption step at relative of pCNT, pCNT@GL, and pCNT@FE@GL is compared and
pressure P/P0 ≈0.4–0.5 attributed to the cavitation effect,[35] the illustrated in Figure S7 (Supporting Information). The total
adsorption branch of isotherm was used to analyze the pore- nitrogen content of each carbon catalyst is similar to ≈11 at%,
size distribution. while the relative composition of graphitic N and/or pyridinic
The chemical composition and crystalline nature of carbon N compared to pyrrolic N significantly increases with the depo-
catalysts were confirmed by powder X-ray diffraction (XRD) sition of highly graphitic overlayer on pCNT for both pCNT@
analysis (Figure S6, Supporting Information) for pCNT and GL and pCNT@Fe@GL. The high-resolution Fe 2p spectrum
pCNT@Fe@GL samples. The relatively sharp main carbon for pCNT@FE@GL (Figure 3d) shows noticeable peaks cen-
peak centered at 24.9° was observed corresponding to the tered at 725.2 eV assigned to Fe 2p1/2 of Fe(III) and Fe(II),
(002) graphitic carbon, and the other peaks around 41.5° and ≈711 to ≈713 eV assigned to Fe 2p3/2 of Fe(II) and Fe(III) ions,
49.2° corresponding to iron carbide were also confirmed after and a peak at 718.7 eV assigned to a satellite peak, indicating
the deposition of the Fe-containing graphitic carbon overlayer. the co-existence of Fe(II) and Fe(III).[31,37] The peak at ≈708 eV
The elemental composition and chemical bonding of carbon can be assigned to zero-valence metallic or iron carbide peak,

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Figure 4.  a) CV curves of pCNT, pCNT@GL, and pCNT@Fe@GL in N2 (dotted line) or O2 (solid line) saturated 0.1 m KOH electrolyte. b) LSV curves
of as-prepared carbon catalysts and Pt/C in O2-saturated 0.1 m KOH electrolyte at a rotation speed of 1600 rpm with a sweep rate of 10 mV s−1. All
currents were corrected for the background current measured in N2-saturated electrolyte, and all potentials were corrected for the ohmic loss. c) LSV
curves of pCNT@Fe1.5@GL at various rotation rates (inset: corresponding Koutecky–Levich plots). d) Peroxide yield and electron transfer number
of as-prepared carbon catalysts and Pt/C catalyst at various potentials based on the RRDE data. e) LSV curves of as-prepared Fe,N-embedded porous
carbon catalysts and Pt/C in O2-saturated 0.1 m HClO4 electrolyte at a rotation speed of 1600 rpm with a sweep rate of 10 mV s−1. f) LSV curves of
pCNT@Fe1.5@GL at various rotation rates. g) Corresponding Koutecky–Levich plots derived from panel (f). h) Peroxide yield and electron-transfer
number of as-prepared Fe,N-embedded porous carbon catalysts and Pt/C catalyst at various potentials based on the RRDE data. i) LSV curves before
(solid line) and after (dashed line) 10 000 cycles from 0.6 VRHE to 1.0 VRHE in O2-saturated 0.1 m HClO4 at 50 mV s−1.

and the weak intensity is attributed to the low density of aggre-
gated metallic Fe, and an encapsulation of Fe-Nx active sites by
the carbon matrix.[23,25,38]
To investigate the separate and synergistic effects of the
deposition of ultrathin graphitic overlayer and the formation
of FeNx moiety on the ORR activity of hierarchically porous
carbon structure, cyclic voltammetry (CV) was performed first,
and then rotating disk electrode (RDE) and rotating ring-disk
electrode (RRDE) measurements were performed in 0.1 m KOH
medium. As shown in Figure 4a, the CV curves of all tested
carbon catalysts show no redox peak in N2-saturated electrolyte,
whereas the well-defined cathodic peak is observed in O2-sat-
urated electrolyte, which implies its electrocatalytic activity
toward ORR. The cathodic peak of metal-free, N-doped pCNT
is shifted to positive potential from 0.81 to 0.84 VRHE by the
deposition of an ultrathin graphitic overlayer, and it is further
shifted to 0.86 VRHE by combination of graphitic overlayer and
the introduction of Fe ions. And then, the catalytic activities of
the as-prepared carbon and Pt/C catalysts were investigated by
linear sweep voltammetry (LSV) with the RDE configuration
at a sweep rate of 10 mV s−1 and are illustrated in Figure 4b.
The pCNT exhibit ORR electrocatalytic performances with the
potential at j = 0.3 mA cm−2 (Ej = 0.3 = 0.911 ± 0.008 VRHE),
half wave potential (Ehalf = 811 ± 0.003 VRHE) comparable to
those of the Pt/C catalyst with a loading amount of 80 µg cm−2
(i.e., 16 µgpt cm−2, Ej = 0.3 = 0.946 ± 0.007 VRHE, Ehalf = 0.845 ±
0.004 VRHE), attributed to the homogeneous nitrogen distribu-
tion, high specific surface area, and hierarchical dual porous

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structure. The catalytic activity of Pt/C could be evaluated by LSV
with different loading amount of 80, 200, and 300 µgpt/C cm−2
(16, 40, and 60 µgpt cm−2, respectively), and the corresponding
half wave potentials ranges in 0.841 to 0.906 VRHE are shown
in Figure S8a (Supporting Information). After the deposition of
the highly graphitic overlayer, the pCNT@GL exhibits positive
shift in Ej = 0.3 and Ehalf attributed to the PDA-derived sp2 domi-
nant structure providing continuous electron pathway replacing
the ZIF-8-derived sp3 dominant microporous structure.[39] More
importantly, the incorporation of Fe onto carbon framework
significantly boosts the ORR catalytic activity, attributed to the
formation of highly active FeNxC active sites, and consequently
pCNT@Fe1.5@GL exhibits drastically enhanced Ej = 0.3 and Ehalf
of 0.957 ± 0.007 and 0.867 ± 0.005 VRHE compared to those of
unmodified pCNT and commercial Pt/C catalyst. Note that
the limiting current density of our catalysts was in the range
of 5.5–6.0 mA cm−2 except for pCNT (5.3 mA cm−2), and the
measured values showed less than 10% deviation. We also
provide the LSV curves of pCNT@Fe1.5@GL with a loading
amount of 0.1, 0.2, and 0.3 mg cm−2 in Figure S8b (Supporting
Information). The parameters including half-wave potential
and limiting current density showed no significant difference.
The statistical data with error bars on catalytic activity in
terms of the potential at Vj = 0.3 and half wave potentials for the
tested catalysts are summarized in Figure S9 (Supporting Infor-
mation). It is noted that the statistical data were collected from
four individual runs for each sample. The Tafel slope of pCNT
(79 ± 4 mV dec−1) at low overpotential, which is similar to that
of Pt/C (85.8 ± 5 mV dec−1), is significantly decreased upon
enwrapping with highly graphitic layer (69.1 ± 4 mV dec−1)
and further reduced to 65.2 ± 4 mV dec−1 with embedded Fe
and the deposition of graphitic layer (Figure S10, Supporting
Information). Furthermore, the key roles of Fe incorporation
were systematically investigated by tuning the amount of Fe,
and the LSV curves obtained from RDE test are illustrated in
Figure S11a (Supporting Information). All of the Fe incorpo-
rated catalysts exhibit significantly enhanced ORR activity com-
pared to the Fe-free carbon catalyst, revealing the successful
formation of FeNxC moiety and its excellent catalytic activity.
The optimized Fe content with our condition is 1.5 wt% for
onset and half wave potentials. Further increase in Fe con-
tent results in reduced electrocatalytic activity, possibly due
to the aggregation of inactive Fe nanoparticles. To investigate
the electron transfer ability of the pCNT@Fe@GL catalyst, an
RDE test was conducted at various rotating rates at 10 mV s−1
(Figure S11b, Supporting Information), and it is fitted withy
by the Koutecky–Levich (K-L) plot in Figure S11c (Supporting
Information). The linearity of the K-L plots for pCNT@Fe@GL
demonstrates the first-order reaction kinetics and the calcula-
tion with the K-L equation reveals that the transfer number is
from 3.96 to 3.99 over the potential range from 0.2 to 0.7 VRHE.
This electron transfer number is close to that of Pt/C catalyst
(3.95–4.00), indicating a favorable four-electron oxygen reduc-
tion reaction process. It is worth noting that all of the carbon
catalysts exhibit similar electron transfer number of close to
four regardless of additional graphitic layers and/or embedded
Fe, revealing the advantages of the rational design of MOF-
derived carbon framework with tubular structure toward ORR
(Figures S12 and S13, Supporting Information). An RRDE test
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was carried out to investigate the electron transfer mechanism
and hydrogen peroxide yields (Figure S14, Supporting Informa-
tion). For all the carbon catalysts, the hydrogen peroxide yields
are below 6% and the electron transfer number is 3.85–4.02
(Figure 4c), which coincide with the values obtained from the
K-L equation. Another important criterion of ORR catalyst to
replace Pt/C catalyst is long-term stability and tolerance toward
methanol crossover. The LSV curves before and after contin-
uous 10 000 cycles from 0.6 VRHE to 1.0 VRHE were recorded
and compared. The change in the half-wave potential of Fe-N-C
is negligible (Figure S15a, Supporting Information), whereas
the negative shift of Pt/C is about 30 mV (Figure S15b, Sup-
porting Information), indicating Fe de-metallization can be
efficiently prevented by the encapsulation of Fe-N-C active sites
by graphitic carbon overlayer and wiring them into carbon
nanotubes.[30] The methanol tolerance is also confirmed with
rapid methanol injection at 300 s after the chronoamperometric
measurement (Figure S15c, Supporting Information). It is
found that Pt/C catalyst shows obvious performance decay after
methanol injection. In contrast, pCNT@Fe@GL shows nearly
identical retention current regardless of methanol injection,
revealing its superior stability than the former. Such an excel-
lent stability of pCNT@Fe@GL can be ascribed to its unique
structure providing a dual-protection strategy of active sites by
embedding FeNxC active sites into carbon framework and by
covering them with highly graphitic overlayer simultaneously.
The formation of FeNx moieties and/or Fe3C encapsulated in
the graphene shell is believed to have a good catalytic activity
especially in acidic electrolyte.[22–24,40] Thus, the electrocata-
lytic activities toward ORR in acidic media for Fe and N-doped
carbon catalysts were also investigated. Additionally, the postan-
nealing process in an NH3 atmosphere at 950 °C for 5 min was
conducted on pCNT@Fe1.0@GL and pCNT@Fe1.5@GL. It is
well proven that the ammonia treatment can further increase
the catalytic activity particularly in acidic media attributed to
the higher basicity and porosity and disorder in the structure
of carbon matrix.[41] After the ammonia treatment, the total Fe
content is increased from 0.91% to 1.11% for pCNT@Fe1.0@
GL and from 1.35% to 1.72% for pCNT@Fe1.5@GL, as con-
firmed by ICP analysis. Note that the ammonia treatment
was accompanied with a weight loss of about ≈25%, which is
similar to that previously reported.[22] There was no significant
change on the nanostructure and chemical composition of
pCNT@Fe@GL, as confirmed by SEM (Figure S16, Supporting
Information) and XPS (Figure S17a,b, Supporting Informa-
tion) analyses. The surface area after the ammonia treatment
is slightly increased to 1220 m2 g−1 (Figure S17c, Supporting
Information).
As shown in Figure 4d, the pCNT@Fe1.5@GL catalyst
exhibits excellent ORR catalytic activity in terms of the potential
at Ej = 0.3 (0.921 ± 0.006 VRHE) and Ehalf (0.818 ± 0.004 VRHE)
comparable to those of the Pt/C catalyst (0.956 ± 0.008 VRHE
and 0.869 ± 0.006 VRHE) in 0.1 m HClO4 electrolyte. A similar
trend in catalytic activity versus the amount of Fe embedded
in carbon framework is also observed, whereas the Fe-free
pCNT@GL exhibit much poor ORR activity, indicating the
crucial role of FeNxC toward ORR in acidic medium. Remark-
ably, postammonia treatment onto our optimized pCNT@
Fe1.5@GL shows a further boost in the ORR catalytic activity
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with further positive potential at Ej = 0.3 (0.936 ± 0.011 VRHE) and
Ehalf (0.883 ± 0.006 VRHE), superior to the counterparts of Pt/C.
Note that the limiting current density of our catalysts was in
the range of 5.6–5.9 mA cm−2 except for Fe-free pCNT@GL,
and the measured values ​​showed less than 10% deviation. It is
proven that the ammonia-treated FeNxC catalysts have the same
Fe-centered moieties as the counterpart without ammonia treat-
ment, and that the much higher activity of NH3-treated FeNxC
catalyst is rather dependent on its physicochemical properties
of the carbon support.[22] The enhanced ORR catalytic activity
after the ammonia treatment can be attributed to the increased
number of accessible active site, and/or the higher basicity of
the carbon matrix.[22,41,42] The statistical data with error bars of
catalytic activity in terms of the potential at Vj = 0.3 and half wave
potentials in acidic medium are also summarized in Figure S18
(Supporting Information). These values of our Fe-,N-doped
carbon catalysts outperform the state-of-art nonprecious cata-
lysts with nonprecious metal in both alkaline and acidic media
(Table S1, Supporting Information).[9,12,14,22,27,41,43,44]
However, such an ammonia-treatment-induced boost in
catalytic activity in acidic condition is less effective in alka-
line condition (Figure S19, Supporting Information). Because
the total Fe amount in pCNT@Fe@GL is low in the range of
0.48–1.92 wt%, the catalytic activity is dependent on the mass
loading of the carbon catalyst[45,46] (Figure S20a, Supporting
Information). It is proven that metal-free NxCy active site has
certain ORR activity in acidic medium.[47] In our study, the
carbon catalyst pyrolyzed from an argon atmosphere with/
without Fe shows significantly different catalytic activities in
alkaline and acidic media. It mainly stems from the relatively
poor activity of NxCy active sites in Fe-free carbon catalysts par-
ticularly in acidic medium. Although it is debatable whether
the Fe constitutes the core of the active center,[41,48] the signifi-
cant boost in the catalytic activity in both alkaline and acidic
media by the incorporation of Fe suggests the key role of the
formation of FeNx moieties. The catalytic activity of pCNT@
Fe2.5@GL indicates that the excess amount of Fe induces the
formation of inactive Fe bulk nanoparticles. The enhanced cat-
alytic activities after the ammonia treatment suggest that the
FeNx moieties in highly basic carbon matrix have intrinsically
higher ORR activity in acidic medium. Note that the specific
and mass activities of the control sample Pt/C are, respec-
tively, 0.284 A cmpt−2 and 0.142 A mgpt−1, based on the elec-
trochemical active surface area of 49.9 cmpt2 gpt−1, which are
similar to the values in the literature.[49] The kinetic parameters
were obtained by conducting the RDE experiments at various
rotating rates and at 10 mV s−1 in O2-saturated 0.1 m HClO4
electrolyte (Figure 4f), and it was fitted by K-L plot as shown
in Figure 4g. The electron transfer number of pCNT@Fe1.5@
GL was calculated to be 3.94–4.0 at various potentials, which
is close to that of Pt/C catalyst and ammonia-treated pCNT@
Fe1.5@GL (Figure S21, Supporting Information), indicating
that pCNT@Fe@GL also facilitates mainly a direct four-elec-
tron oxygen reduction process. An RRDE test was also car-
ried out to investigate the electron-transfer mechanism and
hydrogen peroxide yields in acidic medium (Figure 4h). The
Fe-embedded carbon catalysts exhibit an electron transfer
number of ≈4.0 within 0.2 ≈0.6 V versus RHE, and its H2O2
yield is below 5%, which are close to those of Pt/C catalyst.
Adv. Mater. 2017, 1606534 1606534  (7 of 10)
www.advmat.de
As shown in Figure S20b (Supporting Information), pCNT@
Fe1.5@GL exhibits a Tafel slope of 89.8 ± 6 mV dec−1 at the low
overpotential region. After the ammonia treatment, the value
of Tafel slope is 61.9 ± 3 mV dec−1, which is superior to that
of Pt/C (77.6 ± 4 mV dec−1), revealing the synergistic effects
of the unique, highly porous 1D structure and FeNx moiety in
highly basic, disordered carbon matrix.[22,29,41] The durability of
carbon and Pt/C catalysts in acidic medium is tested by con-
tinuous 10 000 cycles in O2-saturated HClO4 electrolyte from
0.6 VRHE to 1.0 VRHE (Figure 4i). The half-wave potential shift of
pCNT@Fe1.5@GL is only 15 mV, which is advantageous com-
pared to most noble metal-free catalysts,[23,46,50] indicating that
the FeNxC active sites are successfully protected by ultrathin
graphitic overlayer. In contrast, Pt nanoparticles are directly
exposed to acidic electrolyte, leading to the preferential disso-
lution of small nanoparticles and sintering to coalesced parti-
cles (Figure S22a, Supporting Information). The stability of the
ammonia-treated FeNxC is relatively poor, as confirmed by the
half-wave potential shift of 75 mV (Figure S22b, Supporting
Information) due to the protonation of the highly basic surface
N-groups by oxygen radicals.[51] The change in the chemical
composition and nanostructure of pCNT@Fe@GL during
continuous cycles at high potential was investigated after the
stability test for 30 000 cycles in 0.1 m HClO4 electrolyte. The
overall structure of nanotube was well preserved after the sta-
bility test (Figure S23, Supporting Information). The signifi-
cant change of the overall N1s spectrum after the stability test
is observed (Figure S24, Supporting Information). The rela-
tive peak intensity of pyridinic N (398.5 eV) reduced and that
of pyrrolic N (399.7 eV) increased, while the overall N content
remained largely constant. It suggests that the pyridinic N plays
an essential role in improving the ORR catalytic activity of the
Fe-N-doped carbon under acidic conditions.[45,47,51]
The practicality of the application of pCNT@Fe1.5@GL as
an air catalyst for ZAB further demonstrates its excellent ORR
catalytic activity and the chemical stability. To investigate the
role of carbon catalyst toward ORR in ZABs, a decoupled con-
figuration (Figure S25, Supporting Information) composed
of two independent channels was used. The ORR electrode
is made of carbon or Pt/C catalyst uniformly deposited onto
carbon nanofiber paper (CNF) with a loading of 1 mg cm−2. The
decoupled, nonprecious ZABs were assembled with Fe-N-C
carbon ORR electrode and Ni-Fe LDH OER electrode, while
the decoupled, precious ZABs were assembled with the Pt/C
ORR electrode and IrO2 nanoparticles on a titanium mesh as
the OER electrode. As shown in Figure 5a, the initial round-trip
overpotential of the Fe-N-C pCNT + NiFe LDH is 0.58 V, which
is very similar to that of Pt/C + IrO2 (0.60 V), which indicates
that the excellent catalytic activities of these nonprecious cata-
lysts are effective in decreasing the overall overpotential. More
specifically, the initial discharge potential of the pCNT@Fe@
GL ORR electrode at ≈1.36 V shows no significant change after
the charge and discharge cycles over 140 h, while that of Pt/C
decreased from ≈1.36 to ≈1.32 V attributed to calcinations of
exposed active sites. After a period of 300 h corresponding to 72
discharge–charge cycles (Figure 5b), the final round-trip over-
potential of the Fe-N-C pCNT + NiFe LDH is increased from
0.58 to 0.64 V, which is mainly attributed to the difference in
the initial and final charge potentials corresponding to the OER
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
(a)
2.2 IrO2 OER + Pt/C ORR
NiFe LDH OER + pCNT@Fe1.5@GL ORR
2.0
Cell voltage (V)
1.8
1.6 Theoritical
Overpotential
1.4
1.2
0 20 40 60 80 100 120
Time (h)
Figure 5.  a) The discharge and charge voltage profiles of Zn-air batteries with IrO2/Ti mesh + Pt-C/CNF and NiFe LDH/NiF + pCNT@Fe1.5@GL/CNF
decoupled catalysts at a current density of 1 mA cm−2 at room temperature. b) Early five cycles and last five cycles of the rechargeable Zn-air battery
with pCNT@Fe1.5@GL/CNF (ORR) + NiFe LDH/NiF (OER) electrodes with a period of ≈300 h (72 discharge–charge cycles). The current density is
1 mA cm−2, and the electrolyte is 6 m KOH added with 0.2 m ZnCl2 solution.
part of, ≈1.95 and ≈1.99 V, respectively, while the counterpart of
the discharge potential corresponding to the ORR part is rela-
tively small (≈1.36 and ≈1.35 V).
In summary, a unique hierarchical structure of Fe-,N-doped
porous carbon nanotubes has been successfully constructed
via directed growth of MOF on the surface of porous tellurium
nanotube used as a sacrificial template. It is found that the
synergistic effects between the homogeneous distribution of
abundant FeNx moiety and hierarchical dual-porous structure
boosts the ORR catalytic activity. The number of FeNxC active
sites that are embedded into the carbon framework has been
systematically tuned to investigate its crucial role on ORR cata-
lytic activity. The superior electrocatalytic activity and the long-
term stability toward ORR in both alkaline and acidic media
have been confirmed compared to those of conventional Pt/C
catalyst, revealing the advantages of confined FeNx moiety in
dual porous carbon framework covered with a highly graphitic
overlayer. The rechargeable zinc-air battery in a decoupled con-
figuration was assembled with a pCNT@Fe@GL/CNF ORR
electrode and a Ni-Fe LDH/NiF OER electrode. The ZABs with
these nonprecious catalysts exhibit charge–discharge overpo-
tentials similar to the counterparts of Pt/C ORR electrode and
IrO2 OER electrode. The high ORR catalytic activity of pCNT@
Fe@GL in both alkaline and acidic media demonstrates the
possibility to replace the expansive Pt catalyst in fuel cells
and metal-air batteries. Although tellurium is a rather expen-
sive metal, this study demonstrates the superiority of catalytic
activity when porous FeNxCy catalysts derived from MOF are
formed into a 1D structure. A similar template-based approach
using low-cost templates or self-template approach is expected
to show similar structure and catalyst performance.
Experimental Section
Synthesis of Porous Tellurium Nanotubes: The porous tellurium
nanotubes were prepared as described previously with some
modifications.[52] Typically, 1.44 g of tellurium oxide powder and 1.8 g of
polyvinylpyrrolidone (average MW = 40 000) were dissolved in 150 mL
of ethylene glycol in a 250 mL round flask at 200 °C until it turned to
clear colorless solution. And then, 0.9 g of sodium hydroxide was added
to the solution, and it was kept at 200 °C for 25 min. Afterward, 1 mL
Adv. Mater. 2017, 1606534
www.advmat.de
(b)
NiFe LDH/NiF OER
pCNT@Fe1.5@GL ORR
2.0 Initial
charge
Cell voltage (V)
potential
1.8
Theoretical
1.6 potential
0.58 V 0.64 V
1.4 Initial
disharge
potential
140
20 30 280 290 300
Time (h)
of ammonia solution (28%) was injected into the solution and kept for
30 min under continuous magnetic stirring. Finally, the solution was
cooled down to room temperature naturally, and the resulting product
was collected by filtration and washed with water and ethanol twice.
Synthesis of Porous Carbon Nanotubes Composed of ZIF-8-Derived
Carbon Framework: The porous tellurium nanotubes were re-dispersed in
100 mL of methanol solution by sonication for 10 min. For the direct
growth of ZIF-8 on the surface of porous tellurium nanotubes, 2.5 g of
zinc nitrate hexahydrate and 1.2 g of 2-methyl imidazole were dissolved
in 100 mL of methanol separately by sonication for 10 min and rapidly
poured into the above tellurium nanotubes – methanolic solution under
vigorous magnetic stirring for 3 h. The resulting product (denoted as Te
NT@ZIF-8) was collected by filtration and washed with methanol twice.
The porous carbon nanotubes (denoted as pCNT) were obtained after
pyrolysis under argon at 950 °C for 3 h with a ramping rate of 5 °C min −1.
Synthesis of Fe Embedded, Graphitic Layer Coated Porous Carbon
Nanotubes (Denoted as pCNT@Fe@GL): The as-prepared Te NT@ZIF-8
was re-dispersed in 80 mL of tris-buffer solution (pH = 8.5) by sonication
for 10 min. The content of dopamine hydrochloride (10–100 wt% to
Te NT@ZIF-8, and typically 20 wt% was used) and iron(III) chloride
(0.5–2.5 wt% to final weight of carbon after the pyrolysis process,
typically 20 wt% dopamine and 1.5 wt% FeCl3 were used for pCNT@
Fe@GL) was systematically tuned and added to the solution. After
magnetic stirring at room temperature for 12 h, it was collected by
filtration and washed with deionized water twice. The pCNT@Fe@
GL was obtained after pyrolysis under argon at 950 °C for 3 h with a
ramping rate of 5 °C min−1.
Catalytic Ink Preparation: 10 mg of the as-prepared carbon catalyst
was dispersed in 1950 µL of isopropanol and 50 µL of Nafion solution
(5 wt.%) by sonication for 30 min to make a homogeneous black ink
solution. The homogeneous Pt/C catalytic ink was prepared by mixing
10 mg of Pt/C (20 wt% on Vulcan XC-72, ETEK), 40 µL of Nafion
solution (5 wt.%), 3 mL of deionized water and 2 mL of isopropanol via
ultrasonication for 1 h.
Rotation Disk Experiment and Rotating Ring-Disk Experiment: For
the experiments in alkaline medium, typically 8 µL of the as-prepared
carbon catalyst ink was deposited onto glassy carbon electrode with a
diameter of 5 mm to give a loading of ≈0.2 mg cm−2, and the catalytic
activity was compared to that of Pt/C with a loading amount of ≈0.08
and 0.2 mg cm−2 (16 and 40 µgpt cm−2). For the experiments in acidic
medium, typically 0.6 mg cm−2 of carbon catalysts was deposited to
compare the catalytic activity with that of Pt/C catalyst with a loading
amount of 0.08 mg cm−2 (16 µgpt cm−2). Prior to the electrochemical
analysis, N2 or O2 flow was bubbled for 30 min for 0.1 m KOH or 0.1 m
HClO4 electrolyte to give a saturated state. Electrochemical analysis was
performed with a potentiostat (Autolab PGSTAT302N) and a rotation
control device (Pine Research Instrumentation) with a conventional
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three-electrode configuration consisting of a glassy carbon electrode as a a titanium mesh. A polished zinc plate was employed as the anode
working electrode, platinum mesh as a counter electrode, and saturated and the electrolyte was 6 m KOH with 0.2 m of ZnCl2 solution. For the
calomel electrode (SCE) as a reference electrode. The potential versus decoupled cell configuration, the cycling performance was determined
reversible hydrogen electrode (ERHE) was converted from potential with two independent channels on an Arbin 2000 battery cycler at a
versus SCE (ESCE) following the Nernst equation current density of 1 mA cm−2 in air. Each charge and discharge period
was set to be 2 h with a 5 min rest time.
E RHE = E SCE + 0.059 × (pH) + 0.242 (1) Physical Characterizations: SEM images were obtained with an FEI
 Quanta 650 SEM. TEM and HRTEM images and element mapping
analysis were conducted on a JEOL 2010F TEM. X-ray photoelectron
CV analysis was performed at a scan rate of 5 mV s−1 in N2 or
spectra (XPS) were recorded with Kratos Axis Ultra DLD with
O2 saturated 0.1 m KOH solution. LSV curves were obtained in O2
Al Kα (1486.6 eV) X-ray source. XRD patterns were collected on
saturated 0.1 m KOH or 0.1 m HClO4 solution at different speed rates
Rigaku MiniFlex 600 with Cu Kα radiation with a scan step of 0.05°
from 400 to 2400 rpm at 10 mV s−1. Statistical data were collected from
between 10° and 80°. N2 adsorption–desorption isotherms and pore-
four individual runs for each sample. All currents were corrected for
size distributions were determined at 77 K with a Quantachrome
the background current measured in N2-saturated electrolyte and all
AutoSorb iQ2. Textural properties such as the specific surface area,
potentials were iR-compensated. The durability of the electrocatalysts
pore volume, and pore-size distribution were calculated from each
was evaluated by continuous 10 000 potential cycles from 0.6 to 1.0 VRHE
corresponding N2 adsorption–desorption isotherm, applying the BET
with triangle wave at 50 mV s−1 in O2-saturated 0.1 m KOH or 0.1 m
equation and QSDFT model for slit shaped, spherical, and cylindrical
HClO4 electrolyte. The durability of catalyst toward methanol crossover
pores. The content of Fe was measured with an ICP analyzer
was assessed by chronoamperometry analysis by rapidly injecting 2 m of
(Agilent 7700).
methanol into O2 saturated 0.1 m KOH solution within ≈300 s.
The kinetics parameters during ORR were determined according to
the Koutecky–Levich equation given below
Supporting Information
1 1 1 1 1
= + = + (2) Supporting Information is available from the Wiley Online Library or
J JL JK Bω 1/2 JK
 from the author.

1
−
B = 0.62nFC 0 (D 0 )
2/3 (3)
ν 6

Acknowledgements
where J is the measured current density at specific potential, JK is the This work was supported by the U.S. Department of Energy, Office of
kinetic current density, JL is the diffusion limited current density, ω is Basic Energy Sciences, Division of Materials Sciences and Engineering
the electrode rotation rate, F is Faraday constant (F = 96485 C mol−1), under award number DE-SC0005397.
and C0 is the bulk concentration of O2 (1.2 × 10−3 mol cm−3) for both
0.1 m KOH and 0.1 m HClO4 solutions. D0 is the diffusion coefficient of
O2 (1.9 × 10−5 cm2 s−1 for 0.1 m KOH solution and 1.93 × 10−5 cm2 s−1
for 0.1 m HClO4 solution) and ν is the kinetic viscosity of the electrolyte Keywords
(0.01 cm2 s−1 for both 0.1 m KOH solution and 0.1 m HClO4 solution).
The electron transfer number can be obtained from the slope of the K-L 1D nanotubes, metal-organic frameworks, oxygen reduction reaction,
plot. zinc-air batteries
RRDE tests were carried out in O2 saturated 0.1 m KOH or 0.1 m
HClO4 solution at 1600 rpm with a scan rate of 10 mV s−1, and the Received: December 2, 2016
potential of the Pt ring was set at V = 1.3 VRHE. The electron transfer Revised: January 27, 2017
number (n) and the yield of hydrogen peroxide released during ORR Published online:
were calculated based on the following equation

ID
n = 4× (4)
IR /N + ID

IR /N
% H2O 2 = 200 × (5)
IR /N + ID
 [3] Y. Liang, Y. Li, H. Wang, J. Zhou, J. Wang, T. Regier, H. Dai,
where ID is the disk current, IR is the ring current, and N is the collection
coefficient of the Pt ring (N = 0.37).
Zinc-Air Battery Test: The rechargeable zinc-air battery tests were
carried out with a home-made polytetrafluoroethylene (PTFE) layered
battery mold. For the decoupled configurations, the air electrode for ORR
was prepared by a uniform deposition of the as-prepared carbon or Pt/C
catalysts onto a hydrophobic CNF (0.75 × 0.75 cm2). To make an ORR
air electrode, the catalytic ink solution including 10 mg catalyst, 60 µL
5wt% Nafion solution, 600 µL deioinized water, and 300 µL isopropanol
was uniformly coated onto the CNF to make an electrode with a mass
loading of ≈1 mg cm−2. The nonprecious OER electrode was made
by a solution-based, direct growth of nickel iron oxyhydroxide onto a
commercial nickel foam as previously reported.[53] An IrO2 thin film on a
titanium mesh (IrO2/Ti) was prepared according to a method presented
in the literature[54] by electrophoretically depositing IrO2 colloidal onto
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