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Boronization-Induced Ultrathin 2D Nanosheets with

Abundant Crystalline–Amorphous Phase Boundary
Supported on Nickel Foam toward Efficient Water Splitting
Hongbin Xu, Ben Fei, Guanghui Cai, Yuan Ha, Jing Liu, Huaxian Jia, Jichao Zhang,
Miao Liu, and Renbing Wu*

Hydrogen has become one of the most

The conversion of crystalline metal–organic frameworks (MOFs) into metal promising energy carriers due to its
compounds/carbon hybrid nanocomposites via pyrolysis provides a promising highest gravimetric energy density and
solution to design electrocatalysts for electrochemical water splitting. However, carbon-free emission.[1–8] Electrochemical
water splitting provides a green and sus-
pyrolyzing MOFs generally involves a complex high-temperature treatment,
tainable way for hydrogen fuel production
which can destroy the coordinated surroundings within MOFs, and as a especially when it was integrated with
result not taking full advantage of their electrolysis properties. Herein, a other intermittent energy sources (e.g.,
simple and room-temperature boronization strategy is developed to convert wind and solar). However, two-core half
nickel zeolite imidazolate framework (Ni-ZIF) nanorods into ultrathin Ni-ZIF/ reactions, i.e., the hydrogen evolution
NiB nanosheets with abundant crystalline–amorphous phase boundaries. reaction (HER) at the cathode and oxygen
evolution reaction (OER) at the anode
The combined experiment, and theoretical calculation results disclose that are thermodynamically uphill, leading
the ultrathin thickness allows fast electron transfer and ensures increased to a high overpotential and low reaction
exposure of surface coordinatively unsaturated active sites while the crystalline– kinetics. Noble Pt-based metals and Ru-/
amorphous interface elaborately changes the potential-determining step to Ir-based oxides are regarded as the state-
energetically favorable intermediates. As a result, Ni-ZIF/NiB nanosheets of-the-art catalysts for HER and OER,
respectively. Unfortunately, the scarcity
supported on nickel foam (NF) require overpotentials of 67 mV for the hydrogen
and high cost of these noble metals seri-
evolution reaction and 234 mV for the oxygen evolution reaction to achieve a ously hamper their large-scale application.
current density of 10 mA cm−2. Remarkably, Ni-ZIF/NiB@NF as a bifunctional Therefore, the exploration of low-cost and
electrocatalyst for overall water splitting enables an alkaline electrolyzer with highly active electrocatalyst based on earth
10 mA cm−2 at an ultralow cell voltage of 1.54 V. The present work may open a abundant elements for both HER and
OER is urgently demanded.[9–16]
new avenue to the design of MOF-derived composites for electrocatalysis.
Metal–organic frameworks (MOFs), a
class of crystalline porous materials con-
structed by metal ions and coordinated
H. Xu, B. Fei, Y. Ha, J. Liu, Prof. R. Wu organic ligands, have received considerable interest in energy
Department of Materials Science conversion-related catalysis owing to their structural diversity,
Fudan University tunable porosity, and high specific surface area.[17–21] Neverthe-
Shanghai 200433, P. R. China less, most MOF electrocatalysts still suffer from poor electrical
E-mail: rbwu@fudan.edu.cn
conductivity and low accessibility of active metal centers
G. H. Cai, H. X. Jia, Prof. M. Liu
blocked by organic ligands, thus exhibiting slow charge-transfer
Institute of Physics
Chinese Academy of Sciences kinetics and limited catalytic efficiency. To circumvent these
Beijing 100190, P. R. China shortcomings, ultrathinning bulk MOFs into 2D layered struc-
Dr. J. Zhang ture in the form of nanosheets has been demonstrated to be an
Shanghai Synchrotron Radiation Facility effective strategy. In comparison with traditional bulk MOFs,
Zhangjiang Laboratory 2D MOF nanosheets not only ensure easy mass transport of
Shanghai Advanced Research Institute
Chinese Academy of Sciences molecules/ions and rapid electron transfer, but also have larger
Shanghai 201204, P. R. China specific surface area and higher percentage of surface coordi-
Prof. M. Liu natively unsaturated metal sites to guarantee more exposure
Songshan Lake Materials Laboratory of active sites, thus leading to an enhanced electrocatalytic
Dongguan, Guangdong 523808, P. R. China performance. For example, Zhao et al. synthesized ultrathin
NiCo bimetal–organic framework nanosheets via ultrasonica-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201902714.
tion exfoliation and found that they exhibited an excellent OER
catalytic activity with a current density of 10 mA cm−2 at an
DOI: 10.1002/aenm.201902714 overpotential of 250 mV, much smaller than that of bulk MOF

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counterpart (317 mV).[22] Huang et al. developed an electro­
chemical/chemical exfoliation strategy to prepare ultrathin
2D Co-MOF nanosheets as an efficient electrocatalyst to catalyze
OER.[23] Duan et al. reported an in situ growth of nanosheets of
2D NiFe MOF arrays on nickel foam, showing a bifunctional
catalytic activity for overall water splitting with a current density
of 10 mA cm−2 at a cell voltage of 1.55 V.[24] Despite the great
achievements have been made in this field, the synthesis of
these catalytically active 2D MOFs is mainly limited to complex
exfoliation, which is usually tedious and time-consuming with
low yields. In this regard, it remains great challenge to develop
an efficient and simple method to synthesize ultrathin MOFs
under mild conditions toward electrocatalysis.
On the other hand, converting MOFs into metal (compounds)/
carbon hybrid nanocomposites via high-temperature pyrol-
ysis have been proposed as another strategy to utilize them for
electrocatalysis.[25–33] During the pyrolysis process, the active
metal species come from the metallic nodes in the MOF pre-
cursor, while the carbon matrices are converted from the
carbonization of organic ligands. Benefiting from the conduc-
tive carbon scaffolds and the high homogeneity in spatial
distribution of active metal species, these MOF-derived hybrid
nanocomposites exhibited a promising electrocatalytic per-
formance. However, the pyrolysis strategy generally requires
a high-temperature treatment with large energy consump-
tion, which thoroughly destroy the coordinated surrounding
around the metal center within MOFs, thus decreasing the
exposure of active sites and hardly taking full advantage of
MOFs for electrocatalysis.
Considering the merits of ultrathin MOFs and drawbacks
of the MOF-derived composites obtained by pyrolysis, herein,
we present a convenient boronization method for achieving
Figure 1. Schematic illustration of the synthetic process of Ni-ZIF/NiB@NF.
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a room-temperature conversion of nickel zeolite imidazolate
framework (Ni-ZIF) nanorods into ultrathin Ni-ZIF/NiB
nanosheets with rich crystalline–amorphous phase boundaries
serving as a highly efficient bifunctional electrocatalyst for both
HER and OER. By carefully changing the boronization time,
we can control the conversion degree of MOFs and thus tune
the morphology, microstructure, and chemical composition of
the resulting products. As a demonstrated example, the Ni-ZIF/
NiB nanosheets supported on nickel foam obtained by 4 h
boronization of Ni-ZIF exhibited an exceptional electrocatalytic
performance toward overall water splitting with an ultralow cell
voltage of 1.54 V at 10 mA cm−2, representing a new level for
MOF-based electrocatalyst.
The formation of 2D nanosheets with crystalline–amor-
phous boundaries supported on nickel foam catalyst involves
two major steps as illustrated in Figure 1. First, Ni-ZIF
nanorods were uniformly grown on the skeleton of nickel foam
(Ni-ZIF@NF) by the coordination of nickel ions and 2-methyl-
imidazole (2-MeIm) through a hydrothermal reaction. Second,
Ni-ZIF@NF was immersed into NaBH4 solution to allow the
conversion of Ni-ZIF into ultrathin 2D nanosheets supported
on NF. During this process, partially coordinated 2-MeIm
within Ni-ZIF would be preferentially etched and exfoliated by
alkaline NaBH4, leading to the formation of ultrathin crystal-
line–amorphous Ni-ZIF/NiB nanosheets. Nevertheless, as
the boronization time further increases to 24 h, the crystal-
line Ni-ZIF would completely convert into amorphous NiB,
accompanied by the evolution of sheet-like shape into worm-
like morphology. Note that the products gained by boronization
time 0, 2, 4, 9, and 24 h are denoted as Ni-ZIF@NF, Ni-ZIF/
NiB@NF-2, Ni-ZIF/NiB@NF-4, Ni-ZIF/NiB@NF-9, and
NiB@NF-24, respectively.
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Figure 2. Field-emission scanning electron microscopy (FESEM) images of a) Ni-ZIF@NF, b) Ni-ZIF/NiB@NF-2, c) Ni-ZIF/NiB@NF-4, d) Ni-ZIF/
NiB@NF-9, and e) NiB@NF-24. f) XRD patterns of all the samples.
To investigate the morphology evolution of Ni-ZIF@NF during
boronization within NaBH4 solution, field-emission scanning
electron microscopy (FESEM) images of products obtained at
the time-dependent reactions are provided. Figure 2a displays
FESEM image of the Ni-ZIF@NF precursor. It can be seen that
many stacked Ni-ZIFs with rod-like morphology are evenly grown
on Ni foam. After the reaction with NaBH4 for 2 h, the obtained
products still preserve the uniform distribution on NF, while their
morphology is significantly different as compared with that of Ni-
ZIFs and changes into oriented 2D sheet-like structure, indicating
the possible occurrence of phase transformation (Figure 2b).
With increasing the boronization time to 4 h, the morphology
of Ni-ZIF/NiB@NF-4 is similar to that of Ni-ZIF/NiB@
NF-2 except that the nanosheets are thinner and more unfolded
(Figure 2c). Atomic force microscopy measurements further
verified their ultrathin feature with a thickness around 1.7 nm
(Figure S1, Supporting Information). As boronization time is fur-
ther prolonged, the partial collapse of these nanosheets could be
observed in the Ni-ZIF/NiB@NF-9 (Figure 2d). Upon boroniza-
tion time increased to 24 h, the nanosheets are completely invis-
ible and the worm-like NiB structures densely covered on the
surface of NF could be found (Figure 2e). To further investigate
the phase transformation from Ni-ZIF to NiB, X-ray diffraction
(XRD) characterizations of products obtained at different boroni-
zation time were conducted. XRD pattern of Ni-ZIF is shown
in Figure 2f. A preferential of strong diffraction peak at around
12° corresponding to (211) crystal planes of Ni-ZIF could be
identified, which is similar to previously reported Ni-ZIF.[20,21]
With the prolongation of boronization time, the diffraction peak
of Ni-ZIF becomes weaker and finally disappears, demonstrating
the transformation from crystalline Ni-ZIF phase to amorphous
NiB phase. Note that the Ni-ZIF is hardly reduced to be Ni
nanoparticles or cluster, as evidenced by XRD patterns of product
obtained by immersing Ni-ZIF@NF into NaBH4 solution for 24 h
(Figure S2, Supporting Information).
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The microstructures of products obtained at different boroni-
zation times were characterized by high-resolution transmis-
sion electron microscopy (HRTEM). Figure 3a shows a HRTEM
image of Ni-ZIF, from which a clear lattice spacing value of
0.707 nm indexing to the (211) facet of Ni-ZIF can be clearly
observed. After a boronization with NaBH4, locally disordered
lattice structures originated from the amorphous phase began
to appear in the crystalline phase, creating a large number
of crystalline–amorphous phase boundaries (marked with
white curve in Figure 3b and Figure S3 in the Supporting
Information). Correspondingly, the lattice fringes in the HRTEM
image gradually become indistinct (Figure S4, Supporting Infor-
mation). When the boronization time was increased to 24 h, no
lattice fringes could be found, confirming a complete crystal-
line–amorphous transformation from Ni-ZIF to NiB, which
is consistent with the XRD results. Figure 3d–h shows high-
angle annular dark-field scanning transmission electron micros-
copy (HAADF-STEM) and the corresponding energy-dispersive
X-ray spectroscopy (EDS) elemental mapping images of Ni-ZIF/
NiB-4, suggesting the coexistence and homogeneous disper-
sion of C, N, Ni, and B in the sheet-like framework.
X-ray absorption spectroscopy was further employed to
study the local structure of Ni-ZIF/NiB. Figure 3i displays the
X-ray absorption near edge-structure (XANES) at Ni K-edge of
Ni-ZIF/NiB-4 and Ni-ZIF with Ni foil and NiO as references.
The peak intensity of Ni-ZIF/NiB-4 is higher than that of Ni
foil but lower than that of NiO, suggesting NiN and NiB
bindings and the valence state of Ni ranging from 0 to 2.[34]
The difference in the pre-edge intensity may be attributed to
the NiB bonding. Further local structure information could
be found in extended X-ray absorption fine structure (EXAFS)
spectra (Figure 3j). A mainly distinct peak around 1.4 Å can be
found in the EXAFS spectrum of Ni-ZIF, which can be attrib-
uted to NiN bond, further indicating the structure and coor-
dination environment of Ni-ZIF. By contrast, in the EXAFS
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Figure 3. HRTEM images of a) Ni-ZIF, b) Ni-ZIF/NiB-4, and c) NiB@NF-24. d–h) HAADF-STEM and the corresponding EDS elemental mapping
images of Ni-ZIF/NiB-4. i) XANES and j) EXAFS spectra of the as-prepared Ni-ZIF/NiB-4, Ni-ZIF, Ni foil, and NiO samples. k) Wavelet transforms
for EXAFS signals of Ni-ZIF/NiB. l) N 1s, m) Ni 2p, and n) B 1s XPS spectrum of Ni-ZIF, Ni-ZIF/NiB@NF-4, and NiB-24.

spectra of Ni-ZIF/NiB-4, two broad peaks around 1.4 and
1.7 Å mainly originate from the NiN and NiB bonding.[35] As
the NiB is amorphous, the distance of Ni and B is nonuniform
and thus a peak would be broadened. The peak at 2.65 Å is prob-
ably related to the NiNi paths in the amorphous NiB.[36] By
observing the wavelet transform (WT) contour plot of Ni-ZIF
(Figure S5, Supporting Information), the only maximum inten-
sity is around 7 Å−1, corresponding to the NiN. For Ni foil and
NiO (Figures S6 and S7, Supporting Information), the maximum
intensity is mainly at around 8 Å−1, corresponding to the NiNi
binding in Ni foil and NiO.[37] Figure 3i shows the WT contour
plot of Ni in Ni-ZIF/NiB. The intensity at 4 Å−1 is mainly due to
NiN in Ni-ZIF and NiB in NiB, while the strong intensity at
11 Å−1 may be attributed to the NiNi in the amorphous NiB,
which is in agreement with EXAFS results. The low intensity of
NiB interaction may be due to the low interaction of X-rays with
B atoms together with disordered crystalline structure, which
also confirm the existence of crystalline/amorphous boundaries.

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To provide insight into boronization-induced conversion of
Ni-ZIF mechanism, X-ray photoelectron spectroscopy (XPS)
analysis was carried out to monitor the changes in the Ni-ZIF-
based N and Ni coordination environment. The peak fitting
of N 1s from Ni-ZIF was composed of three peaks centered at
398.8, 398.1, and 400.1 eV, which can be attributed to NiN
species in Ni-ZIF frameworks (NiNZIF), N1:N and N2:NH in
2-MeIm ligands (Figure 3l and Figure S8 (Supporting Infor-
mation)).[38] Upon boronization occurs, not only Ni-NZIF N
1s peak gradually decreases and finally disappears but also a
new N 1s peak appears at 399.4 eV, which can be assigned to
an intermediate species within Ni-ZIF/NiB-4. The Ni 2p XPS
spectra of Ni-ZIF, Ni-ZIF/NiB-4, and NiB-24 were also
shown in Figure 3m. With increasing the time of boronization,
both Ni 2p1/2 and Ni 2p3/2 peaks shift to lower binding energy,
which may be related to the breakage of NiN bonds in Ni-ZIF
and the formation of NiB bonds.[39] As a result, the formation
of ultrathin 2D nanosheets with crystalline–amorphous phase
boundary began with a partial breakage of NiNZIF bonds,
creating a 2-MeIm and intermediate species, which further
reacts with NaBH4 to accomplish the conversion of crystalline
Ni-ZIF into amorphous NiB (Figure 3n).[40]
The electrocatalytic performance of products was assessed
using a three-electrode cell system. The catalytic activity of
Ni-ZIF/NiB@NF-4 toward OER was first investigated in 1.0 m
KOH. Before electrochemical tests, the Hg/HgO electrode
was calibrated with respect to reversible hydrogen electrode in
a three-electrode system under 25 °C. As shown in Figure S9
(Supporting Information), the average of two potentials at
which the zero-current-crossing points was employed to be
the thermodynamic potential for hydrogen electrode reactions
(0.920 V). Figure 4a shows a linear sweep voltammetry (LSV)

Figure 4. a) OER LSV curves recorded at scan rate of 1 mV s−1, b) Tafel slopes, c) EIS spectra, inset in (c): the simulated equivalent circuit model
extracted from the Nyquist plots, d) Cdl values of Ni-ZIF@NF, Ni-ZIF/NiB@NF-2, Ni-ZIF/NiB@NF-4, Ni-ZIF/NiB@NF-9, and NiB@NF-24;
e) the current–time curve of Ni-ZIF/NiB@NF-4 at a controlled potential (1.456 V), inset in (e): FESEM image of the cycled Ni-ZIF/NiB@NF-4
catalyst. f) the high-resolution O 1 s XPS spectrum in the cycled Ni-ZIF/NiB@NF-4. g) HER LSV curves recorded at a scan rate of 1 mV s−1, h) Tafel
slopes, and i) EIS spectra of samples for HER, inset in (i): the simulated equivalent circuit model extracted from the Nyquist plots.

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curves scanned at 1 mV s−1. Ni-ZIF/NiB@NF-4 requires an
overpotential of 234 mV at a current density of 10 mA cm−2,
which is not only much smaller than Ni-ZIF@NF (307 mV),
Ni-ZIF/NiB@NF-2 (280 mV), Ni-ZIF/NiB@NF-9 (292 mV),
and NiB@NF-24 (294 mV) but also superior to commercial
IrO2@C catalysts (322 mV) and most reported Ni-based
catalysts (Table S1, Supporting Information). Note that this
value is also significantly lower than that of blank NF (370 mV),
indicating that the excellent catalytic activity of Ni-ZIF/NiB@
NF-4 is mainly originated from ultrathin crystalline–amorphous
Ni-ZIF/NiB instead of NF. Additionally, the repeatability is
also important for practical application. As shown in Figure S10
(Supporting Information), OER LSV curves of five Ni-ZIF/
NiB@NF-4 samples obtained using the same method exhibit
almost no change, demonstrating good repeatability. The cor-
responding Tafel plots derived from LSV curves are further
provided (Figure 4b), among which the Ni-ZIF/NiB@NF-4
delivers the lowest Tafel slope of 57 mV dec−1 compared to
Ni-ZIF@NF (130 mV dec−1), Ni-ZIF/NiB@NF-2 (76 mV dec−1),
Ni-ZIF/NiB@NF-9 (88 mV dec−1), and NiB@NF-24
(95 mV dec−1), suggesting its favorable OER catalytic kinetics in
alkaline conditions. To understand the significantly improved
OER catalytic activity of Ni-ZIF/NiB@NF-4, electrochemical
impedance spectroscopy (EIS) and the electrochemical surface
area (ECSA) of the catalysts were analyzed. On the basis of the
simulated equivalent circuit model extracted from the Nyquist
plots (Figure 4c and its inset), Ni-ZIF/NiB@NF-4 exhibits the
lowest charge transfer resistance (Rct = 20.85 Ω), indicating its
stronger electron transfer ability during OER (Figure S11 and
Table S2, Supporting Information).
The ECSA that is directly reflected from the double-layer
capacitance (Cdl) can be evaluated by deriving from the cyclic
voltammetry curves versus different scan rates (Figure S14,
Supporting Information). As presented in Figure 4d, Ni-ZIF/
NiB@NF-4 has the largest Cdl value of 92 mF cm−2 among the
studied catalysts, implying that the ultrathin 2D nanosheets with
abundant crystalline–amorphous boundary may provide more
catalytically active sites for electrocatalysis during the OER pro-
cess. In addition, the long-term durability of electrocatalyst was
also evaluated by controlled potential electrolysis (1.464 V). As
shown in Figure 4e, the Ni-ZIF/NiB@NF-4 exhibits excellent
stability with a negligible decay after 36 h at a current density
of 10 mA cm−2. The morphology of the OER-cycled Ni-ZIF/
NiB@NF-4 is shown in the inset of Figure 4e, from which the
originally ultrathin 2D nanosheet structure was still preserved.
The surface chemical state of Ni-ZIF/NiB@NF-4 after cycling
was also investigated by XPS. As shown in Figure 4f, the high-
resolution O 1s XPS spectrum was deconvoluted into two peaks
positioned at 531.8 and 531.2 eV, which can be attributed to the
typical NiO and OH bonds, suggesting the formation of sur-
face oxidation layer on the catalysts. It also can be corroborated
by the XPS spectrum of Ni 2p in Figure S13 (Supporting Infor-
mation), as the binding energy slightly increases compared to
that before OER cycle. Such thin layer might be favorable for
optimizing the Gibbs free energy of the reaction intermediate
during electrocatalytic OER process.[41,42]
The HER performance of Ni-ZIF/NiB@NF-4 was also
studied and compared with those of Ni-ZIF@NF, Ni-ZIF/
NiB@NF-2, Ni-ZIF/NiB@NF-9, NiB@NF-24, and Pt/C@NF
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in 1.0 m KOH electrolyte. The LSV curves in Figure 4g demon-
strate that the Ni-ZIF/NiB@NF-4 has an overpotential of
67 mV at the current density of 10 mA cm−2, much smaller than
those of Ni-ZIF@NF (218 mV), Ni-ZIF/NiB@NF-2 (136 mV),
Ni-ZIF/NiB@NF-9 (130 mV), and NiB@NF-24 (195 mV). It
is worth noting that this performance even outperforms com-
mercial Pt/C catalyst supported on NF (135 mV) and the state-
of-the-art MOF-derived HER catalyst (Table S3, Supporting
Information). Similar to OER case, the performance of blank
NF for HER (324 mV) is also very poor. Figure S14 (Supporting
Information) shows HER LSV curves of five Ni-ZIF/NiB@
NF-4 samples obtained using the same method (Supporting
Information), demonstrating again the good repeatability of
Ni-ZIF/NiB@NF-4 for HER. In addition, the Ni-ZIF/NiB@
NF-4 catalyst exhibits the lowest Tafel slope (108 mV dec−1)
(Figure 4h), and the smallest Rct value (12.93 Ω, Figure 4i and
Figure S15 and Table S4 (Supporting Information)) among
the compared catalyst, further revealing its favorable reaction
kinetic and outstanding charger transfer ability. A prolonged
chronoamperometry was carried out to investigate the stability
of Ni-ZIF/NiB@NF-4. As shown in Figure S16 (Supporting
Information), it displays no obvious degradation of current den-
sity at a constant potential of −0.067 V over 64 h, demonstrating
the excellent durability over the long-term HER electrolysis.
Density functional theory (DFT) calculations were fur-
ther performed to understand the enhanced electrocatalytic of
Ni-ZIF/NiB@NF-4. Figure S17 (Supporting Information)
shows the DFT model and intermediate products for OER and
HER process of NiB, Ni-ZIF, and Ni-ZIF/NiB. To construct
the surface model with two phase boundaries, a simplified tran-
sition process from Ni-ZIF to Ni-ZIF/NiB was considered. The
2-MeIm exfoliates from the unit of Ni-ZIF and the NiB bonds
were formed. The connection between the Ni-ZIF and NiB
can be considered as the phase boundary, where the catalytic
reactions take place. In an alkaline media, the OER generally
undergoes a four-electron step process and the oxygen interme-
diates mainly involve OH*, O*, and OOH*. Figure 5a depicts
profiles of the free energy changes for the OER steps. Obvi-
ously, it can be found that the potential-determining step (PDS)
for Ni-ZIF is the initial adsorption of OH* and it requires
2.36 eV at U = 1.23 V. By contrast, the PDS for amorphous
NiB changes to form the *OOH with a reaction ΔG as high
as 1.23 eV. On the other hand, the Ni-ZIF is more favorable for
the step from *O to *OOH, while the NiB has better catalytic
activity for the formation of *OH. As expected, upon coupling
Ni-ZIF with NiB, not only the energy barrier for *OH is
effectively reduced but also the reaction free energy from *O
to *OOH would be lowered, demonstrating the intrinsically
enhanced activity in Ni-ZIF/NiB with crystalline–amorphous
boundary. Regarding the HER process, the adsorption free
energy of H* (ΔGH*) has also been calculated for Ni-ZIF, NiB,
and Ni-ZIF/NiB structural models. The ΔGH* value is an
important descriptor of activity and typically the closer to zero,
the better. According to the calculation results presented in
Figure 5b, compared with the Ni-ZIF and NiB, the Ni-ZIF/
NiB catalyst shows a more optimal ΔGH* that is closer to zero,
indicating its higher catalytic HER activity.
Motivated by the impressive OER and HER performance of
Ni-ZIF/NiB@NF-4, a two-electrode electrolyzer employing
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Figure 5. a) The calculated free-energy diagram of the OER at the thermodynamic equilibrium potential 1.23 V; b) the calculated free-energy diagram of
the HER. c) The polarization curves of Ni-ZIF/NiB@NF-4||Ni-ZIF/NiB@NF-4, and Pt/C@NF||IrO2/C@NF for overall water splitting at a scan rate
of 1 mV s−1; d) comparison of the cell voltages to drive a current density of 10 mA cm−2 for the Ni-ZIF/NiB@NF-4 with recently reported transition
metal–based bifunctional catalysts. e) The duration test of Ni-ZIF/NiB@NF-4 for water splitting at a controlled potential of 1.54 V.

Ni-ZIF/NiB@NF-4 catalysts as both the anode and cathode
was constructed to evaluate electrocatalytic performance for
overall water splitting in 1 m KOH solution. As shown in
Figure 5c, the Ni-ZIF/NiB@NF-4||Ni-ZIF/NiB@NF-4 can
achieve a current density of 10 mA cm−2 at the cell voltage of
1.54 V at scan rate of 1 mV s−1, which is lower than that of
noble Pt@C||IrO2@C couple (1.58 V). The inset in Figure 5c
shows a digital photograph of the electrolyzer system, where
the obvious hydrogen and oxygen bubbles formed on the
surface of electrodes. In addition, it also exhibits a superior
activity in comparison to most of previously reported transi-
tion metal–based bifunctional electrocatalysts for overall water
splitting (Figure 5d and Table S5 (Supporting Information)).
More importantly, the assembled Ni-ZIF/NiB@NF-4||Ni-
ZIF/NiB@NF-4 electrolyzer at 1.54 V showed remarkable
cycle durability with a negligible current density decay after
a long-term operation up to 64 h (Figure 5e). Additionally,
we have conducted stability test at a higher current density
(50 mA cm−2) at a potential of 1.71 V. As shown in Figure S18
(Supporting Information), our catalyst still exhibits a remark-
able stability without no obvious degradation after 64 h. The
Faradic efficiency test was conducted at 1.8 V, which estimated
by comparing the experimentally quantified gas with theo-
retically calculated gas is nearly 99% for both HER and OER,
and the value ratio of H2 and O2 is 2:1, demonstrating good
catalytic selectivity and no side reactions during electroca-
talysis (Figure S19, Supporting Information). Encouragingly,
Ni-ZIF/NiB@NF-4||Ni-ZIF/NiB@NF-4 electrolyzer can be
effectively powered by a single-cell AAA battery with a nominal
voltage of 1.5 V (Figure S20, Supporting Information), sug-
gesting a great potential of Ni-ZIF/NiB@NF-4 in the prac-
tical electrolysis.
In summary, for the first time, we have developed ultrathin
Ni-ZIF/NiB nanosheets with abundant crystalline–amorphous
phase boundaries via a controlled room-temperature boroni-
zation of Ni-ZIF nanorods. The optimized Ni-ZIF/NiB
nanosheets supported on nickel foam required only a small
overpotential of 234 and 67 mV to drive OER and HER pro-
cess at a current density of 10 mA cm−2 in alkaline condition,
respectively. Remarkably, it enables an alkaline electrolyzer with
a current density of 10 mA cm−2 for overall water splitting at
an ultralow cell voltage of 1.54 V, outperforming commercial
Pt@C||IrO2@C couple and most of the transition metal–based
bifunctional electrocatalysts reported to date. The excellent cata-
lytic performance can be attributed to 2D ultrathin nanosheets
and rich crystalline–amorphous boundaries resulting in more
accessible surface areas and active sites, accelerated mass
diffusion and charge transfer ability, as well as an optimal
adsorption energy change of intermediates. Considering the
convenience and simplicity of this strategy, our work may
provide a new inspiration to design MOF-based electrocatalysts
for future energy conversion applications.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Adv. Energy Mater. 2019, 1902714 1902714 (7 of 8) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Acknowledgements
H.X., B.F., and G.H.C. contributed equally to this work. This work was
financially supported by the National Natural Science Foundation of
China (Grant Nos. 51672049, 51871060, 51831009, and 11705270),
Shanghai Sailing Program (17YF1423600), the FDUROP (Fudan’s
Undergraduate Research Opportunities Program), the CURE (Hui-Chun
Chin and Tsung-Dao Lee Chinese Undergraduate Research Endowment),
and the National University Student Innovation Program. The authors
also would like to thank beamline BL14W1 and BL15U1 of the Shanghai
Synchrotron Radiation Facility (SSRF, China) for providing the beamtime.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
boronization, crystalline/amorphous boundaries, nanosheets, Ni-ZIF,
overall water splitting
Received: August 20, 2019
Revised: November 8, 2019
Published online:
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