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nanostructures as efficient electrocatalysts for
25878 integrating highly selective methanol conversion
and less-energy intensive hydrogen production†
Bin Zhao, ‡a Jian-Wen Liu,‡ac Ya-Ru Yin,a Dan Wu,a Jing-Li Luo ab

and Xian-Zhu Fu *a

Received 4th September 2019
Accepted 24th October 2019
DOI: 10.1039/c9ta09782a
rsc.li/materials-a
H2 generation from water electrolysis is a key enabling technology for a clean and sustainable future but is
still restricted by the sluggish oxygen evolution reaction (OER). So exploring an ideal electrocatalytic
valorization reaction to replace the sluggish OER and boost H2 production is desirable. Methanol, as the
most important liquid C1 resource with huge production capacity, is rather inexpensive and practical for
utilization. In this work, in situ synthesized carbon nanofibers@NiSe (CNFs@NiSe) core/sheath
nanostructures act as robust and stable electrocatalysts for highly selective methanol conversion to
value-added formate with a high production rate and faradaic efficiency. Notably, the methanol
conversion replaces the sluggish OER to boost H2 production at a high generation rate that is 7.5 times
that in the absence of methanol, thus lowering the energy consumption. Density functional theory (DFT)
calculations reveal that the high electrocatalytic selectivity is attributed to the unique exposed NiSe (102)
facets, which facilitate the methanol conversion to formate by suppressing further oxidation to the
greenhouse gas CO2.

Recently, selective oxidation of organics has been reported to

1. Introduction
Hydrogen (H2) generation from water electrolysis has been
considered as a key enabling technology to meet the future
environmentally friendly energy requirements.1–3 Conventional
water electrolyzers simultaneously produce H2 and O2 via the
hydrogen evolution reaction (HER) at the cathode and the
oxygen evolution reaction (OER) at the anode, respectively.4,5
Unfortunately, the overall reaction rate is mainly restricted by
the sluggish kinetics of the OER, due to which a higher over-
potential is necessary for this rate determining step to match
the rate of the HER with high energy consumption, resulting in
a considerable decrease of energy conversion efficiency.6,7
Meanwhile, O2 as the product of the OER is not of high value,
and the unavoidable mixing of H2 and O2 poses an explosive
risk.8
a
College of Materials Science and Engineering, Shenzhen University, 1066 Xueyuan
Avenue, Shenzhen 518055, Guangdong Province, China. E-mail: xz.fu@szu.edu.cn
b
Department of Chemical and Materials Engineering, University of Alberta, Edmonton,
Alberta T6G 2G6, Canada
c
National Supercomputing Center in Shenzhen, 9 Duxue Road, Shenzhen 518000,
Guangdong Province, China
† Electronic supplementary information (ESI) available: Details of the
experimental method, XRD, SEM, EDS, electrochemical results, gas and ion
chromatography traces, etc. See DOI: 10.1039/c9ta09782a
‡ These authors contributed equally to this work.
be more thermodynamically and kinetically preferable for
hydrogen production with less energy consumption. Unfortu-
nately, the full electrooxidation of some organic species (alco-
hols, hydrazine, urea, etc.) is not economically viable, though it
can boost the HER in water.9–12 The valorization motivated
selective oxidation of organics, instead of the OER, is an excel-
lent strategy as it can not only boost the HER but can also yield
value-added organic products.6,8,13–16 Examples include the
selective electrocatalytic oxidation of 5-hydroxymethylfurfural
(HMF),6,8,14,16,17 alcohols (C2, C3 or C7),18,19 primary amines,13
and tetrahydroisoquinolines.20
Methanol (MtOH), as a basic organic material, has huge
production capacity.10 More importantly, it is rather inex-
pensive and practical for utilization as the most important
liquid C1 resource.10,21,22 Methanol electrooxidation was also
reported to assist the HER, in which methanol was fully
electrocatalytically oxidized to the greenhouse gas CO2 in
order to decrease the energy consumption. Full oxidation of
methanol to CO2 is not only a huge waste of organic carbon
source but also contributes to an increase of greenhouse gas.
Undoubtedly, it is of great signicance to investigate the
selective methanol conversion to value-added liquid organics
(e.g. formate) over suitable electrocatalysts. However,
previous studies on methanol conversion were mainly
centered on the use of noble electrocatalysts,21–25 methanol-

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assisted HER,10,26 or full conversion from methanol to CO2 in
fuel cells.27,28
Earth-abundant metal chalcogenides have been reported
very recently as attractive electrocatalysts for clean energy
conversion and storage.4,6,8,9,13,29–35 Nickel selenide (NiSe), as one
of the most typical chalcogenide catalysts, possesses unique
electron states and has shown excellent performance in HER,
OER and extensive electrocatalytic oxidation applica-
tions.4,13,32–35 However, metal chalcogenides are semi-conductive
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electrocatalysts with low conductivity, so merging electro-
catalysts with conductive supports is an efficient approach to
improve their electrocatalytic activity, which can also create
more active sites by improving the catalysts' dispersibility on
the support.7,36,37
Carbon-based nanomaterials (e.g. graphene series,36–39
carbon nanotubes,37,40 and nanobers40–44) are intensively re-
ported as conductive supports for electrocatalysis due to their
unique physicochemical characteristics, such as high chemical
inactivity and good conductivity.7,37,40,41 Among the various
alternatives, carbon nanobers (CNFs), with lower cost
compared with the 2D graphene series and 1D carbon nano-
tubes, have great potential as a conductive support due to their
superior strength, corrosion resistance and conductivity.40–44
More importantly, CNFs forming a superior 3D microporous
conductive network can effectively stabilize the electrical
contact with catalysts, which facilitates rapid electron transfer
and also prevents the catalyst nanoparticles from agglomer-
ating, resulting in greatly improved electrocatalytic effi-
ciency.41–44 Furthermore, CNFs having suitable dimensions
(diameter:
100–200 nm, length: dozens of micrometers, typi-
cally) should be a promising candidate for in situ growth of
catalyst nanocrystal sheaths.43,44 However, there are two critical
issues when applying this type of graphitized carbon as a cata-
lyst support: (1) achieving the in situ growth of nickel chalco-
genides on carbon nanobers through a facile one-step
approach.44 (2) It is a challenge to uniformly grow nickel chal-
cogenide nanocrystals on the surface of CNFs with great dis-
persibility through a simple process.45
In this work, carbon nanobers@NiSe (CNFs@NiSe) core/
sheath nanostructures are synthesized via a facile one-pot hot
injection. The NiSe nanocrystals homogeneously anchored on
CNFs build up a highly dispersed 3D network, acting as robust
and stable electrocatalysts for integrating the selective meth-
anol conversion and hydrogen production (Fig. 1), achieving
highly selective electrocatalytic methanol conversion to value-
added formate. Notably, this organic upgrading process
replaces the sluggish OER in order to boost H2 production at
a high generation rate that is 7.5 times that in the absence of
methanol, thus considerably lowering the energy consumption.
2. Experimental section
Synthesis
In a typical procedure, Ni(acac)2 (256.9 mg), CNFs (137.7 mg)
and 20 mL oleylamine (OLA) were added to a 100 mL round-
bottom Schlenk ask at room temperature. The stoichio-
metric mass ratio between the equivalent NiSe and CNFs is 1 : 1,
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Fig. 1 Schematic illustration of CNFs@NiSe core/sheath nano-
structures as efficient electrocatalysts for highly selective methanol
conversion to value-added formate and boosting hydrogen produc-
tion with less energy consumption. (Inset: modeling of the NiSe lattice
structure according to the CIF file of NiSe with ICSD 029310).
controlled by the dosages of precursors. The mixture in an
argon atmosphere was heated to 80  C for 30 min to completely
dissolve the Ni(acac)2 in OLA. Then the sealed ask was treated
via sonication at 60  C for 4 hours in order to improve the
dispersibility of CNFs in OLA. At the same time, DPDSe (156.1
mg) was mixed with 4 mL OLA in a vial, which was preheated to
80  C on a hot plate. When the temperature of the ask reached
200  C, the DPDSe solution was injected with a syringe. Aer
injection, the reaction was allowed to proceed at 215  C for
8 min with continuous stirring. The reaction was terminated by
taking the ask away from the heating oil bath and allowed to
cool to room temperature naturally. The as-synthesized
CNFs@NiSe sample was then washed using xylene and iso-
propanol twice each and separated by centrifugation. The NiSe
nanocrystals in the absence of CNFs were also synthesized
through the same procedure for comparison.
Catalyst characterization
The as-synthesized CNFs@NiSe core/sheath nanostructures
were characterized using eld emission scanning electron
microscopy (FESEM, Hitachi SU-70 system) at accelerating
voltages of 5–20 kV. TEM analysis was conducted using a JEOL
JEM-F200 eld emission microscope equipped with an EMSIS
Xarosa CCD camera and Oxford INCA (Aztec) EDS facility with
the potential of performing scanning transmission electron
microscopy (STEM) and EDS elemental analysis (line scan and
mapping). X-ray photoelectron spectroscopy (XPS) measure-
ments were performed on a photoelectron spectrometer using
Al Ka radiation as the excitation source (ESCALAB 250Xi). All the
peaks were calibrated with the C 1s spectrum at a binding
energy of 284.8 eV.
Electrocatalytic experiments
The preparation details of the working electrode are given in the
ESI.† The electrochemical experiments were conducted in an H-
type two-compartment cell in which the anode and cathode
compartments were separated by an anion exchange membrane
(AMI-7001, MI, USA). The electrochemical measurements were
conducted on a CHI 760E electrochemical workstation (CH
Instruments, Inc., Shanghai, China) at room temperature with
J. Mater. Chem. A, 2019, 7, 25878–25886 | 25879

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a standard three-electrode system. Linear Sweep Voltammetry
(LSV) was performed at a scan rate of 5 mV s1. All potentials
were referenced to an Ag/AgCl (sat. KCl) reference electrode. All
potentials were calibrated with respect to the reversible
hydrogen electrode (RHE) through RHE calibration. Evs. RHE ¼
Evs. Ag/AgCl + ERHE vs. Ag/AgCl. The potentials were corrected
according to the formula E ¼ Eapplied  iR, where i is the current
owing through the cell, and R is the ohmic resistance of the
cell. The resistances (R) were measured by the iR compensation
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function available on the electrochemical workstation. Electro-
chemical impedance spectroscopy (EIS) measurements were
taken in a frequency range from 100 to 0.01 kHz at 1.62 V vs.
RHE with an AC amplitude of 5 mV. The double-layer capaci-
tance (Cdl) was obtained by collecting CV curves at scan rates of
20 to 120 mV s1 with an interval of 20 mV s1 in the potential
range of 1.00 V to 1.10 V (vs. RHE).
Methanol conversion and product quantication
The electrochemical methanol conversion was carried out at
room temperature with stirring by chronoamperometry (i–t) at
0.6 V vs. Ag/AgCl (sat. KCl) (¼1.62 V vs. RHE) for 0–20 hours. The
formate product was identied by Nuclear Magnetic Resonance
(NMR) spectroscopy and quantied by Ion Chromatography
(IC). The anode solution was then proportionately (200 fold)
diluted and analyzed by Ion Chromatography (IC) to detect
formate generation. Ion Chromatography (IC) was carried out
on a CIC-D120 ion chromatograph (Shenghan Chromatography
Technology Co., Ltd, Qingdao, China) equipped with an SH-AC-
3 column. The details are given in the ESI.†
H2 production at the cathode and product quantication
When the electrochemical methanol conversion was carried out
at room temperature with stirring by chronoamperometry (i–t)
as mentioned above, the H2 production at the cathode was
detected by gas chromatography (GC9790plus, Fuli Instru-
ments) with a thermal conductivity detector (TCD). Argon
(purity: 99.999%) was used as a carrier gas with a constant ow
rate of 20 cm3 min1. The GC sampling was conducted every 10
minutes. The details for the identication and quantication of
the H2 products are given in the ESI.†
Density functional theory (DFT) calculations
Spin-polarized density functional theory (DFT) calculations
were performed using the Vienna ab initio Simulation Package
(VASP). The generalized gradient approximation (GGA) with the
Perdew–Burke–Ernzerhof (PBE) functional was used to describe
the electronic exchange and correlation effects. The computa-
tional details are given in the ESI.†
3. Results and discussion
The typical morphology of the CNFs@NiSe hybrid nano-
structures was observed in SEM images under different
magnications (Fig. 2). NiSe nanocrystal aggregates are hardly
seen in the global view SEM image of well-dispersed CNFs under
low magnication (Fig. 2a). The diameter of CNFs mostly ranges
25880 | J. Mater. Chem. A, 2019, 7, 25878–25886
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Fig. 2 FESEM images of the as-synthesized CNFs@NiSe core/sheath
nanostructures under different magnifications.
from 100 to 200 nm and their lengths are dozens of microns. In
the higher magnication SEM image of Fig. 2b, uniform NiSe
nanocrystals are homogeneously anchored on CNFs with a high
distribution. The further magnied SEM images (Fig. 2c and d)
clearly show NiSe nanocrystals with a size of about 30–50 nm.
Notably, the surface of CNFs is not completely covered by NiSe
nanocrystals, so naked surface regions of CNFs still exist, which
can facilitate rapid electron inter-transfer among the individual
nanobers in the 3D CNF network.4,34 The corresponding EDS
mapping results (Fig. S1, ESI†) demonstrate that C, Ni and Se
are uniformly distributed throughout the sample, in agreement
with the successful in situ chemical reaction between Ni and Se
precursors on CNFs under one-pot hot injection. Furthermore,
the untreated CNFs and as-synthesized NiSe nanocrystals were
also characterized by SEM (Fig. S2, ESI†), suggesting that CNFs
can act as excellent separators to prevent the NiSe nanocrystals
from agglomerating during the reaction process.
The TEM image of Fig. 3a shows that a large number of NiSe
nanocrystals are well dispersed on the surface of a carbon
nanober, which also conrms the core/sheath feature of
CNFs@NiSe nanostructures. The HRTEM image of Fig. 3b
shows that the short-range ordered lattice fringes correspond
well with the (102) and (101) planes of hexagonal Sederholmite
NiSe. It is worth noting that abundant lattice dislocations exist
in the NiSe nanocrystal structures, shown in Fig. 3b, where the
long-range ordered lattice greater than 3 nm is hardly captured.
The imperfect lattice structure in NiSe nanocrystals as well as
numerous dislocations may produce a large number of active
sites for enhancing the electrocatalytic activity,46 which is also
a probable reason for increasing the proportion of exposed (102)
facets of NiSe. Fig. 3c shows the EDS elemental line scan con-
ducted in STEM DF mode with the direction 45 slanted across
the carbon nanober. The results conrm that NiSe nano-
crystals with nearly synchronized elemental intensities of Ni
and Se are just anchored on the outer surface of the CNF. The
diameter of the CNF (140 nm) can be estimated by the calcu-
lation of the carbon elemental distance multiplied by sin a,
where a is the angle between the direction of the line scan and
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Fig. 4 (a) XPS survey spectrum and (b–d) high-resolution XPS spectra
in the (b) Ni 2p, (c) Se 3d and (d) O 1s regions for the as-prepared
CNFs@NiSe nanostructures.

Fig. 3 (a) TEM and (b) HRTEM images of the as-synthesized Fig. 5a shows the LSV curves at a scan rate of 5 mV s1 in
CNFs@NiSe core/sheath nanostructures; (c) EDS elemental line scan 1.0 M KOH containing 1.0 M methanol aer iR compensation
across the carbon nanofiber in STEM DF mode with the direction for CNFs@NiSe/CC, CNFs/NiSe/CC, NiSe/CC, IrO2/CC, CNFs/CC
indicated by the arrow at the bottom of the inset image; (d) the STEM and pristine carbon cloth (CC) electrodes. The potentials re-
DF image and the corresponding EDS elemental mapping images.
ported in our work are referenced to the reversible hydrogen
electrode (RHE). The corresponding polarization curves of
the 1D carbon nanober. Fig. 3d shows the STEM DF image and CNFs/CC and pristine CC exhibit negligible catalytic current.
EDS elemental mapping of the corresponding area, which The commercial IrO2 was loaded on CC as the anode for
conrms the presence of C, Ni and Se, in which Ni is highly a comparison study, showing an onset potential of 1.42 V (vs.
localized with Se, consistent with the formation of NiSe nano- RHE) and reaching a current density of 100 mA cm2 at
crystals distributed throughout the entire carbon nanober. a potential of 1.71 V, while the NiSe containing samples show
The crystallographic information (XRD) on CNFs, NiSe higher electrocatalytic oxidation activities. The NiSe/CC shows
nanocrystals and CNFs@NiSe hybrid nanostructures (Fig. S3, an onset potential of 1.39 V (vs. RHE) and reaches a current
ESI†) conrms the co-existence of hexagonal NiSe (PDF # 01-
075-0610, ICSD no. 029310) and CNFs in CNFs@NiSe. Notably,
the intensity ratio of (102) : (101) of NiSe lattice planes in
CNFs@NiSe is obviously higher than that in pure NiSe nano-
crystals, suggesting that the proportion of exposed (102) facets
of NiSe is increased in the presence of CNFs in the in situ growth
process.
The XPS spectra (Fig. 4) show the Ni 2p, Se 3d, and O 1s
regions for the as-prepared CNFs@NiSe. The high-resolution Ni
2p3/2 and Ni 2p1/2 centered at 855.9 and 873.8 eV (Fig. 4b)
correspond to the +2 oxidation state of Ni.13 The peak at 54.7 eV
is representative of the Se 3d binding energy (Fig. 4c), signifying
the 2 oxidation state of Se, and the weak broad peak centered
at 59.0 eV suggests a very low quantity of the surface oxidation
state of Se species.33 The O 1s XPS spectrum in previous studies
usually showed the presence of oxidized Ni in their freshly
synthesized NiSe due to partial surface oxidation.13,29,33 Inter-
Fig. 5 Electrocatalytic analysis of CNFs@NiSe hybrid nanostructures
estingly, in this study, the O 1s spectrum centered at 532.1 eV and the control samples in 1.0 M KOH containing 1.0 M methanol. (a)
(Fig. 4d) conrms that only adsorbed H2O exists on the surface LSV curves of CNFs@NiSe/CC, CNFs/NiSe/CC, NiSe/CC, IrO2/CC,
of CNFs@NiSe, without showing the XPS signals of OH and CNFs/CC and pristine carbon cloth at a scan rate of 5 mV s1; (b) the
O2 species, indicating that in situ growth of NiSe on CNFs via corresponding Tafel plots; (c) Nyquist plots of CNFs@NiSe/CC, CNFs/
NiSe/CC, NiSe/CC, CNFs/CC and pristine carbon cloth recorded at
hot injection can effectively prevent the partial oxidation of NiSe
a given potential of 1.62 V (vs. RHE) with a frequency range of 10 kHz to
nanocrystals. All these characterization results support the 0.01 kHz; (d) charging current density differences plotted against scan
successful preparation of CNFs@NiSe nanostructures. rates.

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Journal of Materials Chemistry A
density of 100 mA cm2 at a potential of 1.56 V. When intro-
ducing CNFs with a physical mixing procedure, CNFs/NiSe/CC
exhibits an improved methanol conversion activity with an
onset potential of 1.38 V (vs. RHE) and reaches a current density
of 100 mA cm2 at a potential of 1.51 V. CNFs@NiSe/CC,
fabricated by in situ growth of NiSe nanocrystals on carbon
nanobers in this work, exhibits the best methanol conversion
performance compared with the control samples. The
CNFs@NiSe/CC presents an onset potential of 1.36 V (vs. RHE)
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and a current density of 100 mA cm2 at a potential of 1.43 V in
the presence of 1.0 M methanol in 1.0 M KOH. Notably,
CNFs@NiSe/CC exhibits high current densities of 200, 300 and
400 mA cm2 at potentials of 1.47, 1.50 and 1.55 V, respectively,
which are much smaller than those potentials achieving the
corresponding current densities for NiSe containing control
samples (Table S1, ESI†). One possible reason for such excellent
performance is that NiSe nanocrystals with imperfect lattice
structures well dispersed on the conductive CNF 3D networks
could create abundant active sites for efficient electron
transfer.41–44
The corresponding Tafel plots are obtained from the polar-
ization curves to explore the methanol conversion kinetics for
the as-fabricated electrocatalysts. As shown in Fig. 5b, the NiSe
containing samples of CNFs@NiSe/CC, CNFs/NiSe/CC and
NiSe/CC exhibit Tafel slopes of 24, 40 and 77 mV dec1, which
are lower than the Tafel slope of IrO2/CC (89 mV dec1). Addi-
tionally, the Tafel slopes for CNFs/CC and pristine CC (Fig. S4,
ESI†) are much higher than those of NiSe containing samples.
Particularly, the superior methanol conversion activity of
CNFs@NiSe/CC is conrmed by its lowest Tafel slope (24 mV
dec1) in Fig. 5b, which is much lower than those of reported
catalysts applied for the electrocatalytic oxidation or OER
approaches4,8–12,14,18,29,33 (Table S2, ESI†).
To further investigate the electrode kinetics, and ionic and
charge transport resistances of electrocatalytic methanol
conversion, EIS measurements were conducted at 1.62 V vs. Ag/
AgCl (sat. KCl) in 1.0 M KOH containing 1.0 M methanol. Fig. 5c
shows the corresponding Nyquist plots of electrocatalysts. The
equivalent circuit model used to t the Nyquist plots is given in
Fig. S5 (ESI).† The charge transfer resistance (Rct) relevant to
electrocatalytic kinetics can be obtained from the semicircle in
the high frequency range, and low Rct can provide an efficient
electronic transmission at the interfaces between electrodes
and electrolytes.4,18 The CNFs@NiSe/CC possesses the smallest
Rct of about 2.5 U among all samples, indicating the rapid
electron transfer in CNFs@NiSe and good electrocatalytic
performance during electrochemical reactions.18
In addition, the double-layer capacitance (Cdl) results of the
electrocatalysts were obtained via cyclic voltammetry (CV)
measurements at different scan rates in order to estimate the
relative electrochemically active surface area (ECSA). Fig. 5d and
S6 (ESI)† show that the capacitive currents of the as-prepared
electrocatalysts at different scan rates are all collected in the
potential range of 1.00 V to 1.10 V (vs. RHE) where no apparent
faradaic process occurs. The results in Fig. 5d show that
CNFs@NiSe/CC has the highest specic capacitance of 3.65 mF
cm2 compared with other samples (2.89 mF cm2 for CNFs/
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NiSe/CC, 2.38 mF cm2 for NiSe/CC, 1.79 mF cm2 for CNFs/
CC, and 1.52 mF cm2 for CC). The in situ growth of NiSe on
CNFs makes a remarkable contribution to the promotion of
electrocatalytic performance, probably because a superior 3D
microporous conductive network of CNFs@NiSe can provide
a large number of active sites for enhancing the electrocatalytic
activity.41–44
The OER performance of CNFs@NiSe/CC was investigated in
the absence of methanol at the anode. As shown in Fig. 6a, the
methanol conversion achieves a high current density of 100 mA
cm2 at a potential of 1.43 V (vs. RHE), which is 220 mV lower
than the potential (1.65 V) necessary to drive the OER at the
same current density. In the absence of methanol, Ni2+ to Ni3+
oxidation is observed as a pre-oxidation peak between 1.38 and
1.48 V vs. RHE,13,29,33,47–49 while the Ni2+ to Ni3+ oxidation peak is
not visible any more in the presence of methanol. The invisible
feature of Ni oxidation denitely correlates with the presence of
methanol and might be overlaid by it.16 The XPS results (Fig. 7)
for the used CNFs@NiSe aer electrocatalytic methanol
conversion also demonstrate the formation of Ni3+ and the
increased peak intensity of SeOx. The higher oxidation state of
transition metals (e.g. Ni3+) is suggested by previous studies as
a necessary prerequisite for electrooxidation of alcohols and
Fig. 6 Selective electrocatalytic methanol conversion to formate and
hydrogen production performance with CNFs@NiSe electrocatalysts.
(a) LSV curves of CNFs@NiSe/CC in 1.0 M KOH with and without
adding 1.0 M methanol in the anode compartment; (b) i–t curve of
CNFs@NiSe/CC at a specified voltage of 1.62 V (vs. RHE) for formate
generation from the anode compartment and the passed charge; (c)
the generated formate concentration with the CNFs@NiSe/CC anode
over time starting with 1.0 M KOH containing 1.0 M methanol; (d) the
corresponding faradaic efficiencies for formate generation; (e) i–t
curves of the CNFs@NiSe/CC anode in 1.0 M KOH with and without
adding 1.0 M methanol in the anode compartment; (f) the generation
rate of H2 from the cathode compartment; (g) the corresponding
faradaic efficiencies for H2 generation.
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CH3OH + OH / HCOO + 2H2 (3)

In this case, the generated hydroxyl ions (eqn (2)) are trans-
ferred from the cathode to the anode compartment through the
anion exchange membrane to maintain the electrolyte balance.
Overall, the generation of formate in an alkaline environment is
accompanied by an equivalent consumption of hydroxyl ions
(eqn (3)). In order to verify our presumption, the electro-
chemical methanol conversion was also carried out under
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identical experimental conditions for 20 h, but the membrane

was replaced by a cationic one (CMI-7000, MI, USA). The related
i–t curve (Fig. S8, ESI†) indicates that the generated OH ions
cannot be transferred from the cathode to the anode compart-
ment. Alternatively, potassium ions are transferred from the
anode to the cathode compartment through the cationic
Fig. 7 (a) XPS survey spectrum and (b–d) high-resolution XPS spectra exchange membrane to maintain the electrolyte balance, sug-
in the (b) Ni 2p, (c) Se 3d and (d) O 1s regions for the CNFs@NiSe after
gesting that the formate generation theoretically consumes a 5-
20 hours of electrocatalytic methanol conversion.
fold amount of hydroxyl ions in the anode compartment (eqn
(1)). As expected, the current density is dramatically decreased
to 100 mA cm2 aer 20 hours of electrocatalysis, indicating
aldehydes.16,49,50 The catalytic current beyond 1.5 V vs. RHE was
that the high alkaline concentration is benecial for improving
accompanied by visible O2 bubble release upon further positive
the methanol conversion activity.
scan in the absence of methanol. In the presence of methanol,
The 1H and 13C NMR spectra (Fig. S9, ESI†) conrm the
the bubbles were not observed at the CNFs@NiSe/CC anode at
molecular structure of formate in the anode product obtained
potentials lower than 1.7 V vs. RHE. The results of Gas Chro-
through the electrochemical methanol oxidation at 1.62 V vs.
matography (GC) shown in Fig. S7 (ESI)† demonstrated that
RHE for 20 hours. The identication and quantication of the
oxygen (O2) and other gas products were not detected from the
formate product are conducted by Ion Chromatography (IC) and
anode when chronoamperometry (i–t) was conducted at 0.6 V vs.
determined by the calibration curve (Fig. S10, ESI†). Fig. 6c
Ag/AgCl (sat. KCl) (¼1.62 V vs. RHE) in the anode compartment.
shows the formate concentration generated with the
The LSV results in Fig. 6a imply that the CNFs@NiSe/CC is
CNFs@NiSe/CC anode at 1.62 V vs. RHE (0.60 V vs. Ag/AgCl) in
preferable for the methanol conversion at lower positive
20 hours, exhibiting an almost constant production rate of
potential than those required for water oxidation in alkaline
formate, which is 8.98 mmol L1 h1 based on a linear tting.
media and the methanol conversion takes place kinetically
Starting with 1.0 M KOH containing 1.0 M methanol, a consid-
prior to the OER in alkaline media at the same potential.
erable concentration of 179.78 mmol L1 formate was generated
Compared with the traditional water electrolysis, electrical
aer 20 hours of electrocatalytic methanol conversion. The
energy could be saved to produce H2 by co-electrolysis of water
faradaic efficiency (FE) of formate generation in Fig. 6d was
and methanol.
calculated based on the passed charge as a function of time
The electrochemical methanol conversion was carried out at
(Fig. 6b) combined with the actual production of formate
room temperature with stirring using a chronoamperometry (i–
(Fig. 6c). The CNFs@NiSe/CC anode displays a substantial FE
t) method at 0.6 V vs. Ag/AgCl (sat. KCl) (¼1.62 V vs. RHE) for 20
(formate) greater than 98% in the rst 4 hours for the selective
hours. The i–t curve in Fig. 6b indicates that the current density
methanol conversion to formate, and the FE (formate) still
of CNFs@NiSe/CC has an obvious increase in the initial period
remains at 97.90% for the overall electrocatalysis in 20 h,
of the electrochemical oxidation process from 0 to 2 hours,
demonstrating that the observed oxidation current is fully
which is attributed to the co-catalysis of the generated formate
attributed to the highly selective conversion from methanol to
as an active species to improve the electrocatalytic oxidation
formate. The experimental error values for formate production
activity of methanol.21 The current density slightly decreases
and FE (formate) are given in Table S3 (ESI).†
during the overall electrochemical reaction, but it still remains
The electrochemical oxidation of methanol was also carried
at around 250 mA cm2 aer 20 hours of electrolysis. Presum-
out at room temperature with stirring by chronoamperometry
ably, the slight decrease of current density is mainly attributed
(i–t) at 0.3–1.0 V vs. Ag/AgCl (sat. KCl) (¼1.32–2.02 V vs. RHE) for
to the decreased alkaline concentration over electrocatalysis
1 hour. The results (Fig. S11 and Table S4, ESI†) indicate that
time. Similar to the selective electrooxidation of other alco-
the observed oxidation current fully contributes to the highly
hols,19 the equations describing the anode, cathode and overall
selective conversion from methanol to formate at 1.42, 1.52 and
electrochemical reactions in this study are proposed as follows.
1.62 V vs. RHE as their FE (formate) is close to 100%. The FE
(formate) is gradually decreased from 99.94% to 83.74% with
CH3OH + 5OH / HCOO + 4H2O + 4e (1)
the increase of working voltage from 1.62 to 2.02 V vs. RHE due
4H2O + 4e / 2H2 + 4OH (2) to competition from the traditional OER intensifying at higher
voltage. Notably, high FE (formate) greater than 93% can be

This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 25878–25886 | 25883

Journal of Materials Chemistry A
maintained in a broad voltage window (1.42–1.82 V vs. RHE)
when applying CNFs@NiSe/CC as the anode.
The electrocatalytic methanol upgrading process can boost
the H2 production in the counter electrode compartment. To
demonstrate this promotion, electrocatalytic reactions in the
presence and absence of 1.0 M MtOH in the anode compart-
ment were conducted at room temperature with stirring using
a chronoamperometry (i–t) method at 0.6 V vs. Ag/AgCl (sat. KCl)
(¼1.62 V vs. RHE). Fig. 6e shows that the instant current
Published on 31 October 2019. Downloaded by University of New England on 1/2/2020 6:44:06 PM.
densities of methanol conversion at 40, 50 and 60 min are
280.61, 281.62 and 282.76 mA cm2, which are much higher
than those densities of the OER (40.07, 40.35 and 40.47 mA
cm2) at the same potential, respectively. The identication and
quantication of the H2 product in the cathode (counter elec-
trode, in 1.0 M KOH) compartment were conducted by Gas
Chromatography (GC) and determined by the calibration curve
(Fig. S12, ESI†). The generation rate of H2 has a low value of 4.77
 108 mol s1 (Fig. 6f) from the cathode compartment when
methanol is not added into the anode compartment, accom-
panied by an FE(H2) of 92.08% (Fig. 6g). Remarkably, the
generation rate of H2 reaches a high value of 35.67  108 mol
s1 (Fig. 6f) from the cathode compartment when the methanol
conversion to formate is implemented at the anode in 1.0 M
KOH + 1.0 M MtOH, which is about 7.5 times that in the absence
of methanol, and the corresponding FE(H2) is 98.17% (Fig. 6g).
The experimental error values for H2 production and FE(H2) are
given in Table S5 (ESI).†
As a surface-sensitive characterization technique, XPS was
used to study the variation of surface chemical states of
CNFs@NiSe before and aer electrocatalytic methanol conver-
sion reaction. Compared with the XPS spectra (Fig. 4) for the
freshly prepared CNFs@NiSe, the used CNFs@NiSe exhibits
newly emerged XPS peaks (Fig. 7b) centered at 856.8 eV (Ni 2p3/2)
and 874.8 eV (Ni 2p1/2), suggesting the partial formation of Ni3+
aer electrocatalytic methanol conversion. The oxidation
phenomenon is also revealed by the increased peak intensity of
SeOx near 59.0 eV in the high-resolution Se 3d XPS spectrum of
Fig. 7c. Furthermore, the appearance of the O2 species (lattice
oxygen) indicated by a very weak peak centered at 530.0 eV
(Fig. 7d) conrms the presence of a small proportion of oxidized
Ni aer the electrocatalysis. The XPS peak centered at 531.1 eV
(Fig. 7d) also demonstrates the existence of OH on the surface
of the used CNFs@NiSe aer electrocatalysis in an alkaline
environment. Nevertheless, the surface atomic layers of NiSe are
still mainly composed of non-oxidized Ni2+, indicated by the XPS
spectra of Fig. 7b and d. The XPS results in previous studies13,33
indicated that their NiSe catalyst experienced severe oxidation
aer the electrocatalytic valorization process, demonstrating
that the CNFs@NiSe electrocatalyst employed in this study is not
only active but also more stable than those reported in previous
studies.13,33
XRD results indicate the formation of a high proportion of
exposed (102) facets of NiSe via the in situ growth process
through hot injection. HRTEM results demonstrate that an
imperfect lattice structure and numerous dislocations exist in
NiSe nanocrystals, increasing the proportion of the exposed
(102) facets of NiSe. XPS analysis also suggests that the NiSe
25884 | J. Mater. Chem. A, 2019, 7, 25878–25886
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Paper
lattice structure is still maintained as the major surface
composition aer electrocatalysis. Previous studies demon-
strated that the lattice defects and dislocations may produce
a large number of active sites for enhancing the electrocatalytic
activity.46 In this work, the (102) facets of NiSe are proposed as
a critical factor for the high selectivity of methanol conversion.
For a better understanding of the origins of the high selectivity
of methanol conversion, density functional theory (DFT)
calculations were further performed to investigate the reactivity
of methanol conversion to formate on the exposed (102) facets
of NiSe.
The mechanism for methanol conversion is proposed and
the DFT optimized structures of the most favorable adsorbed
intermediates for the oxidation of CH3OH to carbonate are lis-
ted in Fig. 8a. The electrocatalytic conversion from alcohols to
carboxyls in an alkaline environment contains the reaction
steps of adsorption, deprotonation (proton-decoupling), elec-
tron loss (electron transfer, oxidation), and hydroxyl addition.
Fig. 8b shows the Gibbs free energy diagrams (DG) for the
methanol conversion process on the NiSe (102) surface, where
DG values required for the proposed elementary reaction steps
are calculated.
The process originates from the molecular adsorption of
methanol on NiSe accompanied by a downhill (0.42 eV) energy
step, and then the required h initially starts from the formation
of M/CH3O with an energy of 0.57 eV for the rst proton-
decoupled electron-transfer step. Apparently, the free-energy
step subsequently becomes more thermodynamically facile for
the subsequent steps, as the adsorption energy decreases
slightly from 0.15 eV to 0.02 eV, and in turn to 0.04 eV,
indicating that the formation of formic acid (M/HCOOH) is
thermodynamically favorable on the exposed (102) facets of
NiSe. To further understand the high selectivity of methanol
conversion to formate, the adsorption energy for M/HCOOOH
Fig. 8 (a) DFT optimized structures of the most favorable adsorbed
intermediates for the oxidation of CH3OH on exposed (102) facets of
NiSe. (b) Gibbs free energy diagrams for the electrocatalytic methanol
conversion process on exposed (102) facets of NiSe. The distances are
given in Å.
This journal is © The Royal Society of Chemistry 2019

Paper
was also calculated for comparison, which is a precursor for the
formation of carbonic acid and carbon dioxide. It can either
form carbonic acid via an intra-molecular hydrogen rearrange-
ment or form CO2 via a H2O elimination reaction. However, the
formation of M/HCOOOH is very difficult thermodynamically,
and requires much higher energy (1.21 eV) compared with that
to form M/OCH3 (0.57 eV). In addition, the adsorption energy of
formic acid (M/HCOOH) on NiSe (102) facets is only 0.04 eV,
so it is easily desorbed and consequently reacts with OH to
Published on 31 October 2019. Downloaded by University of New England on 1/2/2020 6:44:06 PM.
form formate in the alkaline electrolyte, thus protecting its
further oxidation, resulting in the high selectivity of methanol
conversion to formate.
4. Conclusions
In this study, an economically viable and environmentally
friendly strategy was developed for integrating liquid C1 organic
upgrading and clean H2 energy harvesting. The synthesized
CNFs@NiSe core/sheath nanostructures act as excellent elec-
trocatalysts for highly selective methanol conversion to value-
added formate at the anode, which achieves a nearly constant
rate of 8.98 mmol L1 h1 for formate production and
a concentration of 179.78 mmol L1 aer 20 hours of electro-
catalysis with a high faradaic efficiency (FE) of 97.90% at the
anode. Notably, the methanol upgrading process supplants the
sluggish OER to considerably boost H2 production at a high
generation rate of 35.67  108 mol s1 at the cathode, which is
7.5 times that in the absence of methanol, thus lowering the
energy consumption for clean energy harvesting. The high
selectivity of methanol conversion to formate was further
studied by DFT calculations, indicating that the methanol
conversion to formic acid (formate) is thermodynamically
favorable on the unique exposed NiSe (102) facets, which also
prevents its further oxidation to HCOOOH, namely, the
precursor of CO32/CO2. In an alkaline environment, formic
acid is readily desorbed and consequently reacts with OH to
form the formate species and avoid its further oxidation.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The authors acknowledge the nancial support of the National
Natural Science Foundation of China (No. 21805187 and
21975163). The authors also acknowledge the Instrumental
Analysis Center of Shenzhen University (Xili Campus) for their
assistance with TEM observation.
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