Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode

Article abstract of DOI:10.1002/anie.201807717

For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (?CH₂?NH₂) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H₂ production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that Ni^II/Ni^III may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.

Full text of DOI:10.1002/anie.201807717

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Accepted Article
Title: Boosting Hydrogen Production via Anodic Oxidation of Primary
Amines over a NiSe Nanorod Electrode
Authors: Yi Huang, Xiaodan Chong, Cuibo Liu, Yu Liang, and Bin
Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201807717
Angew. Chem. 10.1002/ange.201807717
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Angewandte Chemie International Edition
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COMMUNICATION
Boosting Hydrogen Production via Anodic Oxidation of Primary
Amines over a NiSe Nanorod Electrode
†
†
Yi Huang, Xiaodan Chong, Cuibo Liu, Yu Liang, and Bin Zhang*
Abstract: For electrocatalytic water splitting, the sluggish anodic
oxygen evolution reaction (OER) has extremely restricted the
cathodic hydrogen evolution reaction (HER). Therefore, developing
an alternative anodic reaction with accelerating kinetics to produce
value-added chemicals, especially coupled with HER, is of great
importance. Here, a thermodynamically more favourable primary
synthesis of various chemicals (Scheme S1) have been widely
[
6]
studied, which display that most primary amines show lower
oxidation potential than water. Among the products, nitriles as
one important class of intermediate in chemistry and biology are
widely used in synthesis of agrochemicals, pharmaceuticals, and
[
7]
fine chemicals. Typically, nitriles are synthesized through the
nucleophilic substitutions of alkyl and aryl halides or the classic
Sandmeyer reaction, but the use of HCN or metal cyanides
severely restricts their practical applications for serious
amine (-CH
arrays in water is reported to replace OER for enhancing HER. The
increased H production can be obtained at cathode, meanwhile, a
2 2
-NH ) electrooxidation catalyzed by NiSe nanorod
2
[
8]
variety of aromatic and aliphatic primary amines are selectively
electrooxidized to nitriles with good yields at anode. Mechanistic
safety/environment concerns. Efforts have been made to
develop an efficient alternative method to synthesize nitriles
II
III
[9]
investigations suggest that Ni /Ni may serve as the redox active
specie for the primary amines transformation. Impressively,
hydrophobic nitrile products can readily escape from aqueous
electrolyte/electrode interface, avoiding the deactivation of the
catalyst and thus contributing to continuous gram-scale synthesis.
This work opens a facile and environmentally benign aqueous
electrocatalytic way for the production of both hydrogen and nitriles
at much lower potential than that of overall water splitting.
through dehydrogenation of primary amines. However, most of
the reported catalytic systems usually need oxidants (e.g.
TEMPO) and high-pressure oxygen or air, and are conducted in
organic solvents at elevated temperatures. Thus, an aqueous,
easy scale-up and oxidant-free electrooxidation of primary
amines to nitriles at low potential over earth-abundant catalysts,
especially coupled with efficient HER, is economically attractive
and highly desirable.
Herein, we demonstrate a facile but effective approach for
boosting H
amines oxidation over a NiSe nanorod electrode in water (Figure
). The increased H production can be obtained at cathode,
2
production by replacing OER with the primary
Developing
hydrogen (H
a technology capable of efficiently generating
[1]
2
) alternative to fossil fuels is a critical topic.
is a key component among
1
2
Electrolysis of water to generate H
many clean energy technologies. Two half-reactions, H
2
2]
meanwhile, the primary amines at NiSe anode can be selectively
converted into the corresponding nitriles with high yields and
good substrate tolerances. Hydrophobic nitrile products can
readily float onto the surface of electrolyte, avoiding the
deactivation of the catalyst and thus contributing to continuous
large-scale synthesis. Potential-dependent Raman spectra
[
2
and
O
2
evolution reaction (HER and OER), are involved in water
splitting. Unfortunately, the sluggish kinetics of OER often
restricts the overall reaction rate, thus high overpotentials are
needed to drive water splitting at high current densities.
Although many advanced non-noble-metal electrocatalysts have
been developed to achieve attractive OER activities, the OER
still demands a much higher overpotential to match up with the
rate of HER, leading to low energy conversion efficiency.
Recently, an efficient strategy to replace OER with
electrooxidation of thermodynamically more favorable species
[3]
II
III
reveal that Ni /Ni in situ formed on the surface of NiSe nanorod
electrode serves as a redox active specie to efficiently promote
the conversion of primary amines into nitriles.
[4]
(
alcohols, hydrazine, and urea) over non-noble-metal
NiSe
1.0 M KOH, RT
R
NH2
R CN
hydrophobic
[
5]
electrocatalysts is adopted to boost H
2
production in water.
hydrophilic
However, the anodic oxidation products are mostly hydrophilic,
leading to both the overoxidation with low selectivity and the
difficult scale-up synthesis, caused by occupying active sites.
R: aromatic, aliphatic


high yield (> 93%)
oxidant-free
 easy scalable
organic-solvent-free
easy collection of product
from hydrophilic reactant
[
5h-j]
Additionally, in some cases,
the products are of low value.


Therefore, it is challenging to utilize electrooxidative power to
drive organic transformations instead of OER for both boosting
(
to hydrophobic product)
2
H production and yielding value-added organic products with
high selectivity.
Figure 1. Electrocatalytic conversion of primary amines into nitriles integrated
with H production in water.
Selective oxidation of primary amines holding a pivotal role in
2
[
†]
[†]
[*]
Dr. Y. Huang, X. Chong, Dr. C. Liu, Y. Liang, Prof. B. Zhang
Tianjin Key Laboratory of Molecular Optoelectronic Sciences,
Department of Chemistry, School of Science, Tianjin University, and
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin 300072, China
NiSe electrode was synthesized by direct selenization of
commercially available nickel foam (for details see the
Supporting Information). This facile method can be easy to be
scaled up (Figure S1). Scanning electron microscopy (SEM)
images (Figure 2a and Figure S2) show that nanorod arrays are
grown on nickel foam (Figure S3). All the diffraction peaks in the
X-ray diffraction (XRD) pattern (Figure S4) can be indexed to
E-mail: bzhang@tju.edu.cn
These authors contributed equally to this work.
†
[
]
Supporting information for this article is given via a link at the end of
the document.
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Angewandte Chemie International Edition
10.1002/anie.201807717
COMMUNICATION
NiSe (JCPDS No. 75-0610) and Ni. The transmission electron
microscopy (TEM) image indicates the diameter of nanorod is
about 15 nm. The high-resolution TEM (HRTEM) image (Figure
bubbles appear. To explore the potential dependence of BA
oxidation products, long-term chronoamperometry was carried
out at different potentials with 1 mmol BA. No product of BA
oxidation can be collected at 1.3 V vs. RHE. At 1.35 to 1.45 V vs.
RHE, after passing charge of ~385 C (a theoretical charge for
the complete oxidation of BA to benzonitrile (BN)), the product
was collected. The BN with the yields of ~99 % and the Faradaic
efficiencies (FEs) of ~99 % can be achieved (Figure S6 and
2b,c) displays a lattice fringe of 0.274 nm indexed to the (101)
plane of NiSe. The X-ray photoelectron spectroscopy (XPS)
spectra show the characteristic peaks of NiSe (Figure S5).
Additionally, the energy-dispersive X-ray spectroscopy (EDS)
elemental mapping images (Figure 2d) reveal
distribution.
a uniform
Figure 3b). Noticeable O
.50 V, and the FEs for BN and O
respectively.
2
bubbles can be observed at above
1
2
are ~86 and ~13 %,
We then investigated the general applicability of NiSe
electrode for other primary amine oxidation (Table 1). The
electrooxidation strategy shows good compatibility with various
substrates. Both aromatic primary amines with electro-
withdrawing/donating groups on aryl ring and aliphatic primary
amines can be facilely oxidized to corresponding nitriles with
good yields at lower potentials than that of OER (Figure S7).
Note that, the olefinic bond in 2g is retained, which can be
further polymerized for industry production including dacron
[
7a]
fabrication,
implying the well tolerance of functional group.
Figure 2. (a and inset) SEM, (b) TEM, (c) HRTEM and (d) EDS elemental
mapping images of NiSe nanorod arrays.
Furthermore, the di-nitriles compound (2h) can also be feasibly
prepared under the optimal conditions. These extending results
demonstrate that PAEOR is more thermodynamically favorable
than OER, which provides a facile oxidant-free route to the
synthesis of nitriles. What’s more, most of the primary amines
studied in this work show good solubility in water, while their
corresponding nitriles are hydrophobic and float on the surface
of electrolyte (Figure S8), benefitting the efficient collection of
a 2
b 100
50
00
50
00
1 mmol BA
without BA
2
1
1
O2 generation
80
60
40
O2
BN
[
10]
5
0
20 no product
0
nitriles (e.g. collection by oil–water separation membranes ).
0
1
.1
1.2
1.3
1.4
1.5
1.6
1.30 1.35 1.40 1.45 1.50 1.55
Table 1. Substrate scope of electrocatalyzed transformation of primary
E / V vs. RHE
E / V vs. RHE
[
a]
amines into nitriles over NiSe anode.
c
d 1
yield
FE
00
NiSe
.0 M KOH, RT
2
1
1
00
add BA
Oil product
R
NH2
R CN
1
8
6
4
2
0
0
0
0
0
1
2
50
00
Aromatic substrates
Aliphatic substrates
CN
CN
CN
5
0
0
R'
~ 385 C
2e
2f
96% (~96%)
0
4
8
12
16
1
2
3
4
5
6
97% (~97%)
2
2
2
a, R' = H, 99% (~99%)
b, R' = p-F, 97% (~97%)
c, R' = p-OMe, 95% (~95%)
t / h
Cycles
CN
NC 4CN
6CN
-
1
2d, R' = m-OMe, 93% (~94%)
Figure 3. (a) LSV curves of NiSe anode at a scan rate of 5 mV s in 1.0 M
KOH with and without 1 mmol BA. (b) FEs of BN and O at different potentials.
c) j-t curve of NiSe at 1.40 V vs. RHE with the intermittent addition of 1 mmol
2
g
2h
2i
96% (~97%)
2
9
4% (~95%)
96% (~96%)
(
BA. The inset shows the partial electrolyte solution after six runs and the oil
droplets are marked by Oil Red O. (d) Cycle-dependent yields and FEs of BN.
[a] The reaction conditions: primary amines (1 mmol), NiSe (working area: 1
2 o
cm ), 1.0 M KOH (40 mL), room temperature (RT, 25 C). Yields are
determined by gas chromatography. FEs are displayed in parentheses.
Next, the durability test for BA oxidation was investigated. By
applying a constant potentials of 1.40 V vs. RHE, the durability
test was performed in the presence of 1 mmol BA, and another 1
mmol of BA was subsequently added to the reaction cell after
the previous run was completed. The catalytic activity of the
NiSe is retained after six runs (Figure 3c). The oil droplets
The electrocatalytic oxidation reactions of primary amines
PAEOR) were carried out in 1.0 M KOH. Benzylamine (BA) is
selected as the model candidate to evaluate the PAEOR activity.
Figure 3a shows the linear sweep voltammetry (LSV) curves of
BA and water oxidations over NiSe anode in the presence and
absence of BA, respectively. Without BA, the onset potential is
(
(
marked by Oil Red O) are clearly observed floating on the
~
1.48 V vs. RHE (reversible hydrogen electrode) and the
surface of electrolyte (inset of Figure 3c and Figure S9). The
yields and FEs of BN formation are ~99% (Figure 3d), illustrating
the robust durability of the anode.
The NiSe electrode after BA oxidation (hereafter, post-BA
NiSe) is further characterized. The SEM and TEM images of
obvious current density for OER is observed at above 1.55 V.
II
III [4a-
The oxidation peak centered at ~1.37 V is ascribed to Ni /Ni .
c]
After the addition of BA, the current density sharply increases
from ~1.32 V. When the potential is increased to ~1.48 V, O
2
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post-BA NiSe indicate the inheritance of the nanorod array
configuration. EDS elemental mapping analysis reveals the
compositions of Ni, O and Se (Figure S10). In addition, the high-
resolution XPS spectra confirm the oxidation of NiSe after
PAEOR (Figure S11). These observations suggest that the
oxidized Ni species on the surface of NiSe may act as the actual
active sites for PAEOR, as observed for most Ni-based
peak of NiOOH from in situ Raman spectra cannot be detected
in the initial process of BA oxidation. Similar to the organic (e.g.
2
+
[12]
II
III
TEMPO) and metal-ion (e.g. Co ) redox mediates, Ni /Ni on
the surface of NiSe nanorod electrode can be acted as an
efficient redox active specie to promote the conversion of
primary amines into nitriles.
With the high activity of NiSe anode for PAEOR in hand, we
made an electrolyzer in a two-electrode configuration using NiSe
[
11]
electrocatalysts during OER.
[
13]
as an anode for BA oxidation and high-performance CoP
Figure S13) as a cathode for HER. For comparison, overall
(
a
no BA
with BA
b
no BA
472
with BA
8
4
0
4
5
53
water splitting was also tested using the same electrolyzer
without BA. As displayed in Figure 4d and its inset, after
introducing 1 mmol BA, the NiSe ‖ CoP exhibits superior
performance. For instance, the required potential for achieving
4
72
0
.90 V
0.85 V
.80 V
5
53
0
-
0.75 V
0.75 V
0.70 V
0.65 V
0.60 V
0.55 V
0.50 V
0
.2
0.4
0.6
0.8
0.70 V
E / V vs. Hg/HgO
0
0
.65 V
.60 V
-2
the current density of 20 mA cm dramatically decreases from
1.70 V (without BA) to 1.49 V (with BA), suggesting much better
energy conversion efficiency of HER integrated with PAEOR
c
d
V
e-
0.55 V
.50 V
0
OOH
R
R
CN
H2
0.40 V
0.40 V
initial
NiⅢ
e-
H+
initial
NiⅡ
H+
NH2
400
800
400
800
compared to overall water splitting. To quantify the produced H
and BN over NiSe‖CoP, a long-term electrolysis at 1.50 V was
performed. The generated H matches well with the calculated
amount of passed charge, leading to a FE of ~100% for H
Figure 4e). The FE for BN formation can reach the high value of
2
anode
cathode
-1
Raman shift / cm
50
e
100
H2
BN
without BA
mmol BA
1
2
4
3
2
1
0
0
0
0
0
without BA
1 mmol BA
80
60
2
1
.7
.6
(
1
1.5
.4
~98%. Furthermore, such a long-term electrolysis can be
repeated for at least six times without no apparent decrease of
FEs, indicating the outstanding durability of NiSe‖CoP for HER
integrated with PAEOR. Most importantly, the PAEOR can be
conducted to ~2 gram scale under our standard conditions.
Good to excellent yields were obtained (Figure S14), implying
the promising practicality.
4
0
1
10
j / mA cm
20
-
2
20
0
1.0
1.2
1.4
E / V
1.6
1.8
1
2
3
4
5
6
Cycles
Figure 4. (a) CV curves of NiSe anode in 0.1 M KOH with and without BA. (b)
Potential-dependent in situ Raman spectra of NiSe anode collected without BA
(
left) and with BA (right). (c) Proposed conversion process of PAEOR over
In summary, we have demonstrated the highly selective
electrooxidation conversion of various primary amines into
nitriles with high yields, good substrate compatibilities and
olefinic bond tolerance in water over NiSe anode, in which
NiSe. (d and inset) LSV curves and potential comparison for achieving
benchmark current densities over a NiSe‖CoP electrolyzer with and without 1
mmol BA. (e) Cycle-dependent FEs of a NiSe‖CoP electrolyzer for both H
and BN production.
2
II
III
Ni /Ni serves as a redox active specie to efficiently promote
their conversion reactions. Owing to the more favorable
thermodynamics of PAEOR than OER, integrated with CoP as a
cathode for HER, the cell voltage is dramatically reduced relative
to that of overall water splitting (e.g. a decrease of 210 mV for
To further investigate the mechanism of BA oxidation over a
NiSe anode, potential-dependent in situ Raman spectra were
measured. The cyclic voltammetry (CV) curves were performed
with and without BA, respectively (Figure 4a). And Raman
spectra were collected as a function of the applied potentials
-2
2
the benchmark current density of 20 mA cm ), and both H and
value-added nitriles can be generated at cathode and anode,
respectively. Additionally, the non-water-soluble feature of
nitriles avoids the occupying of the active sites, and benefits the
continuous gram-scale nitrile synthesis with industrial
practicability. Our work may pave a promising approach to
2
(
(
Figure 4b). Without BA, the CV curve shows an obvious peak
from 0.5 to 0.65 V vs. Hg/HgO). Meanwhile, in situ Raman
spectra show no discernible change compared to that of pristine
NiSe at potentials of < 0.5 V. At 0.55 V, two peaks appear at 472
-1
[4b]
produce both nitriles and H with low cost and high efficiency.
and 553 cm attributing to the Ni-O vibrations of NiOOH. And
the intensity of NiOOH peak increases gradually with the
increased potential. Upon the addition of BA, obvious
enhancement of current can be observed from the CV curve. Acknowledgements
However, the NiOOH peak does not appear until the potential
reaches to 0.75 V, and enhances gradually with the increasing
of potential. Note that the bare nickel foam also shows PAEOR
performance but inferior to that of NiSe (Figure S12). For OER
on Ni-based electrocatalysts in alkaline electrolyte, the first step
We do appreciate the National Natural Science Foundation of
China (No. 21871206), the Natural Science Foundation of
Tianjin City (No. 17JCJQJC44700) and the China Postdoctoral
Science Foundation (No. 2018M630269) for financial support.
[
11]
is the formation of NiOOH. It is reasonably speculated that in
II
the presence of primary amines, the surface Ni is first oxidized
Keywords: hydrogen evolution reaction • electrocatalysis •
energy efficiency • primary amine oxidation • nanostructures
into NiOOH, then primary amines can be quickly oxidized by
NiOOH,
accompanying
with
corresponding
reducing
III
II
transformation from Ni -OOH into Ni (Figure 4c), so that the
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Angewandte Chemie International Edition
10.1002/anie.201807717
COMMUNICATION
COMMUNICATION
†
†
Substitution, higher efficiency.
Hydrogen (H ) production is
2
achieved at lower potential by
replacing OER with the
Yi Huang, Xiaodan Chong, Cuibo
Liu, Yu Liang, and Bin Zhang*
NiSe
.0 M KOH, RT
R
NH2
R CN
hydrophobic
1
hydrophilic
R: aromatic, aliphatic
Page No. – Page No.
electrooxidation of primary
amines in water. The hydrophilic
primary amines at NiSe anode
can be selectively converted into
the corresponding hydrophobic
nitriles with high yields and
selectivity.
 high yield (> 93%)
oxidant-free
 easy scalable
Boosting Hydrogen Production
via Anodic Oxidation of Primary
Amines over a NiSe Nanorod
Electrode



organic-solvent-free
easy collection of product
(
from hydrophilic reactant
to hydrophobic product)
This article is protected by copyright. All rights reserved.