Accelerating H2 Evolution by Anodic Semi-dehydrogenation of Tetrahydroisoquinolines in Water over Co3O4 Nanoribbon Arrays Decorated Nickel Foam

Article abstract of DOI:10.1002/chem.202100249

Coupling the H₂ evolution reaction in water with thermodynamically favorable organic oxidation reactions is highly desirable, because it can enhance the energy conversion efficiency compared with electrocatalytic water splitting, and produce value-added chemicals instead of O₂ in the anodic reaction. Herein, Co₃O₄ nanoribbon arrays in situ grown on nickel foam (Co₃O₄@NF) was employed as an effective electrocatalyst for the selective oxidation of tetrahydroisoquinolines (THIQs). Various value-added semi-dehydrogenation products including dihydroisoquinolines with electro-deficient or -rich groups could be obtained with moderate yields and faradaic efficiencies. Benefitting from the rich surface active sites of Co₃O₄@NF, a two-electrode (Co₃O₄@NF||Pt) electrolytic system drove a benchmark current density of 10 mA cm^?2 at a cell voltage as low as 1.446 V in 1.0 M KOH aqueous solution containing 0.02 M THIQ, which was reduced by 174 mV in comparison with that of overall water splitting.

Full text of DOI:10.1002/chem.202100249

Communication
doi.org/10.1002/chem.202100249
Chemistry—A European Journal
Accelerating H2 Evolution by Anodic Semi-dehydrogenation
of Tetrahydroisoquinolines in Water over Co3O4
Nanoribbon Arrays Decorated Nickel Foam
Ming Xiang,[a] Zhihua Xu,*[a] Jinghao Wang,[b] Xiaoqiu Yang,[a] and Zhaoxiong Yan*[a]
dramatically reduced the working voltage of the whole cell.[25–26]
Nevertheless, oxidizing urea or hydrazine would generate
Abstract: Coupling the H2 evolution reaction in water with
thermodynamically favorable organic oxidation reactions is
valueless decomposition products (CO2, H2O and N2), and
highly desirable, because it can enhance the energy
primary alcohol would be usually oxidized into corresponding
conversion efficiency compared with electrocatalytic water
fully oxidized products (organic acids). Therefore, the develop-
splitting, and produce value-added chemicals instead of O2
ment of effective electrocatalyst towards selective transforma-
in the anodic reaction. Herein, Co3O4 nanoribbon arrays
tions of chemicals into semi-oxidized products will be more
in situ grown on nickel foam (Co3O4@NF) was employed as
challenging and worthy.[27]
an effective electrocatalyst for the selective oxidation of
Dehydrogenation from N-heterocycles under oxidant-free
tetrahydroisoquinolines (THIQs). Various value-added semi-
conditions provided a mild approach to generate unsaturated
dehydrogenation products including dihydroisoquinolines
heteroaromatic compounds with the release of hydrogen
with electro-deficient or -rich groups could be obtained
gas.[28–29] However, most reported thermo-, photo- and electro-
with moderate yields and faradaic efficiencies. Benefitting
catalytic synthetic routes should operate in organic solvents,
from the rich surface active sites of Co3O4@NF, a two-
and usually resulted in the complete dehydrogenation
electrode (Co3O4@NFj jPt) electrolytic system drove
a
products.[30–34] Recently, Zhang group employed Ni2P or NiO as
the electrocatalyst to achieve the aqueous semi-dehydrogen-
ation of tetrahydroisoquinolines (THIQs) by coupling with
effective HER or nitrate reduction reaction, which made a
breakthrough in achieving value-added product dihydroisoqui-
nolines (DHIQs).[27,35] Considering the positive function of DHIQ
in pharmaceutical chemistry,[36–37] it is highly desirable to
develop more readily available electrocatalysts especially based
on other earth-abundant metal elements, which could integrate
the selective oxidation from THIQs to DHIQs with HER in water.
Herein, we report Co3O4 nanoribbon arrays in situ decorated
nickel foam as highly efficient electrocatalyst (Co3O4@NF) for
the selective semi-dehydrogenation of THIQs. When adding
0.02 M THIQ into 1.0 M KOH aqueous solution, the voltage
requirement for the two-electrode electrolyser (Co3O4@NFj jPt)
was only 1.446 V to achieve a benchmark current density of
10 mAcmÀ 2, which not only was reduced by 174 mV in
comparison with that of water oxidation, but also accelerated
hydrogen production from water reduction. For electron-rich as
well as deficient THIQ derivatives, DHIQs could be obtained at
Co3O4@NF anode with moderate yields and faradaic efficiencies
(FEs), which demonstrated potential applications in pharma-
ceutical synthesis.
benchmark current density of 10 mAcmÀ 2 at a cell voltage
as low as 1.446 V in 1.0 M KOH aqueous solution containing
0.02 M THIQ, which was reduced by 174 mV in comparison
with that of overall water splitting.
Electrocatalytic water splitting is emerging as a promising
hydrogen production approach.[1–4] Due to the sluggish oxygen
evolution reaction (OER), a much higher overpotential is needed
at anode to match hydrogen evolution reaction (HER) at
cathode.[5–8] In order to tackle this issue, replacing OER with
thermodynamically more favorable organic oxidation reaction is
considered as an alternative strategy to boost HER.[9–12]
Previously, numerous research efforts focused on organic
molecules like urea, hydrazine and various alcohols (including
methanol, glycerol and 5-hydroxymethylfurfural) as the more
readily oxidized species.[13–24] Compared with OER, they could
not only significantly enhance anodic reaction kinetics, but also
[a] Dr. M. Xiang, Prof. Dr. Z. Xu, X. Yang, Dr. Z. Yan
Key Laboratory of Optoelectronic Chemical Materials and Devices of
Ministry of Education
The Co3O4 nanoribbon arrays were synthesized by a facile
hydrothermal process and
a
subsequent annealing
Jianghan University, Wuhan 430056 (P. R. China)
E-mail: xuzhihua78@sina.com
treatment,[38–39] which were easier to be obtained than the Ni2P
electrode from the aspect of experimental operation. X-ray
diffraction (XRD) was employed to confirm the crystalline phase
of the Co3O4 deposit. As shown in Figure 1a, both the
synthesized sample and the bare NF sample showed three
zhaoxiongyan75@163.com
[b] Dr. J. Wang
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication
CAS Center for Excellence in Nanoscience
National Center for Nanoscience and Technology, Beijing 100190 (P. R.
China)
°
characteristic peaks at 45.1, 52.4 and 77.0 attributed to the
diffraction peaks of the pristine Ni foam (PDF 04–0850). Due to
the strong signal of the substrate NF, the weak diffraction peaks
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without the presence of 1a (Figure 2a). For the Co3O4@NF
electrode, a steep curve appeared at about 1.50 V versus RHE
(reversible hydrogen electrode) in the absence of 1a, with
the appearance of O2 bubbles at the surface of anode.
Besides, two oxidation peaks at about 1.25 V and 1.45 V could
be attributed to CoII/CoIII and CoIII/CoIV, respectively.[42–43]
After adding 0.02 M 1a in 1.0 M KOH, the current density
increased dramatically at about 1.30 V, mainly contributed by
the oxidation current of THIQ. It implied that THIQ oxidation
was thermodynamically more favorable than water oxidation
over the Co3O4 modified electrode. As for the NF electrode,
the enhancement of anodic current was very small after
adding 1a. Thus, we speculated that the oxidation of 1a
primarily depended on the Co3O4 electrocatalyst, not the NF
substrate, which was different from the previous reports.[33,34]
Thus, it could be deduced that Co3O4 could also effectively
catalyze dehydrogenation of N-heterocycles, and the Ni foam
here was mainly functioned as the substrate providing a high
specific surface area to immobilize the Co3O4 nanoribbon
arrays. Subsequently, we examined the effect of potential on
the semi-dehydrogenation reaction. A series of long-term
chronoamperometry at different potentials from 1.25 to
1.60 V were carried out with 0.02 M 1a (Figure 2b). At 1.25 V,
target product 2a was generated with FE of about 98% and
selectivity of nearly 100%. However, the electrocatalytic
reaction was too slow at this potential, resulting in retention
of most substrate 1a. At the potentials from 1.30 to 1.60 V,
after passing a theoretical charge of 38.5 C for the semi-
dehydrogenation of 1a to 2a, the products were collected.
Both FEs and selectivities for this transformation decreased
with increasing anodic potential. At 1.30 and 1.35 V, the
optimal results were obtained with FEs of about 75% and
selectivities of about 90%. Furthermore, the substrate 1a
remained and the product 2a generated at different reaction
times were collected at the constant potential of 1.35 V
(Figure 2c). A charge of 37 C would be passed within 1 hour,
Figure 1. (a) XRD patterns of NF, Co3O4@NF and exfoliated Co3O4. SEM
images for bare NF (b), Co3O4@NF before (c) and after (d) electrocatalytic
THIQ oxidation. XPS spectra in the Co 2p region (e) and the O 1s region (f)
for Co3O4 before (top) and after (bottom) electrocatalytic THIQ oxidation.
of the Co3O4 deposit were masked. After peeling off the black
deposit from the NF, the power XRD pattern revealed a set of
broad peaks marked with asterisks at 31.6, 36.9, 59.5 and 65.4 ,
°
which precisely coincided with the (220), (311), (511) and (440)
planes of the cubic phase of Co3O4 (PDF 43–1003), respectively.
The morphology of Co3O4 nanoribbon arrays grown on the
surface of Ni foam was measured by the scanning electron
microscopy (SEM). Compared with the smooth surface of the
bare Ni foam (Figure 1b), the Co3O4@NF sample displays a
vertically uniform coating of Co3O4 nanoribbon arrays (Fig-
ure 1c). The rough surface morphology supplied a high specific
surface area, which can deliver sufficient contact area for the
reaction substrates. X-ray photoelectron spectroscopy (XPS) was
carried out to identify the element compositions of the
synthesized sample. Two distinct peaks with binding energies
at 779.9 and 795.1 eV (Figure 1e top) were attributed to Co
2p1/2 and Co 2p3/2 spin-orbit peaks of the Co3O4 phase,
respectively. Meanwhile, the O 1s XPS spectra peak at a binding
energy value of around 529.8 eV was assigned to oxygen
species in the Co3O4 phase (Figure 1f top).[40–41] All the above
results clearly confirmed the successful modification of Co3O4
nanoribbon arrays on nickel foam.
In order to evaluate the electrocatalytic performance of
the Co3O4@NF electrode for the anodic semi-dehydrogen-
ation transformation, 1,2,3,4-tetrahydroisoquinoline 1a was
Figure 2. (a) LSV curves of the Co3O4@NF or NF anode at a scan rate of
10 mVsÀ 1 in 10 mL of 1.0 M KOH with or without 0.02 M 1a. (b) FEs and
selectivities of 2a production at different potentials. (c) Conversion of 1a
and yield of its semi-dehydrogenation product 2a over passed charge. (d)
FEs and yields of 2a production after passing a charge of 38.5 C under five
successive cycles. Chronoamperometry experiments of (b), (c) and (d) were
conducted in 10 mL of 1.0 M KOH containing 0.02 M 1a.
selected as
a model substrate. All the electrochemical
measurements were carried out in a standard three-electrode
system. The anodic reaction was first investigated by
applying the linear sweep voltammetry (LSV) method with or
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and the retaining 1 a was 19% with 72% yield of 2a. It
indicated that most 1a could be transformed into 2a quickly
at 1.35 V. The durability test for the Co3O4@NF anode was
also investigated. After five consecutive runs of chronoam-
perometry experiment at 1.35 V, no remarkable loss of the
activity was observed based on the DHIQ yields (Figure 2d).
SEM image of the Co3O4@NF electrode after stability test
(Figure 1d) showed that the nanoribbon array morphology
was still maintained on the surface of NF substrate without
obvious peeling off from the NF, anticipating its robust
electrochemical stability for this electrocatalytic semi-dehy-
drogenation.
To further gain insight into the catalytic activity of
Co3O4@NF electrode for the semi-dehydrogenation of THIQ,
more electrochemical parameters were measured. As shown
in Figure 3a, the cyclic voltammograms (CVs) over Co3O4@NF
electrode were performed. An enhanced anodic current and
an obvious decreased cathodic current between 1.30 and
1.65 V were observed in the presence of 1a compared with
those in the absence of 1a. The enhanced anodic current was
due to the oxidation of 1a by the electrochemically
generated higher-valence cobalt species, as well as the direct
electro-oxidation of 1a on the electrode. Since part of
higher-valence cobalt species was reduced by 1a, the
reduction current of higher-valence cobalt species decreased.
The above phenomenon was an indication that the cobalt
catalyst of variable valence, as a redox mediator like TEMPO32,
was involved in the reaction to promote the anodic oxidation
of 1a. Not only that, the ratio of Co3 + /Co2 + increased after
semi-dehydrogenation reaction by a careful comparison of
the area change of Co3 + and Co2 + in the high-resolution XPS
spectra (Figure 1e and Table S1). Therefore, we speculated
that Co2 + could be converted to Co3 +, and Co3 + then
captured an electron from 1a to go back to Co2 + during the
electrocatalytic oxidation process. Tafel tests were carried out
to investigate the kinetic processes of the oxidation reaction
over the electrocatalysts (Figure 3b). The Co3O4@NF electrode
showed a tafel slope of 137 mVdecÀ 1 for oxygen evolution
reaction. Meanwhile, it is noted that a competitive tafel slope
of 129 mVdecÀ 1 for the oxidation of 1a was observed at a
much lower potential region, indicating that the Co3O4
modified NF exhibited a superior oxidation activity for 1a.
Considering that the double-layer capacitance could reflect
the electrochemically active surface area, we determined
cyclic voltammograms recorded in the non-faradaic potential
range to calculate the double-layer capacitance (Figure S4).
After loading Co3O4 on nickel foam, the double-layer
capacitance improved from 3.2 mFcmÀ 2 to 245.6 mFcmÀ 2
,
suggesting that the Co3O4 nanoribbon arrays offered a much
higher number of electrocatalytically active sites for THIQ
electrooxidation (Figure 3c). Besides, the fitted O 1s XPS peak
at about 531.4 eV was assigned to the surface oxygen species
(eg. hydroxyls) of the electrocatalyst (Figure 1f top). The
abundance of absorbed oxygen species on the anode surface
could capture THIQ via hydrogen bonding, and favor its
subsequent electrooxidation. So it was reasonable to spec-
ulate that the surface oxygen species could modulate the
surface state of catalytically active sites and improve the
oxidative ability of Co3O4 modified anode. It was found that
the proportion of surface oxygen species increased after
electrocatalytic oxidation (Figure 1f and Table S2), which
might contribute to the stability of the Co3O4@NF anode. The
electrochemical impedance spectroscopy (EIS) measurements
were employed to further evaluate the effect of Co3O4
modification. A non-ideal semicircle was observed when
using the pristine nickel foam as anode, however, the
semicircle nearly disappeared in the case of Co3O4@NF
electrode (Figure 3d and Table S3). It revealed that the THIQ
oxidation was limited by the mass transport due to the fast
electron transfer between Co3O4 catalyst and THIQ.
Furthermore, some representative tetrahydroisoquinoline
derivatives were examined to explore the generality of this
electrocatalytic oxidation method over the Co3O4@NF elec-
trode. As summarized in Figure 4a, various THIQs containing
electron-deficient or rich groups on the aromatic ring were
smoothly converted to the corresponding semi-dehydrogen-
ation products in moderate yields (2b–2e, 64%–70%).
Notably, our reaction system could operate in an undivided
cell and in air atmosphere at room temperature, which was
convenient and avoided preparing specific electrochemical
cell. We assembled
a two-electrode electrolyzer with
Co3O4@NF as an anode and platinum plate as a cathode.
Compared with overall water splitting, the Co3O4@NFj jPt
exhibited much better energy conversion efficiency after
adding 0.02 M 1a (Figure 4b). For instance, the required
voltage for achieving the current density of 10 mAcmÀ 2
shifted from 1.620 V (without 1a) to 1.446 V (with 1a),
confirming again that oxidation of THIQ was thermodynami-
cally more favorable than OER (inset of Figure 4b). Besides,
such a two-electrode configuration was applied to couple
semi-dehydrogenation of 1 a and HER with an applied
voltage in the range of 1.5 to 1.7 V (Figure 4c). No apparent
decrease of FEs and selectivities were observed below the
Figure 3. (a) CV curves of a Co3O4@NF anode at a scan rate of 10 mVsÀ 1 and
(b) Tafel plots of a Co3O4@NF anode based on LSV curves at a scan rate of
2 mVsÀ 1 in 1 M KOH with or without 0.02 M 1a. (c) The capacitive current
density at 1.15 V as a function of CV scan rate and (d) Nyquist plots in the
frequency range from 0.01 Hz to 100 kHz in 1 M KOH with 0.02 M 1a (inset:
the equivalent circuit).
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Keywords: Co3O4 electrocatalyst
energy-saving hydrogen evolution reaction
dehydrogenation
·
dihydroisoquinolines
·
·
·
semi-
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The authors declare no conflict of interest.
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Manuscript received: January 21, 2021
Accepted manuscript online: March 26, 2021
Version of record online: April 14, 2021
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