Ordered Porous Nitrogen-Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N-Heterocycles

Article abstract of DOI:10.1002/anie.201805467

Single-atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single-atom sites were stabilized on an ordered porous nitrogen-doped carbon matrix (ISAS-Co/OPNC). ISAS-Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N-heterocycles to release H₂. ISAS-Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N-heterocycles to store H₂, using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS-Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious-metal catalysts. The reaction mechanisms are systematically investigated using first-principles calculations and it is suggested that the Eley–Rideal mechanism is dominant.

Full text of DOI:10.1002/anie.201805467

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Accepted Article
Title: Ordered Porous N-Doping Carbon Matrix with Atomically
Dispersed Co Sites as an Efficient Catalyst for Dehydrogenation/
Transfer Hydrogenation of N-Heterocycles
Authors: Yadong Li, Yunhu Han, Ziyun Wang, Ruirui Xu, Wei Zhang,
Wenxing Chen, Lirong Zheng, Jian Zhang, Jun Luo, Konglin
Wu, Youqi Zhu, Chen Chen, Qing Peng, Qiang Liu, Peijun Hu,
and Dingsheng Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201805467
Angew. Chem. 10.1002/ange.201805467
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COMMUNICATION
Ordered Porous N-Doping Carbon Matrix with Atomically
Dispersed Co Sites as an Efficient Catalyst for
Dehydrogenation/Transfer Hydrogenation of N-Heterocycles
+
+
Yunhu Han , Ziyun Wang , Ruirui Xu, Wei Zhang, Wenxing Chen, Lirong Zheng, Jian Zhang, Jun Luo,
Konglin Wu, Youqi Zhu, Chen Chen, Qing Peng, Qiang Liu, P. Hu, Dingsheng Wang,* and Yadong Li*
Abstract: The coming single atom catalysts (SACs) as potential
substitutes for homogeneous catalysts have been explored widely.
Herein, we report an isolated single Co atomic site catalyst stabilized
on ordered porous N-doped carbon (ISAS-Co/OPNC). The ISAS-
Co/OPNC can be considered as a highly efficient catalyst for
acceptorless dehydrogenation of N-heterocycles to release H .
2
Importantly, ISAS-Co/OPNC also exhibits excellent catalytic activity
for reverse transfer hydrogenation or hydrogenation of N-
which can perform both dehydrogenation of N-heterocycles and
the contrary transfer hydrogenation or hydrogenation of the
dehydrogenated N-heterocycles, are very rare.
[
5, 9]
SACs have attracted the extensive concern of scientific
researchers because of their maximum atom utilization, superior
[10]
reactivity and selectivity.
With development of synthetic
methodology, plentiful SACs were fabricated successfully. They
not only exhibit excellent performance in electrocatalysis, but
also show highly catalytic activity for organic transformations,
because they can potentially succeed to the merits of
2
heterocycles to store H with formic acid or external hydrogen as
hydrogen source. The catalytic performances surpass the reported
homogeneous and heterogeneous precious metal catalysts. The
reaction mechanisms are systematically investigated using first-
principles calculations, and the Eley–Rideal mechanism is
suggested to be dominating.
[
10]
homogeneous and heterogeneous analogues. As known to all,
the catalytic performances of heterogeneous catalysts are highly
[11]
dependent upon support materials.
The optimal support
materials can shorten diffusion pathway and provide sufficient
Catalytic dehydrogenation and transfer hydrogenation or
hydrogenation of N-heterocycles are essential and important
[10b, 12]
interface area accessible to reactants.
Therefore,
extensive applications of SACs still needs to develop rational
and general synthetic methods based on support materials.
[1]
processes for organic transformations.
Therefore, the
dehydrogenation and transfer hydrogenation or hydrogenation of
N-heterocycles have received more considerable attention from
the opinion of organic hydride hydrogen-storage systems,
because the dehydrogenation of N-heterocycles is more feasible
compared to that of cycloalkanes through decreasing the
Quite recently, we developed a template-assistant-pyrolysis
[10b]
(
TAP) method for synthesis of SACs.
The reported SACs
[10b]
were studied on electrocatalysis.
Compared with the widely
studied electrocatalysis, SACs were seldom explored for organic
reactions, let alone catalyzing dehydrogenation and transfer
hydrogenation or hydrogenation of N-heterocycles. Herein, we
report an ordered porous N-doped carbon catalyst with isolated
single Co atomic sites (ISAS-Co/OPNC). With SBA-15 as
sacrificial template, ISAS-Co/OPNC was successfully fabricated,
and the structure was identified by combining aberration
corrected high-angle annular dark-field scanning transmission
electron microscope (AC HAADF-STEM) and X-ray absorption
fine structure (XAFS) measurements. Interestingly, ISAS-
Co/OPNC can perform both dehydrogenation of N-heterocycles
[2-5]
endothermicity of the reactions.
dehydrogenation of N-heterocycles for releasing H
highly efficient process to prepare heterocycles, such as indole,
Additionally, acceptorless
2
provides a
[
6]
quinoline and their derivatives. Although some homogeneous
and heterogeneous metal catalysts have been developed, most
of them either can merely perform transfer hydrogenation or
hydrogenation,
dehydrogenation.
or
can
just
catalyze
the
opposite
[
7,
8]
Nay, those catalysts are mainly
homogeneous noble-metal catalysts. Nevertheless, the catalysts,
to release H
hydrogenation of N-heterocycles to store H
2
, and the opposite transfer hydrogenation or
with formic acid or
Dr. Y. Han, Dr. W. Zhang, Dr. W. Chen, J. Zhang, K. Wu, Dr. Y. Zhu,
Dr. C. Chen, Dr. Q. Peng, Dr. Q. Liu, Prof. Dr. D. Wang, Prof. Dr. Y.
Li
Department of Chemistry
Tsinghua University
Beijing 100084 (China)
E-mail: wangdingsheng@mail.tsinghua.edu.cn
ydli@mail.tsinghua.edu.cn
2
external hydrogen as hydrogen source. The catalytic activities of
ISAS-Co/OPNC for dehydrogenation and transfer hydrogenation
or hydrogenation are better than the reported homogeneous and
heterogeneous noble-metal catalysts (Table S2 and S4). For
comparison, Co-porphyrin and CoNPs/NC were selected as
control catalysts and exhibited low activity for dehydrogenation
and transfer hydrogenation of N-heterocycles. It is evident that
Dr. Z. Wang, Prof. Dr. P. Hu
School of Chemistry and Chemical Engineering, The Queen’s
University of Belfast, Belfast BT9 5AG
R. Xu
ISAS-Co/OPNC can serve as
a fascinating catalyst for
School of Chemistry & Chemical Engineering, Shaanxi Normal
University
Xi’an 710000 (China)
dehydrogenation and transfer hydrogenation or hydrogenation of
N-heterocycles.
Dr. L. Zheng
Figure 1a showed the synthetic method of ISAS-Co/OPNC.
Low-magnification TEM and field emission SEM images (Figure
Beijing Synchrotron Radiation Facility, Institute of High Energy
Physics, Chinese Academy of Sciences
Beijing 100084 (China)
1b, 1c and Figure S1) showed ordered porous structure of ISAS-
Dr. J. Luo
Co/OPNC, which remains the shape of SBA-15. The Co atoms
could be identified as the brighter spots on the N-doped carbon
from AC HAADF-STEM. Several Co atoms were circled in green
Center for Electron Microscopy, Tianjin University of Technology
Tianjin 300384 (China)
[
+] These authors contributed equally to this work.
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Angewandte Chemie International Edition
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COMMUNICATION
for better identifications (Figure 1d). The element mappings of
ISAS-Co/OPNC suggested C, N and Co were evenly distributed
valence is not an integer valence, it is an average valence of
cobalt. The Fourier transformed (FT) k -weighted extended
3
(
Figure 1e). The elemental information of nitrogen and cobalt
EXAFS spectrum of ISAS-Co/OPNC shows one main peak at
1.44 Å, which belongs to Co−N/C first coordination shell, and no
obvious Co−Co peak (2.19 Å) or other high-shell peaks are
found (Figure 2b). Therefore, based on AC HAADF-STEM and
XAFS results, we believe that cobalt is atomically dispersed.
Corresponding EXAFS fitting curves of ISAS-Co/OPNC at k and
q space were shown in Figure 2c and S6. EXAFS fitting was
performed to obtain the structural parameters and take out the
quantitative chemical configuration of Co atoms (Figure 2d). The
coordination number of Co can be confirmed, which is about 4,
and the mean bond length is 1.92 Å (Table S1). These data
indicate that Co atoms are coordinated by four N atoms in ISAS-
Co/OPNC (Figure 2d, inset). In contrast, the best-fit results for
Co foil were displayed in Figure S7.
was studied by XPS (Figure S2 and S3). The N 1s spectrum
was divided into several peaks at 398.3, 399.1, 400.8, and 404.8
eV assigned to pyridinic N, pyrrolic N, graphitic N, and
chemisorbed nitrogen-oxide species, respectively (Figure S2).
According to reported studies, the cobalt coordinate with
pyridinic N to form catalytically active Co-N
revealed that cobalt of Co-porphyrin was in
environment with a high binding energy of Co 2p1/2 at 780.7 eV
(
(
[
13]
[10d, 14]
x
sites.
XPS
a
cationic
Figure S3). For the pyrolysis of Co-2,2-bipy/SBA-15
CoCN/SBA-15) and ISAS-Co/OPNC, the Co 2p1/2 signals down-
shifted to 779.1 eV and 780.0 eV. A similar down-shift of Co 2p
was observed for CoCN/SBA-15 and ISAS-Co/OPNC, the
valence states of the resulting Co were characterized by a slight
[
15]
positive charge because of N-coordination (Figure S3).
XRD
of ISAS-Co/OPNC demonstrated no cobalt particles (Figure S4).
The content of Co was approximately 1.8 wt% determined by
ICP-OES analysis. Nitrogen adsorption-desorption isotherms
showed that ISAS-Co/OPNC possessed a high BET surface
2
−1
area of 587 m g (Figure S5).
Figure 2. (a) XANES spectra at the Co K-edge of ISAS-Co/OPNC, CoO,
Co
3
O
4
and Co foil. (b) Fourier transform (FT) at the Co K-edge of ISAS-
and Co foil references. (c) Corresponding EXAFS
Co/OPNC and CoO, Co
3
O
4
fitting curves of ISAS-Co/OPNC at k space. (d) Corresponding EXAFS fitting
curves of ISAS-Co/OPNC at R space. Inset: Schematic model of ISAS-
Co/OPNC: Co (light blue), N (dark blue), and C (gray).
To examine the catalytic activity of ISAS-Co/OPNC for
dehydrogenation of N-heterocycles, 1,2,3,4-tetrahydroquinoline
was chosen as a model substrate. A blank experiment was first
tested, but only negligible quinoline was observed (Table 1,
entry 1). For contrast, we investigated the catalytic activation of
different cobalt materials (Figure S8-S11). As shown in Table 1,
besides Co-porphyrin and CoCl
2
,
Co-powder, ZIF-67,
Figure 1. (a) Schematic illustration of the synthesis of ISAS-Co/OPNC.
o
o
CoNPs/NC and CoCN/SBA-15 possessed a lower catalytic
activity for the dehydrogenation (Table 1, entries 2-7). However,
ISAS-Co/OPNC gave the best performance with 99%
conversion of 1,2,3,4-tetrahydroquinoline in air, Ar atmosphere
and the presence of butylated hydroxytoluene (BHT) (Table 1,
entries 8-10). Indeed, when compared with the reported, it is
found that ISAS-Co/OPNC has an excellent activity and milder
reaction conditions (Table S2).
Conditions: (1) 80 C, H
images of ISAS-Co/OPNC. (d) AC HAADF-STEM image of ISAS-Co/OPNC.
e) HAADF-STEM image and corresponding EDX mapping of ISAS-Co/OPNC,
2
O/ethanol, (2) 800 C, Ar, (3) NaOH. (b, c) TEM
(
C (violet), N (red) and Co (yellow).
XAFS measurements were performed to analyze the
coordination environment of cobalt at atomic level. Co K-edge X-
ray absorption near-edge structure (XANES) spectra of ISAS-
Co/OPNC and Co foil, CoO, and Co
3 4
O references were showed
in Figure 2a. According to the absorption edge, we conclude that
the valence of Co atom situate between Co and Co . The
We further investigated the dehydrogenation of 1,2,3,4-
tetrahydroquinoline derivatives and other N-heterocycles. As
0
2+
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COMMUNICATION
shown in Table S3, 1,2,3,4-tetrahydroquinoline derivatives with
an electron-donating group (-Me) was transformed smoothly into
the corresponding quinoline compounds with 99% conversion
(
Table S3, entries 1,2). However, 1,2,3,4-tetrahydroquinoline
c
d
Entry
Catalyst
Conv. (%)
Sel. (%)
derivatives with an electron-withdrawing group (-NO ) was
2
2
a
2b
converted slowly into the corresponding quinoline compound
with 98% conversion for 18 hours (Table S3, entry 3). 1,2,3,4-
Tetrahydroquinoxaline of dual N-heterocycle was catalyzed into
quinoxaline with 99% conversion (Table S3, entry 4). Other N-
heterocycles like indoline and 6-nitroindoline showed also an
efficient conversions and high yields (Table S3, entries 5,6).
1
2
3
4
5
6
7
8
none
trace
3
1.1
0.8
0.2
6
1.2
99
99
trace
91
trace
9
3
trace
7
trace
trace
trace
trace
Co-Porphyrin (6 mg)
ZIF-67 (2 mg)
97
99
93
99
99
99
99
CoCl2 (2 mg)
Co Powder (2 mg)
CoNPs/NC (2 mg)
CoCN/SBA-15 (5 mg)
ISAS-Co/OPNC (25 mg)
ISAS-Co/OPNC (25 mg)
a
Table 1. Cobalt-catalyzed dehydrogenation of N-heterocycles.
b
9
a
Reaction conditions: The reactions were carried out with 0.5 mmol reactant,
.5 mol % Co catalyst and 10 eq. HCOOH in 1.5 mL of toluene at 120 C for
.5 hours. The reaction was performed at 100 C for 4 hours. Determined by
GC analysis with n-dodecane as internal standard. Determined by GC-MS
analysis.
o
1
1
b
o
c
d
o
c
Entry
Catalyst
T ( C)
t (h)
Conv. (%)
1
2
3
4
5
6
7
8
none
120
120
120
120
120
120
120
120
120
120
8
8
8
8
8
8
8
8
8
8
0
8
1
Co-Porphyrin (6 mg)
ZIF-67 (2 mg)
ISAS-Co/OPNC was also conducted for transfer
hydrogenation of a broad scope of N-heterocycle substrates.
The reaction results were listed in Table S5. We can observe
that quinoline-derivatives with electron-donating group (-Me or -
OMe) were completely converted to corresponding 3,4-
dihydroquinoline-1(2H)-carbaldehyde derivatives (Table S5,
entries 1-5). 6-Methoxyquinoline was nine tenths converted into
CoCl
2
(2 mg)
5
Co Powder (2 mg)
CoNPs/NC (2 mg)
CoCN/SBA-15 (5 mg)
ISAS-Co/OPNC (25 mg)
ISAS-Co/OPNC (25 mg)
ISAS-Co/OPNC (25 mg)
0.5
1.6
2.3
99
99
99
b
9
b
10
6-methoxy-3,4-dihydroquinoline-1(2H)-carbaldehyde (Table S5,
a
Reaction conditions: The reactions were carried out with 0.5 mmol reactant
entry 6). Moreover, for quinoline derivatives with electron-
withdrawing group (-Cl or -Br), transfer hydrogenation
conversion were also more than 90% (Table S5, entries 7-9).
Apart from the routine substituted quinoline derivatives, other N-
heteroarenes such as 7,8-benzoquinoline remained suitable
reactant for this reaction converting into the corresponding
formamide in moderate to excellent conversion with high
selectivity (Table S5, entry 10). Moreover, the hydrogenation of
quinoline derivatives with external hydrogen as hydrogen source
were also performed under (Table S6). Quinoline derivatives
b
and Co catalysts (Co
dehydrogenation of 1,2,3,4-tetrahydroquinoline performed in Ar atmosphere
and the presence of BHT. Determined by GC analysis using of n-dodecane
as internal standard.
= 1.5 mol%) in 1.5 mL of mesitylene. The
c
We further explored transfer hydrogenation of quinoline to
,4-dihydroquinoline-1(2H)-carbaldehyde (2a) with formic acid
3
as the hydrogen source. Transfer hydrogenation of quinolines
were tested under almost the same conditions as that of the
above dehydrogenation reaction. The product 2a can be easily
with
a
methyl was transformed into the
1,2,3,4-
hydrolyzed
into
the
corresponding
amine,
1,2,3,4-
tetrahydroquinolines compounds with 99% conversion (Table S6,
entries 2,3). However, 2,6-dimethyl-quinoline was converted
slowly into the corresponding tetrahydroquinoline with 95%
conversion (Table S6, entry 4). For quinoline derivatives with
electron-withdrawing group (-Cl or –NO ), the hydrogenation
2
conversion were also high impressive (Table S6, entries 5,6).
tetrahydroquinoline (2b), in quantitative yield simply by using
NaOH/H O/EtOH (Scheme S1). As expected, ISAS-Co/OPNC
2
[
7d]
possessed the best catalytic activity with 99% quinoline
conversion and 99% 3,4-dihydroquinoline-1(2H)-carbaldehyde
selectivity (Table 2, entry 8). However, for blank experiment and
different cobalt materials, their catalytic performances of transfer
hydrogenation can be trifling (Table 2, entries 1-7). When the
o
For heterogeneous catalysis, to avoid the deactivation of
the catalysts resulted from aggregation and leaching of active
metal during the reaction is still a challenging. Therefore, the
reusabilities of ISAS-Co/OPNC in dehydrogenation and transfer
hydrogenation were investigated. For this purpose, ISAS-
Co/OPNC was separated from the reaction system by
centrifugation, washed and dried at 100 °C under vacuum, and
then reused. It was worth mentioning that no obvious attenuation
of catalytic activation was observed. After six runs, the
conversions of the target products were still up to 99% for both
dehydrogenation and transfer hydrogenation (Figure S12). In
addition, when ISAS-Co/OPNC was filtered off, the further
reaction could not be observed (Figure S13 and S14). Figure
S15 and S16 showed that cobalt was still homogeneously
reaction was carried out at 100 C, the reaction time just
prolonged to 4 hours (Table 2, entry 9). In order to verify the
activation of external hydrogen for quinoline hydrogenation, the
experiment of external hydrogen as a hydrogen source was
performed. It was found that quinoline was converted completely
o
into 1,2,3,4-tetrahydroquinoline under 120 C, 1.5 MPa and 50
mg (3 mol% Co) catalyst in 1.5 mL toluene for 12 hours. In like
wise, compared with the reported results, whether using formic
acid or external hydrogen as
a hydrogen source, ISAS-
Co/OPNC has also an outstanding catalytic activity (Table S4).
Table 2. Cobalt-catalyzed transfer hydrogenation of quinoline with formic
a
acid.
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Angewandte Chemie International Edition
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COMMUNICATION
distributed and exhibited a little differences on the morphology
after six runs. Thereby, it demonstrated that the aggregation and
leaching of active centers did not occurred during
dehydrogenation and transfer hydrogenation.
(21521091, 21390393, U1463202, 21471089, 21671117). We
thank the 1W1B station for XAFS measurement in Beijing
Synchrotron Radiation Facility (BSRF).
Keywords: ordered porous
atomically dispersed sites
hydrogenation or hydrogenation
•
N-doping carbon matrix
•
Since the basic reactions of hydrogenation and
dehydrogenation of quinoline are similar, the hydrogenation
reaction was taken as an example to study the mechanism. To
understand the reaction mechanism and energetics, we carried
out first-principles calculations of 1,2,3,4-tetrahydroquinoline
hydrogenation. Hydrogen was chosen as the reductant to simply
the calculations, and the dissociation of hydrogen was assumed
to be in equilibrium. All the possible pathways were considered,
and the free energy profile of the most favorable pathway are
shown in Figure S17. It can be seen that the reaction starts with
the hydrogenation of N atom in 1,2,3,4-tetrahydroquinoline
forming IM1. Then, the carbon next to nitrogen couples with H
forming partially hydrogenated product (p-product). The rest two
carbon are hydrogenated via intermediate state, IM2, giving the
final product. The hydrogenation of p-product is favorable both
thermodynamically and kinetically, suggesting the p-product is
likely to be hydrogenated on ISAS-Co/OPNC. This finding is in
agreement with the experiment result that no p-product is
detected. Furthermore, all the barriers of the four hydrogen
elementary steps are lower than 0.87 eV, indicating the single
Co site are highly active for the hydrogenation of 1,2,3,4-
tetrahydroquinoline. Interestingly, all the most favorable
transition states are via Eley–Rideal (ER) mechanism, in which
hydrogen is on the Co site and the quinoline species attracts
from gas-phase (Figure S18b). The transition states geometries
of the elementary steps with highest barriers, namely the last
hydrogenation step, via Langmuir–Hinshelwood (LH) and ER
mechanism are shown in Figure S18. The barriers of LH and ER
are calculated to be 1.73 eV and 0.87 eV, indicating ER
mechanism is likely to be dominating in the 1,2,3,4-
tetrahydroquinoline hydrogenation on the ISAS-Co/OPNC.
•
dehydrogenation transfer
•
[
[
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In conclusion, we successfully prepared an atomically dispersed
ISAS-Co/OPNC catalyst, which exhibited highly efficient catalytic
activities for both dehydrogenation of N-heterocycles to release
H
2
and the reverse transfer hydrogenation or hydrogenation of
N-heterocycles to store H with formic acid or external hydrogen
2
as hydrogen source. The catalytic activities for dehydrogenation
and transfer hydrogenation or hydrogenation of N-heterocycles
exceeded the reported homogeneous or heterogeneous noble-
metal catalysts due to the lower barriers via ER mechanism.
Organic materials that are amenable to catalyzed reversible
dehydrogenation/hydrogenation may be used as hydrogen-
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2
and thereby
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Acknowledgements
This work was supported by the National Postdoctoral Program
for Innovative Talents (BX201600084), China Ministry of
Science and Technology under Contract of 2016YFA (0202801),
and the National Natural Science Foundation of China
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Angewandte Chemie International Edition
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COMMUNICATION
COMMUNICATION
Isolated single Co atomic site
catalyst stabilized on the ordered
porous N-doped carbon matrix
+
+
Yunhu Han , Ziyun Wang , Ruirui Xu,
Wei Zhang, Wenxing Chen, Lirong
Zheng, Jian Zhang, Jun Luo,
(
ISAS-Co/OPNC)
efficient catalytic performance for
both the acceptorless
dehydrogenation of N-heterocycles
to release in mesitylene at
20 °C for 8 hours, and the reverse
shows
highly
Konglin Wu, Youqi Zhu, Chen Chen,
Qing Peng, Qiang Liu, P. Hu,
Dingsheng Wang,* and Yadong Li*
Page No. – Page No.
H
2
1
transfer
hydrogenation
or
Ordered Porous N-Doping Carbon
Matrix with Atomically Dispersed Co
Sites as an Efficient Catalyst for
Dehydrogenation/Transfer
hydrogenation reaction of N-
heterocycles to store H in toluene
at 120 °C with formic acid or
external hydrogen as hydrogen
source.
2
Hydrogenation of N-Heterocycles
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