Ultra-Stable and High-Cobalt-Loaded Cobalt@Ordered Mesoporous Carbon Catalysts: All-in-One Deoxygenation of Ketone into Alkylbenzene

Article abstract of DOI:10.1002/cctc.201800358

Catalytic deoxygenation represents a straightforward and core methodology for fine-chemical production and biomass upgrading. Generally, the application of homogeneous metal complexes or heterogeneous noble-metal catalysts prevails in academia and the chemical industry. Herein, we introduce cobalt@ordered mesoporous carbon (Co@OMC) catalysts, which are constructed conveniently by a mechanochemical coordination self-assembly based on a renewable tannin precursor. Importantly, the Co@OMC catalysts with a high loading of in situ confined Co species promote the selective deoxygenation of various ketones, aldehydes, and alcohols efficiently into the corresponding alkanes under mild conditions. Therefore, a simple, inexpensive, and heterogeneous catalyst for selective deoxygenation can be expected, meanwhile the solid-state synthesis affords a green, rapid, and scalable pathway to Co@OMC catalysts.

Full text of DOI:10.1002/cctc.201800358

Accepted Article
Title: Ultra-Stable and High Loading Cobalt@Ordered Mesoporous
Carbon Catalysts: All-in-One Deoxygenation of Ketone into
Alkylbenzene
Authors: Pengfei Zhang, Nanqing Chen, Dong Chen, Shize Yang,
Xiaofei Liu, Li Wang, Peiwen Wu, Nathan Phillip, Guang
Yang, and Sheng Dai
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201800358
Link to VoR: http://dx.doi.org/10.1002/cctc.201800358
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10.1002/cctc.201800358
ChemCatChem
COMMUNICATION
Ultra-Stable and High Loading Cobalt@Ordered Mesoporous
Carbon Catalysts: All-in-One Deoxygenation of Ketone into
Alkylbenzene
Pengfei Zhang, a, b, *, + Nanqing Chen,c,+ Dong Chen,a Shize Yang,b Xiaofei Liu, b, d Li Wang,b,d Peiwen
Wu b, Nathan Phillip, b Guang Yang, b and Sheng Dai* b, c
[8-10]
Under such high loading, even a slight migration of Co NPs
on support (e.g., graphene) can result in severe aggregation,
while certainly it is unfavorable in catalysis.[11-12] As to the
Abstract: Catalytic deoxygenation represents a straight-forward and
availability of active Co species, it is primarily governed by the
core methodology for fine-chemical production and biomass updating.
porous structure of support materials. Previous efforts on
Generally, the application of homogeneous metal complexes or
Cobalt@Carbon catalysts suggest that the surface area, pore size,
heterogeneous noble-metal catalysts prevail in academia and
and orderliness of the carbon support actually control those
chemical industry. Herein, we introduce the cobalt@ordered
factors mentioned above.
mesoporous carbon (Co@OMC) catalysts, which are conveniently
Among various carbon supports, ordered mesoporous
constructed by a mechanochemical coordination self-assembly based
carbons (OMCs) with uniform pore channel, wide pore size, large
on renewable tannin precursor. Importantly, those Co@OMC
pore volume, and high surface area are considered as promising
catalysts with a high loading of in-situ confined Co species efficiently
matrixes to incorporate metal species, which can contribute to
promote selective deoxygenation of various ketones/aldehydes/
better dispersion of active center, faster mass transfer, and space
alcohols into the corresponding alkanes under mild conditions.
confining effect.[13-16] For example, the introduction of OMCs as
Therefore, a simple, inexpensive and heterogeneous catalyst for
catalyst supports can enhance the dispersion of active Pd or Au
selective deoxygenation can be expected, meanwhile the solid-state
species that leads to increased catalytic activity in the cross-
synthesis naturally affords a green, rapid and scalable pathway to
coupling and oxidation reactions, respectively.[17-18] In general, the
Co@OMC catalysts.
construction of Metal@OMC catalyst includes hard- or soft-
templating synthesis of OMCs, impregnation or precipitation of
metal salts into OMCs, and reduction of metal precursors.[19-24]
Introduction
However, those complicated approaches still bear several
drawbacks such as: the relying on corrosive reagents (e.g., HF
acid, NH4HF2), the use of carcinogenic and fossil-based
precursors (e.g., formaldehyde, phenol, resorcinol), and the time
(1-3 days)- and organic solvent (e.g., ethanol, THF)-consuming
process for films/membranes.[25-30] To date, the development of a
facile and direct method to construct Co@OMC catalyst with a
high loading of stable Co NPs is highly challenging.
Cobalt@Carbon (Co@C) represents one of the state-of-the-art
heterogeneous
catalysts
for
selective
hydrogenation,
electrochemical oxidation and reduction, and so on, both in
academia and in industrial chemistry. [1-4] Among the parameters
affecting the catalytic activity of Co@C, the stability, loading
volume and availability of active Co phases appear to be the key.
For instance, the harsh catalytic conditions (e.g., high
temperature, reductive atmosphere, high electric current) often
make Co nanoparticles (NPs) with high surface energy grow or
sinter, accompanied by partial or even complete loss of their
activities. [5-7] Thus, it is well acknowledged that the poor stability
of Co NPs is one of the major issues, especially toward
electrochemical processes during which a high loading of Co NPs
(e.g., ~50wt% for oxygen reduction reaction) is usually required.
[a]
[b]
Prof. P. F. Zhang, Dr. D. Chen
School of Chemistry and Chemical Engineering
Shanghai Jiao Tong University
Shanghai 200240, China
E-mail: chemistryzpf@sjtu.edu.cn
Dr. P. F. Zhang, Dr. S. Yang, X. Liu, Dr. L. Wang, Dr. P. Wu,
Prof. S. Dai
Oak Ridge National Laboratory
Oak Ridge 37831, TN, United State
E-mail: dais@ornl.gov
Scheme 1. A Mechanochemical Synthesis of Cobalt-Ordered Mesoporous
Carbon Catalysts from Tannin.
[c]
[d]
Dr. N. Chen, Prof. S. Dai
Department of Chemistry
University of Tennessee
Knoxville 37996, United State
Dr. X. Liu, Prof. L. Wang
Institute of Industrial Catalysis
East China University of Science and Technology
Shanghai 200237, China
In this contribution, we show the one-step mechanochemical
synthesis of Co@OMCs incorporated with as high as 21.5wt%
Co NPs that can keep highly dispersed and less than 5 nm even
at 600oC. The essence of stabilizing Co NPs that are in situ
formed within both mesoporous channel and microporous carbon
wall lies in the ligand-protected pyrolysis and space confining
effect of OMCs. Especially, the solid-state self-assembly
between tannin-Co and block copolymers enables Co@OMC
catalysts with ordered mesopores readily tuned from 4.3 to 9.4
+ Those authors contribute equally to this work.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/cctc.201800358
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nm and high surface areas up to 700 m2g-1. Importantly,
Co@OMCs show a good activity in the direct deoxygenation of
ketones/aldehydes/alcohols, an important and difficult process in
organic synthesis and biomass updating.
21.5wt%) (Table 1), and thus the tannin-mediated coordination
functioned well toward incorporating Co into carbon materials. It
is understandable if the abundant catechol- and pyrogallol-like
sites on tannin for chelating are considered.[34] The thermal
treatment of Co@OMC precursor was monitored by X-ray
diffraction (XRD). No Co-containing phases were observed in the
sample from 400oC (Figure S1), while the reduction of Co2+ by
neighbor carbon occurred at a higher temperature (600oC). All
Co@OMC products showed peaks at 2θ = ~45° that can be
assigned to (111) reflection of the cubic Co lattice (Figure S2). We
observed that the peaks were extremely broad, revealing the
small crystalline size of Co species (Scherrer’s formula). The
phenolic chelate may stabilize Co centers during pyrolysis, and
similar phenomena were reported in the pyrolysis of metal-
organic frameworks (MOFs).[35-36] But, the abundant, renewable,
and inexpensive characters (<$20/Kg) of tannin are more
attractive than most ligands for MOFs.
Results and Discussion
The Co@OMC catalysts were fabricated by mechanochemical
assembly of tannin-Co2+ coordination polymer and triblock
copolymer, as shown in Scheme 1. Tannin is a mimosa-derived
polyphenol with gallic acid and phloroglucinol units at the end.
Firstly, a mixture of tannin (1 g) and triblock copolymer (0.4-0.8 g)
was ball ground (0.5 h) to form a mesophase composite via -
PhOH···-O- hydrogen bonding interaction.[32] Secondly, Co(OAc)2
was added into the mixture for tannin-Co2+ coordination
polymerization by ball milling (0.5 h).[33] Finally, the gel-like
composite was thermally treated at 600oC in N2. It enabled the
copolymer template removed by decomposing into gaseous
product, and at the same time Co2+ ions were reduced into
metallic Co NPs by carbon nearby, resulting in the Co@OMC
catalysts. A number of triblock copolymers ((poly(ethylene oxide)-
poly(propylene oxide)-poly(ethylene oxide), PEO–PPO–PEO)
such as F38, F68, F98, F127, P123, L43, and additives
(mesitylene) were studied, in order to obtain Co@OMC catalysts
with different pore sizes. The products were designated like
Co@F1270.4, Co@F1270.6, Co@P1230.8, etc., where “F1270.4
”
means F127 copolymer (0.4 g) was added in the raw mixture.
Table 1. Characterization data of Co@OMC catalysts. a)
Sample
Co
Co
SBET
(m2 g-
Pore
Size
(nm)
Pore
Content
(wt%)
Size
(nm)
Volume
(cm3 g-1)
1
)
Co@F1270.4
Co@F1270.6
16.0
12.6
4.6
5.8
537
536
5.3
7.5
0.37
0.49
Co@F1270.8
Co@F380.8
12.8
13.0
21.5
13.5
20.9
9.0
4.7
-
613
432
700
589
606
545
532
603
548
7.6
4.3
4.4
6.0
5.1
6.7
5.0
8.2
9.4
0.63
0.29
0.50
0.51
0.61
0.43
0.40
0.60
0.56
Co@F680.8
-
Co@F980.8
5.6
4.9
-
Co@P1230.8
Co@Bj350.8
Co@L430.8
21.2
18.3
20.2
6.5
-
Figure 1. The N2 sorption isotherms of Co@OMC catalysts at 77 K, and the
Co@F1270.8+M0.12
Co@F1270.8+M0.17
corresponding pore size distributions.
5.0
The porosity of Co@OMC catalyst that reflects the
accessibility of active sites to the reactants, was then investigated
by N2 adsorption-desorption measurements at 77K. In the
presence of F127, all Co@OMC catalysts displayed type IV
isotherms with increasing N2 uptakes between P/P0=0.5-0.8 and
sharp hysteresis loops (Figure 1a). The corresponding pore size
distributions (PSDs) by Barrett-Joyner-Halenda (BJH) model
using adsorption branches were narrow and centered from 5.3-
7.6 nm (Figure 1b). Compared with Co@F1270.8 (7.6 nm),
Co@F1270.4 possessed a smaller pore size of 5.3 nm. It seems
reasonable because more tannin-Co precursors would embed
a) Characterization Details: Co contents were measured by ICP-AES. Co sizes
were calculated by the average sizes of particles in TEM images. Specific
surface areas were calculated using the BET equation in the relative pressure
range of ~0.05–0.20. Pore sizes were obtained from pore distribution maxima
calculated by adsorption branch isotherm according to the BJH model. Pore
volume referred to single point pore volumes at relative pressure of ~0.98.
Initially, the Co contents in the carbon samples were studied
by inductively coupled plasma-atomic emission spectroscopy
(ICP-AES). As expected, the Co contents were quite high (9.0-
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10.1002/cctc.201800358
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into the hydrophilic PEO moiety of micelle in the case of F1270.4
and the reduced template directs smaller pores.
isotherms toward higher relative pressure, hinting the formation of
larger pore size (Figure 2e). Indeed, the pore size moved from 7.6
nm to 9.4 nm in the presence of 17wt% mesitylene additive, as
shown in the PSDs (Figure 2f). Therefore, it seems fair to say that
current strategy can direct Co@OMCs with pore sizes easily
tuned from 4.3 nm to 9.4 nm. The specific surface areas of
Co@OMCs by Brunauer–Emmett–Teller method lie within the
range of 432-700 m2g-1 with high pore volumes up to 0.63 cm3g-1
(Table 1). Besides ordered mesopores, the surface area of
Co@OMC is primarily contributed by the ubiquitous micropores
inside carbon walls.
The porous morphology of Co@OMCs was then examined by
scanning transmission electron microscope in high-angle annular
dark-field (STEM-HAADF). Both Co@F1270.4 and Co@F1270.6
display honeycomb-like mesopores staying side by side from
surface to bulk, and those mesopores roughly follow a cubic-like
array (Figures 3a-3d). The apparent pore size of Co@F1270.4 is
estimated to be ~ 5.0 nm, which matches well with that (5.3 nm)
by PSDs (Figure 3b). Importantly, hexagonally ordered
mesopores were observed in the cases of Co@F1270.8 and
Co@P1230.8. The uniform pore channels could be witnessed in
the domain of hundreds of nanometers (Figures 3e-3h, Figures
S3-S4). Those images together with the N2 sorption results
suggest that the cobalt-mediated coordination self-assembly
functions well for engineering ordered mesopores.
To investigate the effect of hydrophilic/hydrophobic sections
for porosity control, triblock copolymers with different PEO and
PPO composites were studied. In comparison to F127 (PEO
chain: 70wt%), P123 with a shorter PEO chain (30wt%) resulted
in a smaller pore size of 5.1 nm (Figure 1c-1d). In addition,
copolymers containing various PPO molecular weights (F98, F68,
F38) were used in the synthesis of Co@OMCs. The pore size
roughly shrank with the decreasing of PPO molecular weight,
which is relating to the size of hydrophobic PPO micelle core
(Figure 1e-1f). For instance, Co@F380.8 had a pore size of 4.3 nm
(Molecular weight of PPO chain in F38: 950 g mol-1). Several
nonionic surfactants such as L43 and Brij@35 also worked well
for generating mesopores (Figure 2a-2d). In especial, the PSD of
Co@L430.8 was quite narrow, and located around 5.0 nm (Figure
2b). Actually, surfactants with weak hydrogen-bonding abilities
(e.g., L43, Brij@35) have been rarely succeeded in soft-
templating synthesis of OMCs, and the solvent-free
mechanochemical grinding may strengthen the self-assembly. [37-
38]
What’s attractive is the confining talent of this coordination-
based assembly. It is clear that Co NPs even with a high loading
of 20.9 wt% can be evenly dispersed in the mesoporous channel
(Figure 3g-3h, Figures S5-S6). In addition, Co NPs on OMCs are
small and highly stable. The average particle sizes of Co are in
the range of 4.6-6.5 nm (Table S1-S6). Actually, it is of great
difficulty to keep Co NPs so small at a temperature of 600oC. A
control sample with 20wt% Co on soft-templating OMC prepared
Table 2. Selective Hydrogenation of Acetophenone by Co@OMC Catalyst.a
Sel. (%)
EB
CBf
(%)
Conv.
(%)
Entry
1
Catalyst
-
PE
-
ECH
-
98.5
<1
-
2
3
Co@F1270.8
Co@F1270.8+M0.17
Co@L430.8
12
21
19
53
54
51
2
39
32
44
40
56
52
20
-
53
65
45
56
42
40
80
94
6
2
9
3
-
98.6
99.5
4
97.5
5
Co@P1230.8
Co@P1230.8
Co@P1230.8
Co@P1230.8
Co@P1230.8
96.3
6b
7c
8d
9e
98.3
Figure 2. The N2 sorption isotherms of Co@OMC catalysts at 77 K, and the
6
-
101.2
100.2
100.7
corresponding pore size distributions.
Among the surfactants studied above, F127 with the highest
PPO molecular weight (4000 g mol-1) and PEO percent (70 wt%)
generated the largest pore size (7.8 nm). Then, we tried to further
enhance the pore size by adding mesitylene into F127. In that way,
bigger hydrophobic micelles are expected. It is interesting that the
mesitylene additive pushes the hysteresis loops in N2 sorption
>99
5
a)
Reaction Conditions: acetophenone 1 mmol, cyclooctane 1 mmol (Internal
Standard), hexane 4 mL (Solvent), catalyst 10 mg, H2 1 MPa, 100oC, 23
h. b) H2 2 Mpa. c) H2 3 Mpa. d) 80oC. e)120oC. f) Carbon balance.
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Figure 3. STEM-HAADF images of Co@F1270.4 (a-b), Co@F1270.6 (c-d), Co@F1270.8 (e-f), and Co@P1230.8 (g-i).
by an impregnation method and thermally treated at 600oC.
Severe growth and aggregate of Co NPs were seen in the
corresponding TEM image, in turn arguing for the confining talent
of current Co@OMCs (Figures S7-S8). Co NPs with clear lattice
fringes exposed the [111] and [011] crystal facets of metallic Co,
as observed in high-resolution image (Figure 2i).
Selective transformation of aromatic ketones/aldehydes/
alcohols into alkylbenzene is of great interest in organic synthesis
and biomass updating.[39-47] It is a deoxygenation process, and
typical model molecules include acetophenone, benzaldehyde
and benzyl alcohol. With acetophenone as an example, direct
the exceptional features of Co@OMC catalysts encourage us to
try this process.
The hydrogenation of acetophenone was initially studied
under mild conditions (100oC, H2 1 MPa). No products were
observed in the blank run (Table 2, entry 1). In the presence of
Co@OMC catalysts, the hydrogenation occurred with 1-phenyl
ethanol, ethylbenzene and ethylcyclohexane as products. Among
four catalysts investigated in the hydrogenation, Co@P1230.8
afforded a higher conversion (53%) than others (Table 2, entries
2-5). We attribute it to the structural features of Co@P1230.8
,
which includes ordered mesoporous channels (5.1 nm) and a high
loading (20.9 wt%) of Co NPs (4.9 nm) with an even dispersion.
Since the selectivity for ethylbenzene (56%) is moderate,
reaction parameters were then optimized to convert 1-phenyl
ethanol intermediate into ethylbenzene. The H2 pressure does
not remarkably affect the catalytic result. When the H2 pressure
deoxygenation of acetophenone into ethylbenzene is
a
complicated process that covers hydrogenation of ketone to
alcohol, dehydration and hydrogenation of benzyl C=C bond.
Hence, a versatile hydrogenation catalyst working for two types of
chemical environments (ketone and C=C bond) is required, while
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was increased from 1 MPa to 2 and 3 MPa, the acetophenone
conversion and the product selectivity are almost preserved
(Table 2, entries 6-7). The Van’t Hoff approximation rule suggests
that the rate constant would increase by 2–3 times if the reaction
temperature increases by 10 K. Then, efforts were made toward
adjusting reaction temperature. Limited products (Conv.: 2%)
were observed at 80oC (Table 2, entry 8), while a high conversion
(>99%) of acetophenone with a good selectivity to ethylbenzene
(94%) was got at 120oC (Table 2, entry 9). With this satisfied result
on hand, we then studied the catalyst stability under the optimized
condition. As a solid catalyst, the Co@P1230.8 can easily be
separated from the reaction solution by centrifugation, which was
dried at 80oC for subsequent test. The liquid products were
collected by hot filtration after the hydrogenation and analyzed by
ICP-AES. A very low amount of dissolved cobalt (<0.1% of the
total cobalt) was detected in the solution. It is clear that
Co@P1230.8 catalyst can be reused at least ten times without a
significant difference on catalytic performance, porosity and
structural morphology (Figures S9-S11). Therefore, it seems fair
to say that Co@P1230.8 is a promising catalyst for direct
deoxygenation of carbonyl group.
24%) was also observed, suggesting that the transformation
between acetophenone and 1-phenyl ethanol may be reversible
in the presence of Co@P1230.8 catalyst and H2. The
hydrogenation of carbonyl group on acetocyclohexane was also
possible yet affording a lower conversion (Conv.: 7%), in
comparison to the value (Conv.: 53%) of acetophenone. The
conjugated structure of benzene ring and carbonyl group should
make this difference, and the hydrogenation of aromatic carbonyl
group is easier than the processing of aliphatic carbonyl group.
Moreover, styrene can be hydrogenated smoothly into
ethylbenzene by Co@P1230.8 (Conv.: >99%, Sel.: 96%). The
hydrogenation of both intermediates 1-phenyl ethanol and styrene
to ethylbenzene is possible by Co@P1230.8 catalyst and H2.
Therefore, a deoxygenation pathway from acetophenone via 1-
phenyl ethanol and styrene to ethylbenzene may undergo in this
Co@P1230.8/H2 system.
Table 3. Selective deoxygenation of ketones/aldehydes/alcohols by
Co@P1230.8 catalyst. a)
Conv.
(%)
Sel.
(%)
Entry
1
Substrate
Product
>99%
>99%
>99%
>99%
>99%
95%
97%
2
3
4
5
6
>99%
>99%
95%
>99%
>99%
a) Substrate 1 mmol, Co@P1230.8 catalyst 10 mg, cyclooctane 1 mmol (internal
stardard), hexane 4 mL, H2 1 Mpa, 120℃, 23 h.
To probe the scope of current Co@P1230.8 catalyst, various
ketones, aldehydes and alcohols were deoxygenated at 120-130
oC and 1 MPa H2 (Table 3). Aromatic ketones with different
Scheme 2. Catalytic deoxygenation of model molecules. Reaction conditions:
Substrate 1 mmol, Co@P1230.8 catalyst 10 mg, cyclooctane 1 mmol (internal
stardard), hexane 4 mL, H2 1 Mpa, 100oC, 23 h.
chainsboth
benzaldehyde
and
propiophenone
were
transformed into the corresponding alkylbenzenes with high
conversions. The Co@P1230.8 catalyst also enabled the
deoxygenation of diphenylmethanone with a steric hindrance into
diphenylmethane in a high yield (Table 3, Entry 3). Alcohols are
actually intermediate molecules during the hydrogenation of
ketones, and we then moved toward the deoxygenation of
alcohols. As expected, the Co@P1230.8 catalyst functioned well in
the selective removal of -OH groups in aromatic alcohols (benzyl
To study the deoxygenation pathway, control reactions with
three model molecules (1-phenyl ethanol, acetocyclohexane,
styrene) were carried out under the same conditions (Scheme 2).
The deoxygenation of 1-phenyl ethanol gave ethylbenzene as the
main product (Sel.: 72%), and it may proceed by the
deoxygenation of alcohol and hydrogenation of C=C bond. At the
same time, the dehydrogenation product-acetophenone (Sel.:
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In summary, a family of ordered mesoporous Co@Carbon
catalysts have been fabricated via a direct, sustainable and
efficient mechanochemical coordination self-assembly with
inexpensive biomass tannin as the precursor. No solvents are
needed, and this solid-state process is complete in 1 h.
Co@OMC catalysts possess uniform mesoporous channels,
tunable pore size (4.3-9.4 nm), and high surface areas (up to 700
m2g-1). Co NPs with a high loading up to 21.5 wt% are
homogeneously dispersed in the ordered mesoporous matrix
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good stabilities. This catalytic system provides a facile and
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COMMUNICATION
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10.1002/cctc.201800358
ChemCatChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
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COMMUNICATION
A mechanochemical self-assembly
method was developed to directly
prepare ordered mesoporous
Pengfei Zhang,* Nanqing Chen, Dong
Chen, Shize Yang, Xiaofei Liu, Li Wang,
Peiwen Wu, Nathan Phillip, Guang Yang
and Sheng Dai*
cobalt@carbon, which does not need
any solvents and can complete in 60
mins. This strategy enables a high
loading of cobalt nanoparticles exactly
confined inside ordered mesoporous
channels. Those cobalt catalysts
possess good stability and activity in
the selective deoxygenation of
Page No. – Page No.
Ultra-Stable and High Loading
Cobalt@Ordered Mesoporous Carbon
Catalysts: All-in-One Deoxygenation
of Ketone/Aldehyde/Alcohol
Ketones/Aldehydes/Alcohols.
This article is protected by copyright. All rights reserved.