Isopropanol as a hydrogen source for single atom cobalt-catalyzed Wacker-type oxidation

Article abstract of DOI:10.1039/d0cy00409j

The first example of a heterogeneous cobalt catalytic system for Wacker-type oxidation catalyzed by a single atom dispersed Co-N/C catalyst using alcohol as the hydrogen source under an oxygen atmosphere is presented. By combining a well-designed, controlled experiment and various methods of characterization, we determined that single atom cobalt was the active center rather than nanoparticle or oxide counterparts.

Full text of DOI:10.1039/d0cy00409j

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Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
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Isopropanol as hydrogen source for single atom cobalt-catalyzed
Wacker-type oxidation
Received 00th January 20xx,
Accepted 00th January 20xx
Guanwang Huang,ab Lianyue Wang,*b Huihui Luo,b Sensen Shang,b Bo Chen,c Shuang Gao,*b Yue
An*a
DOI: 10.1039/x0xx00000x
The first example of the heterogeneous cobalt catalytic system for the of hydrogen, is widely used in hydrogenation reactions.
Wacker-type oxidation catalyzed by single atom dispersed Co-N/C catalyst However, it is rarely reported that that isopropanol provides
using alcohol as hydrogen source under oxygen atmosphere is presented. hydrogen for Wacker-type oxidation reactions.9 Therefore, the
Combined with the reasonably designed control experiment and various of development of sustainable and efficient catalysts to achieve
characterization we finally determined that the single atom cobalt was the this strategy is highly desirable.
active center rather than the nanoparticles or oxides counterparts.
Single atom catalysts (SACs) have attracted extensive
attention in the field of catalysis. Due to the lack of metal-
metal bond, the single metal sites in SACs more or less
resemble the peripheral atoms of metal nanoparticles in
supported nanoparticle catalysts. Moreover, single metal sites
are found to have cationic character compared to their
nanoparticle counterparts. SACs possess unparalleled
superiority such as high catalytic activity, stability, selectivity,
and 100% atom utilization.10a The unique structures of SACs
and the favourable interaction between the metal sites and
supports make it exhibit the high activity characteristics of
homogeneous catalyst. On the basis of the unique electronic
properties and our recent investigations on the Co-Nx single
atom catalyst in organic reactions,10b-d we envisaged the Co
single atoms would be made a good candidate for the Wacker-
type oxidation. To the best of our knowledge, this is the first
heterogeneous cobalt-based catalyst for the target reaction.
Herein, we presented an unprecedented strategy for Wacker-
type oxidation of aryl alkenes to acetophenones over a
nitrogen-doped carbon dispersed with single atom cobalt using
isopropanol as hydrogen source. The catalyst showed high
activity and exclusive regioselectivity. The satisfactory yields of
a broad scope of substrate can be obtained under oxygen
atmosphere. Characterizations and control experiments
disclose that the single atom cobalt is the active centre rather
than the nanoparticles or oxides counterparts. Furthermore, a
series of control experiments and free radical capture
experiments provide a fundamental understanding of the
reaction pathway.
Wacker oxidation, developed by the researchers at Wacker
Chemie in 1959,1 is one of the most important reactions in
industrial chemistry, where carbonyl compounds are prepared
from olefins with catalytic PdCl2 and stoichiometric CuCl2
under aerobic atmosphere.2 Although this transformation is
one of the most important reactions in industrial chemistry, it
still exists some limitations. For example, acetophenone was
great difficult to be synthesized by Wacker-type process from
styrene owing to their facile polymerization and oxidative
cleavage to benzaldehydes and/or benzoic acids.4 To achieve
highly efficient Wacker-type oxidation of styrene derivatives,
various methods have been developed. For example,
Fernandes and co-workers combined the Pd(II) and
Dess−Martin periodinane, simple styrene derivatives are
proved to be excellent substrates for the generation of
corresponding acetophenones.5 Ding and co-workers
performed the oxidation of the substituted styrenes using the
benzoquinone/NaNO2/HClO4 catalytic system.6 Wang and co-
workers used Pd(OAc)2 and trifluoroacetic acid can realize the
Tsuji−Wacker oxidation of terminal olefins to methyl ketones
under
oxygen
atmosphere.7
Very
recently,
hydrofunctionalizations of olefins can give ketones, but such
methods need equivalent hydrogenalkoxysilanes as hydrogen
source which highly hindering the development of its
industrialization.8 Isopropanol, as a safe and sustainable source
a. a.College of Chemistry and Chemical Engineering, Liaoning Normal University,
Huanghe Road 850#, Dalian 116029, P.R. China.
The catalysts were prepared by mixing cobalt acetate with
phenanthroline in ethanol, addition of the support activated
charcoal (DARCO®G-60) followed by removal of the solvent
and subsequent pyrolysis at different temperatures. The
obtained powders were treated with acid to afford the final
b. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics,
the Chinese Academy of Sciences, Dalian 116023, China.
c. Henan Chemical Industry Research Institute Co., Ltd., 37 Jianshe East Rd.,
Zhengzhou, 450052, China.
†
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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Journal Name
Table 1. Optimization Conditionsa
View Article Online
DOI: 10.1039/D0CY00409J
OH
O
catalyst, solvent
0.4 MPa O2, 150 o , 6 h
+
C
1a
Entry
3a
2a
Yieldb (%)
Conversionb
(%)
Catalyst
Solvent
2a
12.1
12.6
1.2
1.9
8.0
trace
12.8
7.4
1.3
trace
0
3a
37.8
71.5
95.8
84.8
79.6
53.0
58.2
48.1
2.5
1
2
3
4
5c
6
7
8
9
Co-N/C-600
Co-N/C-700
Co-N/C-800
Co-N/C-900
Co-N/C-800
Co-N/C-800
Co-N/C-800
Co-N/C-800
Co-N/C-800
Co-N/C-800
Co-N/C-800
Co-N/C-800
iPrOH
iPrOH
57.6
88.9
99.9
99.8
97.4
77.1
82.2
99.7
11.8
10.4
8.8
iPrOH
Figure 1. (a) SEM images of Co−N/C-800 under BED mode, (b and c) Nanoparticles of
TEM images in Co−N/C-800, (d and e) HADDF-STEM images of Co−N/C-800.
iPrOH
iPrOH
MeOH
EtOH
desorption (Figure S14). From SEM images under BED mode,
there co-exists a large amount of huge cobalt nanoparticles
(150-300 nm) and small counterparts (20-50 nm) before acid
treatment (Figure S5) while fewer nanoparticles can be
observed after the catalyst was acid leached (Figure 1a and
S4). Such nanoparticles were believed to be embedded in the
carbon layers. TEM images showed highly graphitized carbon
and sporadic cobalt nanoparticles which were shielded by a
thick and compact carbon layers (Figure S7-12). These
encapsulated nanoparticles can hardly be removed in the acid
treatment step (Figure 1b, 1c and S10). HAADF-STEM images
from several randomly selected areas are given in Figures 1d,
1e and S13. The support was densely decorated with isolated
bright dots, clearly showing the atomic dispersion of Co.
To further determine the local chemical bonding of these
isolated Co atoms in the Co–N/C-800 catalyst, the catalyst was
analysed using Co K-edge X-ray absorption spectroscopy
encompassing both the near-edge and extended energy
regions, XANES and EXAFS, respectively. The results are
presented in Fig. 2a. From XANES spectra (Fig. 2a), the pre-
edge at 7714-7716 eV was regarded as a fingerprint of Co-N4
square-planar structures.10e The position of the white line peak
for Co-N/C-800 shifted to Co foil compared to Co-N/C-700A
which was passed for only possessing single atom cobalt
without any nanoparticles according to the literature.9 This
indicated that the average valence of Co in Co-N/C-800 is
situated between that of Co0 and CoII due to the contribution
of Co0. The peak at 1.88 Å in EXAFS spectra (Fig. 2b) was
attributed to the formation of Co0. The peak at 1.44 Å was
assigned to Co-Nx shell which aroused both in Co-N/C-800 and
Co-N/C-700A.11 XPS was used to determine the chemical states
of Co and N in the samples (Figure S15). The N 1s spectrum
and Co 2P3/2 spectrum indicated that the Co2+ spaces were
coordinated with N atoms in Co-N/C-800 (More details see
Supporting Information).12 The XRD patterns of Co-N/C-800
were shown in Figure S17.
1,4-dioxane
CH3CN
tAmOH
iPrOH
10
11d
12e
2.8
0
0
iPrOH
30.4
0
aReaction conditions: 0.25 mmol of styrene, 5 mol% catalyst, 20 mol% K2CO3,
4 mL solvent. Conversion and yield were determined by GC using biphenyl
as the internal standard. c130 oC. dWithout K2CO3. eN2.
b
catalysts labelled as Co-N/C-X (X: pyrolysis temperature). More
details see Supporting Information.
The obtained dispersed Co-N/C catalyst was evaluated in the
Wacker-type oxidation of aryl alkenes to acetophenones. To
optimize the reaction conditions, styrene was tested as a
model substrate. Typically, this model reaction was performed
i
using PrOH as the solvent with catalytic amounts of K2CO3 as
o
base under 0.4 MPa O2 at 150 C. The results are summarized
in Table 1. First, the pyrolysis temperature was investigated
o
(Table 1, entries 1-4). The highest reactivity occurs at 800 C
producing acetophenone in 95.8% yield with a 1.2% 1-
phenylethanol as the major by-product (Table 1, entry 3). With
the increase of pyrolysis temperature, the activity shows a
volcanic lower reaction temperature resulted in the decreasing
yields (Table 1, entry 5). Next, different solvents were
investigated. Solvents such as methanol, ethanol and dioxane,
which are easy to provide protons, can give acceptable yields
(Table 1, entries 6-8). The reaction, however, was difficult to
proceed when the aprotic solvent acetonitrile was used (Table
1, entry 9). When solvent with larger steric hindrance than
isopropanol on -OH (tert-amyl alcohol), the reaction ends with
3.4% of the product (Table 1, entry 10). Based on these results,
a hypothesis can be suggested, that is, to make the reaction
work, the participation of protons are needed and the further
research will be described below. When there was no K2CO3
(Table 1, entry 11) or O2 was replaced with N2 (Table 1, entry
12), no target product was obtained. It is worth noting that
the presence of phenylacetaldehyde is not detected in the
product, which demonstrates good regioselectivity.
After obtaining the optimal reaction conditions, our focus
was switched to the substrate scope and functional group
tolerance of the catalytic system. As shown in Table 2, the
electronegativity of substituents has little effect on the
reaction. It can be found that the steric hindrance of
substituents has a great influence on the reaction. The
substituents with smaller steric hindrance gave higher yields
(Table 2, 3b-3i, 3k-3n). For the substituents with larger steric
To better understand the origin of catalyst activity, extensive
characterizations, such as, SEM, TEM, HAADF-STEM, XPS and
XAS techniques, were adopted to study the structure and
morphology of our catalysts. Under LED or UED modes of SEM
images (Figure S3), it can be clearly seen that the catalyst was
composed of amorphous carbon with porous structure, which
was in good accordance with the N2 adsorption-
2 | J. Name., 2012, 00, 1-3
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the active sites. The results were shown in Table S2. The
reaction cannot occur without Co or N elements (Table S2,
40
35
30
25
20
15
10
5
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DOI: 10.1039/D0CY00409J
Co foil
Co-N/C-700A
Co-N/C-800
a)
b)
Co foil
Co-N/C-700A
Co-N/C-800
entries 1 and 2), as did the physical mixtures of Co/C-800 and
N/C-800 or Co/C-800 and N/C-800 (Table S2, entries 3 and 4).
When the catalyst was not pyrolyzed (Table S2, entry 5), there
was no reactivity, suggesting that the active species should be
formed during pyrolysis.
0
0
1
2
3
4
5
6
7700 7720 7740 7760 7780 7800
Energy (eV)
R (Å)
To exclude the active sites of metallic Co or CoOx
nanoparticles, acid-leaching experiments were conducted.
After the fresh catalyst was acid treated, the Co content was
reduced from 3.6 wt % to 1.8 wt %, but the yield of 2a
increased from 75.1% to 86.6% (Figure 3). It is reported that
the graphite wall of carbon nanotubes can activate oxygen by
encapsulating iron nanoparticles to regulate the electronic
structure.13 However, in this case, when the graphite walls
were more than three layers, the activation effect attenuated
significantly with the increase of carbon layer. Although there
exist some large nanoparticles when catalysts were acid
leached, there were encapsulated by extremely thick graphitic
carbon nanoshells and far more than three layers (Figure 2).
These results suggested that metallic Co or CoOx nanoparticles
may not be the active sites and even counterproductive.
In order to further confirm the true active sites, SCN- was
introduced into our reaction system as it can block the
monodisperse active sites while retain the activity of large
nanoparticles.14 In the presence of KSCN, the performance of
the catalyst before and after pickling was first investigated.
The results were shown in Figure 3. When SCN- was introduced
into the reaction system to poison the single atom cobalt in
Co-N/C-800, the yields of 2a decreased from 86.6% to 30.8%.
This phenomenon indicates that the contribution of single
atom cobalt which was survived from being titrated by SCN-
tothe yields. While the Co-N/C-800-non-acid which contains
single atom cobalt equal to Co-N/C-800 was exposed to SCN-,
the yield of 2a was only reached to 15.5%. The experiment
carried above clearly shows the side effects of nanoparticles.
Then, the effect of the amount of KSCN on the reaction was
further investigated. The results were shown in Figure S19. The
yield of acetophenone decreased with the increase of SCN-,
and reached the minimum when 3 eqiv. of SCN- was added
into the reaction system. In addition, the relationship between
the selectivity and amount of KSCN was also discussed in detail
in the Supporting Information (Figure S21). To this, we can
deem that the active site of this reaction is the monodisperse
cobalt atom instead of metallic Co or CoOx nanoparticles.
To gain more insights into the reaction process of this
Figure 2. (a) XANES spectra at the Co K-edge of Co-N/C-800, Co foil, and Co-N/C-
700A. (b) Fourier transform (FT) at the Co K-edge of Co-N/C-800, Co foil, and Co-
N/C-700A.
Table 2. Wacker-type oxidation of aryl terminal alkenes over Co-N/C-800a
O
Co-N/C-800, iPrOH
R
R
0.4 MPa O2, 150 o , 6 h
C
1
3
O
O
O
O
tBu
F
O
3e
3i
3d
3h
, 82.5%
3b
, 83.2%
, 78.0%
3c
3g
3k
, 74.6%
O
O
F
O
Cl
O
Cl
Br
, 82.3%
O
, 60.5%
, 78.0%
O
3f
, 67.9%
Br
O
O
F
Cl
[b]
3m
3j
, 73.2%
, 47.3%
, 84.3%
O
3l
, 76.4%
O
O
Br
O
3p
3n
, 73.7%
, 70.5%
3o
3q
, 56.1%
, 54.1%
aReaction conditions: 0.25 mmol of styrene, 5 mol% catalyst, 20 mol% K2CO3, 150
i
°C, 4 mL PrOH. Yields were determined by GC using biphenyl as the internal
standard. bMeOH, 12 h.
Table 3. Wacker type oxidation of 1,1-disubstituted styrenes over a Co-N/C-800a
Co-N/C-800, iPrOH
OH
R1
R2
R1
R2
0.4 MPa O2, 150 o , 12 h
C
4
5
OH
OH
OH
OH
F
Cl
Br
5c
＞
5a
＞
,
99%
,
99%
OH
5b
, ＞99%
OH
Cl
5f
, 94.9%
5e
＞
99%
5d
＞
,
,
99%
aReaction conditions: 0.25 mmol of styrene, 5 mol% catalyst, 20 mol% K2CO3, 150
i
°C, 4 mL PrOH. Yields were determined by GC using biphenyl as the internal
standard.
hindrance (Table 2, 3o-3q), the yield of the reaction decreased. transformation, some possible intermediates originate from
The larger substituents in the o-position (Table 2, 3i, 3j and 3o) reaction were examined. The results were shown in Scheme
may have a negative impact on the reaction. It should be S1, when possible intermediates 6a and 7a were subjected to
noted that, though the yield was moderate, no aldehydes, the standard conditions, no target products were detected. It
obtained by the anti-Markownikov rule addition, were is obvious that 3a can be obtained from 2a. A kinetic study of
detected which shows great regioselectivity.
the oxidation of styrene was carried out (Figure S20), which
To further explore the application scope of the substrates, showed that styrene was oxidized to 3a and minor amounts of
1,1-disubstituted styrenes were used as substrates (Table 3). 2a, rapidly. With increasing reaction time, 2a can also be
All of the substrates were almost oxidized to the oxidized to 3a. It’s worth noting that the reaction of 3a under
corresponding tertiary alcohol quantitatively (Table 3, 5a-5f).
Next, a series of control experiments were designed to prove
the standard conditions did not give 2a which was different
from the previous work.10,15 These results suggested that 2a
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Notes and references
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DOI: 10.1039/D0CY00409J
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Figure 3. Titration experiment of active sites with KSCN. For the Co-N/C-800-non-
acid, 5 mol% of catalyst (20 mg) was added to the reaction system. In order to
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the superoxide species were formed by the electron transfer
from Co-3d orbitals to O2, where O2 was chemically adsorbed
on the single cobalt centres (A).16,17a-b According to the report
of literature, with the help of K2CO3, the iPrOH was
deprotonated to form E.17c-d Intermediate B formed through
intermediated F by abstracting proton by A from E.17a-b
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In summary, the first heterogeneous cobalt catalyst used in
Wacker-type oxidation has been reported. This strategy
features the characteristics of high efficiency and good
environment. Catalysed by single atom dispersed Co-N/C
catalyst using isopropanol as hydrogen source, styrene was
oxidized to acetophenone with excellent yield (95%) and
regioselectivity (100%). Extensive characterization and control
experiments show that the active site of Wacker-type
oxidation reaction is monodisperse cobalt atom rather than
their nanoparticles counterparts. This work would provide an
alternative catalyst for the Wacker-type oxidation of aryl
alkenes to high-value-added chemicals.
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Financial support from the Department of Science and
Technology of Liaoning Province (No. 2019-ZD-0470) and he
National Natural Science Foundation of China (No. 21773227,
21403219, 21773232, and 21902151).
Conflicts of interest
There are no conflicts to declare.
4 | J. Name., 2012, 00, 1-3
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Catalysis Science & Technology
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DOI: 10.1039/D0CY00409J
Isopropanol as hydrogen source for single atom
cobalt-catalyzed Wacker-type oxidation
Guanwang Huang,ab Lianyue Wang,*b Huihui Luo,b Sensen Shang,b Bo Chen,c
Shuang Gao,*b Yue An*a
a College of Chemistry and Chemical Engineering, Liaoning Normal University,
Huanghe Road 850#, Dalian 116029, P.R. China.
b Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics,
The Chinese Academy of Sciences, Dalian 116023, China.
c Henan Chemical Industry Research Institute Co., Ltd., 37 Jianshe East Rd.,
Zhengzhou, 450052, China.
* corresponding author: anyue_11@163.com ; sgao@dicp.ac.cn;
lianyuewang@dicp.ac.cn
The first example of Wacker-type oxidation catalyzed by single atom cobalt catalyst
under dioxygen using isopropanol as hydrogen source was established.