Conversion of a metal-organic framework to N-doped porous carbon incorporating Co and CoO nanoparticles: Direct oxidation of alcohols to esters

Article abstract of DOI:10.1039/c5cc01588j

A Co-based metal-organic framework, ZIF-67, has been exploited as a selflate to afford N-doped porous carbon incorporating Co NPs with surface-oxidized CoO species, which exhibit excellent catalytic activity, selectivity and magnetic recyclability toward the direct oxidation of alcohols to esters with O₂ as a benign oxidant under mild conditions.

Full text of DOI:10.1039/c5cc01588j

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Conversion of Metal−Organic Framework to N-doped
Porous Carbon Incorporating Co and CoO
Cite this: DOI: 10.1039/x0xx00000x
Nanoparticles: Direct Oxidation of Alcohols to Esters
Received 00th January 2012,
Accepted 00th January 2012
Yu-Xiao Zhou, Yu-Zhen Chen, Lina Cao, Junling Lu and Hai-Long Jiang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
(oxide) nanoparticles (NPs), distributing throughout the porous
carbonaceous matrix with preserved MOF morphology, could be
well accessible and very effective for heterogeneous catalysis.10,11
Herein, a zeolite-type MOF, Co(2-Methylimidazole)2 (ZIF-67),12
as a hard template, has been thermally converted to Co-CoO@N-
doped porous carbon nanocomposite with regular shape, in which
crystalline Co NPs with surface-oxidized CoO species are well
dispersed throughout the N-doped porous carbon. Remarkably, the
nanocomposite presents excellent catalytic activity and is
magnetically recyclable toward selective and direct oxidation of
alcohols to esters with molecular oxygen as an oxidant under mild
conditions. It is proposed that the special structure of the catalyst and
the synergistic effect between Co and CoO account for the superb
catalytic performance. To the best of our knowledge, this is the first
MOF-derived catalyst and extremely rare non-precious metal-based
heterogeneous catalyst for such reaction to date.
A Co-based metal-organic framework, ZIF-67, has been
exploited as a self-template to afford N-doped porous carbon
incorporating Co NPs with surface-oxidized CoO species,
which exhibit excellent catalytic activity, selectivity and
magnetic recyclability toward the direct oxidation of alcohols
to esters with O2 as benign oxidant under mild conditions.
Esterification represents one of the most important and fundamental
transformations in organic synthesis, as esters are very important
moieties and hold broad applications in bulk synthesis, fine
chemicals, natural products, and polymers.1 Esters are traditionally
prepared by a two-step synthetic procedure from alcohols, involving
the synthesis of the carboxylic acids or activated acid derivatives,
and subsequent reaction with alcohols. As we all know, multistep
reaction process usually results in the waste of reagents and produces
unwanted by-products that are environmentally and economically
undesired. Given the wide availability of alcohols, the direct
oxidation of alcohols to esters in a single step, avoiding the use of
the corresponding acids or acid-derivatives, is green, economic and
very attractive. However, the relevant reports for this reaction are
limited to precious metal-based catalysts, mostly in homogeneous
systems, which are economically unfavorable.2 To the best of our
knowledge, extremely rare non-precious metal catalysts have been
reported for direct oxidative esterification of alcohols thus far.3
Therefore, the development of cost-effective, highly efficient and
recyclable heterogeneous catalysts for such transformation under
mild conditions is of great interest and pivotal importance.
An aqueous solution of Co(NO3)2 and 2-methylimidazole being
stirred at room-temperature yielded ZIF-67 nanocrystals,12 which
underwent pyrolysis at different temperatures under N2 to afford Co-
CoO@N-doped porous carbon nanocomposites with regular shape
(Scheme 1), hereafter denoted as NC-T-t (NC, T and t represent
nanocomposite, pyrolysis temperature and time, respectively).
As a relatively new class of crystalline porous materials, metal-
organic frameworks (MOFs) have received growing interest.4
Currently, MOFs have been found potential applications in many
fields, such as gas storage and separation, catalysis, sensing, drug
delivery, proton conductivity, etc.5-8 Given that metal clusters and
organic linkers are well organized in the framework, MOFs with
superb structural tunability offer congenital conditions as precursors
for constructing nanostructured metal (oxide)/carbon and their
nanocomposites, primarily via pyrolysis.9 In the solid-solid
transformation process, MOFs behave as ideal sacrificial templates
and their long-range ordering and porosity can be partially preserved.
Although in its infancy, it is highly possible and expected that, upon
thermal decomposition of MOF hard templates, the resultant metal
Scheme 1 Schematic illustration of the synthesis of Co-CoO@N-doped
porous carbon nanocomposites via the pyrolysis of ZIF-67.
The pure phase of ZIF-67 has been approved by powder X-ray
diffraction (PXRD) (Fig. S1a). Upon thermal treatment at different
temperatures, all PXRD patterns show weak broad peak at ~26º
assigned to the typical (002) diffraction of graphitic carbon from the
organic moiety and three sharp peaks characteristic for metallic β-Co
(Fig. S2, S3a), the intensity of which gradually increases along with
elevated annealing temperature, revealing the improved crystallinity
of metallic Co and its significant effect with annealing temperature.
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Raman spectra exhibit two dominant peaks at about 1350 and 1600 becomes much stronger while the peaks from Co2+ and O 1s almost
cm-1, corresponding to D and G bands, respectively (Fig. S3b). The disappear upon 15 s or longer Ar+ sputtering. The results imply that
intensity of the peaks gradually increases along with elevated Co0 on the external surface is partially oxidized to Co2+ while the
annealing temperature, indicating the formation of abundant defects inner Co0 well remains in NC-700-3h, which is in agreement with
and disordered carbon during the pyrolysis. The contents of Co the elemental mapping and EDS results as well as our assumption
element are 21.6%, 29%, 32.9% and 39.7%, respectively for NC- above. To further understand the existing form of Co species in NC-
500-3h, NC-600-3h, NC-700-3h and NC-800-3h based on the 700-3h, temperature programmed reduction (TPR) has been
o
inductively coupled plasma-atomic emission spectrometry (ICP- conducted and it displays the only peak at ~472 C (Fig. S9), which
AES) data (Table S1). N2 sorption measurements show the typical is assigned to the reduction of Co2+ ions to metallic cobalt15 and
type I isotherms for ZIF-67, matching to its microporous character supports the XPS results above. All these characterizations suggest
(Fig. S1b). Upon pyrolysis, all N2 sorption isotherms are close to that the direct pyrolysis of ZIF-67 leads to N-doped porous carbon
type-IV with a hysteresis loop and the NC-700-3h possesses the incorporating well-dispersed crystalline Co NPs, the outer surface of
highest SBET (291 m2/g) and its pore sizes fall into 1-2.5 nm (Fig. which are partially oxidized to CoO species.
S4).
Given that the cobalt with variable chemical valences is able to
The structure and morphology of ZIF-67 and its pyrolysis product transfer electron and act as the active site for oxygen transfer,11 the
NC-700-3h as a representative have been investigated by scanning obtained Co and CoO NPs could be effective in catalytic oxidation.
electron microscopy (SEM) and transmission electron microscopy The high-density Co and CoO sites in ZIF-67-derived
(TEM) observation. Comparing with polyhedral ZIF-67 nanocrystals nanocomposites are uniformly distributed throughout the porous
in 200-500 nm (Fig. S5), the pyrolysis product NC-700-3h evolves carbon matrix and well accessible, and the pore structure not only
to uniform concave nanocubes with size shrinkage to some extent greatly facilitates the transfer of substrates/products but also limit the
(~150 nm, Fig. 1a). Many NPs in 5-20 nm with high contrast are migration and aggregation of the active NPs, which would render the
uniformly distributed in a porous matrix assigned to carbon (Fig. 1b, nanocomposites excellent in catalytic oxidation.
Fig. S6). The high-resolution TEM (HRTEM) image unambiguously
Table 1 Methyl esterification of benzyl alcohol and methanol over
shows the presence of graphitic layer domains and the crystalline Co
different Co-CoO@N-doped carbon catalysts.a
with clear lattice spacings of 0.2 nm (Fig. 1c). The selected area
electronic diffraction (SAED) pattern further supports the presence
of polycrystalline Co (Fig. 1b inset). The elemental mapping for NC-
700-3h demonstrates the co-existence and homogenous dispersion of
Selectivity (%)b
Co, C, N and a small amount of O species (Fig. 1d), while energy
dispersive spectrometer (EDS) analysis verifies the crystalline
particle is composed by Co only and very few O even it is there (Fig.
S7). It is assumed that the trace oxygen may be contributed from
surface oxidation of cobalt in air,9f which cannot be detected by EDS
as a bulk phase characterization tool.
Conversion
Entry
Catalyst
(%)b
51
79
71
78
100
98
95
48
4
1b
36
73
82
87
100
99
95
56
28
49
100
4
1c
64
27
18
13
0
1
2
NC-500-3h
NC-600-3h
NC-700-1h
NC-700-2h
NC-700-3h
NC-700-4h
NC-800-3h
NC-700-3h-250-3h
Co/AC
3
4
5
6
1
7
5
8
44
72
51
0
9
10
11
12d
13e
14f
CoO/SiO2
0.8
65
6
NC-700-3h-Nc
NC-700-3h
NC-700-3h
NC-700-3h
96
85
93
40
16
15
7
aReaction conditions: 1 mmol benzyl alcohol (1a), 8 mL CH3OH, 25 mg
catalyst, 0.2 mmol K2CO3 otherwise mentioned, 1 mmol dodecane was added
c
as an internal standard. bDetermined by GC or GC-MS. NC-700-3h with
increased N contents. dWithout base and O2. eWithout base. f Without O2.
Fig. 1 Microstructure observation for NC-700-3h. (a) SEM image (Inset:
enlarged particle). (b) TEM image with inset SAED pattern. (c) HRTEM
image showing lattice fringes of the crystalline Co NPs and the graphitic
layer domains. (d) Elemental mapping showing the uniform dispersion of Co,
C, N and a small amount of O elements.
Encouraged by the above considerations, the as-prepared Co-
CoO@N-doped carbon nanocomposites were employed for the
cross-esterified oxidative reaction between benzyl alcohol and
methanol with O2 as the oxidant and K2CO3 as a base (ESI†, Section
2). As shown in Table 1, the NC-700-3h performed the best activity
and selectivity to the only targeted product within 12 hours (entry 5).
For comparison, the nanocomposites obtained with other pyrolysis
temperature and time showed lower activity or/and selectivity to
various extents (entries 1-7). Given that Co3O4 NPs were reported to
be the active for the reaction,3a intuitively we attempted to convert
both Co and CoO in NC-700-3h into Co3O4 by oxidation at 250 oC in
The X-ray photoelectron spectroscopy (XPS) results show that Co,
C, N and O are detectable on the surface of NC-700-3h and the Co is
composed by Co0, Co2+ and Co-OH species (Fig. S8).13 In addition,
the N 1s spectrum presents four distinct peaks with binding energies
of 398.8 eV, 399.8 eV, 401.1 eV and 403 eV, which are assignable
to pyridinic, pyrrolic, graphitic and oxidized nitrogen, respectively.14
To gain the structure information in more detail, Ar+ sputtering has
been applied for NC-700-3h. Remarkably, the signals of Co 2p and
O 1s present significant changes, where the peak assigned to Co0
o
air for 3 h after 700 C calcination to produce NC-700-3h-250-3h
(Fig. S2b). Unfortunately, the conversion lowered to 48% and the
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selectivity to methyl benzoate was 56% (entry 8), revealing that
Upon the optimization of reaction conditions with MeOH using
Co3O4 is not very active in our case. Unexpectedly, both Co/AC and benzyl alcohol as a probe substrate, different derivatives of benzylic
CoO/SiO2 offered very low catalytic activity and selectivity (entries alcohol have been examined over NC-700-3h catalyst (Table 2). The
9, 10). Increasing N contents in the NC-700-3h was found to be even reaction of diverse derivatives of benzene methanol in the presence
harmful to the conversion (entry 11, ESI†, Section 2). The presence of MeOH afforded the corresponding methyl esters in excellent
of base and O2 was demonstrated to be necessary for the conversion conversions (entries 2-7). In addition, the oxidative esterification of
(entries 12-14). These results suggest that the special structure of heterocyclic alcohols with methanol has also been examined, where
NC-700-3h and the synergistic effect between Co and CoO could 2-furanemethanol and 2-thiophenemethanol were obtained with 98%
play crucial roles in the high catalytic activity and selectivity.
and 85% conversions, respectively (entries 8-9).
To further demonstrate the general applicability of the NC-700-
3h catalyst, diverse benzyl alcohols were investigated in cross-
esterification reactions with other aliphatic alcohols (Table S2). Not
surprisingly, all these cross-esterifications for both benzyl and
heterocyclic alcohols have shown excellent conversion and
selectivity. The benzyl alcohol reacts with other aliphatic alcohols to
give their target products in high yields (entries 1-3) and the direct
self-esterification of benzyl alcohol also displays high conversion up
to 77% and provides only one product (entry 4). Next, the oxidative
esterification of both benzyl and heterocyclic alcohols with ethanol
has also been investigated. To our delight, ethyl esters of both benzyl
and heterocyclic alcohols were obtained in up to 98% conversion
(entries 5-12).
Fig. 2 (a) Conversion and selectivity of six runs of reaction and (b) catalytic
recyclability and filtration test of esterification reaction between benzyl
alcohol and methanol over NC-700-3h. Inset of (b): the photographs
demonstrate the facile separation of the catalyst by a magnet.
Moreover, the oxidative homocoupling reactions with aliphatic
alcohols (Table S3), although seldom studied,2c,d have been
demonstrated to be feasible over ZIF-67-derived catalyst. In the
presence of NC-700-3h, ethanol is able to undergo oxidative
esterification and affords ethyl acetate with 54.2% yield under mild
conditions (entry 1). Propanol and butanol also exhibit good
reactivity to the corresponding aliphatic esters in 57.6% and 59.8%
conversion (entries 2-3).
To demonstrate the stability and reusability of NC-700-3h, five
more recycles were conducted. As shown in Fig. 2a, both catalytic
activity and selectivity remained very well in the six consecutive
runs. TEM observation clearly demonstrated the maintained NP size
and shape of the catalyst after recycling (Fig. S10), suggesting its
great stability and recyclability. After 6 h of reaction, the catalyst
was filtered out and the results showed that no further product was
formed even after 24 h under the same conditions (Fig. 2b), inferring
that no leaching occurred to the catalyst and the process should be
truly heterogeneous. Therefore, the NC-700-3h nanocomposite
presents superb catalytic activity and selectivity and possesses truly
heterogeneous catalytic nature with excellent catalytic stability and
recyclability for the esterification reaction. In addition, taking
advantage of the strong magnetic properties, the catalyst can be
easily separated from reaction solution and the cloudy suspended
solution turns transparent within a few seconds with an external
magnet (Fig. 2b, inset).
Based on the above results, a possible reaction mechanism for the
oxidative esterification of alcohols over Co-CoO@N-doped carbon
nanocomposites could be illustrated in Scheme 2. The direct
synthesis of methyl esters from primary alcohols can be divided to
three steps: First of all, alcohols are converted to aldehydes with O2
as the oxidant and this is considered to be the rate-determining step,
probably caused by the abstraction of β-H from alcohols.16 Secondly,
aldehydes and methanol are able to undergo condensation reaction to
give hemiacetal species in the absence of catalyst, mainly due to the
electrophilic properties of aldehydes and nucleophilic properties of
methanol. Finally, intermediate transforms directly to ester products
over Co-CoO@N-doped carbon using O2 as an oxidant. In this
sense, the catalyst can be used for both cross- and homo-coupling
esterifications in only one procedure under mild conditions and the
use of harmful oxidants is avoided.
Table 2 Methyl esterification of benzyl alcohol derivatives and
methanol over NC-700-3h catalyst.a
Selectivity (%)b
Conversion
Entry
R1
(%)b
1d
1e
1
2
100
100
0
98
97.8
2.2
3
4
100
91
100
92
99
89
88
90
0
8
Scheme 2 Proposed mechanism for direct oxidative esterification of alcohols
over Co-CoO@N-doped porous carbon.
5
95.6
100
90
1
In summary, a facile route has been developed to generate
Co NPs with surface-oxidized CoO species uniformly
incorporated in N-doped porous carbon by one-step pyrolysis of
monodispersed and structurally well-organized MOF, ZIF-67,
as a hard template. The approach effectively avoids the
aggregation of incorporated high-density NPs. The resultant
nanocomposites as inexpensive, stable and magnetically
recyclable catalysts exhibit excellent catalytic performance for
direct homo- and cross-coupling esterifications of primary
alcohols under mild conditions, with 1 bar of O2 as an
OH
6c
7
11
12
10
HO
6a
8
98
9
85
89
11
aReaction conditions: 1 mmol benzyl alcohols (1a-9a), 8 mL CH3OH, N-700-
3h (25mg), 0.2 mmol K2CO3 otherwise mentioned, 1 mmol dodecane was
b
c
added as an internal standard. Determined by GC or GC-MS. NC-700-3h
(50 mg) and 0.4 mmol K2CO3, and the product was dimethyl terephthalate.
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environmentally friendly oxidant. The special structure of the
nanocomposite and the synergistic effect between Co and CoO
NPs are proposed to be responsible for the superior activity to
other related catalysts. The N-doped porous carbon scaffold not
only stabilizes the NPs but also greatly facilitates the
accessibility and adsorption of substrates to the active sites and
the diffusion of products. The current direct pyrolysis of MOF-
based template approach is facile and versatile and thus paves a
way to diverse metal or metal oxide NPs thoroughly distributed
porous carbon nanocomposites, which might find broad
applications in many fields, especially in catalysis.
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