Boosting selective oxidation of cyclohexane over a metal-organic framework by hydrophobicity engineering of pore walls

Article abstract of DOI:10.1039/c7cc06166h

A porphyrinic metal-organic framework (MOF), PCN-222(Fe), was found to exhibit sound activity and selectivity to cyclohexanone and cyclohexanol (known as KA oil) toward cyclohexane oxidation. Remarkably, hydrophobicity engineering of the MOF pore walls le

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Boosting Selective Oxidation of Cyclohexane over a Metal-Organic
Framework by Hydrophobicity Engineering of Pore Walls
Received 00th January 20xx,
Accepted 00th January 20xx
Luyan Li, Qihao Yang, Si Chen, Xudong Hou, Bo Liu, Junling Lu and Hai-Long Jiang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A porphyrinic metal-organic framework (MOF), PCN-222(Fe), was
found to exhibit sound activity and selectivity to cyclohexanone
and cyclohexanol (known as KA oil) toward cyclohexane oxidation.
Remarkably, the hydrophobic engineering of the MOF pore walls
led to significantly enhanced activity and selectivity to KA oil, far
superior to that of the homogeneous porphyrin catalyst.
The oxidation of cyclohexane, one of the most valuable
1
reactions in industrial and synthetic chemistry, usually takes
place under harsh conditions to give complex products, such as
cyclohexanol, cyclohexanone, adipic acid and acid anhydride, Scheme 1. Schematic illustration showing the fabrication of PCN-
2
n
22(Fe)-F via postsynthetic modification
etc. Amongst them, cyclohexanol and cyclohexanone, also
called KA oil, the intermediates in the production of Nylon-6
and Nylon-66, are important petrochemical feedstock and
more expected than others. Thus, the selective C-H bond
insertion of cyclohexane to produce KA oil under mild
conditions is of considerable interest and many catalysts have
organic ligands. The periodic structure of MOFs leads to the
separation of the catalytic sites and avoids their dimerization
5
during the reaction. Moreover, given the highly tunable
character of MOFs, the pore environment can be furnished to
be hydrophobic by grafting particular molecules, contributing
to the concentration of hydrophobic substrates and facilitating
1
, 2
been developed.
Particularly, metalloporphyrin, a type of
biomimetic homogeneous catalyst, presents sound activity in
the oxidation of cyclohexane at mild temperatures and
2
pressures. Nonetheless, the intrinsic difficulty in the
6
their rapid conversion. Unfortunately, to our knowledge,
highly efficient metalloporphyrin-based MOF catalyst with
stable recyclability performance for cyclohexane oxidation has
not been reported yet, which might be attributed to the
following reasons: 1) most metalloporphyrin MOFs are easily
destroyed in the presence of the strong oxidant (e.g.
peroxide); 2) the rapid transport of substrates/products in
small sizes of MOF pores is difficult, lowering the catalytic
recyclability of homogeneous catalysts and the tendency to
dimerization of metalloporphyrin greatly impedes their further
3
application. Therefore, the development of heterogeneous
catalysts involving the active metalloporphyrin would be highly
desired.
Metal-organic frameworks (MOFs), a promising platform
4
with great potential for applications in diverse fields, are built
activity. Therefore, the fabrication of a highly stable
metalloporphyrinic MOF catalyst with large hydrophobic pores
would be of great importance and highly desired to achieve
excellent activity of cyclohexane oxidation with satisfied
selectivity to KA oil.
by metal ions/clusters and a variety of organic building units
and could be ideal porous materials to immobilize
metalloporphyrin units by using M-TCPP (M = Fe, Mn, Co, Ni,
2
Cu, Zn, H ; TCPP = tetrakis(4-carboxyphenyl)-porphyrin) as
Bearing these in mind, we rationally fabricated PCN-222(Fe)
decorating with hydrophobic pore environment via
postsynthetic modification (Scheme 1). The grafting PCN-
222(Fe) with different chain lengths of perfluoroalkyl acids by
microwave reaction gave a series of modified PCN-222(Fe).
Delightedly, the modified samples showed desired
hydrophobicity and better adsorption for cyclohexane than the
parent PCN-222(Fe). Particularly, thanks to the hydrophobic
Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key
Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of Suzhou
Nano Science and Technology, School of Chemistry and Materials Science,
University of Science and Technology of China, Hefei, Anhui 230026, P.R. China
E-mail: jianglab@ustc.edu.cn; Fax: +86-551-63607861; Tel: +86-551-63607861
†Electronic Supplementary Information (ESI) available available: Experimental
procedures and figures referred in the text. See DOI: 10.1039/x0xx00000x.
This journal is © The Royal Society of Chemistry 20xx
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Fig. 2 a) (upper) Static water contact angles of A) PCN-222(Fe), B) PCN-
Fig. 1 a) Powder XRD patterns for simulated PCN-222(Fe), as-
2
22(Fe)-F
3
,
C) PCN-222(Fe)-F
5
and D) PCN-222(Fe)-F
7
;
(bottom)
water–
cyclohexane (1:1 v/v) biphasic mixture. b) Adsorbed cyclohexane
synthesized PCN-222(Fe) and PCN-222(Fe)-F
sorption isotherms for PCN-222(Fe) and PCN-222(Fe)-F
7 K.
n
(n = 3, 5, 7); b) N
2
Photograph of corresponding samples dispersed in
a
n
(n = 3, 5, 7) at
7
amounts by PCN-222(Fe) and PCN-222(Fe)-F
acetonitrile along with time.
n
(n = 3, 5 and 7) in
pore environment, all modified PCN-222(Fe) exhibit superior
activity and ~90% selectivity to KA oil, far surpassing the
1
selectivity requirement (more than 80 %) in industry, in
hydrophobicity in the latter (Fig. S5). In a more visualized
experiment, the enhanced hydrophobicity of PCN-222(Fe)-F is
n
reference to parent PCN-222(Fe) and homogenous iron-
porphyrin catalysts, in the cyclohexane oxidation.
observable in the water-cyclohexane biphasic mixture: the
MOF gradually transfer from aqueous phase to organic phase
along with increased chain length of perfluorinated alkyls (Fig.
The iron-porphyrinic MOF, PCN-222(Fe) (also called MOF-
7
45 or MMPF-6), featuring high chemical and thermal
5
2
a bottom). To further judge whether the created
stability,
is
constructed
by
Zr (μ -O) (μ -
6 3 4 3
hydrophobicity beneficial to substrate diffusion/enrichment,
liquid cyclohexane adsorption of PCN-222(Fe) and PCN-
OH) (OH) (H O) (COO) clusters and TCPP linkers with Fe(III)
8
4
4
2
4
centers (Fe-TCPP) to give a 3D network, in which zirconium-
carboxylate layers form a Kagome-type pattern in the ab
plane, pillared by Fe-TCPP linkers. Importantly, it exhibits very
large hexagonal 1D open channels with a diameter as large as
2
22(Fe)-F
temperature. Results indicated that the hydrophobic PCN-
22(Fe)-F displayed increased liquid-phase cyclohexane
adsorption rate and amount compared to the parent PCN-
22(Fe), clearly supporting the more favourable diffusion and
n
in acetonitrile were investigated at room
2
n
3.7 nm along the c-axis, as can be observed by transmission
2
electron microscope (TEM) (Fig. S1). To introduce the
hydrophobic pore environment, three perfluorocarboxylic
enrichment of the substrate in hydrophobic channels (Fig. 2b).
It is expected that the enhanced hydrophobicity and more
favourable adsorption of hydrophobic cyclohexane by PCN-
acids with different chain lengths, trifluoroacetic acid (F3),
pentafluoropropionic acid (F ) and heptafluorobutyric acid (F ),
7
5
222(Fe)-F
toward the oxidation of cyclohexane. Therefore, the reaction
over PCN-222(Fe)-F in the presence of tert-butyl
n
would lead to the improved catalytic performance
were grafted onto the pore walls by replacing the –OH groups
of Zr (μ -OH) (OH) (H O) (COO) clusters in PCN-222(Fe) with
6
3
8
4
2
4
8
n
carboxylates to give PCN-222(Fe)-Fn (n = 3, 5, 7), leaving
perfluorinated alkyls toward the pore space to feature
hydroperoxide (TBHP) as the oxidant was carried out. To
examine the optimized amount of TBHP, a series of control
experiments were conducted and results showed that the yield
of KA oil was improved along with more TBHP (Table 1). Given
that excessive TBHP was harmful to the crystallinity of MOF
due to the oxidative destruction, as a result, an optimal TBHP
amount (8 μL, 5.5 mM) was adopted to give balanced activity
8
hydrophobic property. The successful introduction of
perfluorinated alkyls into PCN-222(Fe) was demonstrated by
1
9
the F nuclear magnetic resonance (NMR) (Fig. S2) and diffuse
reflectance infrared fourier transform spectra (DRIFTS) (Fig.
S3). Powder X-ray diffraction (XRD) patterns indicated that the
crystallinity and structure of PCN-222(Fe) remained well after
a
the hydrophobic modification (Fig. 1a). In addition, N2 Table. 1 The cyclohexane oxidation under different conditions.
physisorption isotherms of PCN-222(Fe)-F were similar to that
n
of PCN-222(Fe) in shape and the appreciable decrease of
surface area was ascribed to the pore space occupation and
mass contribution of grafted perfluorinated alkyls (Fig. 1b).
V(TBHP)
Conv.
(%)
Sel. of KA
oil (%)
Yield of KA
oil(%)
Entry
b
Delightedly, though the surface area decreased, the mesopore
(μL)
character in PCN-222(Fe)-F was still retained (Fig. S4).
n
The created hydrophobicity for the MOF was demonstrated
by the water contact angle measurement. The contact angle of
water droplet on pristine PCN-222(Fe) is ~10°, while it quickly
increases to 51°, 110° and 137° upon introducing F , F and F ,
1
2
3
0
4
8
-
-
-
29.8
50.2
75
89
90
68
26.1
46.2
51
4
20
3
5
7
a
Reaction condition: cyclohexane (0.1 mmol), PCN-222(Fe)-F
(25.6 mg), 1 bar O
7
respectively (Fig. 2a upper), clearly suggesting that
perfluorinated alkyls transform the MOF from hydrophilic to
hydrophobic. The water adsorption experimental results for
PCN-222(Fe) and PCN-222(Fe)-F7 further support the
o
(20 mg), CH
refluxing for 24 h;
3
CN (2.5 mL), AgBF
A
4
2
, 80 C,
indicates
indicates cyclohexanol,
K
b
cyclohexanone. Catalytic reaction products were analyzed and
identified by gas chromatography.
2
| J. Name., 2012, 00, 1-3
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a
Table 2 The catalytic performance of different catalysts.
Conv. Sel. of KA oil
Yield of KA oil
(%)
Entry
Catalyst
(%)
(%)
1
PCN-222
TCPP(Fe)
-
-
-
b
2
<2
20.5
45
-
<2
3
4
5
6
PCN-222(Fe)
PCN-222(Fe)-F
PCN-222(Fe)-F
PCN-222(Fe)-F
PCN-222(Fe)-F
81
16.6
36.9
41.0
46.2
3
5
7
7
86.9
89
46
50.2
90.1
c
7
46.7
86.5
40.4
Fig. 3 a) The conversion-time plots of cyclohexane oxidation over PCN-
222(Fe) and PCN-222(Fe)-F (n = 3, 5, 7). b) Proposed mechanism for
cyclohexane oxidation.
a
Reaction condition: cyclohexane (0.1 mmol), catalyst (20 mg),
n
o
CH
refluxing for 24 h, K indicates cyclohexanone. Catalyst (10 mg),
DMF (1 mL) and CH CN (1.5 mL). A mixture of CH CN and DMF was
used due to the low solubility of TCPP in CH CN. 1 bar O
replaced by 1 bar N
3
CN (2.5 mL), TBHP (8 μL), AgBF
4
(25.6 mg), 1 bar O
2
, 80 C,
b
3
3
o
80 C indicates that PCN-222(Fe) and PCN-222(Fe)-F
c
n
possess
3
2
was
the similar kinetics (Fig. 3a). The results reveal that the
generated hydrophobicity in PCN-222(Fe)-F accelerates the
2
.
n
conversion of cyclohexane due to the substrate confinement,
while does not change the reaction order.
and selectivity toward cyclohexane oxidation.
It is accepted that metal ions located in the porphyrin center
are critical to the catalytic activity for cyclohexane
4
Upon the introduction of AgBF into the reaction system, it
-
is assumed that the weak ligand (BF ) in reference to chlorine
2
a, 5c, 5d
1
oxidation.
The Cl atom bound to the Fe(III) center in the
4
atom coordinated to the Fe center is beneficial to the
porphyrin ligand (Fe-TCPP) is assumed to be unfavorable to
catalytic activity. It was reported that the activation of
hydroperoxide O-O bond over iron-porphyrin catalysts was
hampered by the electron-withdrawing ligands attached onto
Fe(III), such as Cl, which was detrimental to the generation of
interaction between Fe(III) and TBHP, facilitating the
generation of TCPP-Fe(IV)-oxo active species, which is
responsible for the high percentage of cyclohexanone in KA oil
product (Fig. S6a). To gain additional experiment evidence,
excess TBHP has been added into the reaction system. Results
clearly show that gradually increased K/A ratio from 7.5/1 to
9
reactive intermediates. Therefore, it is desired to remove the
coordinated Cl atom from Fe(III). To this end, AgBF
4
with
1
0/1 can be achieved along with more TBHP introduced (Fig.
weaker coordination strength was employed to replace Cl
1
0
S6b). It is proposed that the TBHP complexing with TCPP-Fe(III)
leads to the formation of additional TCPP-Fe(IV)-oxo.
4
atom. Interestingly, the presence of AgBF was though not
able to improve the catalytic selectivity to KA oil, the ratio of
K/A was significantly increased to 12/1, which has never been
observed yet in previous reports (Table S1). Such high
percentage of cyclohexanone achieved in the catalytic reaction
products would be very important in the simplification of the
cumbersome cyclohexanone purification for subsequent
caprolactam production in industry.
Therefore, the introduction of AgBF
4
and/or TBHP is beneficial
to the generation of TCPP-Fe(IV)-oxo, which, assumed to be
1
1
active species based on previous report, firstly oxidizes
cyclohexane to cyclohexanol and then further catches with
cyclohexanol to produce cyclohexanone (Fig. 3b).
On the basis of the above experimental results and
assumptions, a catalytic cycle to the formation of cyclohexanol
and cyclohexanone has been proposed (Fig. S7). It is
hypothesized that TCPP-Fe(IV)-oxo is generated by transferring
With the optimized reaction parameters, the cyclohexane
oxidation over different catalysts has been investigated (Table
2
). The results clearly show that the Fe(III) located in the
porphyrin center is indeed the active site for the reaction
entries 1, 3). Surprisingly, the homogeneous iron porphyrin is
1
2
one electron from Fe(III) center to coordinated TBHP.
Subsequently, this reaction is initiated by TCPP-Fe(IV)-oxo
complexing with cyclohexane, generating TCPP-Fe(IV)-
(
almost inactive under similar conditions (entry 2). It is possibly
●
●
6 6 11
OH(C H11 ). Cyclohexanol can be produced via (C H )
due to the formation of bridged µ-oxide dimers that might
2
b
hinder the access to the catalytic sites. In addition, all PCN-
22(Fe)-F present superior catalytic activity to the pristine
2
n
PCN-222(Fe) (entries 3-6), reflecting that the hydrophobicity of
pore walls is beneficial to the conversion and selectivity to KA
3
oil. Moreover, the longer -CF chain is grafted to the pore walls,
the better catalytic performance can be achieved. It is
proposed that the hydrophobicity of inner pore surface affords
a driving force for substrate enrichment due to the interaction
between cyclohexane and the terminal perfluorinated alkyls,
thus promoting the catalytic process. The activity and Fig. 4 a) Catalytic conversion and selectivity of PCN-222(Fe)-F during
7
selectivity to KA oil for PCN-222-F
7
and other MOF-based the 3 runs of cyclohexane oxidation. Reaction conditions: cyclohexane
(
0.1 mmol), catalyst (20 mg), CH
3
CN (2.5 mL), TBHP (8 μL), AgBF
, 80 C, refluxing for 24 h. b) Powder XRD patterns of
simulated PCN-222(Fe), as-synthesized PCN-222(Fe)-F and PCN-
22(Fe)-F after 3 catalytic runs.
4
(25.6
cataysts have been compared and show the considerable
advantages (Table S2).
o
mg), 1 bar O
2
7
The oxidation reaction progress over different catalysts at
2
7
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-
oxidized by TCPP-Fe(IV)-OH , accordingly TCPP-Fe(III) is
generated after this oxidation process. Subsequently,
cyclohexanol can also coordinate with TCPP-Fe(IV)-oxo to give
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●
-
6
(C H11O ), which is able to be oxidized by TCPP-Fe(IV)-OH to
2
50.
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PCN-222(Fe)-F as a representative clearly demonstrate that
no noticeable change occurs to its activity and selectivity
during the three consecutive runs (Fig. 4a). In addition, powder
XRD patterns show that the structural integrity and crystallinity
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In conclusion, hydrophobicity engineering of pore walls for
an iron-porphyrinic MOF, PCN-222(Fe), has been successfully
developed to boost the catalytic performance toward the
cyclohexane oxidation. Grafting perfluorinated alkyls onto the
pore walls significantly increases the hydrophobicity and
improves the interaction with cyclohexane, resulting in
enhanced conversion and selectivity to KA oil. By contrast, the
homogeneous iron porphyrin is almost inactive for this
5
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-
weak coordination between the BF
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a
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