Amine-functionalized Zn(ii) MOF as an efficient multifunctional catalyst for CO2 utilization and sulfoxidation reaction

Article abstract of DOI:10.1039/c8dt01297k

Herein, a zinc(ii)-based 3D mixed ligand metal organic framework (MOF) was synthesized via versatile routes including green mechanochemical synthesis. The MOF {[Zn(ATA)(L)·H₂O]}_n (ZnMOF-1-NH₂) has been characterized by var

Full text of DOI:10.1039/c8dt01297k

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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Amine Functionalized Zn(II) MOF as an Efficient Multifunctional
Catalyst for CO2 Utilization and Sulfoxidation Reaction
Parth Patel,a,c Bhavesh Parmar,b,d Rukhsana I. Kureshy,a,d Noor-ul H. Khan*a,c,d and Eringathodi
Suresh*b,d
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Zinc (II) based 3D mixed ligand metal organic framework (MOF) was synthesized by versatile routes including green
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mechanochemical synthesis. MOF {[Zn(ATA)(L).H2O]}n (ZnMOF-1-NH2) has been characterized by various physico-chemical
techniques
including
SCXRD
and composed
of
bipyridyl-based Schiff base,
(E)-N′-(pyridin-4-
ylmethylene)isonicotinohydrazide (L) and 2-aminoterephthalic acid (H2ATA) ligands as linkers. The MOF material has been
explored as a multifunctional heterogeneous catalyst for the cycloaddition reaction of alkyl and aryl epoxides with CO2 and
sulfoxidation reactions of aryl sulfides. The influence of various reaction parameters were examined and optimized the
performance of the catalytic reactions. Solvent free catalytic reaction offered good catalytic conversion in the case of cyclic
carbonates and for sulfoxide good conversion and selectivity is achieved in presence of DCM as a solvent medium at
ambient reaction conditions. Chemical and thermal stability of the catalyst was good and the catalyst was active up to four
catalytic cycles without significant loss of activity. Based on the catalytic activity and structural evidence plausible
mechanism
for
both
catalytic
reaction
is
also
proposed.
appropriate materials that are able to selectively capture the
CO2 and facilitate catalytic conversion through chemical
fixation into useful products.10-14 The coupling reaction of CO2
with epoxides to provide cyclic carbonates in presence of
different catalysts is considered as one of the best strategies
for CO2 conversion due to its excellent reactivity and high atom
efficiency. Cyclic carbonates are well known with significant
and extensive applications as aprotic polar solvents, precursors
for affording polycarbonates, and chemical intermediates in
organic synthesis.15-26 Many homogeneous catalysts have been
developed for cycloaddition reaction with CO2 and epoxides as
well as for sulfoxidation reactions with good activity and
efficiency.27-39 Complex separation, purification, and recycling
problems in homogenous catalysis severely limit their
application in industry. This demands the need for a robust,
recyclable multifunctional heterogenous catalyst with good
chemical and thermal stability that can works efficiently under
mild reaction conditions.40 Materials with following features
such as high surface area/ porosity and good adsorption
capacity, adequate Lewis/Brønsted acidic or basic sites, high
chemical and thermal stability upon exposure to the reaction
conditions including substrates favors efficient heterogenous
catalytic reactions. Several types of heterogeneous catalysts
based on porous materials such as zeolites, silica-supported
salts, microporous organic polymers (MOPs) have been
explored for the synthesis of cyclic carbonates and
sulfoxidation reactions.41-48
Introduction
The quests for green technologies that utilize the emission of
CO2 from industries and power plants as well as sulfoxidation
of organic compounds to value added chemical intermediate
by appropriate catalytic reaction is a prime area of research to
contain the greenhouse effect and human healthcare
respectively.1-3 Recent years have witnessed the advent of
adaptable catalysts that promote the transformation of CO2 to
cyclic carbonates which has relevance in green and sustainable
environment and oxidation of organic sulfides to value added
drug intermediate in pharmaceutical industry.4-9 For justifying
the adverse effect of the greenhouse gas, utilization of CO2 as
a chemical feedstock to produce valuable chemicals is an
alternative sustainable approach. Significant efforts are
therefore currently being devoted for the development of
As a new kind of crystalline porous material, Metal organic
frameworks (MOFs) are constructed from multidentate
organic building blocks linking metal or metal clusters which
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display periodic architectures and inherent porosity with wide an efficient heterogeneous catalyst for the chemical fixation of
range of application. The captivating uniqueness of MOFs is CO2 to cyclic carbonates and sulfoxidation of organic sulfides
the tunability and tailoring of the structure through a delicate under mild reaction conditions. Interestingly, ZnMOF-1-NH2
design of molecular building units in the form of organic linkers catalyst could be synthesized in good yield, crystallinity and
and the coordination geometry around the metal nodes. MOFs phase purity by green mechano-chemical method.
have emerged as porous frameworks for various applications
attributable to their robust/ high thermal stability, large
Results and discussion
surface area and tunable composition for the adsorption and
separation of gas molecules including greenhouse gas CO2.49-54
Characterization and Structural Features of ZnMOF-1-NH2
Recently, MOFs have also been revealed as efficient catalysts
for heterogeneous catalysis reactions.55-60 Nevertheless, the
Physical characterization of ZnMOF-1-NH2 synthesized by
adaptable routes to elucidate the bulk phase purity and
field of MOFs as heterogeneous catalysts for CO2 conversion
detailed structural analysis by SCXRD has been reported by us
elsewhere.97 Conventional synthetic approach of MOF is based
and sulfoxidation reaction in particular has remained largely
untapped. Park et al. and Ma et al. has done some pioneering
on reflux and solvothermal methods which often lead to the
work in the area of MOF catalyzed CO2 fixation reactions at
issues of solvent molecules remaining in the network as well as
ambient reaction condition to yield value added
low yield. Mechano-chemistry (milling or grinding) offers an
intermediates.61-72 It is worth mentioning here reports by Ma
alternative green approach for the preparation of MOFs using
et al. and Jiang’s group for CO2 cycloaddition under mild
the metal salts and the ligand precursors in appropriate
stoichiometry.98-99 In addition, mechanochemical (milling or
condition (at room temperature and under 1 bar CO2 pressure)
by MOF with nbo topology and Al based MOF USTC-253-TFA
respectively.73-74 On the other hand, one of the most
grinding) reactions supports advantages such as low energy
requirement, less time consumption, minimal solubility issues
important catalytic reactions is the oxidation of sulfides to
and environment friendly for synthesis MOF materials with
sulfoxides and sulfones, which has potential usage in the
good yield and phase purity. Our synthetic strategy of the bulk
chemical industry, biology, and medical chemistry.75-79 There
catalytic material (ZnMOF-1-NH2) cover adaptable approaches
are many reports of the H2O2-based oxidation of sulfides by
which includes conventional reflux and the green
homogeneous
organo-catalysts
and
heterogeneous
oxidative
mechanochemical method. Particulars of the MOF synthesis by
different route and their characterization by Powder X-ray
diffraction (PXRD), FTIR and TGA is provided in the supporting
data.
polyoxometalates.80-84
Heterogeneous
desulfurization of sulfides by MOF catalyst is scantly reported
in the literature and most of these reactions involves
polyoxometalates (POMs) encapsulated metal organic
framework (MOF). Albeit, enantioselective sulfoxidation has
been studied using chiral MOFs as catalyst.85-92 In these
contexts, the development of an efficient oxidation of various
kinds of sulfides with high yield and selectivity to sulfoxide is
still in demand.
MOF with functional moieties in the ligand such as
amino/amide group aligned on the pore wall can act as active
sites which can increase the affinity to the substrate/ CO2 in
the catalytic reaction by supramolecular interactions. Presence
of active Lewis acidic sites of the metal ions uniformly
distributed in the MOF can also activate the catalytic
efficiency.93-96 The robust nature of MOF and their chemical
and thermal stability imparts excellent recyclability of these
materials. From the above background and perspective, we
envisioned that the rationally designed MOF materials could
serve as a good candidate for heterogeneous catalysts for the
chemical conversion of CO2 to cyclic carbonates and
sulfoxidation reaction. Herein, we report a mixed ligand three
Figure 1. FE-SEM images for ZnMOF-1-NH2 (a) conventionally synthesized, (b)
mechanochemically synthesized, (c) recovered after 4th catalytic cycle of
cycloaddition, and (d) recovered after 4th catalytic cycle of sulfoxidation reaction.
dimensional
MOF
{[Zn(ATA)(L)].H2O}n
(ZnMOF-1-NH2)
synthesized by versatile synthetic routes, viz., diffusion of
precursor solutions, conventional reflux, and green
mechanochemical (grinding) reactions from bipyridyl-based
Schiff base, (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide
(L) and amino functionalized 2-aminoterephthalic acid (H2ATA)
as linkers and its catalytic performance. Uniformly distributed
Zn(II) Lewis acidic sites and amino/ amide functional groups of
the ligand moiety on the pore walls attributes ZnMOF-1-NH2
The phase purity/ bulk homogeneity, chemical /thermal
stability of the pristine catalyst as synthesized and recovered
after 4 catalytic cycles have been characterized PXRD, FTIR, FE-
SEM and TGA analysis. Simulated PXRD data of the CIF file
from CCDC data matches well with the experimental PXRD
pattern of the MOFs synthesized by different routes,
suggesting bulk phase purity of the catalysts (Figure S1). As
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depicted in Figure S2, FTIR data of both pristine and recovered
catalyst revealed good agreement establishing the structural
and chemical stability of ZnMOF-1-NH2 after the catalytic
reaction and the TGA profile indicate the thermal stability up
to ~ 280-310 oC. (Figure S3). FE-SEM images depicted in Figure
1 clearly revealed well defined morphology for the crystalline
material for the pristine MOF as well as the compound
recovered after
4 catalytic cycles retaining the textural
features of the catalyst.
Gas sorption analysis of activated ZnMOF-1-NH2 in vacuum at
120 °C reveals selectively towards CO2 over N2 (Figure S4). Due
to their structural flexibility, 2D Zn(II) MOFs belonging to the
same family having different substituents in the dicarboxylic
acid and the same N-donor Schiff base ligand has been
reported to show very interesting sorption properties and
disclosed selective adsorption of CO2 over N2. Pores size,
polarity or kinetic issue can influence the sorption property of
the nets for the preference of CO2 over N2 adsorption. The
polar amide functional group of the acyl hydrazone Schiff base
ligand /-NH2 from the ATA ligand of the framework can
interact with high quadrupole moment of CO2.100-101 The
adsorption analysis reveals that activated ZnMOF-1-NH2
adsorb CO2 having smaller kinetic diameter (3.30 Å) over larger
N2 (3.64 Å) and no significant uptake of N2 is observed. As
depicted in (Figure S4), CO2 adsorption curve with hysteresis in
the present case can be attributed to the guest-induced
framework response. BET surface area and Langmuir surface
area for ZnMOF-1-NH2 are 1.1554 m²/g and 0.4612 ± 0.1069
m²/g respectively.
Figure 2. (a) Coordination environment around Zn metal centre in ZnMOF-1-NH2, (b) 2D
[Zn2(ATA)2]n sql sheets of ZnMOF-1-NH2 showing amino decorated dicarboxylate
moiety coordinated with Zn(II) metal centre and (c) Packing along b-axis showing 2-fold
interpenetrated 3D network in ZnMOF-1-NH2
3D framework with interpenetration can self-orient
themselves upon supramolecular interaction between the
polar CO2 groups with arylhydrazones moiety of the Schiff base
ligand /NH2 group of the dicarboxylate decorating the
framework pores favoring better affinity for CO2 over N2 and
the hysteresis observed in the adsorption profile. The
measured CO2 uptakes at 273 K is 1.4181 mmol of CO2 per
gram of MOF at 0.99 Relative Pressure (P/Po) which can favors
the cycloaddition reaction in the present investigation. The
acidity (amount and strength) of the catalyst was determined
by NH3-TPD measurement (Figure S29). The NH3-TPD
experiment shows that NH3 is desorbed in the temperature
range of 50–400 oC with major peaks at 315 oC (desorbed
amount of NH3 27.081 mmol/g). Crystal structure analysis
revealed that ZnMOF-1-NH2 crystalized in triclinic system with
ꢀ
1 space group and comprehend a 3D framework in which
P
Zn(II) metal nodes are linked via dicarboxylate and N-donor
Schiff base ligand (Figure 2a). As depicted in Figure 2b, dimeric
clusters of [Zn2(COO)2] secondary building units are linked by
the carboxylate oxygens of symmetrically disposed ATA ligands
creating a two dimensional [Zn2(ATA)2]n sql sheets. Double-
pillaring of [Zn2(ATA)2]n sql net by the terminal nitrogen atoms
of the bipyridyl-based N-donor Schiff base ligand ensuing a
three dimensional network with pcu topology for ZnMOF-1-
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NH2 (Figure 2c). The effective void of the 3D framework is
reduced due to the two-fold interpenetration of the 3D nets
via N-H···O hydrogen bonding between the amide hydrogen of
L and carboxylate oxygen of ATA and probably the lattice
water molecules are occupied in the void by supramolecular
interactions. Penta coordination with coordinatively
unsaturated Zn(II) metal center can act as an active catalytic
site and the amide/amine functional groups of the ligand
moiety may also favours the catalytic performance of the MOF
material by efficient supramolecular interaction with the
substrates (Figure 2a).
Table 1. Cycloaddition of styrene oxide and CO2 for styrene
carbonate.*
Catalyst/
Co-
SO
Conversion
(%)
SC
Selectivit
y (%)
99
En
PCO2
Temp.
(oC)
Time
(h)
try
(MPa)
catalyst
None
1
2
0.8
0.8
80
80
8
8
11
TBAB
14
99
ZnMOF-
1-NH2
3
0.8
80
8
38
72
99
98
ZnMOF-
1-NH2/
TBAB
4
0.8
60
4
Cycloaddition of CO2 with Epoxides
ZnMOF-
1-NH2/
TBAB
5
6
7
8
0.8
0.8
0.8
1.0
60
80
80
80
6
6
8
8
78
88
95
93
98
97
96
97
The cycloaddition of CO2 with styrene oxide (SO) was selected
as a model reaction to optimize the reaction conditions. Our
preliminary catalytic experiments on the cycloaddition of
carbon dioxide and epoxides by ZnMOF-1-NH2 were focused
mainly to establish the reaction parameters in presence of a
co-catalyst tert-butyl ammonium bromide (TBAB), tert-butyl
ammonium Iodide (TBAI) and potassium Iodide (KI) using
styrene oxide (SO) as a model substrate under solvent free
condition. The reactions were performed at 0.8/1.0 MPa CO2
pressure, temperature 60/80 oC with the reaction mixture
covering SO (20 mmol), catalyst (0.21 mmol) and the
respective co-catalyst (0.5 mmol) in a 50-mL stainless-steel
autoclave with a magnetic stirrer at 600 rpm. Details of the
reaction conditions and parameters are given in Table 1 and
controlled experiments with complete absence of catalyst/co-
catalyst and in presence of only TBAB, SO conversion was
negligible (Table 1, entry 1 and 2), while catalytic reaction with
pristine MOF yielded 38% styrene carbonate (SC) within 8 h
reaction time (Table 1, entry 3). Keeping CO2 pressure 0.8
MPa, variation of time and temperature was also monitored
for ZnMOF-1-NH2/TBAB system and a maximum of 95% SO
conversion is achieved at 80 oC with 8 h reaction time (Table 1,
entry 4-7). When the pressure is increased up to 1.0 MPa
retaining other reaction conditions (Table 1, entry 10) revealed
slight reduction in product yield. Notably, the conversion of SO
is comparatively lower when TBAB was replaced by TABI or KI
as the co-catalyst (Table 1, entry 9 and 10). Under the same
reaction condition using 2.5 mol% of respective co-catalyst the
product yield is in the order TBAB > KI > TBAI with % yield of
product (SO to SC) is 88%, 85% and 81% respectively (Table 1,
entry 7, 9 and 10).
ZnMOF-
1-NH2/
TBAB
ZnMOF-
1-NH2/
TBAB
ZnMOF-
1-NH2/
TBAB
ZnMOF-
1-NH2/
TBAI
9
0.8
0.8
0.8
80
80
80
8
8
8
86
90
94
97
98
96
ZnMOF-
1-NH2/KI
ZnMOF-
1-NH2G/
TBAB
10
11
*Table Footnote Reaction conditions: SO = 20 mmol (2.28 mL at 25 oC), 600 rpm.
Catalyst mol%: ZnMOF-1-NH2 1.0 mol% (0.21 mmol, 0.1 g); tetrabutyl
=
ammonium bromide (TBAB) = 2.5 mol% (0.5 mmol, 0.161 g).
Higher activity was observed with the bromide compared to
iodine salts in contrast to literature reports in which iodide
was found to be the best promoters (in accordance to the
increasing nucleophilicity). This may be due to bigger size of
the iodide hindered the diffusion in the reaction process.102-103
Thus, we can deduce that the co-catalyst TBAB has an
important role in the catalytic reaction which may be
attributed to the presence of labile leaving group Br-.
Representative reaction for mechanochemically prepared
ZnMOF-1-NH2 for the cycloaddition reaction of CO2 with SO
has been conducted which showed no significant deviation in
the product yield (Table 1, entry 11).
To explore the optimal reaction conditions, a series of
reactions were designed upon incremental variation in CO2
pressure, temperature, reaction time duration and catalyst
amounts to obtain the best possible combination. The effect of
variation of incremental addition of CO2 on ZnMOF-1-NH2
-
catalyzed SO-CO2 cycloaddition is depicted in Figure 3. The
conversion of SO steadily increased up to 32% upon 0.4 MPa
pressure and faster styrene carbonate formation is observed in
the pressure range 0.4-0.8 MPa with a maximum of 95% and
no further significant conversion above 0.8 MPa CO2 pressure.
The improved SO conversion can be attributed to the
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enhancement in the solubility of CO2 in the liquid phase in -1.2 mol% of catalyst loading. 1 mol% catalyst is retained as
presence of the heterogeneous catalyst with pressure which is optimised loading in further catalytic experiments.
in agreement with the previous report by Han et al.104
Figure 3. Effect of pressure (MPa) on styrene carbonate formation. (Reaction
conditions: SO = 20 mmol (2.28 mL at 25 oC), Catalyst mol%: ZnMOF-1-NH2 = 1.0
mol% (0.21 mmol, 0.1 g); tetrabutyl ammonium bromide (TBAB) = 2.5 mol% (0.5
mmol, 0.161 g), 80 oC, 8 h, 600 rpm)
Figure 5. Effect of reaction time (h) on styrene carbonate formation. (Reaction
conditions: SO = 20 mmol (2.28 mL at 25 oC), tetrabutyl ammonium bromide (TBAB) =
2.5 mol% (0.5 mmol, 0.161 g), PCO2 = 0.8 MPa, 80 oC, 8 h, 600 rpm)
Figure 4. Effect of temperature (oC) on styrene carbonate formation. (Reaction
conditions: SO = 20 mmol (2.28 mL at 25 oC), Catalyst mol%: ZnMOF-1-NH2 = 1.0 mol%
(0.21 mmol, 0.1 g); tetrabutyl ammonium bromide (TBAB) = 2.5 mol% (0.5 mmol, 0.161
g), PCO2 = 0.8 MPa, 8 h, 600 rpm)
Figure 6. Effect of catalyst loading (mol%) on styrene carbonate formation. (Reaction
conditions: SO = 20 mmol (2.28 mL at 25 oC), tetrabutyl ammonium bromide (TBAB) =
2.5 mol% (0.5 mmol, 0.161 g), PCO2 = 0.8 MPa, 80 oC, 8 h, 600 rpm.
The scope and generality of the mentioned series of
experiments clearly authenticate for setting up optimized
parameters for catalyst/co-catalyst, temperature and pressure
Effect of temperature upon conversion of styrene carbonate is
provided in Figure 4. The efficiency of substrate conversion is
improved with temperature keeping other parameters
constant; increasing temperatures from 25 to 80 °C,
conversion of SO increases from 25% to the final 95%
employing 8 h of catalytic reaction. As shown in Figure 5,
conversion of styrene oxide increases with increasing reaction
time and finally a total conversion of 95% is achieved with in 8
h reaction time and no further improvement is observed upon
additional increment in reaction time. Effect of catalyst loading
is also optimised which is shown in Figure 6. Keeping all other
parameters set, upon incremental addition of the catalyst
revealed that maximum conversion of 95-96% is achieved at 1
as ZnMOF-1-NH2/TBAB,
8 h, 0.8 MPa respectively in
cycloaddition reactions for different aromatic and aliphatic
substrates to yield the respective cyclic carbonate. Thus,
coupling reactions of CO2 with different epoxides catalyzed by
ZnMOF-1-NH2/TBAB were investigated, and the results are
summarized in Table 2. The catalytic system could convert all
epoxides studied to the corresponding cyclic carbonates
effectively under the optimized reaction conditions with good
yield and selectivity (Table 2, entry 1 to 6) except in the case of
cyclohexene oxide (Table 2, entry 7). In the case of
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functionalized aliphatic propylene oxide, increase in assist the activation of CO2 by the MOF favoring the catalytic
substituents/chain length has a decreasing effect in product performance.
yield (Table 2, entry 2, 3, and 5).
Table 2. Substrate Screening Using ZnMOF-1-NH2 Catalyst in the cycloaddition of
epoxide with CO2.*
Conversion
(%)
Yield
(%)
Entry
Epoxide
1
93
88
2
3
96
91
93
89
4
5
92
88
89
84
Figure 7. Proposed catalytic mechanism for the cycloaddition of CO2 to epoxide using
ZnMOF-1-NH2 as catalyst and TBAB as co-catalyst.
6
7
73
18
72
18
Catalytic Oxidation of Sulfides to Sulfoxide
Bearing in mind the importance of sulfoxides as efficient
synthetic auxiliaries and as valuable pharmaceuticals
precursors, we explored the catalytic oxidation of aromatic
sulfides using ZnMOF-1-NH2 possessing good thermal and
chemical stability as a heterogeneous catalyst. The oxidation of
thioanisole (0.5 mmol) was selected as a model reaction to
evaluate the catalytic performance of ZnMOF-1-NH2 in
presence of tert-butyl hydroperoxide (TBHP, 1.0 mmol) as an
oxidant and dichloromethane (DCM, 4.0 mL) as solvent in a 10-
mL glass tube at 200 rpm to optimise the reaction condition
(Table 3). The influence of oxidants (H2O2/TBHP/UHP) was
firstly studied for oxidation of thioanisol in optimization
experiments. Of the three oxidants, TBHP proved to be the
best one, which gave the product with satisfactory conversion
when 1 mmol was used. Subsequently oxidation reactions
were performed at 25 oC with varying reaction time as 1, 2 and
3 h and the corresponding sulfide conversion was 77, 91 and
99% with selectivity 78, 88 and 95% respectively (Table 3,
entry 5-7). Indeed, TBHP and H2O2 alone produced 23% and
trace amount of product at 3 h and 12 h reaction time, but
catalyst/ H2O2 combination at 25 and 40 oC offered 22 and 50%
sulfide conversion upon 12 h of reaction time (Table 3, entry 1-
*Table FootnoteReaction conditions: Epoxide = 20 mmol, Catalyst mol%: ZnMOF-
1-NH2 = 1.0 mol% (0.21 mmol, 0.1 g); tetrabutyl ammonium bromide (TBAB) = 2.5
mol% (0.5 mmol, 0.161 g), PCO2 = 0.8 MPa, 8 h, and 80 oC, 600 rpm.
For aromatic epoxide, bulky substitution such as Br on the
aromatic ring showed radical decrease in the corresponding
cyclic carbonate product, may be due to the steric factor
retarding the approach of the substrate towards Lewis acidic
metal nodes (Table 2, entry 1, 4 and 6). Compared to terminal
epoxide, internal epoxide 1,2-epoxycyclohexane does not
undergo any significant cycloaddition reaction (18% product
yield) can be attributed to sterically hindered cyclohexene
moiety (Table 2 entry 6).105 In all the catalytic reactions, the
product analysis is performed by both GC and NMR
spectroscopy (Figure S6-S17).
Based on the previous reports61,65,106-107 and on the basis of
crystal structure of ZnMOF-1-NH2 probable mechanism of the
catalytic reaction is projected and illustrated in Figure 7. The
proposed coupling reaction mechanism is initiated by the
attack of the oxygen atom from the epoxide with the vacant
coordinatively unsaturated Zn(II) Lewis acid site of ZnMOF-1-
NH2 which could activate the epoxy ring. In the second step Br-
generated from the TBAB attack the less hindered carbon
atom of the coordinated epoxides followed by the ring-
opening step. Subsequently, CO2 interacted with the oxygen
anion of the opened epoxy ring forming alkyl carbonate anion
which is converted into the corresponding cyclic carbonate
through the ring closure. The good catalytic performance of
ZnMOF-1-NH2 is believed to be synergistic effect of the
catalytic system in presence of TBAB. Presence of Lewis basic
site such as amine functionality in the ligand moiety can also
o
4). ZnMOF-1-NH2/UHP combination at 25 C also furnished
poor yield with 25% conversion of sulfide in 3 h reaction time
(Table 3, entry 10).
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5). As revealed in Table 5, maximum product yield and
selectivity under the optimized reaction condition was
obtained in the case of thioanisole and upon increase in chain
length/ substitution on the phenyl ring in subrates showed
decrese in product yield. In the case of ortho bromo
thioanisole extended reaction time from 3 h to 6 h produced
the desired sulfoxide product with lower conversion and
selectivity (Table 5, Entry 5). This may be attributed to the slow
diffusion and steric hindrance sustained upon substitution by
the bulky substrates hampers the easy accessibility towards
the catalytically active metal sites.
Table 3. Oxidation of thioanisole into methyl phenyl sulfoxide*
Sulfide
Sulfoxide
Catalyst/
Oxidant
Temp. Time
Entry
Conversion Selectivity
(oC)
(h)
12
12
(%)
(%)
1
2
H2O2
ZnMOF-1-NH2/
H2O2
25
Trace
-
25
22
4
ZnMOF-1-NH2/
H2O2
3
4
5
40
25
25
12
3
52
23
77
38
72
78
TBHP
ZnMOF-1-NH2/
TBHP
1
Table 5. Substrate Screening Using ZnMOF-1-NH2 Catalyst in the Oxidation of Sulfides
ZnMOF-1-NH2/
TBHP
6
7
25
25
40
40
25
2
3
1
2
3
91
99
99
99
28
88
95
93
86
90
into Sulfoxide.*
ZnMOF-1-NH2/
TBHP
Time
(h)
Conversion
(%)
Yield
(%)
Entry
Sulfide
ZnMOF-1-NH2/
TBHP
8
1
3
3
99
95
95
92
ZnMOF-1-NH2/
TBHP
9
ZnMOF-1-NH2/
UHP
2
3
4
5
10
*Table Footnote Reaction conditions: Thioanisole = 0.5 mmol (0.06 mL at 25 oC),
Catalyst mol%: ZnMOF-1-NH2 = 2.1 mol% (0.021 mmol, 0.010 g); H2O2/tert-Butyl
hydroperoxide (TBHP)/ UHP = 1.0 mmol, DCM = 4.0 mL, 200 rpm.
3
3
6
89
90
73
83
88
71
Reaction variable such as temperature and time was
modulated in ZnMOF-1-NH2/TBHP and the sulfide conversion
at 40 oC with 1 and 2 h interval time displayed 99% conversion;
however, the selectivity was 93 and 86% respectively (Table 3,
entry 8 and 9). The lower selectivity in the entry 8 and 9 may
be due to the further oxidation of sulfoxide to sulfone under
the protracted settings.
*Reaction conditions: Sulfide = 0.5 mmol, Catalyst mol%: ZnMOF-1-NH2 = 2.1
mol% (0.021 mmol, 0.010 g); tert-Butyl hydroperoxide (TBHP) = 1.0 mmol, DCM =
4.0 mL, 200 rpm. 25 oC, 3 hr.
Table 4. Oxidation of thioanisole into methyl phenyl sulfoxide in different solvent.*
Entry
Solvent
Conversion (%)
Selectivity (%)
1
DCM
99
95
2
3
4
5
6
DMSO
Ethanol
99
83
72
55
42
81
95
94
98
92
Ethyl Acetate
Diethyl Ether
H2O
*Reaction conditions: Thioanisole = 0.5 mmol (0.06 mL at 25 oC), Catalyst mol%:
ZnMOF-1-NH2 = 2.1 mol% (0.021 mmol, 0.010 g); tert-Butyl hydroperoxide (TBHP)
= 1.0 mmol, Solvent = 4.0 mL, 200 rpm.
The solvent effect on thioanisol conversion in catalytic
reactions were also investigated in a variety of solvents
including water and displayed in Table 4. With DCM as solvent
medium the product yield and selectivity was maximum (99%
conversion and 95% selectivity) and DCM is chosen as the ideal
solvent for further catalytic reactions (Table 4, entry 1).
Tracing the above experiments, the reaction conditions are
optimized at 25 oC with ZnMOF-1-NH2/TBHP as
catalyst/oxidant combination in DCM with cocentration of the
precursors as mentioned in the Table 3., for further
sulfoxidation reaction of different aromatic substrates (Table
Figure 8. Proposed catalytic mechanism for the sulfoxidation reaction using ZnMOF-1-
NH2 and TBHP as oxidant.
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In summary, it is reasonable to conclude that the activity and The catalyst is recovered after 4 cycles by centrifugation and
selective oxidation of various sulfides retained using ZnMOF-1- filtration followed by through washing is subjected to different
NH2 as an efficient heterogenous catalyst and with increase in physico-chemical analysis such as FTIR, PXRD and SEM to
size of the substrates the conversion and selectivity decrease establish the chemical stability. As shown in Figure 9b, the
slightly owing to the larger steric hindrance. In all the catalytic PXRD patterns before and after the catalytic reaction are
reactions, the product analysis is performed by both GC and identical and matches well with the simulated from of SCXRD
NMR spectroscopy (Figure S18-S27). The sulfoxide formation is data and the FTIR spectrum of the material after the catalytic
further established unambiguously by crystalizing the product perfomance retains the characteristic peaks of the compound,
obtained in reaction (Table 5, entry 3) and solving the crystal indicating that the structural components are stable (Figure
structure of phenyl methyl benzyl sulfoxide (Figure S28). S2). To support further, the FE-SEM images of the compound
Plausible mechanism for sulfoxide formation is shown in Figure also retained the well-defined crystalline morphology and
8. Penta coordinated Zn(II) dimeric cluster possessing a vacant texture of the material before and after the catalytic reactions
coordination site is accessible for coordination with the oxygen (Figure 1). To estimate any leaching out of the metal from the
atom of the TBHP in the formation of an oxygenated ZnMOF-1-NH2 catalysts during the reaction, solid catalyst was
intermediate. The oxygenated intermediate undergoes a separated from both the reaction mixture after 50% reaction
nucleophilic attack on the sulfide ensuing concerted oxygen time. The reaction was further continued without catalyst in
transfer resulted in the formation of sulfoxide.91
presence of only filtrate. No further increase in the product
yield for both reactions clearly confirms the catalytically active
sites resides on the catalyst and no leaching of the metal has
Chemical Stability and Catalytic recyclability of ZnMOF-1-NH2
In the catalytic process, the chemical stability and recyclability been taken place (Figure S5). Therefore, the above evidence
of catalyst is highly important for industrial application. The clearly support that ZnMOF-1-NH2 is a robust and excellent
catalytic performance remains high in both catalytic reactions multifunctional heterogeneous catalyst for CO2 fixation as well
using ZnMOF-1-NH2 as a catalyst and the recovered catalyst is as sulfoxidation reactions which can be synthesized by green
reused till four consecutive cycles without much loss of mechanochemical method having good recyclability. The good
efficiency (figure 9a).
catalytic activity of ZnMOF-1-NH2 for the catalytic reactions
can be mainly credited to synergic effect of well oriented high
density of active metal sites/ amino and amide functional
moieties of the ligand exposed for interactions with the
substrates.
Conclusions
Judicious choice of catalytically active metal nodes and ligands
incorporating appropriate functional groups as linkers has
great influence in developing efficient and benign catalysis
systems. In summary, we have synthesized and characterized
amine functionalized three-dimensional metal organic
framework involving Zn(II) metal nodes and aromatic
dicarboxylate/ N-donor Schiff base ligand as linkers by
different routes. The synthesized ZnMOF-1-NH2 possessing
unsaturated coordination sites and functional groups in the
ligand moiety has been exploited as a multifunctional
heterogeneous catalyst for the CO2-epoxide coupling reaction
and oxidative desulfurization of sulfides with high conversion
and selectivity. Excellent chemical stability, easy separation
and recyclability with no obvious decrease in catalytic activity
approve this material as a potential heterogenous catalyst.
Conflicts of interest
There are no conflicts to declare.
Figure 9. (a) Recycling of catalyst ZnMOF-1-NH2 up to 4 recycles for cycloaddition and
sulfoxidation reactions and (b) Comparison of PXRD data of ZnMOF-1-NH2 as
synthesized with recovered after 4 catalytic recycle of cycloaddition and sulfoxidation
reactions.
Acknowledgements
The registration number of this publication is CSIR-CSMCRI –
061/2018. Financial support from DST Project HCP0009 (PP),
8 | J. Name., 2012, 00, 1-3
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Satyaveer Gothwal for TGA data, Mr. Vinod Kumar Agrawal for
FTIR data, Mr. Viral Vakani for CHN analysis, Mr. Jayesh
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Dalton Transactions
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DOI: 10.1039/C8DT01297K
Graphical Abstract
Zn(II) based 3D MOF used as a heterogenous multifunctional catalyst for cycloaddition of CO2 with
epoxides and sulfoxidation reaction.