A multifunctional organic-inorganic hybrid structure based on Mn III-porphyrin and polyoxometalate as a highly effective dye scavenger and heterogenous catalyst

Article abstract of DOI:10.1021/ja209196t

A two-step synthesis strategy has led to a unique layered polyoxometalate-Mn^III-metalloporphyrin-based hybrid material. The hybrid solid demonstrates remarkable capability for scavenging of dyes and for heterogeneous selective oxidation of alkylbenzenes with excellent product yields and 100% selectivity.

Full text of DOI:10.1021/ja209196t

Communication
pubs.acs.org/JACS
A Multifunctional Organic−Inorganic Hybrid Structure Based on
MnIII−Porphyrin and Polyoxometalate as a Highly Effective Dye
Scavenger and Heterogenous Catalyst
Chao Zou,† Zhijuan Zhang,‡ Xuan Xu,† Qihan Gong,‡ Jing Li,*,‡ and Chuan-De Wu*,†
†Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
‡Department of Chemistry and Chemical Biology, Rutgers University, Piscataway, New Jersey 08854-8087, United States
S
* Supporting Information
combining these two components in a hybrid structure. Herein
ABSTRACT: A two-step synthesis strategy has led to a
unique layered polyoxometalate−MnIII−metalloporphyrin-
based hybrid material. The hybrid solid demonstrates
remarkable capability for scavenging of dyes and for
heterogeneous selective oxidation of alkylbenzenes with
excellent product yields and 100% selectivity.
we report the synthesis and characterization of the intercalated
metalloporphyrin−POM-based hybrid framework {[Cd-
(DMF)2MnIII(DMF)2TPyP](PW12O40)}·2DMF·5H2O (1)
(DMF = N,N-dimethylformamide; TPyP = tetrapyridylpor-
phyrin), which demonstrates excellent capability for scavenging
of dyes and for highly selective oxidation of alkylbenzenes.
To resolve the solubility issue of POMs (soluble in water)
and porphyrins (soluble in organic solvents) under moderate
reaction conditions, a reaction of H3PW12O40 with MnIIICl−
TPyP in DMF was first carried out to form the zwitterionic
complex {[MnIII(DMF)2TPyP](PW12O40)}2−. The combined
components could subsequently be dissolved effectively both in
water and organic solvents (e.g., DMF, MeOH, etc.). By this
strategy, we successfully isolated brownish crystals of 1 upon
reaction of a mixture of the zwitterionic complex and
Cd(NO3)2·4H2O in a mixed solvent of DMF and acetic acid
at 80 °C for 48 h.18
rystalline organic−inorganic hybrids are a class of
C
materials that integrate organic struts, inorganic clusters,
and metal nodes in a framework structure. By incorporation of
choice functional organic moieties and metal oxide clusters via
self-assembly, grafting, or intercalation, such hybrid structures
are formed with multiple functionalities and often new features
as a result of blending of distinctively different components.1
Within the context of nanostructured solids, complex hybrid
systems provide a new pathway for combining multiple
functional groups in a multilevel hierarchical framework at
the molecular scale,2 which demonstrates great potential for
applications in diverse fields such as selective adsorption,
catalysis, explosives detection, optics, optoelectronics, and
electrochemics.3−7
Single-crystal X-ray diffraction (XRD) analysis revealed that
1 crystallizes in the monoclinic C2/c space group and that its
structure is built on alternate layers of POM anions and
porphyrin-containing cationic nets.19 Each CdII ion octahedrally
coordinates to the four pyridine groups of four TPyP ligands
[Cd−N = 2.34(1)−2.36(1) Å] at the equatorial positions and
two DMF molecules [Cd−O = 2.27(1) Å] at the apical sites.
Each TPyP acts as a tetradentate ligand bridging four CdII ions
to propagate a two-dimensional lamellar network of [Cd-
(DMF)2MnIII(DMF)2TPyP]n3n+ parallel to the ab plane (Figure
1a). The MnIII ion adopts a coplanar conformation with the
porphyrin unit and coordinates to the four pyrroles of the
porphyrin core [Mn−N = 1.99(1)−2.03(1) Å] and two DMF
molecules [Mn−O = 2.21(1) Å] in an octahedral geometry.
Polyoxometalates (POMs) are a unique class of discrete
anionic metal−oxygen clusters. POMs have attracted significant
contemporary interest because of their unique functionality,
making them active constituents in various materials.8−11
Particularly, the combination of POMs in hybrid networks
can improve interactions between the organic molecules and
the surface of metal oxides for efficient catalytic applications.12
Metalloporphyrins, which have unique biological, chemical,
physical, and catalytic functionalities, represent a remarkable
class of molecule-based solids.13,14 Because of their distinctive
catalytic activities,15 the inclusion of metalloporphyrins in
porous coordination networks has gained intense attention, and
some of them have shown very interesting catalytic properties
in heterogeneous reactions.14,16
It is without question that the combination of POMs and
metalloporphyrins in a porous hybrid material will not only
retain the individual functionality but also introduce new and
unique properties. However, the adverse solubility of these two
moieties makes the synthesis of metalloporphyrin−POM-based
hybrids extremely difficult.17
The lamellar 2D nets of [Cd(DMF)2MnIII(DMF)2TPyP]n
3n+
are packed in an ...AA... stacking sequence with a layer
separation of 12.437(1) Å. The [PW12O40]3− polyanions are
located between the lamellar networks [Figure 1 and Figure S1
in the Supporting Information (SI)]. It is interesting to note
that only one of the two cavities between the lamellae is
occupied by a [PW12O40]3− polyanion, while the other one is
vacant to accommodate solvent molecules. As a result,
compound 1 becomes porous upon solvent removal, with
large cavities with dimensions of 10.07(1) Å × 10.09(1) Å ×
To meet such a challenge, we have developed a new
synthetic method that has proved to be very efficient in
Received: September 29, 2011
Published: December 9, 2011
© 2011 American Chemical Society
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Figure 2. (a−c) UV−vis spectra of (a) methylene blue, (b) crystal
violet, and (c) rhodamine B before (red lines) and after (blue lines)
the addition of solid 1. The inset photographs highlight the scavenging
effects. (left) before scavenging; (right) after scavenging. (d)
Comparison of the dye capture capacities of 1 (red), the MnCl−
TPyP ligand (pink), and [Bu4N]3[PW12O40] (blue).
Figure 1. (a) Arrangement of a single layer of the lamellar framework
of [Cd(DMF)2MnIII(DMF)2TPyP]n3n+ and a layer of the [PW12O40]3−
polyanions, as viewed down the c axis. (b) Perspective view of the
packing diagram of 1 along the [110] direction. Color scheme: MnIII,
orange; Cd, cyan; {WO6}, green octahedra; P, purple; N, blue; C, gray.
DMF molecules and H atoms have been omitted for clarity.
for a slightly deepened color. However, the PXRD pattern of
the treated sample showed significant changes. Single-crystal
XRD analysis revealed that the resultant compound {[Cd-
(H2O)2MnIII(H2O)2TPyP](PW12O40)}·10H2O (2) was very
similar to 1, except that the DMF ligands were replaced by
water molecules (Scheme 1).19 The space group of 2 is
12.44(1) Å and 1D channel openings with dimensions of
5.36(1) Å × 12.44(1) Å as viewed along the [110] direction.
PLATON calculations indicated that 1 contains 27.6% void
space (2756.4 Å3 per unit cell) that is accessible to solvent
molecules.20 Thermogravimetric analysis showed that a weight
loss of 5.5 wt % occurred between 25 and 164 °C,
corresponding to the loss of guest DMF and H2O molecules
(calcd 5.5%). The release of DMF ligands occurred in the 164−
241 °C region (calcd, 6.7%; found, 6.7%). No further weight
loss was observed until 509 °C, above which 1 began to lose
porphyrin ligand and framework decomposition occurred.
When a sample of 1 was heated under vacuum at 100 °C for
Scheme 1. Schematic Representation of the Single-Crystal to
Single-Crystal Transformation from 1 to 2 Induced by
Ligated Solvent Exchange (See Figure S2 and Table S3 for
Details)
1
12 h, H NMR spectroscopy indicated that the lattice DMF
molecules were almost fully evaporated (Figure S6b). Powder
XRD (PXRD) analysis of the sample showed a sharp diffraction
pattern identical to that of the pristine sample, indicating that
the porous framework was maintained after the removal of
solvent molecules.
Because of their complex structures and poor biodegrad-
ability, decolorization of widely used dyes is very difficult.21
Thus, scavenging such dyes from polluted water remains a
challenging task. As compound 1 consists of two types of active
components in its network structure, we used this material to
remove dyes from aqueous solutions. When samples of 1 were
added to aqueous solutions of methylene blue, rhodamine B,
and crystal violet at room temperature, the dyes were almost
fully adsorbed from their water solutions by solid 1, as
monitored by UV−vis absorption spectroscopy (Figure 2a−c).
As shown in Figure 2d, 1 g of solid 1 can adsorb 0.033 mmol of
methylene blue, 0.063 mmol of rhodamine B, and 0.057 mmol
of crystal violet. A comparison of the amounts of adsorbed dye
indicates that 1 has significantly higher capture capability than
either MnCl−TPyP or [Bu4N]3[PW12O40] (Figure 2d).
To identify the adsorption sites of the dye molecules (e.g., on
the solid surfaces or in the open channels), we immersed a
sample of 1 in an aqueous solution of methylene blue at 50 °C
for 24 h. After this treatment, the crystals of 1 showed no
apparent difference in comparison to the original form except
tetragonal P42/mmc as opposed to monoclinic C2/c for 1. The
single-crystal to single-crystal (SC−SC) transformation is
accompanied by a reduction of the c axis length from
24.8738(8) to 23.636(4) Å and large variations in the angles.
Combining this observation with the captured amounts of the
dyes, it can be concluded that the adsorption of the dyes occurs
on the solid surfaces.
As 1 contains catalytically active MnIII−TPyP species and its
backbone remains intact after the substitution of the ligated
DMF by water molecules, we were encouraged to evaluate the
catalytic ability of 1 in the oxidation reaction of alkylbenzene.
Oxidation of ethylbenzene (EB) by 1 was conveniently
performed in H2O at 80 °C for 12 h using tert-
butylhydroperoxide (TBHP) as the oxidant (see Scheme 2).
GC−MS analysis showed that only one product, acetophenone,
was formed in an excellent yield of 92.7% (Table 1, entry 1).
For comparison, a series of control catalysts were also
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Communication
by filtration and subsequently used in successive runs with only
slightly decreased product yields (Table 1, entries 10 and 11).
On the contrary, the catalytic activity was greatly depressed
when the recovered homogeneous MnIIICl−TPyP was used
instead of solid 1 (Table 1, entry 12).
Scheme 2. Oxidation Reaction of Alkylbenzenes
We monitored the accessibility of the open channels to
several substrate molecules by H NMR, GC−MS, and liquid-
Table 1. Selective Oxidation of Alkylbenzenes for the
Formation of Phenyl Ketones
1
a
phase adsorption experiments (see the SI for details). The
NMR spectrum is clearly indicative of pore accessibility to EB
molecules. A more quantitative analysis was conducted by GC−
MS and liquid-phase adsorption, from which uptake amounts of
13.2 and 15.2 wt % were obtained, respectively. On the
1
contrary, no detectable amount was observed by either H
NMR or GC-MS analysis for larger substrate molecules such as
4-ethylbiphenyl and 1-(tert-butyl)-4-((4-ethylphenoxy)methyl)-
benzene under the same experimental conditions. Additionally,
gas-phase CO2 adsorption experiments were carried out on
both samples of 1 and 2 in the vicinity of room temperature (0,
15, and 25 °C; see Figure S12) to evaluate the porosities of 1
and 2. The estimated Langmuir and Brunauer−Emmett−Teller
surface areas were 133 and 65 m2/g for 1 and 124 and 82 m2/g
for 2, respectively. These combined results suggest that the
MnIII sites in the channel walls are indeed reachable by
substrates of relatively small sizes, thus allowing much higher
catalytic performance than in the case of larger substrates. The
latter molecules have difficulty entering the interior pore spaces,
and reactions can only occur at exterior solid surfaces. It is
interesting to note that after the reaction of 1 in a mixture of
EB, H2O, and TBHP at 80 °C for 24 h, the backbone of the
resultant structure {[Cd(H2O)2MnIII(H2O)2TPyP](PW12O40)}
(3) was identical to that of 2.19
It has been proposed that hydrocarbon oxidation catalyzed
by metalloporphyrins involves the formation of reactive
oxometalloporphyrin intermediates.22 However, a big disad-
vantage in homogeneous catalysis using metalloporphyrins is
that suicidal inactivation is inevitable because of the formation
of catalytically inactive μ-oxo metalloporphyrin dimers.23 The
remarkable stability of compound 1 should be attributed to the
very robust layered framework of the MnIII−porphyrin units
separated by [PW12O40]3− polyanions, which prevents the
formation of inactivated dimers.
In summary, we have developed a new strategy for the
effective synthesis of a novel POM−MnIII−metalloporphyrin-
based hybrid layered framework. Compound 1 combines
multiple functional groups in a single structure. It exhibits
remarkable capability for scavenging of dyes and heterogeneous
selective oxidation of alkylbenzenes with high yields and 100%
selectivity. Our results from catalytic reactions have also
demonstrated excellent size selectivity of 1 in accordance
with its pore dimensions. This work provides a new pathway for
the future synthesis of POM−porphyrin hybrid materials with
merged functionality for potential applications.
a
Conditions: a mixture of catalyst (0.01 mmol), alkylbenzene (0.1
mmol), and TBHP (0.5 mmol) in water (5 mL) was stirred at 80 °C
for 12 h. Based on GC analysis. The second cycle. The sixth cycle.
b
c
d
employed in the same catalytic experiments. MnIIICl−TPyP
was considerably less efficient, with a 73.6% yield for
acetophenone, while [PW12O40]3− showed no activity (Table
1, entries 2 and 3). These results suggest that the catalytic
activity of 1 is superior to those of its precursors. Under the
same catalytic conditions, catalyst 1 can also oxidize
propylbenzene and tetrahydronaphthalene, giving rise to the
corresponding ketones in excellent yields with 100% selectivity
(Table 1, entries 4 and 5). Much lower yields were obtained in
the cases of larger substrate molecules, most likely because the
reactions occur only on the solid surfaces (Table 1, entries 7−
9).
After a mixture of solid 1 and TBHP in H2O was heated at
80 °C for 12 h under stirring, EB and additional TBHP were
subsequently added into the hot filtrate, which was heated at 80
°C for another 12 h. GC analysis indicated that the mixture was
unreactive. This experiment proved that the hybrid catalyst
system is heterogeneous in nature. Solid 1 was easily recovered
ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental procedures, additional figures and tables, and
crystallographic data. This material is available free of charge via
the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
jingli@rutgers.edu; cdwu@zju.edu.cn
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ACKNOWLEDGMENTS
■
This work was financially supported by the NNSF of China
(Grant 21073158), the Zhejiang Provincial Natural Science
Foundation of China (Grant Z4100038), and the Fundamental
Research Funds for the Central Universities (Grant
2010QNA3013). The RU team acknowledges partial support
from DOE (Grant DE-FG02-08ER46491).
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