Bimetallic Metal Organic Frameworks as Magnetically Separable Heterogeneous Catalysts and Photocatalytic Dye Degradation

Article abstract of DOI:10.1002/cplu.201800546

A new bimetallic MOF (BMOF) has been synthesized using iron and zinc as inorganic metal nodes and 1,4-benzenedicarboxylic acid (BDC) as the organic linker molecule. BMOF was confirmed by single-crystal X-ray diffraction (SCXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy high-angle annular dark-field imaging (TEM-HAADF), field emission scanning electron microscopy energy-dispersive X-ray analysis (FESEM-EDX), vibrating sample magnetometry (VSM) and inductively coupled plasma mass spectrometry (ICP-MS) analysis. The synthesized BMOF shows excellent optical and magnetic properties. BMOF acts as a heterogeneous catalyst and shows high catalytic activity towards bis(indolyl)methane synthesis and photocatalytic degradation of methylene blue (MB) under visible-light illumination.

Full text of DOI:10.1002/cplu.201800546

Accepted Article
Title: Bimetallic metal organic frameworks: Magnetically separable
heterogeneous catalyst for efficient organic transformation and
photocatalytic dye degradation
Authors: Jaspreet Kaur Randhawa, Ashish Tiwari, Prateep singh
Sagara, and Vicky Varma
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COMMUNICATION
Bimetallic Metal Organic Frameworks as Magnetically Separable
Heterogeneous Catalyst for Efficient Organic Transformation and
Photocatalytic Dye Degradation
Ashish Tiwari#[a], Prateep Singh Sagara#[b], Vicky Varma and Jaspreet Kaur Randhawa*
[b]
[a]
Abstract: A new bimetallic MOF (BMOF) has been synthesized using
iron and zinc as inorganic metal nodes and 1-4, benzenedicarboxylic
acid (BDC) as organic linker molecule. BMOF was confirmed with
Single crystal X-ray diffraction (SCXRD), X-ray photoelectron
spectroscopy (XPS), Transmission electron microscopy-high angle
annular dark-field imaging (TEM-HAADF), Field emission scanning
electron microscopy-energy dispersive x-ray analysis (FESEM-EDX),
Vibrating sample magnetometer (VSM) and inductively coupled
plasma-mass spectrometry (ICP-MS) analysis. The synthesized
BMOF shows excellent optical and magnetic properties. BMOF acts
as a heterogeneous catalyst and show high catalytic activity towards
bis(indolyl)methane synthesis and photocatalytic degradation of
methylene blue (MB) under visible light illumination.
Besides, some studies have dealt with photocatalytic properties
of hybrid MOFs such as Fe/M(M=Mn, Co, Ni) MOFs, Fe(II)@MIL-
100(Fe) and MIL-53(Fe) MOFs.[20],[21] Thus, the rational design
and synthesis of hybrid structure with multi-functionalities could
achieve enhanced physicochemical properties and efficiency.
Inspired with the possibility to improve the properties through
introducing a new metal component in MOF, we hereby report the
synthesis and crystal structure of
a new bimetallic MOF
composed of divalent Zn and trivalent Fe ions linked with 1, 4-
benzenedicarboxylic (BDC) acid to form Fe-Zn BDC MOF.
The pristine MOF doped or incorporated with another metal
provide a scope to tune the electronic band gap. Recent studies
show that the incorporation of iron as second metal in MOF
decreases the band gap of parent MOF and enhanced its
absorption into visible region.[22] The band gap values of MIL-53
and MOF-5 are 2.6 eV[23] and 3.5 eV[24] whereas the BMOF in
present work assessed band gap value ca. 1.9 eV which suggest
that the presence of second metal decrease the band gap. As,
Fe-Zn BDC BMOF exhibits the band gap of 1.90 eV and this was
exploited for the photocatalytic degradation of methylene blue
The motive of crystal engineering is to develop new crystals with
precise control of morphology, porosity and functionality.[1] Metal
organic frameworks (MOFs) are one such a class of cross breed
products of crystal engineering, comprising nodes of transition
2
+
3+
4+
metals (M , M and M ) connected by organic linkers of amine
and carboxylate functionalities that unlock the potential for new
crystal design for respective applications.[2] The node and linker
union form assemblies from linear, angular, trigonal or tetrahedral
symmetries with variety of frameworks and surface properties.[3]
For example, divalent M2+ metal nodes form fragile framework [4]
act as week Lewis acid sites that limit their catalytic activity.
(
MB). The photocatalytic degradation efficiency ca. 57% was
achieved in 90 minutes under visible light illumination. Organic
transformation of indoles to bis(indolyl) is one of the most
ubiquitous heterocycle among natural products. This encompass
wide applications i.e. antibacterial, antifungal, antimicrobial, anti-
[25]
inflammatory and anticancer activities.
Variety of Lewis acid
4
+
Similarly, tetravalent metal cations (M ) provide stronger Lewis
acid sites [ , but the synthetic route for obtaining phase pure
crystals of these metal nodes are yet to be developed.
catalysts such as metal halides, nitrates, and oxychlorides were
employed in this reaction with harsh reaction conditions and
solvents.[26] The present work demonstrates use of Fe-Zn BDC
BMOF as heterogeneous catalysts for the synthesis of
bis(indolyl)methanes. The reaction shows 94% conversion
efficiency of bis(indolyl)methanes. The catalyst can be efficiently
recovered from the reaction mixture magnetically and reused
further for catalytic activity. BMOF was obtained from a single step
5]
Designing bimetallic MOF[6],[7] containing more than one metal
nodes could be one of the alternatives for achieving improved
properties as compared to their monometallic counterparts.[8] For
instance, MOF-5 is moisture sensitive under atmospheric
conditions and doping Ni(II) in MOF-5 enhance its hydrostability.[9]
Likewise, bimetallic Zn-Cu BTC MOF revealed higher
desulfurization capacity than the monometallic Cu-BTC and even
zeolites.[10] Similar studies showed that bimetallic MOF have
superior catalytic activities over monometallic MOF being used as
heterogeneous catalyst for organic coupling reactions[11],[12] such
as heck reaction,[13] C-H bond halogenation,[14] catalyzing OER
solvothermal synthesis method using Zn(NO
3 2 2
) .6H O and
Fe(NO .9H O in DMF/ethanol solvent in 4:1 ratio. The metal
3
)
3
2
salts were thoroughly mixed with 1, 4-benzenedicarboxylic (BDC)
acid by magnetic stirring for 30 min. This solution was then
transferred to a Teflon-lined stainless-steel Parr autoclave and
heated to 150°C for 20 hrs. A pale yellow colored crystals, stable
in atmospheric conditions were attained. Single crystal X-ray
diffraction analysis revealed the formation of monoclinic crystal
reactions,[15] selective oxidation of aromatic substrates[16]
Knoevenagel condensation[17] and Suzuki coupling reaction.[18],[19]
,
2
system with C /C space group having 3D porous framework. The
asymmetric unit as shown in Figure 1b reveals that each Zn(II) is
forming coordinate bonds with a slightly distorted geometry with
[
a]
Mr. Ashish Tiwari and Dr. Jaspreet Kaur Randhawa*
School of Engineering, Indian Institute of Technology Mandi,
Mandi, Himachal Pradesh, India, 175005.
three oxygen atoms (O
The fourth coordination is satisfied by carboxylate oxygen (O
1
, O
2
, O
5
) from three different BDC ligands.
) of
E-mail: jaspreet@iitmandi.ac.in
3
[
b]
#]
Mr. Prateep Singh Sagara and Mr. Vicky Varma
School of Basic Sciences, Indian Institute of Technology Mandi,
Mandi, Himachal Pradesh, India, 175005.
another BDC linker (Figure 1a). The second metal Fe(III) is
surrounded by six oxygen atoms. The Zn-O bond distance are in
the range of 1.944-1.978 Å and Fe-O bond lengths are in range
of 2.042 to 2.213 Å.
[
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the
document.
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The carboxylate linker offers the conformational freedom where it
bridges with metal node in three different modes that includes
(ICP-MS) data (Table S1 SI) revealed the presence of iron and
zinc in Fe-Zn BDC BMOF with slightly less Zn2+ content than Fe3+.
Fe-Zn-BDC BMOF has a zeta potential value of −3.54 mV. The
particle size of grinded Fe-Zn-BDC BMOF revealed from TEM
images as well as measured average hydrodynamic size from
DLS was in the range of 10–100 nm which favor the negative zeta
potential value.
monodentate (κ
bridging (μ -κ :κ
1
), monoatomic bridging (μ
2 2
-κ ) and bidentate
) as shown in Figure 1e.[
27]
The distance
2
1
1
calculated between Zn-Zn, Fe-Zn and Fe-Fe are 6.5098, 3.2549
and 14.59 Å respectively. The SCXRD studies revealed that half
of the three BDC molecules links with one Zn(II) ion and half of
two BDC molecules link with Fe(III) ion. Fe-Zn BDC BMOF crystal
forms pillared square grid framework (Figure 1d) where the
complete polymorphic unit arrangement underlines Zn atom
coordinated to four oxygen atoms in tetrahedral symmetry and Fe
atom is coordinated with 6 oxygen atom in octahedral symmetry
respectively. In a larger preview, intra-framework space is formed
of 2D layers connected together by the ligand to generate 3D
structure. The complete crystal structure along b axis, space fill
diagram and polyhedron structure of unit cell are shown in Figure
Thermogravimetric experiments were undertaken to analyse the
thermal stability as depicted in Figure S11 (SI). The thermogram
demonstrates steady weight loss from room temperature to 350°C
which constitute to removal of solvents. Above 350°C, the
decomposition of BDC linker from the framework take place with
complete breakdown of the structure at around 500°C. FTIR
spectra as shown in Figure S12 (SI) highlights the characteristic
bridging modes of metal oxygen bonds and functional groups. Fe-
Zn BDC BMOF shows characteristic bands of BDC at 1371 and
1565 cm−1 for symmetric and asymmetric stretching vibrations.
The separation of 194 cm−1 between antisymmetric and
1d, Figure S0 and S0a (SI) respectively.
The bulk identity of Fe-Zn BDC BMOF crystals was studied by
comparing the PXRD pattern of the as synthesized sample with
the simulated pattern as shown in Figure 2a without any pre-
treatment. The similarity of the patterns indicates that crystals are
formed in pure phase. XPS analysis illustrates distinct
characteristic peaks of C1s, O1s, Fe2p and Zn2p in full survey
spectrum of Fe-Zn BDC BMOF (Figure 2b). Further, deconvoluted
Fe2p spectra showed two distinct peaks at binding energies of
[
32]
symmetric bridging carboxyl groups is similarly reported.
The
−1
−1
peaks in the range of 1602–1560 cm and 1406–1364 cm may
be attributed to bridging and chelating carboxyl groups.[ The
metal oxygen bonds were identified at 560 cm-1 which correspond
to Fe-O and at 420 cm-1 for Zn-O respectively. A broad peak
ranging 3000-3400 cm-1 corresponds to O-H stretching of
carboxylic groups and surface adsorbed hydroxyl groups.[
Raman spectra as depicted in Figure S13 (SI) displayed various
bands spotted for Fe and Zn based MOF. The bands spotted at
32]
33]
711.7 eV for Fe2p3/2 and 719.2 eV for Fe2p1/2 respectively,
accompanied by one prominent shake-up satellite peak (714 eV)
which are characteristic peaks of Fe3+ (Figure S1 SI).[28]
Additionally, deconvoluted Zn2p spectra showed two distinct
peaks at binding energies of 1021.5 eV for Zn2p3/2 and 1044.6 eV
for Zn2p1/2 demonstrating the presence of Zn2+ (Figure S2 SI).[29]
The deconvolution of O1s and C1s also displayed various species
of hydroxyl and carboxyl groups as shown in Figure S3 and S4
−1
635, 864, 1139, 1433, and 1615 cm resemble for MOF-5
respectively.[34] Further, the present BMOF shows specific Fe-MIL
MOF bands in its spectrum featuring at 210 and 450 to 600 cm−1
which may be attributed to crystalline iron based framework
structure and lattice vibrations with network binding modes
respectively.[35] The band spotted at 1617 cm−1 could be assigned
to C=C stretching mode of BDC only appears due to g parity under
(
SI).[30] Optical properties as studied by diffuse reflectance (DRS)
spectra showed absorption peaks at wavelength of 330 nm
Figure S5 SI). The band gap value assessed from the steep
C
i
symmetry. Additionally, bands at 1535 and 1430 cm−1 may be
attributed to in-plane asymmetric and symmetric stretching of
ν
asym (COO) and νsym (COO) respectively.[33] Optical behavior of
(
absorption edges was calculated to be 1.9 eV (Figure 2c) using
Kubelka–Munk (K-M) function as described in experimental
section.[31] This band gap specified visible light absorption of Fe-
Zn BDC BMOF. Figure 2d shows magnetic hysteresis (M-H) curve
recorded at 300K. Fe-Zn-BDC BMOF showed saturation
BMOF was analyzed using photoluminescence (PL)
spectroscopy under experimental conditions with excitation
wavelength of 280 nm. Figure S14 (SI) shows two distinct
emission peaks at 445 and 485 nm and one small shoulder peak
at 418 nm. The peaks observed in between 410-430 nm
corresponds to Fe (III) and peak at 485 nm corresponds to Zn (II)
luminescence peak. The emission at 445 nm is due to intra-ligand
emission. However, emission bands of the carboxylate ligands
originated from π*→n transition are weak and it is considered
that carboxylate ligands have no significant contribution to the
fluorescent emission of coordinated structures.[ Specific surface
area and porous structures were determined by nitrogen
adsorption and desorption isotherms at low relative pressure and
the data is presented in Figure S15 and S16 (SI). A sequential
increase in the adsorption isotherms from low to high relative
pressure strongly relates significant interactions of guest
molecules with adsorbents. BET surface area, pore volume and
s
magnetization (M ) of 11.92 emu/gm. FC and ZFC curves studied
at 500 Oe (Figure S6 SI) also stand with the strong magnetic
behavior. Magnetic properties are advantageous for separation of
catalyst after heterogeneous catalysis. Hence, magnetic behavior
was perceived using a magnet in the aqueous suspension of Fe-
Zn BDC when taken near to magnet, corresponding aggregation
towards magnet was clearly observed (Figure S21 SI). This
observation confers easy separation and reusability of catalyst
after catalytic reactions. FESEM images of Fe-Zn BDC BMOF
revealed the formation of micron sized crystals with rod like
morphology as shown in Figure S7 (SI). Elemental analysis using
FESEM-EDX confirmed the presence of Fe and Zn as shown in
Figure S8 (SI). TEM image of grinded sample as displayed in
Figure S9 (SI) revealed the presence of small agglomerates with
an average size of ca 20 nm. High-angle annular dark-field
scanning transmission electron microscopy (HAADF-STEM)
mapping confirmed the presence of Fe and Zn uniformly
distributed throughout the sample, as shown in Figure S10 (SI).
The inductively coupled plasma atomic emission spectroscopy
36]
2
average pore width were calculated to be 107.6 m /g, 0.133 cc/g
and 16.87 Å respectively. High surface area contributes towards
high catalytic activity by increasing adsorption of organic
molecules from aqueous solutions on the surface of photocatalyst.
Inspired by the band gap value of 1.9 eV of Fe-Zn BDC MOF,
photocatalytic degradation of MB in aqueous solution under
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visible light was undertaken as illustrated in Figure 3. The
absorption maximum of MB at 664 nm decreased with time under
the irradiation of the visible light, suggesting the degradation of
MB. Control experiments were executed to compare the
dimethylformamide (DMF), dimethyl sulfoxide (DMSO),
acetonitrile, methanol and water were used; the product yields
were ca. 75, 86, 81, 80 and 50% respectively. Further, on the
basis of high product yield achieved for bis(indolyl)methane
degradation efficiencies of MB in three different environments viz., synthesis in 1, 2 dichloroethane, a number of various aromatic
in dark condition, with H
2
O
2
alone and in presence of Fe-Zn BDC
groups substituted aldehydes were reacted with indoles to
produce bis(indolyl)methanes compounds (Table 1 (1-12)). We
have screened a series of aromatic compounds containing
electron donating and electron withdrawing groups and
heteroaromatic compounds which underwent to reaction with
alone respectively. Photocatalytic activity was found to be
concentration dependent as evident from Figure 3, ca. 57% of MB
was photo catalytically degraded after 90 min of visible light
illumination using 10 mg/L of photocatalyst concentration.
However, in dark conditions and in presence of H
obvious degradation of MB was observed. The visible light
photocatalytic activity enhanced significantly by the addition of
2
O
2
alone no
indole easily to afford
bis(indolyl)methanes with high product yield. Aromatic aldehydes
having electron withdrawing groups (i.e. NO , CN, and F) react
faster than the simple benzaldehyde while electron donating
groups (i.e. CH , OH) which deactivated aryl aldehydes leading to
a
wide range of substituted
2
2 2 2 2
H O . This is because, H O effectively act as charge carrier
scavenger which reduces the possibility of the recombination of
photo-generated charge carriers and accelerate the generation of
hydroxide radicals. The generated hydroxide radical species
rapidly degrade MB and enhance the photocatalytic activity.[28]
For the purpose of practical application it is essential to evaluate
the long term stability of the photocatalyst. Thus, the reusability
studies were carried out for five times and similar degradation rate
3
slow down the reaction resulting delay in product formation. On
the other side, the heteroaromatic aldehydes such as furfural and
2-thiophene carboxaldehyde were more reactive (Entry 8 and 9,
Table 1). A detailed product yield for synthesized substituted
bis(indolyl)methanes is tabulated in Table 1 appropriately. A
plausible mechanism for the synthesis of the bis(indolyl)methane
is shown in Figure S19 (SI). The proposed mechanism for organic
transformation illustrates that carbonyl group in the aromatic
aldehyde is activated by Fe-Zn BDC followed by the nucleophilic
addition of the indole which yields intermediate 1, a transformation
from intermediate 1 to intermediate 2 takes place by elimination
of water molecule. Further, nucleophilic addition of another indole
molecule on intermediate 2 gives intermediate 3 followed by
aromatization to get the desired product bis(indolyl)methane. The
synthesis of bis(indolyl)methane was determined superior using
Fe-Zn BDC in terms of product yield 94% as compared to other
53% degradation was achieved. The chemical stability of
photocatalyst was also evaluated after the degradation reaction
and comparison of PXRD spectra (Figure S22 SI) before and after
photocatalysis show the structural integrity of BMOF.
Photocatalytic degradation mechanism of MB could be
deliberated based on semiconductor band gap theory.[38]
A
detailed mechanism is presented in Figure S18 (SI). Under visible
light illumination, when a photon having energy equal to or greater
than the band gap of photocatalyst falls on the sample, excitation
of electrons from valence band to conduction band happens with
the formation of holes in the valence band. The generated holes
in valance band immediately oxidize the surface adsorbed dye
catalysts such as metal halides and nitrates.
A detailed
comparison[ of various catalysts used for bis(indolyl) methane
synthesis is summarized in Table S4 (SI). In addition, the
reusability of the catalyst was also examined and no significant
change in catalytic activity was found even after seven cycles of
reaction (Figure S20 SI). The results in the present work show
40]
•
molecules or produce hydroxyl radicals ( OH) on reacting with
-
surface adsorbed hydroxyl ions (OH ) due to strong oxidizing
nature. Band gap energy (ca. 1.9 eV) signify that produced holes
possess high oxidation potential for dye degradation. In addition,
hydroxyl radicals also contribute in oxidizing surface adsorbed
dye molecules to accelerate the photodegradation. In the
meantime, electrons present in the conduction band react with the
that using Fe-Zn BDC,
a series of bis(indolyl)methane
compounds can be synthesized with high product yields being an
alternative to metal halides and nitrates catalysts.
surface adsorbed molecular oxygen (O
radicals (O
-). Strong oxidant capability of generated superoxide
radicals leads to degradation of MB. At the same time, electrons
2
) to produce superoxide
2
In summary, a new bimetallic metal organic framework (BMOF)
has been synthesized using Fe and Zn as metal nodes with 1, 4-
benzenedicarboxylic acid as linker molecule named as Fe-Zn
BDC BMOF. The synthesized Fe-Zn BDC BMOF showed superior
catalytic activity in organic transformation of indoles and aromatic
benzaldehydes into bis(indolyl)methane with high product yield of
ca. 94%. In addition, photocatalytic degradation of methylene blue
with efficiency of ca. 57% in 90 minutes under visible light
irradiation was also achieved. With the development of
in conduction bands activate H
which significantly degrade MB.
2
O
2
[
and generate hydroxyl radicals
39]
The photocatalyst exhibits
good magnetic and photodegradation properties making them
advantageous for degradation of organic pollutants in waste water
treatment.
Further, Fe-Zn BDC BMOF was employed for organic coupling
reactions of indoles and benzaldehydes at 80°C in 1, 2
dichloroethane (DCE) solvent as summarized in Scheme 1 and
Table S2 (SI), the product yield was quiet significant. The effect
of different solvents on the product yield of bis(indolyl)methane
was also examined as shown in the Table S3 (SI). For solvent
screening, the reaction was performed using Indole and
benzaldehyde (1:2) with catalyst (10 mg) at 80°C for 12 hours in
preparation and characterization procedure
a well-defined
bimetallic MOF can be obtained. The design of bimetallic MOF in
terms of additional properties and versatility might be anticipated
in various course of applications.
different solvents. When nonpolar solvents such as 1,
2
dichloroethane and tetrahydrofuran were used for the
bis(indolyl)methane synthesis, the product yield was found 94 and
60% respectively. When polar solvents such as N, N-
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Figure 3. (a) Sequential time dependent photodegradation of MB using Fe-Zn
BDC, (b) −ln(C/C
experiments. Experimental conditions: MB concentration (10−5 mol/L), 10 µL of
0% H and photocatalyst concentration (10 mg).
0
) vs. time curve for photodegradation of MB along with control
3
2 2
O
Scheme 1. Synthesis of bis(indolyl)methanes.
Figure 1. SCXRD analysis of Fe-Zn BDC crystals (a) metal coordinated
polyhedron, (b) asymmetric unit of a crystal, (c) a unit cell structure, (d) crystal
structure along b axis and (e) binding moods of metals with BDC linker. (Colour
code: Fe-green, Zn-sky blue, O-Red and C-Black respectively).
Table 1. Substrates scope for the formation of substituted bis(indolyl)methanes.
Entry[a]
Product
code
Product [3 a-l]
Time
[h]
Yield[b]
[%]
1
a
12
94
2
b
14
89
Figure
2.
(a)
PXRD
and
simulated XRD spectra, (b) XPS full survey spectra, (c) DRS plots for band gap
assessment and (d) Hysteresis (M-H) curve of Fe-Zn BDC BMOF.
3
4
c
14
13
90
93
d
5
6
e
10
15
97
89
f
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Conflict of interest
7
g
13
13
85
91
The authors declare no conflict of interest.
Keywords: Metal-organic frameworks• photocatalysis•
Bis(indolyl)methanes• dye degradation•
8
h
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[40] M. Shiri, M. A. Zolfigol, H. G. Kruger, Z. Tanbakouchian, Chem. Rev.
2010, 110, 2250–2293.
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Table of Content
A new bimetallic metal organic framework BMOF (Fe-Zn BDC) is synthesisd using Fe and Zn as metal
nodes with 1, 4-benzenedicarboxylic acid as linker molecule. BMOF showed superior catalytic activity
in organic transformation of indoles and aromatic benzaldehydes into bis(indolyl)methane with high
product yield of ca. 94%. In addition, photocatalytic degradation of methylene blue with efficiency of ca.
5
7% in 90 minutes under visible light irradiation was also achieved.
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