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Zn-BTC MOF as an Adsorbent for Iodine Uptake and Organic Dye

Degradation
Abani Sarkar, Amit Adhikary,* Arnab Mandal, Tonmoy Chakraborty, and Debasis Das*
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ABSTRACT: A porous MOF, [{Zn3(BTC)2(H2O)3}·2.5H2O]n

Downloaded via VIRGINIA COMMONWEALTH UNIV on May 31, 2023 at 17:40:56 (UTC).

(H3BTC = 1,3,5-benzenetricarboxylic acid) was synthesized by

heating ZnCl2 and H3BTC in DMF at pH 8.2. A single-crystal
XRD study reveals a 3D polymeric unit constructed by
paddlewheel SBUs. The title MOF displays remarkable iodine
uptake in both water and hexane medium (84% and 74%,
respectively). The synthesized MOF also reveals heterogeneous
catalytic activity toward rhodamine B (RhB) (degradation
efficiency 85%) and methylene blue (MB) (degradation efficiency
79%) under visible light in the presence of H2O2.

■ INTRODUCTION
Metal−organic frameworks (MOFs) have been continuously
attracting much attention because of their appealing structural
features as well as their potential applications in gas storage,
guest molecule capture, dye degradation, sensing, heteroge-
neous catalysis, etc.1−5 The topology of MOFs is mainly
dependent on the assembly of metals and organic ligands. The
construction of MOFs starting from a simple ligand and metal
ion do not always follow a preprogrammed design
procedure.6−8 However, rational observations of reaction
outcomes can give a hint to the reaction secrets that help to
develop the desired product. The organic ligand 1,3,5-
benzenetricarboxylate (BTC)3− is one of the most versatile
ligands for the construction of MOFs due to its various binding
sites, with a coordination mode in all three directions.9 The
most popular example of a MOF constructed by the (BTC)3−
unit is [Cu3(BTC)2(H2O)3]n (HKUST-1),10 which is highly
stable, having a porosity of 40%. Since the discovery of
HKUST-1, numerous MOFs have been synthesized to replace
reaction of ZnCl2 and H3BTC in a 1:1 ratio in DMF resulted
in [NMe2][Zn(BTC)][DMF].16 Close inspection of this
structure reveals that each BTC3− ligand holds four Zn2+
cations, where two carboxylate groups each hold one Zn2+
cation and one carboxylate group holds two Zn2+ cations. To
get a MOF isostructural with HKUST-1, each carboxylate
group of each BTC3− ligand must hold two Zn2+ cations
(Figure S1 in the Supporting Information). Therefore, two
variations were employed: mole ratio and pH. Variation of the
metal:ligand ratio does not alter the reaction outcome.
However, the pH of the solution plays a crucial role here.
The pH of the solution of reactants for the formation of a
[NMe2][Zn(BTC)][DMF] solution was found to be ∼5.9.
The pH of the solution was varied to get the desired product.
Finally, a single crystal of Zn-BTC MOF was observed at pH
8.2 by adjusting the pH using triethylamine. The optimized
synthesis procedure of Zn-BTC MOF was as follows: ZnCl2
and H3BTC were heated at 75 °C in a 1:1 mole ratio in DMF.
Zn-BTC MOF crystallized in the cubic space group Fm3̅m
(Table S2 in the Supporting Information).

■
the copper metal ion with other transition-metal ions,
especially with Zn2+ to give a MOF isostructural with
EXPERIMENTAL SECTION
HKUST-1.11−15 Until now no single crystal has been
successfully grown with Zn2+ mainly due to the thermody- Materials and Physical Methods. All reagents were purchased
namic stability and the entropy factor. Entropy affects the from commercial sources (Merck India) and used as received. All
other chemicals used were of AR grade. All of the solvents were
configurational assembly of the MOF building units and obtained from commercial sources and dried by standard procedures
therefore affects the thermodynamic stability. Therefore, it is a
challenging task to find out the mystery behind the formation
of Zn@HKUST-1. To the best of our knowledge, for the first Received: August 12, 2020
time we have grown a single crystal of a MOF with Zn2+ that is Revised: October 15, 2020
isostructural with HKUST-1, i.e. [{Zn3(BTC)2(H2O)3}· Published: November 2, 2020
2.5H2O]n (Zn-BTC), more than two decades after the
discovery of HKUST-1. The synthesized MOF also has the
ability to encapsulate iodine and degrade dyes. Initially, the

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.cgd.0c01015

7833 Cryst. Growth Des. 2020, 20, 7833−7839
Crystal Growth & Design pubs.acs.org/crystal Article

before use. Elemental analyses (C, H, and N) were performed using a Table 1. Crystal Parameters for Zn-BTC
PerkinElmer 2400 series II CHN analyzer. The electronic absorption
spectra (800−240 nm) in methanol solution were collected with a CCDC no. 1962948
Shimadzu UV-3101PC spectrophotometer. The single-crystal analysis empirical formula C36H34O35Zn6
was carried out with a Bruker AXS D8 QUEST ECO diffractometer formula wt 1406.79
equipped with a Mo-target rotating-anode X-ray source and a graphite temp/K 292(2)
monochromator (Mo Kα, λ = 0.71073 Å). IR spectra as KBr pellets cryst syst cubic
(4000−500 cm−1) were recorded using a PerkinElmer RXI FT-IR space group Fm3̅m
spectrophotometer. TGA experiments were carried out with a SDT Q
a (Å) 26.5844(8)
Series 600 Universal VA.2E from TA Instruments in the range 25−
b (Å) 26.5844(8)
600 °C. Powder X-ray diffraction (PXRD) analysis was carried out on
a Bruker D8 AVANCE instrument. A gas sorption study was carried c (Å) 26.5844(8)
out using an ASAP 2020 instrument by Micromeritics. DLS studies α (deg) 90
were carried out with a DLS Malvern particle size analyzer (Model β (deg) 90
No. ZEN 3690ZETASIZER NANO ZS 90). γ (deg) 90
Synthesis of [{Zn3(BTC)2(H2O)3}·2.5H2O]n (1). A 42 mg portion volume (Å3) 18788.0(17)
(0.2 mmol) of H3BTC and 54.4 mg (0.4 mmol) of ZnCl2 were placed Z 8
in a round-bottomed flask (Scheme 1). Then 8 mL of DMF was ρcalcd (g/cm3) 0.987
μ (mm−1) 1.567
Scheme 1. Syntheses of Zn-MOF F(000) 13140.0
radiation Mo Kα (λ = 0.71073)
2θ range for data collection (deg) 5.082−34.496
no. of rflns collected 28572
no. of indep rflns 339 (Rint = 0.0901, Rσ = 0.0116)
no. of data/restraints/params 339/0/40
goodness of fit on F2 1.180
final R indexes (I ≥ 2σ(I)) R1 = 0.0900, wR2 = 0.2619
final R indexes (all data) R1 = 0.0997, wR2 = 0.2827

from colorless to dark brown. To carry out the iodine adsorption

experiment in the solution phase, a 100 mg sample was added to
water. Iodine is poorly soluble in water, and so we added some solid
placed in it. The pH of the solution was maintained at 8.2 by a
potassium iodide to the solution. In another test, 100 mg of the
dropwise addition of triethylamine. The solution was stirred with
sample was added to a hexane solution of iodine. The complete
heating at a temperature of 75 °C using a condenser. After 8 h the
experiment was done at room temperature for 12 h. The iodine
solution was kept at room temperature. After a few days a colorless
absorption efficiency (E (%)) was calculated using following equation:
diffractable single crystal was found at the bottom of the container.
E (%) = (C0 − Ce)/C0 × 100%, where C0 and Ce are the initial iodine
Yield: ∼62% based on H3BTC. Anal. Calcd for C36H34O35Zn6: C,
concentration and equilibrium iodine concentration, respec-
30.47; H, 2.42. Found: C, 30.61; H, 2.32. IR (4000−400 cm−1; KBr
tively.21−23
pellet, ν/cm−1) 3443 (br s), 1628 (S), 1525 (W), 1422 (W), 1376
Photocatalytic Dye Degradation. The photocatalytic dye
(S), 1091 (W), 766 (W), 703 (W), 543 (W).
degradation was investigated under visible-light irradiation using a
X-ray Crystallography. A single crystal of Zn-BTC was picked up
500 W halogen lamp as the light source. To perform the study, we
with a nylon loop and was mounted on Bruker AXS D8 QUEST ECO
used the two common dyes rhodamine B (RhB) and methyleneblue
diffractometer equipped with a Mo-target rotating-anode X-ray source
(MB). The whole study was performed at room temperature. For
and a graphite monochromator (Mo Kα, λ = 0.71073 Å). Final cell
each experiment, 2 mg of Zn-BTC was added to a 50 mL aqueous
constants were obtained from least-squares fits of all measured
solution of the dye (10 mg/L for RhB and MB). The whole solution
reflections. Intensity data were corrected for absorption using
was mixed with H2O2 (100 mM) and stirred for 10 min. Then the
intensities of redundant reflections. The structures were solved by
mixture was irradiated under visible light. During the whole
direct methods and subsequent difference Fourier techniques. The
experiment the reaction mixture was constantly stirred. At 10 min
crystallographic data are given in Table 1. The Siemens program
intervals a UV−vis spectrum was measured from 200 to 900 nm of the
SHELXL-2016/6 was used for the refinement.17−19 All non-hydrogen
clear solution after centrifugation up to 1.5 h. From the UV−vis study
atoms were refined anisotropically. Hydrogen atoms were placed at
it was found that photocatalytic degradation follows a pseudo-first-
calculated positions and refined as riding atoms with isotropic
order kinetics. All of the graphs were plotted using the equation
displacement parameters.
ln(C0/Ct) = kt for RhB and MEB, where Ct = concentration of dye at
Powder X-ray Diffraction. Powder X-ray diffraction (PXRD)
time t, C0 = concentration of dye at t = 0, and k is the apparent first-
measurements were performed on a Bruker AXS D8 Advance X-ray
order rate constant.24−29

(Cu Kα radiation, λ = 1.5406 Å) diffractometer in the 5−50° 2θ range
using a 0.02° step size per second. The sample was prepared by
making a thin film from the finely powdered sample (50 mg) over a
glass slide.
Reducing the Particle Size of Zn-BTC by a Hand-Grinding
Method. A 100 mg portion of the synthesized Zn-BTC was taken
separately in a mortar. It was then ground manually for 1 h using a
pestle. The produced nanosized CPs were directly used for
experiments and characterization.20
Iodine Uptake in Water and Cyclohexane Solutions. The
iodine uptake experiment was carried out in the vapor phase as well as
in the solution phase. In the vapor phase 100 mg of Zn-BTC was
placed in a iodine chamber at 65 °C. After 12 h Zn-BTC changes
7834
■
RESULTS AND DISCUSSION
FT-IR Spectroscopy. The Zn-MOF is prepared by using
BTC and the ZnCl2 salt, where BTC acts as a linker and the
ZnCl2 salt acts as a holder. Zn-BTC has been characterized by
FT-IR spectral analyses. An asymmetric stretching vibration at
1640 cm−1 is ascribed to the carboxylate group, and an
asymmetric stretching vibration at 1380 cm−1 is ascribed to a
C−C vibration due to the presence of an aromatic ring. A
stretching vibration at 1004 cm−1 is due to the presence of a
C−O bond, and the vibration at 755 cm−1 is related to the
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Cryst. Growth Des. 2020, 20, 7833−7839
Crystal Growth & Design
Figure 1. Structure of the Zn-BTC MOF illustrating two types of
pores. Color code: C, gray; O, red; Zn, green.
bending of a C−H bond. After completion of the iodine
adsorption experiment in water we collected the FT-IR
spectrum of Zn-BTC and observed no change in the FT-IR
spectrum (Figure S1 in the Supporting Information).
Single-Crystal X-ray Diffraction Studies. The three-
dimensional structure is constructed by dinuclear zinc
carboxylate paddlewheel units where water molecules reside
on axial positions (Figure 1). Each Zn(II) atom has a
pentagonal geometry, coordinated with four carboxylate
groups of four BTC3− units and one water molecule occuping
the fifth position. The distortion (τ)30 of the square-pyramidal
geometry was found to be zero.
The distance between intermetallic zinc atoms of the
paddlewheel is 2.981(2) Å. Paddlewheel units are further
connected by carboxylate bridging of BTC3− units to form a
three-dimensional polymeric structure. The structure contains
two types of mesopores. In contrast to the famous HKUST-14,
which has a pore size of 8.25 × 8.25 Å2, our MOF has a pore
size of 8.36 × 8.36 Å2. If we consider the square shape of the
pore, the edge of the square is 8.25 Å for HKUST-1 and 8.36 Å
for the Zn-BTC MOF. Here we have considered the point of
the square as a carboxylate oxygen. The distance is measured as
one carboxylate oxygen at one end to another carboxylate
oxygen at another end. If we consider the metal center as the
Figure 2. Pore sizes of Zn-BTC and HKUST-1 MOFs.
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Figure 3. Honeycomb-like structure of the Zn-BTC MOF along the
[111] direction.
Figure 4. Photographs of Zn-BTC before (a) and after (b) adsorption
of iodine vapor.
point of the square, then the pore size of HKUST-1 is 11.31 ×
11.31 Å2 and the pore size of the Zn-BTC MOF is 11.18 ×
11.18 Å2 (Figure 2).
Along the [111] direction, a large hexagonal-shaped
honeycomb-like arrangement can be seen (Figure 3). The
nanoscale morphology of the material was then examined by
scanning electron microscopy (SEM). After hand grinding, a
needle-shaped morphology was observed in the nano range
(Figure S4 in the Supporting Information).
Iodine Uptake in Aqueous and Cyclohexane Sol-
utions. The presence of radioactive toxic gases and dyes in the
environment damages living beings.31−34 To prevent this
damage, research has focused on the preparation of selective
porous materials, which can absorb toxic gases form solution
phases as well as gas phases.35−37 Currently dissolution of
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Cryst. Growth Des. 2020, 20, 7833−7839
Crystal Growth & Design
Figure 5. visual color change of iodine solution in (a) hexane and (b) aqueous medium.
Figure 6. Time-dependent UV−vis spectra of (a) water and (b)
hexane solutions of iodine soaked in the Zn-BTC MOF.
Figure 7. Photocatalytic degradation using visible light of the dyes (a)
RhB and (b) MEB.
Figure 8. Photocatalytic degradation using visible light of the dyes (a)
RhB and (b) MB.
spent fuel produces radioactive iodine such as 129I2 and 125I2 in
the environment; due to their long toxic radioactive half-life
(1.57 × 107 years), it hampers human health.38 In general
silver-based zeolites and aerogels are capable to capture
radioactive iodine from solution to some extent but now
scientists are focusing on preparing a material that has a
selective removal efficiency of iodine from water even at very
small concentrations.39
To calculate the surface area of the MOF, an N2 sorption
study was executed and a BET surface area of 252 m2/g was
found (Figure S5 in the Supporting Information). Due to the
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Figure 9. Recycling experiments up to the second run for the
photocatalytic degradation of (a) RhB and (b) MEB by the Zn-MOF.
Figure 10. Proposed mechanism for activation of H2O2 and
degradation of the dyes.
large pores of the MOF and significant surface area, we used
our MOF for capture of the environmentally hazardous iodine.
Before the experiment, crystals were ground for the iodine
adsorption study. A dynamic light scattering (DLS) measure-
ment was carried out in water to check the size of the particles.
From the DLS study it was observed that the average size of
the dispersed Zn-BTC MOF is 415 nm, which is close to a
nano form (Figure S6 in the Supporting Information). The
powder X-ray diffraction (PXRD) pattern of the ground
sample is well matched with the simulated PXRD pattern of
the Zn-BTC MOF (Figure S7 in the Supporting Information).
I2 adsorption experiments have been executed both in vapor
phase and in the solution phase using the crystalline powder of
the synthesized MOF. Before the I2 adsorption experiments
were started, the powdered sample was activated at 80 °C for
12 h under vacuum. The initial experiment was carried out on
the gas phase. In a sealed vessel was placed the MOF sample
along with solid iodine crystal beads. After the experiment, the
Zn-BTC MOF changes from very faint yellow to deep brown
and to almost black (Figure 4). The color change can be
detected easily by the naked eye. Thermogravimetric analysis
(TGA) was performed to check the iodine loading. The
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Cryst. Growth Des. 2020, 20, 7833−7839
Crystal Growth & Design
maximum I2 uptake on the Zn-BTC MOF was ∼20 wt %.
There was a weight loss of ∼55% from 40 to 300 °C for the
MOF sample, while the I2@MOF showed a weight loss of ∼75
wt % from 40 to 300 °C (Figure S8 in the Supporting
Information). Thus, approximately 20 wt % of I2 was adsorbed
by the MOF, which can be calculated as ∼400 mg of I2 per
gram of MOF. An FT-IR and powder XRD study was carried
out before and afterthe I2 adsorption experiment. No major
spectroscopic shift was observed after iodine loading,
confirming the stability of the framework (Figures S1 and S8
in the Supporting Information).
Complementarily, the MOF also reveals I2 uptake in the
solution phase. I2 was dissolved in n-hexane and aqueous
solutions and the MOF was added to them. After the the MOF
was added, the purple color of the n-hexane solution gradually
faded with time. After 5 h, there was almost no change in color
of the solution, indicating that an equilibrium was reached
(Figure 5a). In aqueous medium the MOF was added to a KI3
solution. A drastic color change from dark red to a lighter color
was found in aqueous medium after 3 h (Figure 5b). A time-
dependent UV−vis study was performed, which revealed a
gradual decrease in the concentration of iodine in both n-
hexane and water media (Figure 6).
The percentage of iodine uptake was calculated from a Ct/C0
vs time plot (Figure S9 in the Supporting Information): ∼70%
and ∼80% removal efficiency was achieved from the
calculation in n-hexane and water, respectively (Figure S10
in the Supporting Information). The iodine can be easily
separated from the MOF upon unloading the I2@MOF in
organic solvents. After the iodine-loaded samples were soaked
in fresh ethanol, the MOF changed gradually from dark brown
to red-brown and, correspondingly, the ethanol solution
became dark from the initial colorless. After completing one
cycle (Zn-MOF → I2@Zn-MOF → Zn-MOF), we carried out
an SEM experiment. From these studies we have found a
similar needlelike shape of Zn-BTC after one cycle (Figure S12
in the Supporting Information).
Determination of the Amount of Iodine by a
Titrimetric Method. Energy-dispersive spectroscopy (EDS)
analysis results show the presence of iodine species, which
clearly confirms the uptake of iodine (Figure S11 in the
Supporting Information). To measure the maximum amount
of adsorbed iodine, the MOF was placed in a iodine chamber
and kept in an incubator at 60 °C for 48 h. The iodine-loaded
MOF was then kept at room temperature. Then the iodine-
loaded MOF was added to KI-containing water and the
solution was filtered. The filtrate was titrated against a
standardized Na2S2O3 solution (details of the experiments
are given in the Supporting Information). A maximum of 10.09
mg of I2/50 mg of the MOF, i.e. ∼20% of iodine, can be
adsorbed by the MOF. The percentage of I2 uptake compared
well with results in the literature (Table S2).
Photocatalytic Dye Degradation Study. In recent years,
MOFs have been widely used not only for the capture of toxic
radioactive iodine but also for wastewater treatment. Organic
dyes such as rhodamine B (RhB) and methylene blue (MEB)
are the most common organic pollutants of water.40−42
Degradation of an organic dye by a MOF goes mainly through
two different routes: chemical reaction at the surface of the
MOF and photocatalytic degradation in the presence of an
oxidizing agent such as H2O2 using the MOF as a catalyst. The
solid-state UV spectrum of the synthesized Zn-BTC was
measured in room temperature, as shown in Figure S137 in the
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Supporting Information. The optical band gap energy was
calculated according to the equation (αhν)2 = (hν − Eg),
where where α, ν, and Eg are the absorption coefficient, the
frequency of the incident photon, and the energy gap of the
material, respectively. The band gap energy was estimated to
be 2.84 eV (Figure S13 in the Supporting Information), which
falls in the visible region (>3.1 eV for the UV region). As the
Zn-BTC MOF was insoluble in water, a heterogeneous
photocatalytic process using visible light was investigated.
The photocatalytic activity of the Zn-BTC MOF was
performed using the dyes RhB and MB, which show
absorption maxima at λmax = 553 and 662 nm, respectively.
Several control experiments were carried out to explain the
nature of the photocatalytic reaction. Two sets of experiments
for each dye were performed: with the Zn-BTC MOF under
visible light and with H2O2 under visible light (Figure 7). The
change in absorption peaks in the absence of either the Zn-
BTC MOF or H2O2 was not significant, which proves that this
catalytic oxidation occurs via the generation of a highly reactive
oxidizing species (OH•), produced by both the Zn-MOF and
H2O2 under visible-light irradiation.
The corresponding UV scans of the dyes RhB and MEB are
shown in Figure 8. The reaction follows pseudo-first-order
kinetics. as shown by the equation ln(C0/Ct) vs time, and the
rate constants were found to be 0.0095 and 0.0084 min−1 for
RhB and MEB, respectively, which is far greater than those of
the control experiments (Figure S14 in the Supporting
Information). Recycling experiments of RhB and MEB
degradation were performed under visible light irradiation
(Figure 9), and they show that Zn-MOF keeps its photo-
catalytic activity up to two cycles with a slight loss in the
catalytic activity. However, in the case of the third and fourth
cycles the catalytic efficiency of the MOF abnormally
decreases, which may be due to the degradation of MOF
itself after several attempts of the recycling process. Both
powder XRD and scanning electron microscope (SEM) studies
suggest that after one cycle the crystalline morphology remains
the same (Figure S15 in the Supporting Information).
The degradation efficiencies were found to be 85% and 79%
for RhB and MEB, respectively (Figure 7), within 90 min using
0.1 M H2O2. The corresponding UV scans of the dyes RhB
and MB are shown in Figure S13 in the Supporting
Information The reaction follows pseudo-first-order kinetics,
as shown by the equation ln(C0/Ct) vs time, and the rate
constants were found to be 0.0095 and 0.0084 min−1 for RhB
and MEB, respectively (Figure S14 in the Supporting
Information), which are far greater than those of the control
experiments. The mechanism of the degradation of dyes can
easily be established by a simple experiment, in which the same
experiment was done using tert-butyl alcohol, which can act as
a radical trapper. In this case a hydroxyl radical (OH•) acts as
the main active species during the degradation process. In the
presence of tert-butyl alcohol the degradation efficiency
abnormally decreases, as shown in Figure S16 in the
Supporting Information. On the basis of this experiment, we
propose the most probable mechanism for the degradation of
dyes shown in Figure 10.
■ CONCLUSIONS
In conclusion, we have succeeded in replicating the zinc
version of [M3(BTC)2(H2O)3]·xH2O (HKUST-1), as deter-
mined by a single crystal structure determination. Therefore,
the synthesized MOF will open up the possibility of a library of
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Cryst. Growth Des. 2020, 20, 7833−7839
Crystal Growth & Design
HKUST-1 species with other transition-metal ions and their
varieties of properties. Our synthesized MOF is also able to
adsorb iodine as well as reveals photocatalytic dye degradation
properties, which will help to protect ocean life as well as water
and air pollution.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.cgd.0c01015.
Experimental section, crystal structure, and EDX, TGA,
DLS, and other characterization data as described in the
text (PDF)
Accession Codes
CCDC 1962948 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■
AUTHOR INFORMATION
Corresponding Authors
Amit Adhikary − Department of Chemistry, University College
of Science, University of Calcutta, Kolkata 700009, India;
orcid.org/0000-0002-1435-4585; Email: aadhikary87@
gmail.com
Debasis Das − Department of Chemistry, University College of
Science, University of Calcutta, Kolkata 700009, India;
orcid.org/0000-0003-4570-7168;
Email: dasdebasis2001@yahoo.com
Authors
Abani Sarkar − Department of Chemistry, University College of
Science, University of Calcutta, Kolkata 700009, India
Arnab Mandal − Department of Chemistry, University College of
Science, University of Calcutta, Kolkata 700009, India
Tonmoy Chakraborty − Department of Chemistry, University
College of Science, University of Calcutta, Kolkata 700009,
India; orcid.org/0000-0002-2319-443X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.cgd.0c01015
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.S. is thankful to the CSIR-JRF for providing a fellowship
(sanction number 09/028(1005)/2017-EMR-1). A.A. thanks
the UGC for the DS-Kothari fellowship of award no. F.4-2/
2006 (BSR)/CH/17-18/0182. Financial assistance from the
DST-WB (sanction memo no. 327(sanc)/ST/P/S&T/15G-8/
2016 dt 06/03/2019) to D.D. is duly acknowledged.
■
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