1 Rhodamine functionalized mesoporous silica as chemosensor for efficient sensing of Al 3+ , Cr 3+ and Fe 3+ ions and their removal from aqueous medium Debdas Singha, a Trisha Das, a Lanka Satyanarayana, b Partha Roy* c and Mahasweta Nandi* a a Integrated Science Education and Research Centre, Siksha Bhavana,Visva-Bharati University, Santiniketan-731235, India E-mail: [email protected] b Analytical Chemistry Department, CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad 500007, India c Department of Chemistry, Jadavpur University, Jadavpur, Kolkata-700 032, India E-mail: [email protected]; [email protected] Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
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1
Rhodamine functionalized mesoporous silica as chemosensor for efficient
sensing of Al3+
, Cr3+
and Fe3+
ions and their removal from aqueous medium
Debdas Singha,a Trisha Das,
a Lanka Satyanarayana,
b Partha Roy*
c and Mahasweta
Nandi*a
aIntegrated Science Education and Research Centre, Siksha Bhavana,Visva-Bharati University,
Santiniketan-731235, India
E-mail: [email protected]
bAnalytical Chemistry Department, CSIR-Indian Institute of Chemical Technology, Uppal Road,
Hyderabad 500007, India
cDepartment of Chemistry, Jadavpur University, Jadavpur, Kolkata-700 032, India
E-mail: [email protected]; [email protected]
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
2
Fig. s1 FT-IR spectra of (a) SBA-15, (b) APTES functionalized SBA-15, (c) TFMS, (d) RFMS
and (e) Al-bound RFMS.
Fig. s2 29
Si MAS NMR spectra of TFMS and RFMS.
4000 3000 2000 1000
Tra
ns
mit
tan
ce
(a
.u.)
Wavenumber (cm-1)
a
b
c
d
e
-150 -100 -50 0
RFMS
Chemical shift (ppm)
-150 -100 -50 0
TFMS
Chemical shift (ppm)
3
Fig. s3 13
C CP MAS NMR spectra of TFMS and RFMS.
Fig. s4 Thermogravimetric analysis of (a) SBA-15, (b) 3-APTES loaded SBA-15, (c) TFMS and
(d) RFMS.
180 150 120 90 60 30 0
RFMS
Chemical shift (ppm)
180 150 120 90 60 30 0
TFMS
Chemical shift (ppm)
200 400 600 80070
80
90
100
Temperature (oC)
Weig
ht
loss (
%)
d
c
b
a
4
Fig. s5 UV-vis spectra of RFMS (0.05 g/L) in absence and in the presence of different metal
ions (120 μM) in water/ethanol (14:1, v/v) at room temperature.
Fig. s6 Plot of absorbance of RFMS (at 530 nm) versus concentration of Al3+
ion.
5
Fig. s7 Plot of absorbance of RFMS (at 530 nm) versus concentration of Cr3+
ion.
Fig. s8 Plot of absorbance of RFMS (at 530 nm) versus concentration of Fe3+
ion.
6
Fig. s9 Fluorescence spectra of RFMS (0.05 g/L) in absence and in the presence of different
metal ions (120 μM) in water/ethanol (14:1, v/v) at room temperature.
Fig. s10 Plot of fluorescence intensity of RFMS (at 550 nm) versus concentration of Al3+
ion.
520 560 600 640 680
0.0
3.0x106
6.0x106
9.0x106
1.2x107
1.5x107
Flu
ore
sc
en
ce
In
ten
sit
y (
a.u
.)
Wavelength (nm)
Fe3+
Al3+
Cr3+
RFMS
Na+
Mg2+
Ca2+
Cu2+
Ni2+
Hg2+
Pb2+
Zn2+
Cd2+
Mn2+
Co2+
0 20 40 60 80
0.0
5.0x106
1.0x107
F
luo
rescen
ce In
ten
sit
y (
a.u
.)
Concentration (M)
7
Fig. s11 Plot of fluorescence intensity of RFMS (at 550 nm) versus concentration of Cr3+
ion.
Fig. s12 Plot of fluorescence intensity of RFMS (at 550 nm) versus concentration of Fe3+
ion.
0 20 40 60 80
0.0
5.0x106
1.0x107
1.5x107
F
luo
rescen
ce In
ten
sit
y (
a.u
.)
Concentration (M)
0 20 40 60 80
0.0
9.0x105
1.8x106
2.7x106
F
luo
rescen
ce In
ten
sit
y (
a.u
.)
Concentration (M)
8
Determination of LOD of RFMS:
Limit of detection (LOD) for our probe has been determined by 3σ method by the following
equation: DL = K* Sb1/S. Where K = 2 or 3 (3 in this case); here Sb1 is the standard deviation
of the blank solution (Fig. s13); and S is the slope of the calibration curve obtained from Linear
dynamic plot of F.I. vs [M3+
] µM (Fig. s14, s15 and s16).
Here Sb1= 949.1195, S= 526941.52 (for Al3+
), 310077.16 (for Cr3+
) and 3939.36 (for Fe3+
).
LOD of Al3+
= (3 × 949.1195)/ (541803.820) = 5.40 nM
LOD of Cr3+
= (3 × 949.1195)/ (448979.334) = 9.18 nM
LOD of Fe3+
= (3 × 949.1195)/ (4566.881) = 722.80 nM
Fig. s13 Determination of Sb1 of the blank, RFMS in solution.
0 7 14 21 28 350.00
1.50x104
3.00x104
4.50x104
6.00x104
7.50x104
9.00x104
Concentration of RFMS (mg/L)
Flu
ore
sc
en
ce
In
ten
sit
y (
a.u
.)
9
Fig. s14 Linear dynamic plot of F.I. (at 550 nm) vs. [Al3+
] for the determination of S (slope).
Fig. s15 Linear dynamic plot of F.I. (at 550 nm) vs. [Cr3+
] for the determination of S (slope).
-2 0 2 4 6 8 10 12 14 16
0
1x106
2x106
3x106
4x106
5x106
6x106
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A -360856.27142 189584.72718
B 310077.15857 23823.03163
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.97996 373617.4903 9 <0.0001
------------------------------------------------------------
Flu
ore
scen
ce In
ten
sit
y (
a.u
.)
Concentration of Cr3+
(M)
0 2 4 6 8 10 12 14 16
0
1x106
2x106
3x106
4x106
5x106
6x106
7x106
8x106
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A 68137.96896 172673.68881
B 526941.51513 21697.02661
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99412 340276.69953 9 <0.0001
------------------------------------------------------------
Flu
ore
sc
en
ce
In
ten
sit
y (
a.u
.)
Concentration of Al3+
(M)
10
Fig. s16 Linear dynamic plot of F.I. (at 550 nm) vs. [Fe3+
] for the determination of S (slope).
Fig. s17 Excited state fluorescence decay behavior of RFMS and and its complexes Al3+
, Cr3+
and Fe3+
ions in ethanol/water mixture (1:14, v/v) at room temperature.
0 500 1000 1500
10
100
1000
Co
un
ts (
log
)
Channel
Prompt
RFMS
RFMS + Al3+
RFMS + Cr3+
RFMS + Fe3+
11
Determination of various cations adsorbed on RFMS by Titrimetric Method
Strength of the stock solutions:
Zn-acetate =1.002 (M/100)
Lead nitrate=1.001 (M/100)
Potassium dichromate=1.004 (N/100)
Na2EDTA = 1.005 (M/100)
Determination of Fe3+
Estimated by direct titration with potassium dichromate solution.
Volume of Potassium dichromate solution need for 25 mLof iron solution = 23.7mL
Volume of Potassium dichromate solution need for 25 mL of iron solution treated with 0.10 g of
RFMS =15.4 mL
Therefore in 25 mL of iron solution Fe3+
present = 0.01328g
After treating with RFMS in 25 ml of iron solution Fe3+
present = 0.00863 g
Amount of Fe3+
adsorbed by 0.10 g of RFMS = 0.00465 g
Determination of Zn2+
Estimated by direct titration with Na2EDTA solution.
Volume of Na2EDTA solution need for 25 mL of zinc solution =23.1 mL
Volume of Na2EDTA solution need for 25 mLof zinc solution treated with 0.10 g of RFMS =22
mL
Therefore in 25 ml of zinc solution, Zn2+
present = 0.01517 g
After treating with 0.10 g of RFMS in 25 mLof zinc solution, Zn2+
present = 0.01445 g
Amount of Zn2+
adsorbed by 0.10 g of RFMS =0.00072 g
Determination of Pb2+
Estimated by back titration of excess Na2EDTA with zinc acetate solution. (25 mL metal ion +
50mLNa2EDTA solution)
Volume of zinc acetate solution need for 25 mL of Pb2+
solution = 25.6 mL
Volume of zinc acetate solution need for 25 mL of Pb2+
solution treated with 0.10 g of RFMS =
26.2 mL
12
Therefore in 25 mL of lead solution Pb2+
present = 0.050333 g
After treating with 0.10 g of RFMS in 25 mL of lead solution Pb2+
present= 0.049827 g
Amount of Pb2+
adsorbed by 0.10 g of RFMS = 0.000503 g
For mixture also 0.10 g of RFMS is taken in every case
Determination of Pb2+
and Fe3+
in a mixture
Iron adsorbed =0.0034 g
Lead adsorbed = 0.00221 g
Determination of Zn2+
and Fe3+
in a mixture
Iron adsorbed =0.00425 g
Zincadsorbed = 0.00121 g
13
Table S1 Comparison of some parameters of some recently published related research works
Sl
No.
Probe Metal ion
analyzed
Excitation
(nm)/
Emission (nm)
Fluorescence
intensity
enhancement
LOD (M)
Linearity
range
Application Removal
efficiency
Maximum
uptake
capacity
Ref
1
N
O
O
N
N
HO
Al3+
, Cr3+
and Fe3+
Colorimetric detection (color
change: colorless to yellow);
absorption band at 425 nm
2.16 × 10−6
(Al3+
), 1.27
× 10−8
(Cr3+
)
and 5.03 ×
10−8
(Fe3+
)
0 to 30 μl
(Al3+
), 0 to 60
μl (Cr3+
) and
0 to 60 μl
(Fe3+
)***
Logic gate --- 20
2
O
N
O
N
N NH
O
OH
N N
Al3+
, Cr3+
and Fe3+
480/583 -- 0.22 × 10−6
(Al3+
),
0.63 × 10−6
(Cr3+
) and
0.14 × 10−6
(Fe3+
)
Not
mentioned
No -- -- 21
3
O
N
O
NH
NH
Al3+
, Cr3+
and Fe3+
502/558 31 (Al)
26 (Cr)
41 (Fe)
1.34 × 10−6
(Al3+
), 2.28
× 10−6
(Cr3+
)
and 1.28 ×
10−6
(Fe3+
)
Not
mentioned
(i) Logic
gate
(ii) Cell
imaging
-- -- 22
4
O
N
O
NH
NH
N
OH
Br
Al3+
, Cr3+
and Fe3+
500/552 98 (Al) 50
(Cr) 38 (Fe)
1.18 × 10−9
(Al3+
), 1.80
× 10−9
(Cr3+
)
and 4.04 ×
10−9
(Fe3+
)
Not
mentioned
Logic gate -- -- 23
5
N
N N
NOH HO
Al3+
, Cr3+
and Fe3+
Colorimetric detection (color
change: colorless to light
yellow); absorption band at
~420 nm
2.8 × 10−7
(Al3+
), 2.5 ×
10−7
(Cr3+
)
and 1.× 10−7
(Fe3+
)
Not
mentioned
Logic gate ---
40
6
N
N
NH
O
N
Zn2+
360/509 -- 1.08 × 10−7
0–6 μM Removal of
metal ion
-- 157.2 mg/g
(adsorption
capacity)
25a
14
*** Stock solution of the metal ion is 1× 10‒3
M
7 N
HO
Al3+
325/427 8.5 17.84 × 10−6
Not
mentioned
Removal of
metal ion
87.4% -- 26
8 HN
HN
O
N
O
O HN
HN
Hg2+
497/552 -- 0.1 × 10−9
1.0–100.0 nM Analysis of
metal ion in
real sample
109.5%
recovery
-- 27a
9
N
HO
CH3
NN
O
O
N
N
Hg2+
500/580 -- 1.5 × 10−8
Not
mentioned
Logic gate -- -- 27b
10 N N H
N
O
N
O
O
N
N
Hg2+
530/589 -- 9.05 × 10−7
0–6 × 10‒5
M (i) Removal
of metal ion
(ii) cell
imaging
-- 115.47 mg/g
(adsorption
capacity)
28
11 RFMS Al3+
, Cr3+
and Fe3+
500/550 145 (Al) 174
(Cr) 30 (Fe)
23.5 × 10−9
(Al3+
), 13.4
× 10−9
(Cr3+
)
and 69.7 ×
10−9
(Fe3+
)
0-15 μM
(Al3+
), 2.5-
12.5 μM
(Cr3+
) and 0-
10 μM (Fe3+
)
Removal of
metal ion
97.28 (Al)
97.06 (Cr)
96.87 (Fe)
11.20 (Al),
19.72 (Cr)
and 21.55
(Fe) mg/g
Present
study
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