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Anti-biofouling organic-inorganic hybrid membrane for water
treatment
Ajay K. Singh1, Priyanka Singh
2, Sandhya Mishra
2, Vinod K. Shahi
*1
1 Electro-Membrane Processes Division,
2Salt and Marine Chemicals Division,
Central Salt & Marine Chemicals Research Institute, Council of Scientific & Industrial
Research (CSIR), G. B. Marg, Bhavnagar-364002 (Gujarat) INDIA Tel: +91-278-2569445; Fax: +91-278-2567562/2566970; E-mail: [email protected];
S1. Biosafety precautions during the antibacterial and antifungal activity:
Bacteria/fungi are potentially hazardous and care should be taken while working with them.
Standard bio safety lab techniques were followed while handling bacteria/fungi and various
media. Gloves were used during all experimentation, and any accidental spills were
immediately sterilized using 70 % isopropanol/water followed by bleach. The work area was
also sterilized with 70 % isopropanol/water after completion of work. Unused media and
bacterial suspensions were first deactivated with commercial bleach for 1 h before being
disposed in bio safety bags. All material that had come in contact with bacteria (e.g., pipette
tips, tubes, agar plates, etc.) was also thrown in biosafety bags in tightly closed bins. Bio
safety bags were autoclaved for 2 h before final disposal.
S2. Water uptake measurements
The swelling ratio (Sw) for nanocomposite membranes was determined by water uptake
measurement using following equation (1):
)1(100)(
(%)
D
Dsw
m
mmS
Where mD is weight of dry membrane and ms is weight of wet membrane after wipe out
surface water by absorbing paper.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
S3. Dimensional changes
Dimensional changes of the membranes were investigated by square pieces of the membrane
was immersed in distilled water for 24 h, the surface was wiped and samples were dried at 70
C for 12 h. The thicknesses of membranes were measured by the Mitutoyo digimatic
micrometer. Length and width of membranes were measured by millimetre scale. Volume
fraction (Φ) of water was estimated by equation (2)
)2(zyx
zoyooxzyx
LLL
LLLLLL
Where, zyx LLL ,, may be the length/width/thickness of the swollen membrane and subscript
‘o’ represent the dimension in dry condition.
S4. Ion exchange capacity, surface charge concentration and void porosity
measurements
For determining ion exchange capacity (IEC), accurately weighted dry membrane was dipped
in 1.0 mol/L HCl for 24 h. Afterward the membrane was washed with distil water and then
immersed in 1.0 mol/L NaCl for 24 h. Exchanged H+ was titrated against 0.001 mol/L NaOH
solution using phenolphthalein indicator. The IEC was calculated according to the equation
(3).
)3().( 1
dry
solNa
W
VCmembranedrygmequivIEC
Where Wdry is the weight of the membrane sample under dry condition.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
With the help of IEC and water uptake capability determined the net surface charge density
(m) in the membrane was determined in unit of (moles of ionic sites)/ (unit volume of wet
membrane) by using the equation (4).
)4()(w
dm IEC
Where IEC is expressed in equivalent per gram of dry membrane, d the density of dry
membrane and τ denotes membrane voids porosity. Void porosity (volume of free water
within membrane per unit volume of wet membrane) can be obtained by using the equation
(5).
)5(1 w
w
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S1 1H NMR spectra (a) (COT) 5-(4-chlorophenyl)-1, 3, 4-oxadiazole-2-thiol in d6-
DMSO; (b) 2-(2-chloroethylthio)-5-(4-chlorophenyl)-1,3,4-oxadiazole in d6-DMSO; (c)
APDSMO in d6-DMSO.
Ajay
AJS -4
1 H nmr in Dmso, 200MHzYour comment here
(c)
(b)
ppm (t1)1.02.03.04.05.06.07.08.0
(a)
1 2 3
4 5 6 7
a
b c
d e
f g
h+i j+k+l
m n
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S2 13
C NMR spectra APDSMO in D2O.
(a+b)
(c+d)
(e)
(f+g)
(DMSO)
(h)
(i)
(j)
(n) (o)
(m) (l)
(p+q)
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S3 Synthesis route for hybrid membranes and TEM images of MO-6 membrane (a, b,
and c) at different magnifications.
(a) (b) (c)
2 nm 5 nm 10 nm
1 m
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S4 X-ray diffraction patterns for different hybrid membranes.
10 20 30 40 50 60
0
50
100
150
200
250
300
350
400
MO-6
MO-10
MO-3
Counts
/s
o2Theta
20 nm 20 nm
(A)
Hydrolysed
APDSMO
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S5 SEM image of (a-c) hydrolysed APSMO (low, medium and high resolution,
respectively); (d) MO-5 membrane.
(c) (e)
(j) (k)
(i)
(a)
(c)
(b)
(d)
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S6 TGA curve of different hybrid membranes.
100 200 300 400
20
40
60
80
100
%
weig
ht
loss
Temperature oC
MO-3
MO-5
MO-6
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S7 DSC spectra for MO-6 nanocomposite membranes.
100 200 300 400 500
-1.0
-0.5
0.0
0.5
1.0
R
efe
ren
ce te
mp
(oC
)
Sample temp (oC)
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S8 DMA thermogram for MO-6 membrane at 10 oC/ minute heating rate in N2
atmosphere.
50 100 150 200 250 300
0.0
0.1
0.2
0.3
0.4
Sto
rag
e m
od
ulu
s
Temperature oC
MO-6
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S9 Weight loss (%) for different hybrid membranes after treatment in 5% aqueous
NaOCl solution at 80 C for different time intervals.
0 10 20 30 40 50 60 70
0
1
2
3
4
5
% w
eig
ht
loss
Time (h)
MO-6
MO-5
MO-4
MO-3
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S10 Weight loss (%) for different hybrid membranes after treatment with different
concentrations of: (A) HCl and (B) H2SO4 for 30days.
1 2 3 4 5 6 7 8
0
2
4
6
8
10
12
14
16
18
20
22
24
%
we
igh
t lo
ss
Molar concentration of Sulphuric acid
MO-6
MO-5
MO-4
MO-3
1 2 3 4 5 6
0
2
4
6
8
10
12
14
16
18
% w
eig
ht
loss
Molar concentration of hydrochloric acid
MO-6
MO-5
MO-4
MO-3
(a)
(b)
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S11 Weight loss (%) for hybrid membranes in different organic solvents.
0.30 0.35 0.40 0.45 0.50 0.55 0.60
2
3
4
5
6
7
%
we
igh
t lo
ss
MO-x
NMP
DMF
DMSO
THF
Fig. S12 Ion exchange capacity (IEC) and water uptake values for different hybrid
membranes.
(d)
(g) (h)
25 30 35 40 45 50 55 60 65
1.0
1.1
1.2
1.3
IEC
% water
PVA/ APDSMPO
IEC
6
8
10
12
14
% W
ate
r up
take
APDSMO content (%)
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011
Fig. S13 24 h grown bacteria for membrane antifouling application (OD600=2.3299).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2011