supporting information solvents transport performance for ... · yi li,a eric wong,b alexander...
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Supporting information
Nanofibrous Hydrogel Composite Membrane with Ultrafast
Transport Performance for Molecular Separation in Organic
Solvents
Yi Li,a Eric Wong,b Alexander Volodine,c Chris Van Haesendonck,c Kaisong
Zhang,*d Bart Van der Bruggen,*a,e
a Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium. b Department of Management and Technology, UC Leuven-Limburg, Herestraat 49, 3000, Leuven, Belgiumc Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200 D, 3001 Leuven, Belgiumd Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, 361021, Xiamen, PR Chinae Faculty of Engineering and the Built Environment, Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa
* Corresponding authors.E-mail address: [email protected] (Bart Van der Bruggen); [email protected] (Kaisong Zhang).
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2019
Fig. S1 (a- c) The assumed exfoliation process of Kevlar fiber in DMSO/KOH solution.
Fig. S2 The ANF hydrogel preparation process. (a) ANF dope solution (2.0 wt%). (b) The non-solvent induced phase separation process of ANFs dispersions in water. (c) The as-prepared hydrogels with different shapes. (d) The cut hydrogel cubic from a bulk hydrogel. (e) The hydrogel under compressing with fingers. (f) The interactions between water and ANFs. (g) The nanofibrous structure of ANF hydrogel.
Fig. S3 The solvent resistance investigation of the ANF TFC membrane by immersing the membrane in different organic solvents. The membrane surface was examined after two weeks.
0 30 60 90 120 150 180 2105
1015202530354045
Cont
act a
ngle
(deg
rees
)
Time (s)
Contact angle
5 s
60 s
120 s
180 s210 s
Fig. S4 Variations of water contact angle with time on ANF hydrogel substrate membrane surface.
12 μm
C
O
C
O
H
N
H
N
n
Fig. S5 SEM image of Kevlar fiber.
5.0 μm 2.0 μm
1.0 μm 500 nm
Fig. S6 The SEM images of the surface of the ANF TFC membrane in different magnifications.
Fig. S7 SEM image of the polyolefin (PO) non-woven fabric surface (left) and the ANF TFC membrane with the support of PO fabric.
Fig. S8 (a) SEM image of the cross-section of the ANF hydrogel membrane without non-woven support. (b) TEM observation of the TFC membrane without DMF treatment.
Fig. S9 SEM image of the ANF hydrogel surface on PP/PE non-woven fabric surface (left) and the surface with higher magnification (20,000×) (right).
Fig. S10 (a, b) Cross sectional SEM images of the ANF TFC composite membrane without DMF treatment (The red dashed line showing the interface between polyamide layer and ANF hydrogel). (c, d) Cross-sectional SEM images of ANF TFC membrane with DMF treatment of 16 hours. (Membrane was dried with supercritical CO2)
Fig. S11 Comparison of the interfacial polymerization on conventional polymeric substrate (Left) and nanofibrous hydrogel substrate (Right).
0 5 10 15 20 25 30 350
10
20
30
40
50
60
Tensile stress: 46.5 MPaYoung's modulus: 139.0 MPa
Stre
ss (M
Pa)
Strain (%)
ANF TFC membrane (without non-woven fabric)
Fig. S12 Strain-stress curve of the dried ANF TFC membrane without the non-woven support.
8 12 16 20 24 28 320
20406080
100120140
Hydrogel /PP substrate membrane
Perm
eanc
e
Visc
osity
(1
0-8 L
m-2)
Total Hansen solubility parameter (MPa1/2)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50
200
400
600
800
1000
1200
R2=0.999y=146.662x
1 IPA 2 Ethanol 3 Methanol 4 Acetone
5 DMSO 6 NMP 7 DMF 8 DMAc
9 Water 10 THF
Perm
eabi
lity (L
m-2 h
-1 b
ar-1)
Viscosity-1 (mPa s-1)
1
2 9
10
3
4
7 85 6
y=339.712xR2=0.999
a
b
Fig. S13 (a) The transportation behavior of ANF hydrogel membrane against various solvents. (b) Product of permeance and viscosity of solvent as a function of the total Hansen solubility parameter for an ANF hydrogel membrane.
0 10 20 30 40 50 6020
24
28
32
36
40
Perm
eanc
e (L
m-2 h
-1 b
ar-1)
Reaction time (s)
Permeance
0
20
40
60
80
100
Rejection
Reje
ctio
n (%
)
0 4 8 12 16 20 2405
10152025303540
Perm
eanc
e (L
m-2 h
-1 b
ar-1)
Treatment time (h)
Permeance
0
20
40
60
80
100
Rejection
Reje
ctio
n (%
)
a b
Fig. S14 Effect of DMF treatment time (a) and interfacial polymerization reaction time (b) on the separation performance of ANF TFC membrane. (Feed with the methanol/RB solution with dye concentration of 20 mg L-1, tested at 4 bar, 500 rpm)
0 1 2 3 4 5 6 7 8 9 100.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
RB re
ject
ion
(%)
Met
hano
l per
mea
nce
(L m
-2 h
-1 b
ar-1)
Operation time (h)
Methanol permeance
0102030405060708090100110
RB rejection
1.5 LMHbar-1
99.7%
0 1 2 3 4 5 6 7 8 9 100.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
RB re
ject
ion
(%)
Acet
one
perm
eanc
e(L
m-2 h
-1 b
ar-1)
Operation time (h)
Acetone permeance
0102030405060708090100110
RB rejection
1.7 LMHbar-1
99.9%
0 1 2 3 4 5 6 7 8 9 101.01.52.02.53.03.54.04.55.05.56.0
RB re
ject
ion
(%)
DMF
perm
eanc
e (L
m-2 h
-1 b
ar-1)
Operation time (h)
DMF permeance
0102030405060708090100110
RB rejection
2.4 LMHbar-1
99.8%
0 1 2 3 4 5 6 7 8 9 103.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
RB re
ject
ion
(%)
DMAc
per
mea
nce
(L m
-2 h
-1 b
ar-1)
Operation time (h)
DMAc permeance
0102030405060708090100110
RB rejection
4.7 LMHbar-1
99.7%
0 1 2 3 4 5 6 7 8 9 101.0
1.5
2.0
2.5
3.0
3.5
4.0
RB re
ject
ion
(%)
NMP
perm
eanc
e (L
m-2 h
-1 b
ar-1)
Operation time (h)
NMP permeance
0102030405060708090100110
RB rejection
2.3 LMHbar-1
99.6%
0 5 10 15 20 25 30 35 40 45 50
0
5
10
15
20
25
30
35
40
1
1 NMP2 IPA
3 DMSO 4 DMAc
5 Ethanol 6 DMF7 THF
8 Acetone 9 Methanol
97 8
6
5
34
2
R2=0.932y=0.061x
Solvent permeance
Perm
eanc
e (L
m-2 h
-1 b
ar-1)
Vmcm3 mol-1 cP-1
a b
c d
ef
Fig. S15 (a) Pure solvent permeances against the combined solvent properties (solubility parameter, viscosity and mole volume) for ANF TFC membrane without DMF treatment. (b- f) Separation performance of ANF TFC membrane under solvent of (b) methanol, (c) acetone, (d) DMF, (e) DMAc and (f) NMP, respectively, with rose Bengal (1017 g mol-1) concentration of 40 mg L-1 as the solute at 6 bar with stirring of 500 rpm.
200 250 300 350 400 450 500 550 600 650 700
0.00.51.01.52.02.53.03.54.0
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
RB (MW=1017)
P F
R= 100%
200 250 300 350 400 450 500 550 600 650 700
0.00.51.01.52.02.53.03.54.0
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
EB (MW=836)
P F
200 250 300 350 400 450 500 550 600 650 700
0.00.51.01.52.02.53.03.54.0
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
EY (MW=691.9)
P F
200 250 300 350 400 450 500 550 600 650 700
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
RO16 (MW=618)
P F
200 250 300 350 400 450 500 550 600 650 700
0.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
JGB (MW=511)
P F
200 250 300 350 400 450 500 550 600 650 700
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Abso
rban
ce (a
.u.)
Wavelength (nm)
Retentate Permeate
SBB (MW=457)
P F
200 250 300 350 400 450 500 550 600 650 700
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
MO (MW=327)
P F
200 250 300 350 400 450 500 550 600 650 700-0.20.00.20.40.60.81.01.21.41.61.8
Abso
rban
ce (a
.u.)
Wavelength (nm)
Feed Permeate
DO3 (MW=242)
P F
R= 100%
R= 100%R= 100%
R= 99.9%R= 99.9%
R= 98.6%R= 54.8%
Fig. S16 Rejection of dyes with different molecular weight (MW) for ANF TFC membrane. Inset photographs of the feed and permeate of dye/ethanol solution.
200 400 600 800 10000
20
40
60
80
100
Molecular weight cut-off (MWCO): 339 Da
PEG
reje
ctio
n (%
)
Molecular weight (Da)
ANF TFC membrane
a b
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0
0.5
1.0
1.5
2.0
2.5
Geometric standarddeviation (p):1.51
Mean effective pore diameter (p): 0.545 nm
Prob
abilit
y de
nsity
func
tion
(nm
-1)
Pore diameter (nm)
ANF TFC membrane
Fig. S17 (a) The rejection of PEGs with different molecular weights through ANF TFC membrane. (b) Probability density function curve of the ANF TFC membrane.
0 5 10 15 20 25 30
1400
1600
1800
2000
2200
2400
2600
2800
4 bar 6 bar 10 bar
Flux
(L m
-2 h
-1)
Time (min)
Fig. S18 Compaction of ANF hydrogel substrate tested with pure water at different pressures in the first half an hour.
2.0 cm
Without post-treatment
Withpost-treatment
Fig. S19 Comparison of the ANF hydrogel TFC membrane without (Left) and with post-treatment (Right) after 180 d stored in a sealed bag. The membrane was treated with a mixture solution of isopropanol (IPA) and glycerol in a ratio of 7:3 (v/v) for one day.
80 84 88 92 96 1000
5
10
15
20
25
30
Upper bound This work
ISA membrane TFC membrane via IP TFC membrane via coating Mixed matrix membrane Commercial membrane ANF TFC membrane
Perm
eanc
e (L
m-2 h
-1 b
ar-1)
Rejection of molecule (%)
Fig. S20 Plot of permeance versus rejection of molecules, showing “trade-off” between permeance and selectivity. Typical OSN data of integral asymmetric (ISA) membrane, TFC membrane, mixed matrix membrane and commercial membrane were summarized from reported literature.
Table S1
Information of dyes used in this study.
Dyes StructureChar
ge
Molecular
weight (g
mol-1)
Topological
polar surface
area (Å2)
UV-vis absorption
(nm)
Disperse
Orange 3 (DO3)0 242 96.6 λEtOH = 445;
Methyl Orange
(MO)- 327 93.5
λEtOH =418;
λDMF, λDMAc =424;
λNMP = 430;
λwater = 464;
Sudan Black B
(SBB)0 457 73.5 λEtOH = 606;
Janus Green B
(JGB)+ 511 48 λEtOH = 651
Reactive
Orange 16
(RO16)
- 614 -
λEtOH = 525;
λDMF, λNMP =508;
λDMAc = 506;
Eosin Y (EY) 0 648 76 λEtOH =528;
Erythrosin B
(EB)0 836 76
λEtOH = 530;
λDMF =544;
λDMAc =549;
λNMP = 541;
Rose Bengal
(RB)- 1017 89.5
λEtOH, λMeOH, λAceonte
=559; λDMF, λDMAc
=564; λNMP = 560;
Table S2Water content and swelling degree of the ANF hydrogel. (Size: 4 × 3 cm)
Swelling degree Water content (%)(Wwet- Wdry) * Wdry-1 (g g-1) (Wwet- Wdry) * Wwet-1 *100%
ANF hydrogel 2.5± 0.3 60.0± 3.8
Table S3
Solvent swelling degrees of ANF hydrogel membrane with PP/PE fabric in various organic solvents for two weeks.
Solvent (Wwet- Wdry) · Wdry-1 (Wwet- Wdry) · Wdry
-1· density-1 (cm3 g-1)
Methanol 1.10 1.39
Ethanol 1.37 1.73
IPA 1.12 1.42
Acetone 0.19 0.24
Ethyl acetate 0.42 0.47
THF 1.26 1.42
DMF 1.68 1.78
DMAc 1.79 1.92
NMP 1.92 1.87
DMSO 2.08 1.89
Table S4
Physical properties of solvent used in this work.
a Data were obtained from the book “Hansen Solubility Parameters: A User’s Handbook (second edition)”. Hansen Solubility Parameters, HSP, δd for Dispersion (van der Waals), δp for Polarity (related to dipole moment) and δh for hydrogen bonding.b Data were calculated from the Hansen solubility parameters.
Hansen solubility parameter
Solvent
Molec
ular
weight
(Mw, g
mol-1)
Dens
ity (g
cm-3)
Surface
tension
(γ, mN
m-1, 20
℃)
Visco
sity
(η, cP,
20 ℃)
Relati
ve
permit
tivity
(g)
Mole
volum
e (Vm,
cm3
mol-1) a
δd
(MPa
1/2) a
δp
(MPa
1/2) a
δh
(MPa
1/2) a
δsp
(MPa
1/2) b
Methanol 32.0 0.79 22.7 0.59 32.7 40.7 15.1 12.3 22.3 29.6
Ethanol 46.1 0.79 22.1 1.2 24.5 58.5 15.8 8.8 19.4 26.5
IPA 60.1 0.79 23.0 2.4 19.9 76.8 15.8 6.1 16.4 23.6
Acetone 58.1 0.79 25.2 0.32 20.7 74.0 15.5 10.4 7.0 20.0
NMP 99.1 1.03 40.8 1.67 32.2 96.5 18.0 12.3 7.2 23.0
DMAc 87.1 0.94 36.7 2.14 37.8 92.5 16.8 11.5 10.2 22.8
DMF 73.1 0.94 37.1 0.92 36.7 77.0 17.4 13.7 11.3 24.8
DMSO 78.1 1.10 43.5 2.24 46.7 71.3 18.4 16.4 10.2 26.7
EtOAc 88.1 0.90 24.0 0.46 6.0 98.5 15.8 5.3 7.2 18.2
THF 72.1 0.89 26.4 0.55 7.6 81.7 16.8 5.7 8.0 19.5
Hexane 86.2 0.66 18.4 0.31 1.9 131.6 14.9 0 0 14.9
Water 18.0 1.00 72.8 1.0 78.5 18.0 15.5 16.0 42.3 47.8
Table S5
Comparison of OSN performance in harsh organic solvent for nanofibrous hydrogel TFC membrane in this work with other polymer substrate based TFC membrane via interfacial polymerization.
Materials SolventPermeance(L m-2 h-1
bar-1)Solute (g mol-1) Rejection (%) Ref.
PA/PI Acetone 2.4Styrene oligomers(236- 1200 g mol-
1)
95.0 (236 g mol-1)
[1]
DMF 1.5 91.0 (236 g mol-1)
PA/PI DMF 3.9 Tetracycline (444 g mol-1) 95.0 [2]
(PA-COF)/PI DMF 5.5 Rose Bengal (1017 g mol-1) 99.5 [3]
(DA/TMC)/PI DMF 1.15 Rose Bengal (1017 g mol-1) 99.9 [4]
(PAR-BHPF)/PI Acetone 8.4
Styrene oligomers(236- 1200 g mol-
1)
97.0 (236 g mol-1)
[5]
PA/PAN Acetone 6.0 Oleic acid (282 g mol-1) 92.0 [6]
(Morin-TPC)/PAN NMP 0.3 Brilliant Blue
(826 g mol-1) 96.0 [7]
PA/PBOI DMF 7.7Styrene oligomers(236- 1200 g mol-
1)
>90.0 (600 g mol-1)
[8]
(Tannic acid-TPC)/PAN NMP 0.08 Brilliant Blue
(826 g mol-1) 95.0 [9]
PA/Cellulose DMF 1.4 Amido-Black(617 g mol-1) 92.0 [10]
PA/ANF hydrogel (without solvent
treatment)
DMF 20.3 Methyl orange (327 g mol-1) 64.0 This
work
10.6Reactive orange
16 (618 g mol-1)
92.3
8.1 Erythrosin B (836g mol-1) 99.3
3.5 Rose Bengal (1017 g mol-1) 99.4
DMAc 8.4 Methyl orange (327 g mol-1) 91.4 This
work
7.6Reactive orange
16 (618 g mol-1)
93.0
7.3 Erythrosin B (836g mol-1) 97.1
5.3 Rose Bengal (1017 g mol-1) 99.7
NMP 4.9 Methyl orange (327 g mol-1) 94.4 This
work
8.8Reactive orange
16 (618 g mol-1)
93.1
1.8 Erythrosin B (836g mol-1) 99.9
2.3 Rose Bengal (1017 g mol-1) 99.6
PA/ANF hydrogel (with
solvent treatment)
Acetone 19.0 Rose Bengal (1017 g mol-1) 100.0 This
work
DMF 6.0 99.5 This work
DMAc 10.0 97.0 This work
NMP 5.0 100.0 This work
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