Engineered Ionic Diode Membranes Based on Metal-Organic Frameworks with a High Density of Subnanochannels and Space Charges for

Unprecedented Osmotic Energy Conversion from Organic Solutions

Amalia Rizki Fauziah1, Li-Hsien Yeh1*
1
Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan
E-mail: lhyeh@mail.ntust.edu.tw
Acknowledgement: MOST 110-2223-E-011-003-MY3
MOTIVATION INTRODUCTION OBJECTIVE FABRICATION
Organic Pollutant Salinity gradient Metal Organic Linker ZIF-8/PSSx@ANM Ion selective layer Alumina Nanochannel Membrane (ANM)
Helping to mitigate ZIF-8 PSS
environmental issues power generation 0.3 M H2C2O4 0.3 M H2C2O4
Electropolish Remove Al and
Fulfilling the ever Pre-anodization Etching 1st-anodization
barrier layer
demanding energy needs Zn(NO₃)₂• 6H₂O C4H6N2
Zinc nitrate hexahydrate 2-Methylimidazole (HMIM) Aluminium foil
(99.99(%)) ANM
reuse
ZIF-8 Abundant ordered
channels
Increase of space
charges
• The angstrom-sized Ultrahigh porosity,
enermous surface area and
High density of ZIF-8/PSSx@ANM
functional groups
al nt

windows PSS
c s ve

selective mass transports. from polymer.

W
ni ol
t

in
ion selectivity filters
ga c s

do
A maximum power density of
or ni

HMIM

Ca

w
for selection of ions. Support layer
In rga

4.4 W/m2 was achieved. z

vi
Alumina Nanochannel Membrane (ANM)
O

ty
(Chen et al, Adv. Energy Mater., 2020, 10, 1904098) y • The nanometer-sized High porosity,
•

cavities highly ordered

Zinc nitrate
•

Aminoethanol
x ion conductive pores for nanochannels and Zinc Hydroxide ZHN/PSSx ZHN/PSSX@ANM ZIF-8/PSSx@ANM
highly adjustable. solution solution
Nanostrand (ZHN)
ultrafast ion transport.

RESULT AND DISCUSSION

Material characterization Electrical measurements
SEM Ion Transport Properties Osmotic Power Conversion

d e n s it y
“Large-scale, continuous and pinhole- Diode-like behavior
Vacuum
Low space charge High space charge

d e n s ity
e r
/m
free subnanochannel ZIF-8/PSS Aqueous solvent 5.28 W/m 2

W w
filtration

)
2
R ectification ratio
6

P o(
300 nm
6
4

1 mm 10
2

/m
0

ZIF-8/PSS0@ANM
1 2 3 4 5 6 7

r
10 10 10 10 10 10 10

81mM LiCl-Methanol
E x te r n a l r e s is ta n c e ( )

W )e
6

w
membrane was successfully prepared.” 6Organic solvent
5

5.57

P o (
ZIF-8/PSS5@ANM
4

(W /m 2 )
0
1 2 3 4 5 6 7
10 10 10 10 10 10 10
( )

ZIF-8/PSS9@ANM
E x te rn a l r e s is ta n c e

Current (µA)
4.63 5

R ectification ratio
5 6

Pow er density (W /m )
2
5
3 mm
3 mm 200 nm
N2 sorption isotherm 3.43

500 mM
4

10 mM
0
4 4
ANM ZHN/PSSX@ANM Increasing
400 Adsorption -2 -1 0
Voltage (V)
1 2 2
3
PSS
Desorption S.A.=1289.4 m 2
/g 3

Power density
7x
lu M

0 content
so MI
n

2
Contact angle
t io

EDX
H

dVp/dW
2
1.07 nm

0.74
0.41 nm

ZIF-8/PSS0 ZIF-8/PSS5 ZIF-8/PSS9 1

1.15 nm

ZIF-8/PSS9 300
V (cm (STP)g )

Zn
-1

W/m2
g nm )

111.72 ± 7.62O 0
Negatively charged
-1

1 1 2 3 4 5 6 7
300 mm 10 10 10 10 10 10 10
-1

External resistance ()

200
1.25 nm
1.44 nm
3

n 0 P ow er density
dVp/dW (cm

6 ZIF-8/PSS0@ANM
Dehydrated 5.28
3

1 mm 1 µm 1 2 3 4 5 6 7 6
S 10 10 10 10 10 10 10 ZIF-8/PSS5@ANM

(W /m )
ion

P ow er density(W /m )
ZIF-8/PSS9@ANM
ANM

2
100 O S O
External resistance ()
53.18 ± 6.38O 4 4

-)

Pow er density
0.4 0.8 1.2 1.6 2.0 O2+
= Metal source (Zn
3 mm
100 nm
0 Pore size (nm) = Organic linker (HMIM) Zn 7.64 Å 2 2.07
N 2
ZIF-8/PSSX@ANM
0.0 0.2 0.4 0.6 0.8 1.0 Positively charged C 1.04
Asymmetric O
P/P 0 H 2O 0 0.45
Zeta potential OH OH2+ OH2+ Pore sizes PSS
0
Increasing PSS content XRD FT-IR OH2+ OH2+ OH Charges 10
1 2 3 4
10 10 10 10 10
5 6
10
7 ANM ZIF-8/PSS0 ZIF-8/PSS5 ZIF-8/PSS9
Positive Negative 1.20 Å Homogenous
(112)

(022)

ZIF-8/PSS9
(011)

(013)

Wettabilities
(002)

External resistance () membrane

ZIF-8/PSS0 ZIF-8/PSS5 ZIF-8/PSS9 ZIF-8/PSS9 side R-SO3- Heterogeneous membrane
20.10 mV -23.39 mV -34.17 mV C=N
10
3 0.2V

10
3 0.1 V Subnanochannel Highly ion 𝑽
Intensity (a.u.)

ZIF-8/PSS0 MOF selective

2
Transm ittance (% )

10
ZIF-8/PSS0 side
2
10
Highly
C-N C-H
𝑰
Conductance (µS)

C=N 10
1
1
abundant
10
order
5 10 15 20 25 30 35
ZIF-8 simulated C-N Diode-like HIGH POWER
o
( ) C-N C-H 10
0 0 lD=0.19 nm ~0.4 nm channel behavior
10
DENSITY
C o n d u c t a n c e (µ S )

ANM side
C-N -6 -5 -4 -3 -2 -1 0
10 10 10 10 10 10 10 10
-6
10
-5 -4 -3
10 10 10 10
-2 -1
10
0
at 1 M LiCl-methanol
𝑰 (ICR)
2000 1600 1200 800 C o n c e n t r a i o n (M ) Concentration (M)
40 20 0 -20 -40 -60 -1
Zeta potential (mV) Wavenumber (cm )