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org/ac Article

Highly Rectifying Fluidic Diodes Based on Asymmetric Layer-by-

Layer Nanofilms on Nanochannel Membranes
Shouwei Zhang, Liu Yang, Dong Ding, Pengcheng Gao, Fan Xia,* and Merlin L. Bruening
Cite This: Anal. Chem. 2021, 93, 4291−4298 Read Online

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sı Supporting Information

ABSTRACT: Nanochannel-based fluidic diodes display ion selectivity and ion current
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rectification (ICR), which may prove to be important in energy-harvesting devices and biosensors.
This paper reports asymmetric functionalization of the outer surface of a flexible nanochannel
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polymer membrane to create fluidic diodes that give ICR. Layer-by-layer (LbL) adsorption with
cross-linking of only the underlying part of the polyelectrolyte nanofilm leads to a porosity step
across the film. The combination of a high effective surface charge density and the porosity step in
the film leads to a remarkable maximum ICR factor of ∼200 with a pH gradient across the film.
Incorporation of pH-sensitive polyelectrolyte components enables the ICR factor to increase an
order of magnitude on going from pH 8 to pH 3. Moreover, the coated membrane shows excellent
anion selectivity. Thus, LbL adsorption with partial cross-linking provides a simple method for
creating coated nanochannel membranes that serve as pH-responsive ionic diodes for potential chemical/biosensors.

■ INTRODUCTION
Nanochannel-based fluidic diodes exhibit unique ion-transport
properties including ion current rectification (ICR), ion gating,
and ion selectivity.1−4 Slightly analogous to biological
channels, these fascinating properties rely on the shape and
surface physicochemical properties of artificial solid-state
channels.5−9 Compared to biological nanopores, solid-state
nanochannels have intrinsically greater mechanical robustness
and chemical stability, which are important for practical
applications.3 In ICR, asymmetry in the channel geometry,10,11
surface charge distribution,12−14 wettability,15 or an external
stimuli16−18 result in ion enrichment and depletion in the
nanochannel under different voltage polarities. Nanochannels
containing segments with oppositely charged surfaces, also
known as bipolar junctions, are of interest for chemical/
biosensors.19
Typically, formation of a nanochannel bipolar junction
requires either asymmetric modification of the nanochannel
surface or hybridization of porous materials with different
chemical compositions. Several studies used partial chemical/
physical modification of the nanochannel inner surface to
achieve nanofluidic diodes.15,20−24 Yan et al.25 synthesized a
unique Al2O3/SiO2 heterojunction nanotube as the building
block for nanofluidic diodes that have an ICR factor of 5. The
fabrication includes multistep conformal atomic layer deposi-
tion on silicon nanowire templates, protection/deprotection,
and selective etching and thus is complex. Another type of
bipolar junction consists of heterogeneous membranes,
fabricated by depositing a porous material on a porous
membrane [e.g., anodic aluminum oxide (AAO) or a track-
etched polymer membrane] with an opposite charge.26 Various
other strategies including transfer,27 post ion-etching,28 in situ
growth,29,30 self-assembly,31,32 sputter coating,33,34 drop-coat-
ing,35 spin-coating,36−39 brush-coating,40 filtration,41−43 and
layer-by-layer (LbL) deposition7,44−49 have been developed to
fabricate the related bipolar junctions. The highest ICR factor
of ∼500 occurred in block copolymer/AAO heterogenous
membranes.36 Based on ICR, previous studies investigated
different heterogeneous membranes in biosensing,32,34 ion
gating,36,50 energy conversion,37,40 and ion separation.30
Thinner coatings should reduce the system resistance to
increase ion transport.51−53 However, ionic diodes with
nanoscale porous coatings (e.g., several tens of nanometers
thick) on nanoporous membranes have not yet been reported,
probably because of limitations in the porous materials and
substrates. For example, thick layers of inorganic porous
materials are required to fully cover the surface of nanoporous
membranes.29 Thin layers of block copolymers could not form
an intact homogeneous porous structure over the mem-
branes.54
In this work, we report the formation of a 30 nm thick LbL
nanofilm on a nanochannel membrane. The polyelectrolyte
does not penetrate greatly into the nanochannel because the
dimensions of the polyelectrolyte chains are larger than the
selected pore dimension (∼10 nm). Transmission electron
microscopy (TEM) and time-of-flight secondary ion mass
spectrometry (TOF−SIMS) demonstrate the formation of the
nanofilm and the limited depth of nanofilm penetration in the
Received: December 18, 2020
Accepted: February 13, 2021
Published: February 24, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.analchem.0c05303

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Analytical Chemistry pubs.acs.org/ac Article

Figure 1. LbL modification of nanochannel membranes. (a) Formation of the nanostructured LbL film on a nanochannel membrane (the coiled
blue and orange chains represent PEI and CS, respectively). (b) FTIR spectra confirm the deposition of LbL nanofilms and the formation of cross-
links. ① (PEI/CS)4; ② crosslinked (PEI/CS)4; and ③ (PEI/CS)4/cross-linking/(PEI/CS)3/PEI films. (c) TOF−SIMS depth analysis of CN− and
SO3− fragments in surface nanofilms and in nanochannels indicate limited penetration of the LbL film in nanochannels. (d) Cross-sectional TEM
image of a (PEI/CS)4/cross-linking/(PEI/CS)3/PEI film on a nanochannel membrane. (e) AFM topography of an as-prepared (PEI/CS)4/cross-
linking/(PEI/CS)3/PEI film in pH 8 solution. (f) Water fraction in the underlying cross-linked (PEI/CS)4 layer and surface (PEI/CS)3/PEI layer
in a (PEI/CS)4/cross-linking/(PEI/CS)3/PEI film in pH 3 and 8 solutions. EDC: N-(3-dimethylaminopropyl)-N-ethylcarbodiimide
hydrochloride; NHS: N-hydroxysuccinimide.

nanochannel. Importantly, through selection of pH-sensitive
polyelectrolytes, the LbL nanocoating confers a pH response
to the system. Moreover, through control over cross-linking in
the LbL film, we create a porosity step in solvated films, and
this significantly enhances the ICR factor, demonstrating a
simple method for controlling the structure of fluidic diodes
through incorporation of diverse materials.
the substrates were alternatively immersed in PEI and CS
solutions for 15 min, with two intermediate rinses of 2 min
each using 0.1 M NaCl (pH 8) until the desired number of
layer was reached. At the end of film formation, the
polyelectrolyte films were washed with pure water to remove
entrapped salt and dried with nitrogen. For cross-linking, the
as-prepared membranes were placed in a 0.1 M EDC and NHS

■
MATERIALS AND METHODS
Materials. Branched polyethylenimine (PEI, Mn ca. 60,000,
Mw ca. 750,000 g·mol−1) was purchased from Sigma-Aldrich.
Chondroitin 4-sulfate sodium salt (CS, > 85%), N-(3-
dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride
(EDC, 98%), and N-hydroxysuccinimide (NHS, 98%) were
obtained from Aladdin. Hydrochloric acid (36.0−38.0%),
sodium chloride, and sodium hydroxide were bought from
Sinopharm Chemical Reagent Co. Polyelectrolytes were
prepared at a concentration of 1.0 mg/mL in 0.1 M NaCl
solution (pH 8). Milli-Q water with 18.2 MΩ·cm resistivity
was used in all experiments. Ion track-etched polyethylene
terephthalate (PET) membranes with a 10 nm average pore
diameter, 12 μm thickness, and 5 × 107 pores/cm2 were used
for LbL deposition. PET membranes were provided by the
it4ip company, Louvain-la-Neuve, Belgium.
Construction of Polyelectrolyte Films. The PEI/CS
films were fabricated via a LbL assembly on supporting
substrates, including PET nanochannel membranes and gold-
coated silicon wafers. For in situ current measurements,
polyelectrolyte films were deposited on one side of PET
membranes by using two custom-made polymethylmethacry-
late (PMMA) cells, between which the PET membrane was
clamped (exposed area: 0.283 cm2) (Figure S1). For other
measurements, the films were made by hand dipping. Briefly,
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solution for 30 min, followed by a water rinse.
Electrochemical Measurements. Current−voltage
curves were recorded with a CHI 650D electrochemical
workstation (Chenhua, Shanghai, China) and a Keithley 6487
picoammeter/voltage source (Keithley Instruments, Cleveland,
OH), using two Ag/AgCl wire electrodes (Figure S1).
FTIR Measurements. Fourier transform infrared (FTIR)
spectra were collected at 4 cm−1 resolution (32 passes) on a
FTIR spectrometer (Nicolet iS5, Thermo Scientific) with an
all-diamond iD7 ATR accessory. In this case, gold-coated
silicon wafers were used as supporting substrates for films.
XPS Measurements. X-ray photoelectronic spectroscopy
(XPS) was carried out using a Thermo Scientific K-alpha
photoelectron spectrometer with a monochromatic Al-Kα
source (ESCALAB Xi, Thermo Fisher Scientific, United
States).
SEM and TEM Measurements. The cross section of LbL
films was imaged with scanning electron microscopy (SEM,
SU8010, Hitachi, Japan) and TEM (JEOL JEM-2100F),
operated at 15 and 200 kV, respectively. For TEM slide
preparation, the as-prepared samples were first coated with a
thin layer of carbon (4 nm thick) and then further covered
with an epoxy resin and cured at room temperature. Ultrathin
slides were prepared by cutting the epoxy block using a Leica
EM UC7 ultramicrotome with a diamond knife at room
temperature.
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TOF−SIMS Measurements. The secondary ion mass
spectra along the depth of the LbL-modified PET were
collected using a TOF−SIMS 5 instrument (Ion-tof, GmbH,
Germany). Negative secondary ion spectra were recorded.
Mass calibration was conducted using standard procedures
(mass resolving power > 5000). The depth of etching area was
measured by a profilometer (Bruker Dektak XT, Germany).
Size and Zeta Potential Measurements. The hydro-
dynamic diameters and zeta potentials of PEI and CS
polyelectrolytes in solutions (pH 3 and pH 8) were
determined using a Zetasizer Nano ZS90 instrument (Malvern,
UK). Zeta potential measurements of solid LbL films on PET
membranes were performed using a Surpass instrument
(Anton-Paar, Austria) based on a streaming potential
technique.
Contact Angle Measurements. Contact angles of bare
and LbL-film modified PET membranes were determined with
a DSA100 contact angle analyzer using 5 μL of water (pH 3 or
pH 8). Water droplets on the surfaces were allowed for 5−10
min to reach equilibrium. Three independent samples were
used to obtain average values.
AFM Measurements. Hydrated topography measurements
for LbL films on PET membranes were conducted in water at
pH 3 or pH 8 using a commercial atomic force microscopy
(AFM) instrument (NanoScope VIII MultiMode AFM,
Bruker).
Ellipsometry. The dry and hydrated thickness and water
content of LbL films on gold-coated wafers were determined
using spectroscopic ellipsometry (M-2000V, and alpha-SE, J.
A. Woollam, US), equipped with a liquid cell. Optical
constants (n and k) of a bare gold-coated wafer in air were
first measured by fitting ellipsometric data (Figure S2) using a
B-spline function.55 The obtained dielectric function of the
gold layer was employed for the substrate in subsequent fittings
of films. The refractive indices of water at pH 3 and 8 were also
determined by fitting raw data collected from a gold wafer in
water (Figure S3), following the same protocol, and were used
as the ambient medium for fitting hydrated films. For the dry
thickness of films, a Cauchy dispersion model was used to
describe polyelectrolyte materials. To determine the film’s
hydrated thickness and water fraction, raw ellipsometric data
(ψ and Δ) were fit using an effective medium approximation
(EMA) model which contains a Cauchy material for the LbL
film along with a water ambient, shown in Figure S4. Refractive
indices in the Cauchy material (polyelectrolytes) are described
by Equation S1.
■
RESULTS AND DISCUSSION
Construction of LbL Fluidic Diodes. Asymmetric
functionalization of the outer surface of nanochannel
membranes occurred through LbL assembly on an underlying
cross-linked LbL structure (Figure 1a). When immersed in
solution, this configuration yields a distribution of porosity
inside the nanofilm because of the limited swelling of the
underlying cross-linked layer. Below, we show that this
structure enhances the ICR.
The LbL assembly from a 0.1 M NaCl (pH 8) solution
employed branched polyethylenimine (PEI) (Figure S5a) and
chondroitin 4-sulfate sodium salt (CS) (Figure S5b) as the
polyelectrolyte building blocks. Prior works showed that the
properties of PEI/CS nanofilms depend on pH,56 so we chose
these materials for creating pH-responsive functional nano-
coatings. At pH 8, PEI chains bear a limited positive charge
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due to protonation of some of the amine groups (Figures S5a
and S6). In contrast, CS is highly negatively charged at pH 8
because of the deprotonated carboxylate (pKa 3−5) and
sulfonate (Figures S5b and S6) groups. These charged groups
facilitate the formation of PEI/CS nanofilms on negatively
charged PET membranes. Typical of LbL deposition, the
thickness of the first few layers is low,57,58 and at least six layers
were required to eliminate the influence of the PET substrate
on polyelectrolyte adsorption. The water contact angle
plateaued at 10−20° after adsorption of 7 layers, indicating
that the film controls the surface properties at that point
(Figure S7). Thus, prior to cross-linking, we deposited a 15 nm
thick (PEI/CS)4 film (Figure S8a,c), so the film would cover
the substrate but not provide excessive resistance to ion
transport. Moreover, the as-prepared (PEI/CS)4 film was
uniform over the substrate (Figure S8c). During subsequent
cross-linking, activated free carboxylic acid groups react with
amines within nanofilms to form amide bonds.
FTIR spectroscopy confirms the formation of PEI/CS films
(Figure 1b). The peak at 1648 cm−1 in the spectrum of the as-
prepared (PEI/CS)4 film stems from the amide bonds in CS.
An increase in the intensity of the 1648 cm−1 peak (amide I)
after cross-linking demonstrates the formation of additional
amide bonds in the cross-linking reaction.
Sulfonate groups in the outermost CS “layer” of cross-linked
(PEI/CS)4 films provide a negatively charged surface to enable
further assembly of (PEI/CS)3/PEI on top of the cross-linked
structure. TOF−SIMS depth analysis demonstrates the spatial
distribution of both PEI and CS on the surface and in
nanochannels (Figures 1c, S9). The high intensity of CN− and
SO3− fragments until 120 nm and their low intensity afterward
suggest that LbL assembly happens on the membrane surface
with limited penetration into the pores. Steric hindrance likely
leads to slow diffusion of PEI and CS chains into 10 nm
nanochannels59 and consequently the limited depth of LbL
adsorption in the nanochannels. The average hydrodynamic
sizes of PEI and CS are 1 order of magnitude larger than the
pore size (Figure S10). Cross-sectional TEM images reveal
that the total dry thickness of the (PEI/CS)4/cross-linking/
(PEI/CS)3/PEI nanofilm on the nanochannel membrane was
∼30 nm (Figure 1d), which is in agreement with the
ellipsometric and SEM thicknesses observed for films on
silicon wafers (Figure S8). AFM in a pH 8.0 solution (Figure
1e) shows that the film on the nanochannel membrane has a
roughness of ∼10 nm. The 20 nm spheres are likely to be
complexes of PEI and CS, as the presence of N and S elements
suggests that both PEI and CS are present on the surface of a
PEI-terminated film (Figure S11).
LbL films swell in water, and the swelling depends on the
film composition and degree of cross-linking as well as pH and
ionic strength.60,61 For PEI/CS films, we determined the
hydrated thickness and volume fraction of water using
ellipsometry. Compared to films under ambient conditions
(∼30% relative humidity), in pH 3 and pH 8 solutions, the
thicknesses of (PEI/CS)3/PEI films increase ∼four- and
∼threefold (Figure S12), respectively. Because the film is
very hydrophilic, the deprotonation of carboxylic acid groups
at high pH does not have a large effect on the swelling.
Protonation of −COO− groups at pH 3 should disrupt ionic
cross-links, and AFM images show different film morphologies
(Figures 1e, and S13a) and moduli (Figure S13b,c) in pH 3
and pH 8 solutions. A covalently cross-linked (PEI/CS)4 film
has a relatively low water volume fraction of ∼50% (Figure 1f)
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Figure 2. Evolution of the ICR factor during the fabrication of (PEI/CS)4/cross-linking/(PEI/CS)3/PEI films. (a,b) Illustration of the formation of
ion enrichment (a) and depletion (b) zones under negative and positive voltages, respectively. (c) I−V curves collected in 0.1 M NaCl solution
(pH 8.0) after each polyelectrolyte adsorption and cross-linking step in the formation of a (PEI/CS)4/cross-linking/(PEI/CS)3/PEI film. The
number of layers in the film increases from left to right, and all I−V curves span from −2 to 2 V. (d) Derived ICR factor from I−V curves in (c).
The LbL assembly was continuously performed on one membrane without intermediate drying. At least three independent membranes were
employed to give an average value with a standard deviation.

at either pH 3 or 8. The cross-linked LbL network has a
limited number of pH-sensitive sites.62 Notably, for (PEI/
CS)3/PEI deposited on a cross-linked (PEI/CS)4 film,
ellipsometry suggests that the two sections of the film exhibit
individual swelling properties (Figure 1f). Thus, in solution,
the (PEI/CS)4/cross-linking/(PEI/CS)3/PEI nanofilm on the
surface of a PET membrane should show a variation in
porosity across the film.
LbL Adsorption Monitored by ICR. When PEI adsorbs
on one side of the PET membrane, a charge heterostructure
leads to the formation of an ionic current rectifier. Anionic
counterions should accumulate in the vicinity of the positively
charged LbL film, and cationic counterions will accumulate in
the negatively charged PET nanochannels (at pH 8). This
results in the formation of electrical double layers characterized
by a Debye length (κ−1 = 0.304/I1/2, nm),63 where I is the
ionic strength (mol/L). Within the Debye length, counterions
should carry most of the current.64 The asymmetry in charge
polarity between the LbL film and the nanopores leads to ion
reorganization (enrichment or depletion) that depends on the
sign of the applied electric field (Figure 2a,b). This ion
accumulation or depletion leads to ICR, and we use an ICR
factor (f rec = |I−2V/I2V|) to describe the extent of current
rectification.
We employed I−V curves to monitor the assembly of (PEI/
CS)4/cross-linking/(PEI/CS)3/PEI films on PET nanochannel
membranes (pore size 10 nm) in 0.1 M NaCl solution (pH 8).
Figures S14 and S15 show the evolution of the ICR factor
during adsorption of PEI and CS. After 5 min of adsorption
time, further adsorption leads to minimal change in the ICR
factor. After each adsorption, a rinsing step (0.1 M NaCl, pH
8.0) removes the loosely attached polyelectrolyte chains on the
surface, which causes a minor change in the ionic current as
well as the ICR factors (Figure S14i).
Figure 2c,d summarizes the I−V curves and ICR factors in
0.1 M NaCl (pH 8) after each polyelectrolyte deposition.
Unlike bare PET membranes, the modified membranes exhibit
diode-like I−V curves, with small current magnitudes when the
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voltage is positive (Figure 2c). Moreover, the rectification
factor is larger when films terminate in PEI than when they end
in CS because of the positive charge density in the film, and
the PEI-terminated membrane gives an ICR factor of ∼20,
regardless of the number of adsorbed layers (Figure 2d).
Adsorption of terminal CS should decrease the net positive
charge in the PEI/CS film at pH 8 to reduce the charge
asymmetry across the system and decrease the ICR factor
(Figure 2d). Cross-linking of a (PEI/CS)4 film increases the
ICR factor of the CS-terminated film from ∼5 to ∼10, and
deposition of further CS-terminated bilayers does not alter the
ICR ratio significantly. Further deposition of PEI-terminated
films on the cross-linked (PEI/CS)4 coating maintains the ICR
factor of ∼20 in 0.1 M NaCl (pH 8.0). For PEI-terminated
films, the positive surface charge is likely the dominant factor
behind rectification in the 0.1 M solution, so cross-linking is
not effective to enhance the ICR factor.
pH-Sensitive ICR at Low Ionic Strength. The extent of
ICR in coated nanochannel membranes should depend on
both ionic strength and pH. Ionic strength affects the ion
transport in the nanopores and the LbL nanofilms. When the
ionic strength is < 10−3 M, the Debye length is > 9.6 nm and
comparable in magnitude to the nanopore radius (5 nm), so
the electrical double layer overlap should be nearly complete.
This leads to an extensive ion accumulation and depletion
under different voltage polarities. Thus, low salt concentrations
should increase ionic current rectification. Decreasing the pH
will affect the surface charge density in both the polyelectrolyte
film and the nanopore. At low pH, the polyelectrolyte film will
become more positively charged to enhance exclusion of
cations, whereas the nanopores will become less negatively
charged and less selective for cation transport. Thus, the effect
of lowering the pH on ICR depends on the interplay of
enhanced cation selectivity in the polyelectrolyte film and less
on the anion selectivity in the nanopore. To avoid this
complication, we put solutions with different pH values on the
two sides of the LbL-modified membrane.
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Figure 3. Ion current rectifying behavior. (a,b) I−V curves of different membranes. The terminology 10−4(8)|10−4(3) denotes pH = 8 and 10−4 M
NaCl on the PET side of the membrane and 10−4 M NaCl and pH = 3 on the polyelectrolyte film side of the membrane. (c) Comparison of ICR
factors (f rec) of different membranes in 10−4 M NaCl (the pH at the PET side was maintained at 8, while the film side has a pH of 3, 5, or 8). The
legend in Figure 3a,b gives the symbols defining the membranes. (d) Effective surface charge densities of the film side of modified membranes at
different pH values. Surface charge densities were calculated based on membrane-surface zeta potentials (Figure S16) and Gouy−Chapman theory.
○ Bare PET membrane; ●(pink) (PEI/CS)3/PEI; △(green) cross-linked (PEI/CS)4; ▼(orange) (PEI/CS)4/cross-linking/(PEI/CS)3/PEI;
▲(green) (PEI/CS)7/PEI; ◆(pink) cross-linked (PEI/CS)7/PEI-modified membranes.

We initially examined ionic current rectification through
several different film-coated membranes at a low overall ionic
strength. Figure 3a,b shows the I−V measurements for
different film-coated membranes where the nanochannel
substrate faces a solution containing 10−4 M NaCl at pH 8
and the polyelectrolyte film faces a solution containing 10−4 M
NaCl at pH 3. In Figure 3, we denote this solution
configuration as 10−4(8)|10−4(3), where the numbers in
parentheses are the pH values. Under these conditions, both
the PET and LbL film sides of the system should have a
relatively high surface charge density (see below and Figure
3d). As Figure 3a,b shows, the (PEI/CS)4/cross-linking/(PEI/
CS)3/PEI-coated system exhibits a higher ICR factor than PET
coated with any of the other films. The combination of the
cross-linked (PEI/CS)4 and an overlayer of (PEI/CS)3/PEI
apparently leads to the highest current rectification, with an
average ICR factor of around 200 (Figure 3c). Compared to
the other films examined in Figure 3a, this maximum current
rectification results from both higher current under forward
bias and lower current under reverse bias. Notably, an uncross-
linked (PEI/CS)7/PEI film gives an ICR factor similar to that
of uncross-linked (PEI/CS)3/PEI, showing that the increased
rectification does not simply result from a thicker film, even
though uncross-linked (PEI/CS)7/PEI has a relatively high
surface charge density (Figure 3d). Similarly, a fully cross-
linked (PEI/CS)7/PEI film has an ICR factor only around 30,
suggesting that the cross-linking−induced asymmetric struc-
ture across (PEI/CS)4/cross-linking/(PEI/CS)3/PEI films is
unique in giving rise to the high rectification (Figure 3c).
Indeed, the cross-linked (PEI/CS)4 layers are less swollen and
perhaps less positively charged than the (PEI/CS)3/PEI
overlayer (Figures 1f and 3d), resulting in both porosity and
charge density steps across this hybrid film; this asymmetric
pore and charge distribution may contribute to an overall
enhanced ion enrichment and depletion at −2 and 2 V,
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respectively. The ICR of (PEI/CS)4/cross-linking/(PEI/CS)3/
PEI-coated membranes, however, is an order of magnitude
higher when the LbL film faces a pH 3 solution rather than a
pH 8 solution, despite the higher ionic strength at pH 3 where
protons carry much more current than Na+, and the Cl−
concentration is higher than in the pH 8 solution.
In Figure 2, the current rectification is essentially
independent of the number of PEI-terminated overlayers on
cross-linked (PEI/CS)4. Under the 10−4(8)|10−4(3) condition,
however, a single layer of PEI on cross-linked films is not
sufficient to give the ICR factor of 200 (see Figure S17). The
ICR factor with both (PEI/CS)3/PEI and (PEI/CS)6/PEI
overlayers was 200 (Figure S17), so we focused this work on
(PEI/CS)4/cross-linking/(PEI/CS)3/PEI films.
Trends in rectification at different pH values (derived from
I−V curves in Figures 3a,b and S18) are consistent with surface
charge densities determined in zeta potential measurements. At
pH = 3, all the polyelectrolyte films have a higher surface
charge density than at pH 8 (Figure 3d). Additionally, the very
high surface charge density (8.1 mC/m2) for the (PEI/CS)4/
cross-linking/(PEI/CS)3/PEI film (Figure 3d) is consistent
with the remarkable rectifying properties under this condition.
Moreover, this pH-responsive property is quite robust. The
ICR factor (f rec) with the (PEI/CS)4/cross-linking/(PEI/
CS)3/PEI film changed to ∼30 when the pH of the LbL film
side was changed to 8, and the best rectifying performance
(f rec, ∼600) was recovered when the pH at the LbL film side of
the membrane returned to 3 (Figure S19).
Notably, exposure of the PET substrate to pH 3 solutions
leads to weaker ICR, irrespective of the pH at the LbL film side
(Figure S20). Again, this is consistent with the surface charge
density, as the PET changes from negative to essentially
neutral on going from pH 8 to pH 3. At low pH, the chloride
can readily pass through the PET to limit depletion.
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Analytical Chemistry
Effect of Ionic Strength on ICR at Fixed pH. At a fixed
pH and as the ionic strength increases, the Debye length in the
nanochannel will decrease to give less cation exclusion from
the channel. Only when the Debye length is larger or
comparable to the pore size, will the overlapping electric
double layers result in greatly enhanced transport of counter-
ion carriers through nanochannels.1 To investigate the effect of
ionic strength on ICR, we fixed the pH values on the PET and
LbL film sides of the membrane at 8 and 3, respectively.
Figure 4a shows I−V curves for (PEI/CS)4/cross-linking/
(PEI/CS)3/PEI-modified membranes exposed to solutions
Figure 4. ICR as a function of ionic strength. (a) I−V curves collected
in different asymmetric conditions. The pH of solutions on the PET
and LbL sides of the membrane were fixed at 8 and 3, respectively, to
achieve high surface-charge densities. (b) ICR factors and Cl− ion
selectivity of (PEI/CS)4/cross-linking/(PEI/CS)3/PEI modified
membranes under the different conditions corresponding to (a). (c)
Illustration of ion transport through LbL-modified membranes under
a concentration gradient.
with various ionic strengths. With 0.1 M NaCl on the PET side
of the system, the ionic currents under negative voltage are
nearly independent of the NaCl concentration on the LbL film
side. The Debye length in 0.1 M NaCl is only 0.96 nm, which
is much smaller than the pore size (10 nm) in the PET
nanochannel. Thus, the nanopores should show minimal
permselectivity. Despite this, the coated membranes still show
ICR factors around ∼40 with 0.1 M NaCl on both sides of the
membrane (10−1(8)|10−1(3) system) (Figure 4b), indicating
that anions still carry significantly more current in the LbL film
than in the nanopores even at the highest ionic strength.
Nevertheless, the difference in anion permselectivity between
the LbL film and nanopores is likely higher at lower ionic
strength, so the ICR factor is greater for the 10−1(8)|10−4(3)
system than for the 10−1(8)|10−1(3) system (Figure 4b).
Additionally, the resistance in the film should be more
dominant at the lower ionic strength on the film side of the
membrane. Thus, with low ionic strength on the PET side, the
ICR factor is high because of the low reverse bias current. Low
ionic strength on the PET side leads to especially high
depletion, but it also decreases forward currents.
Under a concentration gradient (Figure 4c), the 10−4 M
NaCl solution in contact with one side of the hybrid
membrane may be low enough in concentration to not
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contribute significantly to the ion current. (Current results
primarily from ions coming from the other side of the
membrane with higher concentration.) This assumption allows
for an estimate of the film ion-transport permselectivity
between the cation and anion. For example, with 0.1 M
NaCl at the film-modified side of the membrane (Figure 4c),
under negative voltages, Cl− ions are driven through the film to
the PET membrane. Because the PET side with 10−4 M NaCl
(pH 8) solution does not provide a significant concentration of
ions, the current is approximately carried only by Cl− ions. At
an opposite voltage polarity, Na+ currents from 0.1 M solution
(pH 3) should dominate transports in the film and the current
is very small (40 nA at 2 V). The inversion of the
concentration gradient caused a large Na+ current at negative
voltage and a small Cl− current at positive voltage. Equation 1
approximately describes Sion as reported previously,65
|ICl−| − |INa+|
Sion =
|ICl−| + |INa+| (1)
where |ICl | and |INa | are the absolute currents carried by Cl−
− +
and Na+ ions, respectively. Under a 10−4/0.1 M concentration
gradient, absolute currents at 2 and −2 V were used to
represent |ICl−| and |INa+|, respectively. The charge heteroge-
neous membranes exhibited excellent anion selectivity with a
Cl− selectivity of 0.98.
■ CONCLUSIONS
In summary, we formed membrane-based fluidic diodes via
coating the top surface of polymeric nanochannel membranes
with LbL nanofilms. Films containing an underlying cross-
linked layer exhibit especially a high ICR. The large Debye
lengths in the dense, cross-linked regions may enable the high
surface charge to effectively regulate ion transport, endowing
the hybrid films on membranes with excellent ICR and anion
selectivity. Moreover, the current rectification depends on the
pH of the bulk solution in dilute solution because of the
incorporation of pH-sensitive materials in LbL films. The
diversity of polyelectrolytes and tunable porous structures in
LbL films should allow for development of a variety of smart
multifunctional diode membranes for potential applications in
energy-harvesting devices and chemical/biosensing.19
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.analchem.0c05303.
Ellipsometric models and data for determining the
optical constants of gold substrates and water, and the
thicknesses of films in air and in water; structures of
branched PEI and chondroitin-4-sulfate (CS); zeta
potentials of CS, PEI, and film-modified membranes;
contact angles and cross-sectional images of film-
modified membranes with different numbers of layers;
TOF−SIMS depth profiles of the etched area on a (PEI/
CS)4/cross-linking/(PEI/CS)3/PEI film on a PET
membrane; dynamic light scattering hydrodynamic
diameters of PEI and CS polyelectrolyte chains in
water; X-ray photoelectron spectra of PEI, CS, and
(PEI/CS)4/cross-linking/(PEI/CS)3/PEI films; AFM
topography and moduli of (PEI/CS)4/cross-linking/
(PEI/CS)3/PEI films on membranes in water.; I−V
curves collected during the formation of (PEI/CS)4/
https://dx.doi.org/10.1021/acs.analchem.0c05303
Anal. Chem. 2021, 93, 4291−4298
Analytical Chemistry
cross-linking/(PEI/CS)3/PEI; I−V curves for (PEI/
CS) 4 /cross-linking/(PEI/CS) 3 /PEI-modified mem-
branes using two different pH values (5 or 8) on the
film side of the membrane; pH-responsiveness of (PEI/
CS) 4 /cross-linking/(PEI/CS) 3 /PEI-modified PET
membrane in 10−4 M NaCl; and I−V curves of (PEI/
CS) 4 /cross-linking/(PEI/CS) 3 /PEI-modified PET
membranes in 10−4 M NaCl solutions with different
pH combinations on the two sides of the membrane
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
Fan Xia − Faculty of Materials Science and Chemistry, China
University of Geosciences, Wuhan 430074, China;
orcid.org/0000-0001-7705-4638; Email: xiafan@
cug.edu.cn, xiafan@hust.edu.cn
Authors
Shouwei Zhang − Faculty of Materials Science and Chemistry,
China University of Geosciences, Wuhan 430074, China;
orcid.org/0000-0001-8124-5322
Liu Yang − Department of Chemistry and Biochemistry,
University of Notre Dame, Notre Dame, Indiana 46556,
United States
Dong Ding − Department of Chemical and Biomolecular
Engineering, University of Notre Dame, Notre Dame, Indiana
46556, United States
Pengcheng Gao − Faculty of Materials Science and Chemistry,
China University of Geosciences, Wuhan 430074, China
Merlin L. Bruening − Department of Chemistry and
Biochemistry and Department of Chemical and Biomolecular
Engineering, University of Notre Dame, Notre Dame, Indiana
46556, United States; orcid.org/0000-0002-4553-5143
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.analchem.0c05303
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation (22090050, 21874121, and 21974126).
This research was supported by the Zhejiang Provincial
Natural Science Foundation of China (grant no.
LD21B050001) and Natural Science Foundation of Hubei
Provience (grant no. 2020CFA037). This research work was
supported by the Open Funds of the State Key Laboratory of
Electro Anal. Chem. (SKLEAC202003) and the National Key
Research and Development Program of China
(2018YFE0206900). This work was also supported by China
Postdoctoral Science Foundation (2020M672437) and Post-
doctoral Innovation program of Hubei Province
(2020035026). M. L. Bruening acknowledges funding from
the Division of Chemical Sciences, Geosciences, and
Biosciences, Office of Basic Energy Sciences of the U.S.
Department of energy through Grant DE-SC0017618. S.Z.
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thanks Qun Ma for his valuable comments and helpful
discussions.
■
REFERENCES
(1) Pérez-Mitta, G.; Toimil-Molares, M. E.; Trautmann, C.;
Marmisollé, W. A.; Azzaroni, O. Adv. Mater. 2019, 31, No. e1901483.
(2) Haywood, D. G.; Saha-Shah, A.; Baker, L. A.; Jacobson, S. C.
Anal. Chem. 2015, 87, 172−187.
(3) Zhang, H.; Tian, Y.; Jiang, L. Nano Today 2016, 11, 61−81.
(4) Wen, L.; Jiang, L. Natl. Sci. Rev. 2014, 1, 144−156.
(5) Guo, W.; Tian, Y.; Jiang, L. Acc. Chem. Res. 2013, 46, 2834−
2846.
(6) Cheng, L.-J.; Guo, L. J. Chem. Soc. Rev. 2010, 39, 923−938.
(7) Wen, L.; Sun, Z.; Han, C.; Imene, B.; Tian, D.; Li, H.; Jiang, L.
Chem.Eur. J. 2013, 19, 7686−7690.
(8) Siwy, Z. S.; Howorka, S. Chem. Soc. Rev. 2010, 39, 1115−1132.
(9) Liu, P.; Xie, G.; Li, P.; Zhang, Z.; Yang, L.; Zhao, Y.; Zhu, C.;
Kong, X.-Y.; Jiang, L.; Wen, L. NPG Asia Mater. 2018, 10, 849−857.
(10) Xiao, K.; Chen, L.; Zhang, Z.; Xie, G.; Li, P.; Kong, X.-Y.; Wen,
L.; Jiang, L. Angew. Chem., Int. Ed. 2017, 56, 8168−8172.
(11) Zhao, X.-P.; Zhou, Y.; Zhang, Q.-W.; Yang, D.-R.; Wang, C.;
Xia, X.-H. Anal. Chem. 2019, 91, 1185−1193.
(12) Vlassiouk, I.; Smirnov, S.; Siwy, Z. ACS Nano 2008, 2, 1589−
1602.
(13) Lin, C.-Y.; Hsu, J.-P.; Yeh, L.-H. Sens. Actuators, B 2018, 258,
1223−1229.
(14) Tagliazucchi, M.; Rabin, Y.; Szleifer, I. ACS Nano 2013, 7,
9085−9097.
(15) Hou, X.; Yang, F.; Li, L.; Song, Y.; Jiang, L.; Zhu, D. J. Am.
Chem. Soc. 2010, 132, 11736−11742.
(16) Lin, C.-Y.; Turker Acar, E.; Polster, J. W.; Lin, K.; Hsu, J.-P.;
Siwy, Z. S. ACS Nano 2019, 13, 9868−9879.
(17) Pérez-Mitta, G.; Marmisollé, W. A.; Trautmann, C.; Toimil-
Molares, M. E.; Azzaroni, O. Adv. Mater. 2017, 29, 1700972.
(18) Liu, P.; Zhou, T.; Teng, Y.; Fu, L.; Hu, Y.; Lin, X.; Kong, X.-Y.;
Jiang, L.; Wen, L. CCS Chem. 2020, 2, 1325−1335.
(19) Huang, X.; Kong, X.-Y.; Wen, L.; Jiang, L. Adv. Funct. Mater.
2018, 28, 1801079.
(20) Vlassiouk, I.; Siwy, Z. S. Nano Lett. 2007, 7, 552−556.
(21) Sheng, Q.; Wang, L.; Wang, C.; Wang, X.; Xue, J.
Biomicrofluidics 2014, 8, 052111.
(22) Yang, C.; Hinkle, P.; Menestrina, J.; Vlassiouk, I. V.; Siwy, Z. S.
J. Phys. Chem. Lett. 2016, 7, 4152−4158.
(23) Han, J.-H.; Kim, K. B.; Kim, H. C.; Chung, T. D. Angew. Chem.,
Int. Ed. 2009, 48, 3830−3833.
(24) Lin, C.-Y.; Combs, C.; Su, Y.-S.; Yeh, L.-H.; Siwy, Z. S. J. Am.
Chem. Soc. 2019, 141, 3691−3698.
(25) Yan, R.; Liang, W.; Fan, R.; Yang, P. Nano Lett. 2009, 9, 3820−
3825.
(26) Zhang, Z.; Wen, L.; Jiang, L. Chem. Soc. Rev. 2018, 47, 322−
356.
(27) Yan, F.; Yao, L.; Yang, Q.; Chen, K.; Su, B. Anal. Chem. 2019,
91, 1227−1231.
(28) Wu, S.; Wildhaber, F.; Vazquez-Mena, O.; Bertsch, A.; Brugger,
J.; Renaud, P. Nanoscale 2012, 4, 5718−5723.
(29) Liu, F.-F.; Guo, Y.-C.; Wang, W.; Chen, Y.-M.; Wang, C.
Nanoscale 2020, 12, 11899−11907.
(30) Zhang, H.; Hou, J.; Hu, Y.; Wang, P.; Ou, R.; Jiang, L.; Liu, J.
Z.; Freeman, B. D.; Hill, A. J.; Wang, H. Sci. Adv. 2018, 4,
No. eaaq0066.
(31) Roghmans, F.; Evdochenko, E.; Martí-Calatayud, M. C.;
Garthe, M.; Tiwari, R.; Walther, A.; Wessling, M. J. Membr. Sci. 2020,
600, 117854.
(32) Wang, C.; Zhao, X.-P.; Liu, F.-F.; Chen, Y.; Xia, X.-H.; Li, J.
Nano Lett. 2020, 20, 1846−1854.
(33) Zhang, Q.; Liu, Q.; Kang, J.; Huang, Q.; Liu, Z.; Diao, X.; Zhai,
J. Adv. Sci. 2018, 5, 1800163.
(34) Zhu, X.; Zhang, B.; Ye, Z.; Shi, H.; Shen, Y.; Li, G. Chem.
Commun. 2015, 51, 640−643.
https://dx.doi.org/10.1021/acs.analchem.0c05303
Anal. Chem. 2021, 93, 4291−4298
Analytical Chemistry pubs.acs.org/ac Article

(35) Xiao, T.; Ma, J.; Liu, Z.; Lu, B.; Jiang, J.; Nie, X.; Luo, R.; Jin, J.;
Liu, Q.; Li, W.; Zhai, J. J. Mater. Chem. A 2020, 8, 11275−11281.
(36) Zhang, Z.; Kong, X.-Y.; Xiao, K.; Xie, G.; Liu, Q.; Tian, Y.;
Zhang, H.; Ma, J.; Wen, L.; Jiang, L. Adv. Mater. 2016, 28, 144−150.
(37) Gao, J.; Guo, W.; Feng, D.; Wang, H.; Zhao, D.; Jiang, L. J. Am.
Chem. Soc. 2014, 136, 12265−12272.
(38) Sui, X.; Zhang, Z.; Li, C.; Gao, L.; Zhao, Y.; Yang, L.; Wen, L.;
Jiang, L. ACS Appl. Mater. Interfaces 2019, 11, 23815−23821.
(39) Yang, L.; Liu, P.; Zhu, C.; Zhao, Y.; Yuan, M.; Kong, X.-Y.;
Wen, L.; Jiang, L. Chin. Chem. Lett. 2020, DOI: 10.1016/
j.cclet.2020.04.047.
(40) Zhang, Z.; He, L.; Zhu, C.; Qian, Y.; Wen, L.; Jiang, L. Nat.
Commun. 2020, 11, 875.
(41) Zhu, X.; Zhou, Y.; Hao, J.; Bao, B.; Bian, X.; Jiang, X.; Pang, J.;
Zhang, H.; Jiang, Z.; Jiang, L. ACS Nano 2017, 11, 10816−10824.
(42) Zhang, M.; Guan, K.; Ji, Y.; Liu, G.; Jin, W.; Xu, N. Nat.
Commun. 2019, 10, 1253.
(43) Wiese, M.; Lohaus, T.; Haussmann, J.; Wessling, M. J. Membr.
Sci. 2019, 588, 117190.
(44) Ali, M.; Yameen, B.; Neumann, R.; Ensinger, W.; Knoll, W.;
Azzaroni, O. J. Am. Chem. Soc. 2008, 130, 16351−16357.
(45) Ma, T.; Gaigalas, P.; Lepoitevin, M.; Plikusiene, I.; Bechelany,
M.; Janot, J.-M.; Balanzat, E.; Balme, S. Langmuir 2018, 34, 3405−
3412.
(46) Ali, M.; Yameen, B.; Cervera, J.; Ramírez, P.; Neumann, R.;
Ensinger, W.; Knoll, W.; Azzaroni, O. J. Am. Chem. Soc. 2010, 132,
8338−8348.
(47) Fang, R.; Zhang, H.; Yang, L.; Wang, H.; Tian, Y.; Zhang, X.;
Jiang, L. J. Am. Chem. Soc. 2016, 138, 16372−16379.
(48) Salloum, D. S.; Schlenoff, J. B. Electrochem. Solid-State Lett.
2004, 7, No. E45.
(49) Evdochenko, E.; Kamp, J.; Femmer, R.; Xu, Y.; Nikonenko, V.
V.; Wessling, M. J. Membr. Sci. 2020, 611, 118045.
(50) Zhang, Z.; Li, P.; Kong, X.-Y.; Xie, G.; Qian, Y.; Wang, Z.; Tian,
Y.; Wen, L.; Jiang, L. J. Am. Chem. Soc. 2018, 140, 1083−1090.
(51) Lin, Z.; Zhang, Q.; Qu, Y.; Chen, M.; Soyekwo, F.; Lin, C.;
Zhu, A.; Liu, Q. J. Mater. Chem. A 2017, 5, 14819−14827.
(52) Malaisamy, R.; Bruening, M. L. Langmuir 2005, 21, 10587−
10592.
(53) Hong, S. U.; Malaisamy, R.; Bruening, M. L. Langmuir 2007,
23, 1716−1722.
(54) Black, C. T.; Forrey, C.; Yager, K. G. Soft Matter 2017, 13,
3275−3283.
(55) Mohrmann, J.; Tiwald, T. E.; Hale, J. S.; Hilfiker, J. N.; Martin,
A. C. J. Vac. Sci. Technol., B: Nanotechnol. Microelectron.: Mater.,
Process., Meas., Phenom. 2020, 38, 014001.
(56) Zhao, Y.; Janot, J.-M.; Balanzat, E.; Balme, S. Langmuir 2017,
33, 3484−3490.
(57) Zhang, S.; Liu, W.; Liang, J.; Li, X.; Liang, W.; He, S.; Zhu, C.;
Mao, L. Cellulose 2013, 20, 1135−1143.
(58) Bertrand, P.; Jonas, A.; Laschewsky, A.; Legras, R. Macromol.
Rapid Commun. 2000, 21, 319−348.
(59) Roy, J. C.; Buron, C. C.; Demoustier-Champagne, S.; Jonas, M.
A. In Multilayer Thin Films: Sequential Assembly of Nanocomposite
Materials; Decher, G.; Schlenoff, B. J., Eds.; Wiley-VCH Verlag & Co.
KGaA: Weinheim, Germany, 2012; pp 613−634.
(60) Köhler, K.; Biesheuvel, P. M.; Weinkamer, R.; Möhwald, H.;
Sukhorukov, G. B. Phys. Rev. Lett. 2006, 97, 188301.
(61) Borges, J.; Mano, J. F. Chem. Rev. 2014, 114, 8883−8942.
(62) An, Q.; Huang, T.; Shi, F. Chem. Soc. Rev. 2018, 47, 5061−
5098.
(63) Fu, W.; Jiang, L.; van Geest, E. P.; Lima, L. M. C.; Schneider,
G. F. Adv. Mater. 2017, 29, 1603610.
(64) Siwy, Z. S. Adv. Funct. Mater. 2006, 16, 735−746.
(65) He, Y.; Gillespie, D.; Boda, D.; Vlassiouk, I.; Eisenberg, R. S.;
Siwy, Z. S. J. Am. Chem. Soc. 2009, 131, 5194−5202.

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