ACS Nano,
Год журнала:
2024,
Номер
18(8), С. 6016 - 6027
Опубликована: Фев. 13, 2024
Ion
exchange
membranes
allowing
the
passage
of
charge-carrying
ions
have
established
their
critical
role
in
water,
environmental,
and
energy-relevant
applications.
The
design
strategies
for
high-performance
ion
evolved
beyond
creating
microphase-separated
membrane
morphologies,
which
include
advanced
to
ion-selective
membranes.
properties
functions
been
repeatedly
updated
by
emergence
materials
with
subnanometer-sized
pores
understanding
movement
under
confined
micropore
channels.
These
research
progresses
motivated
researchers
consider
even
greater
aims
field,
i.e.,
replicating
channels
living
cells
exotic
or
at
least
targeting
fast
ion-specific
transmembrane
conduction.
To
help
realize
such
goals,
we
briefly
outline
comment
on
fundamentals
rationally
designing
pore
ultrafast
specific
conduction,
architecture/chemistry,
materials.
Challenges
are
discussed,
perspectives
outlooks
given.
Advanced Functional Materials,
Год журнала:
2022,
Номер
32(52)
Опубликована: Окт. 17, 2022
Abstract
Ion
exchange
membranes
(IEMs)
that
can
selectively
transport
ions
are
crucial
to
a
variety
of
applications,
such
as
ion
extraction/separation,
fuel
cells,
redox
flow
batteries,
and
water
electrolysis.
IEM
performance,
in
terms
membrane
permeability/conductivity
selectivity,
relies
heavily
on
the
formation
effective
channels
within
membranes,
there
exists
tradeoff
between
which
obstructs
development
widespread
adoption
IEM‐based
processes.
To
overcome
this
advance
IEM‐related
extensive
research
efforts
devoted
construction
tuning
channels,
various
strategies
proposed.
These
mainly
include
1)
inducing
microphase
separation
by
properly
regulating
polymer
architecture,
2)
introducing
third
phase/region
for
transfer,
3)
realizing
high
free
volume
with
polyrotaxanes
or
polymers
sterically
bulky
groups,
4)
constructing
nanoporous
materials.
outlined
summarized
review.
Perspectives
future
directions
also
discussed.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 5, 2023
Abstract
Efficient
Mg
2+
/Li
+
separation
is
crucial
to
combating
the
lithium
shortage
worldwide,
yet
current
nanofiltration
membranes
suffer
from
low
efficacy
and/or
poor
scalability,
because
desirable
properties
of
are
entangled
and
there
a
trade‐off.
This
work
reports
“tagged‐modification”
approach
tackle
challenge.
A
mixture
3‐bromo‐trimethylpropan‐1‐aminium
bromide
(E
1
)
3‐aminopropyltrimethylazanium
2
was
designed
modify
polyethylenimine
–
trimesoyl
chloride
(PEI‐TMC)
membranes.
E
reacted
with
PEI
TMC,
respectively,
thus,
membrane
(hydrophilicity,
pore
sizes,
charge)
were
untangled
intensified
simultaneously.
The
permeance
(34.3
L
m
−2
h
−1
bar
selectivity
(23.2)
modified
about
4
times
higher
than
pristine
membrane,
they
remain
stable
in
30‐days
test.
highest
among
all
analogous
tagged‐modification
method
enables
preparation
large‐area
modules
that
produce
high‐purity
carbonate
(Li
CO
3
simulated
brine.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 8, 2024
Abstract
Membrane
consisting
of
ordered
sub-nanochannels
has
been
pursued
in
ion
separation
technology
to
achieve
applications
including
desalination,
environment
management,
and
energy
conversion.
However,
high-precision
not
yet
achieved
owing
the
lack
deep
understanding
transport
mechanism
confined
environments.
Biological
channels
can
conduct
ions
with
ultrahigh
permeability
selectivity,
which
is
inseparable
from
important
role
channel
size
“ion-channel”
interaction.
Here,
inspired
by
biological
systems,
we
report
monovalent
divalent
cations
functionalized
metal-organic
framework
(MOF)
membranes
(UiO-66-(X)
2
,
X
=
NH
SH,
OH
OCH
3
).
We
find
that
functional
group
(X)
MOF
sub-nanochannel
synergistically
regulate
binding
affinity
dehydration
process,
key
enlarging
activation
difference
between
target
interference
improve
performance.
The
K
+
/Mg
2+
selectivity
UiO-66-(OCH
)
membrane
reaches
as
high
1567.8.
This
work
provides
a
gateway
development
membranes.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Май 30, 2023
The
evolution
of
the
chemical
and
pharmaceutical
industry
requires
effective
less
energy-intensive
separation
technologies.
Engineering
smart
materials
at
a
large
scale
with
tunable
properties
for
molecular
is
challenging
step
to
materialize
this
goal.
Herein,
we
report
thin
film
composite
membranes
prepared
by
interfacial
polymerization
porous
organic
cages
(POCs)
(RCC3
tren
cages).
Ultrathin
crosslinked
polycage
selective
layers
(thickness
as
low
9.5
nm)
are
obtained
high
permeance
strict
sieving
nanofiltration.
A
dual
function
achieved
combining
catalysis.
This
demonstrated
impregnating
highly
catalytically
active
Pd
nanoclusters
(
~
0.7
nm).
While
membrane
promotes
precise
separation,
its
catalytic
activity
enables
surface
self-cleaning,
reacting
any
potentially
adsorbed
dye
recovering
original
performance.
strategy
opens
opportunities
development
other
different
functions
well-tailored
abilities.
State-of-the-art
ion-selective
membranes
with
ultrahigh
precision
are
of
significance
for
water
desalination
and
energy
conservation,
but
their
development
is
limited
by
the
lack
understanding
mechanisms
ion
transport
at
subnanometer
scale.
Herein,
we
investigate
three
typical
anions
(F
−
,
Cl
Br
)
under
confinement
using
in
situ
liquid
time-of-flight
secondary
mass
spectrometry
combination
transition-state
theory.
The
operando
analysis
reveals
that
dehydration
related
ion-pore
interactions
govern
anion-selective
transport.
For
strongly
hydrated
ions
[(H
2
O)
n
F
(H
],
enhances
effective
charge
thus
electrostatic
membrane,
observed
as
an
increase
decomposed
from
electrostatics,
leading
to
more
hindered
Contrarily,
weakly
]
have
greater
permeability
they
allow
intact
hydration
structure
during
due
smaller
size
most
right-skewed
distribution.
Our
work
demonstrates
precisely
regulating
maximize
difference
could
enable
ideal
membranes.
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(8)
Опубликована: Фев. 13, 2024
Understanding
the
molecular-level
mechanisms
involved
in
transmembrane
ion
selectivity
is
essential
for
optimizing
membrane
separation
performance.
In
this
study,
we
reveal
our
observations
regarding
behavior
of
Li
+
and
Mg
2+
ions
as
a
response
to
changing
pore
solvation
abilities
covalent-organic-framework
(COF)
membranes.
These
were
manipulated
by
adjusting
lengths
oligoether
segments
attached
channels.
Through
comparative
experiments,
able
unravel
relationships
between
ability
various
transport
properties,
such
partitioning,
conduction,
selectivity.
We
also
emphasize
significance
competition
with
solvating
modulating
found
that
increasing
length
chain
facilitated
transport;
however,
it
was
COF
chains
containing
two
ethylene
oxide
units
exhibited
most
pronounced
discrepancy
energy
barrier
,
resulting
highest
factor
among
all
evaluated
Remarkably,
under
electro-driven
binary-salt
conditions,
specific
achieved
an
exceptional
/Mg
up
1352,
making
one
effective
membranes
available
separation.
The
insights
gained
from
study
significantly
contribute
advancing
understanding
selective
within
confined
nanospaces
provide
valuable
design
principles
developing
highly
Fast
transport
of
monovalent
ions
is
imperative
in
selective
ion
separation
based
on
membranes.
Here,
we
report
the
situ
growth
crown
ether@UiO-66
membranes
at
a
mild
condition,
where
dibenzo-18-crown-6
(DB18C6)
or
dibenzo-15-crown-5
perfectly
confined
UiO-66
cavity.
Crown
exhibit
enhanced
rates
and
mono-/divalent
selectivity,
due
to
combination
size
sieving
interaction
screening
effects
toward
complete
dehydration.
Specifically,
DB18C6@UiO-66
membrane
shows
permeation
rate
(e.g.,
K
Nature,
Год журнала:
2024,
Номер
635(8038), С. 353 - 358
Опубликована: Ноя. 6, 2024
Abstract
Ion-conducting
polymer
membranes
are
essential
in
many
separation
processes
and
electrochemical
devices,
including
electrodialysis
1
,
redox
flow
batteries
2
fuel
cells
3
electrolysers
4,5
.
Controlling
ion
transport
selectivity
these
largely
hinges
on
the
manipulation
of
pore
size.
Although
membrane
structures
can
be
designed
dry
state
6
they
redefined
upon
hydration
owing
to
swelling
electrolyte
solutions.
Strategies
control
a
deeper
understanding
structure
evolution
vital
for
accurate
size
tuning.
Here
we
report
containing
pendant
groups
varying
hydrophobicity,
strategically
positioned
near
charged
regulate
their
capacity
swelling.
Modulation
hydrated
micropore
(less
than
two
nanometres)
enables
direct
over
water
across
broad
length
scales,
as
quantified
by
spectroscopic
computational
methods.
Ion
improves
hydration-restrained
pores
created
more
hydrophobic
groups.
These
highly
interconnected
channels,
with
tuned
gate
sizes,
show
higher
ionic
conductivity
orders-of-magnitude
lower
permeation
rates
redox-active
species
compared
conventional
membranes,
enabling
stable
cycling
energy-dense
aqueous
organic
batteries.
This
tailoring
approach
provides
promising
avenue
precisely
controlled
molecular
functions.