Abstract
Covalent
organic
networks
(CONs)
are
considered
ideal
for
precise
molecular
separation
compared
with
traditional
polymer
membranes
because
their
pores
have
a
sharp
weight
cut‐off
and
robust
structure.
However,
challenges
remain
regard
to
tuning
as
prerequisite
facile
membrane
fabrication
defect‐free
layer.
Herein,
highly
conjugated
amino‐porphyrin
is
used
exploited
its
tunable
stacking
behavior
fabricate
porphyrin‐based
polyamide
CONs
ordered
structures
through
interfacial
polymerization
acyl
chlorides.
Controlling
the
self‐aggregation
of
porphyrin
conformation
chlorides
can
create
different
covalent
networks.
Acid‐triggered
protonation
offsets
reduce
pore
in
network
from
mesopore
micropore,
enabling
selective
molecule
transport.
Furthermore,
chloride
ligands
control
interlayer
bonding
CONs.
Accordingly,
tailored
diameters
(0.48–0.78
nm)
confirmed
by
rejections
performance
stability
over
25
days
operation,
well
under
various
conditions.
This
study
leverages
chemistry
CON
layer
significantly
lower
(<
330
Da)
than
previously
reported
(>800
Da).
will
pave
way
development
topological
membranes.
Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
Membranes
with
switchable
wettability,
solvent
resistance,
and
toughness
have
emerged
as
promising
materials
for
separation
applications.
However,
challenges
like
limited
mechanical
strength,
poor
chemical
stability,
structural
defects
during
membrane
fabrication
hinder
their
widespread
adoption.
Covalent
organic
frameworks
(COFs),
crystalline
constructed
from
molecules
connected
by
covalent
bonds,
offer
a
solution
due
to
high
porosity,
customizable
properties.
The
ordered
structures
functionality
provide
COFs
lightweight
framework,
large
surface
area,
tunable
pore
sizes,
which
attracted
increasing
attention
applications
in
separations.
Recent
research
has
extensively
explored
the
preparation
strategies
of
COF
membranes
various
processes.
This
review
uniquely
delves
into
influence
techniques,
including
interfacial
polymerization,
layer-by-layer
assembly,
situ
growth,
on
thickness
performance.
It
comprehensively
explores
design
potential
these
methods,
particular
focus
gas
separation,
oil/water
nanofiltration.
Furthermore,
future
opportunities,
within
this
field,
directions
development
are
proposed.
Two-dimensional
covalent
organic
frameworks
(2D
COFs)
are
emerging
as
promising
materials
for
advanced
electronic
applications
due
to
their
tunable
porosity,
crystalline
order,
and
π-conjugated
structures.
These
properties
enable
efficient
charge
transport
bandgap
modulation,
making
2D
COFs
strong
candidates
devices
such
transistors
memristors.
However,
the
practical
application
of
remains
limited
by
challenges
in
achieving
high-quality
thin
films
with
large-area
uniformity
improved
crystallinity.
This
review
explores
recent
advancements
fabrication
conductive
electronics.
Various
synthesis
strategies,
including
direct
growth,
vapor-assisted
conversion,
interfacial
methods,
discussed
context
enhancing
film
quality
scalability.
The
integration
into
is
classified
based
on
operation
mechanism─planar
vertical
field-effect
(FETs),
electrochemical
(ECTs),
memristors─to
highlight
device
performance.
Looking
forward,
large-scale
production,
material
compatibility,
outlined,
alongside
potential
solutions
through
innovative
techniques
collaborative
research
efforts.
By
addressing
these
challenges,
poised
drive
breakthroughs
adoption
next-generation
semiconducting
technologies.
ACS Materials Letters,
Год журнала:
2024,
Номер
unknown, С. 5454 - 5478
Опубликована: Ноя. 18, 2024
Gas
sensing
is
vital
for
ecological
protection
in
agriculture,
early
disease
diagnosis
biomedicine,
and
safety
industrial
production.
Covalent
organic
frameworks
(COFs),
a
new
class
of
porous
polymer
materials,
can
be
customized
through
specific
ligand
selection
to
tailor
pore
sizes
active
sites,
enabling
them
selectively
enrich
interact
with
targeted
gas
molecules,
making
promising
candidates
sensing.
To
advance
their
use
this
field,
it
essential
investigate
the
mechanisms
complex
interactions
between
COFs
target
molecules
as
well
improve
COF
film
fabrication
methods.
This
review
outlines
design
strategies
films
across
multiscale:
molecular
interaction
mechanisms,
macroscopic
interfacial
synthesis
methods,
microscale/nanoscale
approaches
such
double-layer
filtration
micro/nanostructured
improved
transfer.
Finally,
several
key
research
directions
are
proposed
suitability
COF-based
materials
environments.
Precise
separation
of
small
organic
molecules
and
electrolyte
salts
is
critical
for
various
industrial
processes,
necessitating
advanced
membranes
with
uniform
pores.
Proteins,
as
one
typical
nature
polymer
having
the
exactly
same
structure
molecular
weight,
offer
a
promising
material
making
such
membranes.
Here,
hemoglobin
(BHb)
lysozyme
(Lyz)
are
utilized
to
fabricate
precise
nanofiltration
through
amyloid-like
co-assembly,
triggered
by
Tris(2-carboxyethyl)
phosphine.
Molecular
dynamics
simulations
reveal
that
BHb
intercalates
between
Lyz
molecules,
enhancing
tight
assembly
reducing
defects.
The
Lyz/BHb
membrane
exhibits
high
void
volume
27.2%
achieves
an
exceptional
permeance
335
L
m-2
h-1
bar-1.
Amazingly,
ultra-selective
sieving
dyes
unparalleled
factor
1.25
×
103
NaCl/Brilliant
blue.
unique
adaptive
layer
formed
anchoring
dye
into
larger
pores
thus
narrowing
down
pore
size
distribution
electrostatic
repulsion,
endowing
distinctive
salts.
This
study
offers
valuable
insights
finely
tailor
co-assembly
proteins
significantly
enhance
perm-selectivity
creating
protein
property.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 19, 2025
Abstract
Embedding
isomer
entities
onto
crystalline
frameworks
with
precisely
defined
spatial
distributions
represents
a
promising
approach
to
enhancing
the
efficiency
of
oxygen
reduction
reaction
(ORR)
in
fuel
cells.
However,
accurately
constructing
covalent
organic
(COFs)
regulate
energy
state
effectively
remains
significant
challenge.
Herein,
an
innovative
geometric
isomerization
strategy
aimed
at
minimizing
rotational
barrier
(ΔE),
average
local
ionization
(ALIE),
and
Gibbs
free
(ΔG)
for
ORR
within
COFs
is
proposed.
Based
on
this
strategy,
isomeric
Py‐COF‐αα
2,2‐substitution,
Py‐COF‐ββ
3,3‐substitution,
Py‐COF‐αβ
2,3‐substitution
mainchain
have
been
obtained.
The
electronic
states
intermediate
adsorption
capabilities
are
finely
tuned
through
modification,
yielding
controllable
chemical
activity.
Notably,
lower
ΔE
between
thiophenes
achieves
remarkable
performance,
evidenced
by
half‐wave
potential
0.77
V
vs
reversible
hydrogen
electrode
(RHE),
surpassing
most
reported
metal‐free
electrocatalysts.
Combined
theoretical
prediction
situ
Raman
spectra,
it
revealed
that
increased
dipole
moment
non‐uniform
charge
distribution
caused
endows
pentacyclic‐carbon
(thiophene
β‐position)
far
from
sulfur
atoms
efficient
catalytic
This
work
has
opened
up
novel
paradigm
underscores
pivotal
role
regulation
facilitating
catalysis.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 20, 2025
Abstract
Covalent
organic
frameworks
(COFs)
have
emerged
as
prominent
membrane
materials
for
efficiently
fractionating
molecules
and
ions
due
to
their
unique
pore
structure.
However,
the
fabrication
of
free‐standing
COF
nanofilms
with
high
crystallinity
remains
an
arduous
undertaking,
feasible
methods
that
can
enable
precise
control
over
film
microstructure
are
barely
reported.
This
work
conceives
exquisite
interface‐confined
catalytic
strategy
prepare
Tp‐BD(OH)
2
nanofilm
anisotropic
structure
analogously
conventional
polymeric
membranes.
Experimental
data
molecular
simulations
reveal
hydroxyl
groups
on
framework
substantially
capture
anchor
acid
catalyst
through
hydrogen
bonding
interactions
at
incipient
stage
interfacial
polycondensation,
instigating
confined
catalysis
self‐termination
reaction
interface.
The
distinctive
asymmetric
endows
a
record‐breaking
pure
water
permeance
525.3
L
m
−2
h
−1
bar
unprecedented
dye/salt
selectivity
648.6,
surpassing
other
reported
films
state‐of‐the‐art
nanofiltration
membranes,
well
enduring
structural
durability
chemical
stability.
implemented
opens
up
new
avenue
regulating
holds
broad
prospects
rational
design
high‐performance
membranes
sustainable
purification
treatment.
