ACS Nano,
Год журнала:
2023,
Номер
17(8), С. 7584 - 7594
Опубликована: Апрель 7, 2023
Covalent
organic
framework
(COF)
membranes
have
emerged
as
a
promising
candidate
for
energy-efficient
separations,
but
the
angstrom-precision
control
of
channel
size
in
subnanometer
region
remains
challenge
that
has
so
far
restricted
their
potential
gas
separation.
Herein,
we
report
an
ultramicropore-in-nanopore
concept
engineering
matreshka-like
pore-channels
inside
COF
membrane.
In
this
concept,
α-cyclodextrin
(α-CD)
is
situ
encapsulated
during
interfacial
polymerization
which
presumably
results
linear
assembly
(LA)
α-CDs
1D
nanochannels
COF.
The
LA-α-CD-in-TpPa-1
membrane
shows
high
H2
permeance
(∼3000
GPU)
together
with
enhanced
selectivity
(>30)
over
CO2
and
CH4
due
to
formation
fast
selective
H2-transport
pathways.
overall
performance
H2/CO2
H2/CH4
separation
transcends
Robeson
upper
bounds
ranks
among
most
powerful
H2-selective
membranes.
versatility
strategy
demonstrated
by
synthesizing
different
types
LA-α-CD-in-COF
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(26), С. 14236 - 14250
Опубликована: Янв. 25, 2021
Abstract
Imine‐based
covalent
organic
frameworks
(COFs)
are
a
widely
studied
class
of
functional,
crystalline,
and
porous
nanostructures
which
combine
relatively
facile
crystallization
with
tuneable
compositions
porosities.
However,
the
imine
linkage
constitutes
an
intrinsic
limitation
due
to
its
reduced
stability
in
harsh
chemical
conditions
unsuitability
for
in‐plane
π‐conjugation
COFs.
Urgent
solutions
therefore
required
order
exploit
full
potential
these
materials,
thereby
enabling
their
technological
application
electronics,
sensing,
energy
storage
devices.
In
this
context,
advent
new
generation
linkages
derived
from
conversion
locking
bond
represents
cornerstone
synthesis
A
marked
increase
framework
robustness
is
fact
often
combined
incorporation
novel
functionalities
including,
some
reactions,
extension
π‐conjugation.
This
Minireview
describes
most
enlightening
examples
one‐pot
reactions
post‐synthetic
modifications
towards
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(47)
Опубликована: Сен. 14, 2022
Abstract
Covalent
organic
frameworks
(COFs)
are
an
emerging
category
of
polymers
with
highly
porous
crystalline
structures.
In
the
last
decade,
reports
on
use
COFs
as
heterogeneous
photocatalysts
for
transformations
have
shown
significant
progress.
Still,
comprehensive
reviews
mechanisms
photocatalytic
using
lacking.
This
Review
provides
a
and
systematic
overview
COF‐based
transformations.
Firstly,
we
discuss
photophysical
properties
characterization
methods
photocatalysts.
Then,
general
mechanism,
advantages,
strategies
to
improve
efficiency
summarized.
After
that,
advanced
examples
analyzed
regard
underlying
mechanisms.
The
ends
critical
perspective
challenges
prospects.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(14), С. 6583 - 6593
Опубликована: Апрель 5, 2022
Morphological
control
of
covalent
organic
frameworks
(COFs)
is
particularly
interesting
to
boost
their
applications;
however,
it
remains
a
grand
challenge
prepare
hollow
structured
COFs
(HCOFs)
with
high
crystallinity
and
uniform
morphology.
Herein,
we
report
versatile
efficient
strategy
amorphous-to-crystalline
transformation
for
the
general
controllable
fabrication
highly
crystalline
HCOFs.
These
HCOFs
exhibited
ultrahigh
surface
areas,
radially
oriented
nanopore
channels,
quite
morphologies,
tunable
particle
sizes.
Mechanistic
studies
revealed
that
H2O,
acetic
acid,
solvent
played
crucial
role
in
manipulating
hollowing
process
crystallization
by
regulating
dynamic
imine
exchange
reaction.
Our
approach
was
demonstrated
be
applicable
various
amines
aldehydes,
producing
up
10
kinds
Importantly,
based
on
this
methodology,
even
constructed
library
unprecedented
including
different
pore
structures,
bowl-like
HCOFs,
cross-wrinkled
COF
nanocapsules,
grain-assembled
hydrangea-like
This
also
successfully
applied
COF-based
yolk-shell
nanostructures
functional
interior
cores.
Furthermore,
catalytically
active
metal
nanoparticles
were
implanted
into
cavities
diameters,
forming
attractive
size-selective
nanoreactors.
The
obtained
metal@HCOFs
catalysts
showed
enhanced
catalytic
activity
outstanding
size-selectivity
hydrogenation
nitroarenes.
work
highlights
significance
nucleation-growth
kinetics
tuning
applications.
Advanced Optical Materials,
Год журнала:
2021,
Номер
9(23)
Опубликована: Фев. 18, 2021
Abstract
Excited‐state
intramolecular
proton
transfer
(ESIPT)
process
brings
about
ultrafast
keto‐enol
tautomerism,
which
simultaneously
induces
the
unique
four‐leveled
energy
state
cycle
and
concomitant
multi‐emissions.
Such
transformation
is
easily
affected
by
environmental
conditions,
leading
to
intricate
spectral
responses.
In
contrast
with
widely
reported
researches
that
inclined
solution
systems
dissolved
ESIPT
molecules,
materials
including
small
organic
metal‐organic
materials,
covalent‐organic
frameworks,
so
on,
can
be
formed
in
solid
are
emerging
recent
years,
bringing
more
scientific
information
novel
applications
for
family
of
materials.
this
short
review,
progress
different
types
these
will
introduced,
especially
their
optical
sensing
performances
mechanisms,
like
responses
external
physical
stimulations
(pressure,
temperature,
light),
solvent
polarities,
pH,
ions,
molecule
compounds.
And
potential
photophysical
photochemical
also
surveyed.
Abstract
As
a
burgeoning
family
of
crystalline
porous
copolymers,
covalent
organic
frameworks
(COFs)
allow
precise
atomic
insertion
components
in
the
topology
construction
to
form
periodic
networks
and
ordered
nanopores.
Their
2D
bear
great
similarities
graphene
analogs,
therefore
are
essential
additions
family.
Here,
electronic
properties
conductive
2D‐COFs
reviewed
their
bonding
strategies
structural
characteristics
examined
detail.
The
controlling
approaches
toward
morphologies
further
explored,
followed
by
discussion
applications
field‐effect
transistors,
photodetectors,
sensors,
catalysis,
energy
storage.
Finally,
research
challenges
forthcoming
developments
projected.
resulting
survey
reveals
that
extended
with
will
provide
opportunities
innovations
various
electronics
energy‐related
fields.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(19)
Опубликована: Март 2, 2022
The
intrinsic
hydrophobicity
and
limited
light
absorption
especially
in
the
near-infrared
(NIR)
region
of
porous
organic
polymers
are
two
bottlenecks
impeding
their
applications
solar
steam
generation
(SSG).
Herein,
we
develop
a
1,4,5,8-tetrakis(phenylamino)anthracene-9,10-dione
(TPAD)-based
covalent
framework
(COF)
(TPAD-COF)
featuring
both
superhydrophilicity
broad
covering
from
entire
UV/Vis
to
NIR
regions
for
SSG.
TPAD-COF
serving
as
highly
efficient
photothermal
conversion
material
without
any
additives
displays
an
excellent
water
evaporation
1.42
kg
m-2
h-1
achieves
high
energy
efficiency
94
%
under
1
sun
irradiation.
Further
extension
range
TPAD-based
COF
is
realized
through
post-synthetic
modification
by
chelating
BF2
moieties.
Systematic
control
experiments
analysis
confirm
that
hydrophilicity
materials
plays
more
dominant
role
current
COFs
Advanced Functional Materials,
Год журнала:
2023,
Номер
34(1)
Опубликована: Сен. 21, 2023
Abstract
Adsorption‐photocatalysis
technology
based
on
covalent
organic
frameworks
(COFs)
offers
an
alternative
method
for
advancing
the
field
of
uranium
extraction
from
seawater.
When
determining
photocatalytic
activity
COFs,
binding
energy
excitons
(
E
b
)
functions
is
decisive
factor.
Nevertheless,
majority
reported
COFs
have
a
large
,
which
seriously
restricts
their
application
in
photocatalysis.
Using
practical
π‐skeleton
engineering
strategy,
current
study
synthesizes
three
donor‐acceptor
olefin‐linked
containing
amidoxime
units
effort
to
minimize
.
Theoretical
and
experimental
results
reveal
that
construction
planar
continuous
π
‐electron
delocalization
channels
can
significantly
reduce
promote
separation
electron‐hole
pairs,
thereby
enhancing
activities.
Moreover,
TTh‐COF‐AO
with
‐skeleton
donor
reduced,
exhibits
substantially
smaller
(38.4
meV).
Under
visible
light
irradiation,
high
photo‐enhanced
capacity
10.24
mg
g
−1
achieved
natural
seawater
without
addition
sacrificial
reagents,
superior
been
date.
This
study,
therefore,
paves
way
development
tailored,
efficient
photocatalysts
