ACS Materials Letters,
Journal Year:
2024,
Volume and Issue:
6(4), P. 1474 - 1483
Published: March 15, 2024
The
design
and
synthesis
of
covalent
organic
frameworks
(COFs)
with
excellent
reusability
are
promising
ways
to
advance
practical
applications
in
many
fields,
including
as
absorbents
for
environmental
remediation.
However,
a
lack
guiding
principles
makes
it
challenging.
Herein,
two
COFs
(DhaTAT
DhaTAB)
prepared
demonstrated
work
excellently
the
adsorption
removal
representative
pollutant
phenanthrene
(PHE)
highest
capacity
fastest
kinetics
reported
so
far.
Although
having
comparable
PHE
performances,
DhaTAT
displays
much
better
than
DhaTAB.
By
deeply
exploring
underlying
mechanism,
we
reveal
first
time
adverse
effects
adsorption-induced
deformation
phenomenon
on
crystallinity,
morphology,
specific
surface
area,
thus
COFs,
propose
that
introducing
electron-withdrawing
groups
can
alleviate
this
endow
COF-based
adsorbents
reusability.
Such
prediction
is
further
confirmed
by
recycling
performances
new
(DapTFB
DanTFB)
designed
under
guidance
theoretical
calculations.
This
study
provides
valuable
insights
into
application
potential
which
crucial
development
materials
stable
performance
good
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1318 - 1325
Published: Jan. 5, 2024
Sp2-carbon-conjugated
covalent
organic
frameworks
(sp2c-COFs)
have
emerged
as
promising
platforms
for
phototo–chemical
energy
conversion
due
to
their
tailorable
optoelectronic
properties,
in-plane
π-conjugations,
and
robust
structures.
However,
the
development
of
sp2c-COFs
in
photocatalysis
is
still
highly
hindered
by
limited
linkage
chemistry.
Herein,
we
report
a
novel
thiadiazole-bridged
sp2c-COF
(sp2c-COF-ST)
synthesized
thiadiazole-mediated
aldol-type
polycondensation.
The
resultant
sp2c-COF-ST
demonstrates
high
chemical
stability
under
strong
acids
bases
(12
M
HCl
or
12
NaOH).
electro-deficient
thiadiazole
together
with
fully
conjugated
planar
skeleton
endows
superior
photoelectrochemical
performance
charge-carrier
separation
migration
ability.
As
result,
when
employed
photocathode,
exhibits
significant
photocurrent
up
∼14.5
μA
cm–2
at
0.3
V
vs
reversible
hydrogen
electrode
(RHE)
visible-light
irradiation
(>420
nm),
which
much
higher
than
those
analogous
COFs
partial
imine
linkages
(mix-COF-SNT
∼
9.5
cm–2)
full
(imi-COF-SNNT
4.9
cm–2),
emphasizing
importance
structure–property
relationships.
Further
temperature-dependent
photoluminescence
spectra
density
functional
theory
calculations
demonstrate
that
has
smaller
exciton
binding
well
effective
mass
comparison
mix-COF-SNT
imi-COF-SNNT,
suggests
sp2c-conjugated
enhances
dissociation
carrier
light
irradiation.
This
work
highlights
design
preparation
photocatalytic
performance.
ACS Nano,
Journal Year:
2024,
Volume and Issue:
18(33), P. 21804 - 21835
Published: Aug. 8, 2024
Covalent
organic
frameworks
(COFs)
are
crystalline
networks
with
extended
backbones
cross-linked
by
covalent
bonds.
Due
to
the
semiconductive
properties
and
variable
metal
coordinating
sites,
along
rapid
development
in
linkage
chemistry,
utilization
of
COFs
photocatalytic
CO2RR
has
attracted
many
scientists'
interests.
In
this
Review,
we
summarize
latest
research
progress
on
for
CO2
reduction.
first
part,
present
COF
linkages
that
have
been
used
CO2RR,
discuss
four
mechanisms
including
as
intrinsic
photocatalysts,
photosensitive
motifs
metalated
semiconductors
heterojunction
photocatalysts.
Then,
principles
structural
designs
functional
building
units
stacking
mode
exchange.
Finally,
outlook
challenges
provided.
This
Review
is
intended
give
some
guidance
design
synthesis
diverse
different
linkages,
various
structures,
divergent
modes
efficient
photoreduction
CO2.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 18, 2024
Abstract
The
development
of
porous
materials
with
flexible‐robust
characteristics
shows
some
unique
advantages
to
target
high
performance
for
gas
separation,
but
remains
a
daunting
challenge
achieve
so
far.
Herein,
we
report
carboxyl‐based
hydrogen‐bonded
organic
framework
(ZJU‐HOF‐8a)
porosity
efficient
purification
natural
gas.
ZJU‐HOF‐8a
features
four‐fold
interpenetrated
structure
dia
topology,
wherein
abundant
supramolecular
entanglements
are
formed
between
the
adjacent
subnetworks
through
weak
intermolecular
hydrogen
bonds.
This
structural
configuration
could
not
only
stabilize
whole
establish
permanent
porosity,
also
enable
show
flexibility
due
its
interactions
(so‐called
framework).
was
exclusively
confirmed
by
sorption
isotherms
and
single‐crystal
X‐ray
diffraction
studies,
showing
that
flexible
pore
pockets
can
be
opened
C
3
H
8
n‐C
4
10
molecules
rather
2
6
CH
.
leads
notably
higher
uptakes
enhanced
selectivities
than
over
under
ambient
conditions,
affording
one
highest
/CH
selectivities.
gas‐loaded
structures
coupled
theoretical
simulations
reveal
loading
induce
an
obvious
expansion
along
pocket
opening
improve
uptake
selectivity,
while
adsorption.
work
suggests
effective
strategy
designing
HOFs
improving
separation
properties.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(33)
Published: June 6, 2024
Abstract
One‐step
purification
of
ethylene
from
ternary
mixtures
(C
2
H
,
C
4
and
6
)
can
greatly
reduce
the
energy
consumption
separation
process,
but
it
is
extremely
challenging.
Herein,
we
use
crystal
engineering
reticular
chemistry
to
introduce
unsaturated
bonds
(ethynyl
alkyne)
into
ligands,
successfully
design
synthesized
two
novel
Zr‐MOCs
(ZrT‐1‐ethenyl
ZrT‐1‐alkyne).
The
introduction
carbon‐carbon
provides
abundant
adsorption
sites
within
framework
while
modulating
pore
window
size.
Comprehensive
characterization
techniques
including
single
powder
X‐ray
diffraction,
as
well
electrospray
ionization
time‐of‐flight
mass
spectrometry
(ESI‐TOF‐MS)
confirm
that
ZrT‐1‐ethenyl
ZrT‐1‐alkyne
possess
an
isostructural
with
ZrT‐1
ZrT‐1‐Me,
respectively.
Adsorption
isotherms
breakthrough
experiments
combined
theoretical
calculations
demonstrate
effectively
remove
trace
in
achieve
CO
.
also
directly
purify
liquid
solutions.
This
work
a
benchmark
for
MOCs
one‐step
mixtures.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(14), P. 7531 - 7565
Published: Jan. 1, 2024
Covalent
organic
frameworks
(COFs)
have
recently
seen
significant
advancements.
Large
quantities
of
structurally
&
functionally
oriented
COFs
with
a
wide
range
applications,
such
as
gas
adsorption,
catalysis,
separation,
and
drug
delivery,
been
explored.
Recent
achievements
in
this
field
are
primarily
focused
on
advancing
synthetic
methodologies,
catalysts
playing
crucial
role
achieving
highly
crystalline
COF
materials,
particularly
those
featuring
novel
linkages
chemistry.
A
series
reviews
already
published
over
the
last
decade,
covering
fundamentals,
synthesis,
applications
COFs.
However,
despite
pivotal
that
auxiliaries
play
forming
materials
adjusting
their
properties
(
