Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(30)
Published: May 13, 2024
Abstract
Three‐dimensional
covalent
organic
frameworks
(3D
COFs),
recognized
for
their
tailorable
structures
and
accessible
active
sites,
offer
a
promising
platform
developing
advanced
photocatalysts.
However,
the
difficulty
in
synthesis
functionalization
of
3D
COFs
hinders
further
development.
In
this
study,
we
present
series
3D‐
bcu
‐COFs
with
8
connected
porphyrin
units
linked
by
linear
linkers
through
imine
bonds
as
versatile
photocatalyst
design.
The
photoresponse
was
initially
modulated
functionalizing
benzo‐thiadiazole
or
benzo‐selenadiazole
groups.
Furthermore,
taking
advantage
well‐exposed
sites
‐COFs,
photocatalytic
activity
optimized
stepwise
protonation
centers.
dual
protonated
COF
groups
exhibited
enhanced
charge
separation,
leading
to
an
increased
H
2
O
production
under
visible
light.
This
enhancement
demonstrates
combined
benefits
linker
on
efficiency.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(30)
Published: May 13, 2024
Abstract
Three‐dimensional
covalent
organic
frameworks
(3D
COFs),
recognized
for
their
tailorable
structures
and
accessible
active
sites,
offer
a
promising
platform
developing
advanced
photocatalysts.
However,
the
difficulty
in
synthesis
functionalization
of
3D
COFs
hinders
further
development.
In
this
study,
we
present
series
3D‐
bcu
‐COFs
with
8
connected
porphyrin
units
linked
by
linear
linkers
through
imine
bonds
as
versatile
photocatalyst
design.
The
photoresponse
was
initially
modulated
functionalizing
benzo‐thiadiazole
or
benzo‐selenadiazole
groups.
Furthermore,
taking
advantage
well‐exposed
sites
‐COFs,
photocatalytic
activity
optimized
stepwise
protonation
centers.
dual
protonated
COF
groups
exhibited
enhanced
charge
separation,
leading
to
an
increased
H
2
O
production
under
visible
light.
This
enhancement
demonstrates
combined
benefits
linker
on
efficiency.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
Covalent
organic
frameworks
(COFs)
have
gained
considerable
attention
due
to
their
design
possibilities
as
the
molecular
building
blocks
that
can
stack
in
an
atomically
precise
spatial
arrangement.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(42), P. 28932 - 28940
Published: Oct. 11, 2024
Single-crystalline
covalent
organic
frameworks
(COFs)
are
highly
desirable
toward
understanding
their
pore
chemistry
and
functions.
Herein,
two
50–100
μm
single-crystalline
three-dimensional
(3D)
COFs,
TAM-TFPB-COF
TAPB-TFS-COF,
were
prepared
from
the
condensation
of
4,4′,4″,4‴-methanetetrayltetraaniline
(TAM)
with
3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl
(TFPB)
3,3′,5,5′-tetrakis(4-aminophenyl)bimesityl
(TAPB)
4,4′,4″,4‴-silanetetrayltetrabenzaldehyde
(TFS),
respectively,
in
1,4-dioxane
under
catalysis
acetic
acid.
Single-crystal
3D
electron
diffraction
reveals
triply
interpenetrated
dia-b
networks
atom
resolution,
while
isostructure
TAPB-TFS-COF
was
disclosed
by
synchrotron
single-crystal
X-ray
powder
Le
Bail
refinements.
The
nitrogen
sorption
measurements
at
77
K
disclose
microporosity
nature
both
activated
COFs
exceptionally
high
Brunauer–Emmett–Teller
surface
areas
3533
4107
m2
g–1,
representing
thus
far
record
specific
area
among
imine-bonded
COFs.
This
enables
to
exhibit
also
methane
uptake
capacities
up
28.9
wt
%
(570
cm3
g–1)
25
°C
200
bar
all
reported
far.
work
not
only
presents
structures
exceptional
but
provides
an
example
engineering
adjust
permanent
microporous
for
storage.
ACS Materials Letters,
Journal Year:
2024,
Volume and Issue:
6(6), P. 2276 - 2294
Published: May 10, 2024
Solar-driven
water
splitting
into
hydrogen
and
oxygen
fuels
represents
a
promising
way
for
clean
energy
production
to
achieve
carbon-neutral
future.
The
efficiency
of
photocatalytic
strongly
relies
on
the
development
high-performance
catalysts.
Noteworthily,
covalent
organic
frameworks
(COFs)
offer
distinctive
platform
designing
photo-to-chemical
conversion,
benefiting
from
their
tailorable
structure,
ultrahigh
porosity,
robust
framework,
sufficient
light
absorption,
rich
active
sites.
Herein
we
highlight
systematic
overview
recent
research
progress
using
COFs
half-reactions
overall
splitting.
With
an
aim
shed
understanding
structural
design
COF
photocatalysts
splitting,
various
functional
strategies
are
discussed.
Finally,
major
challenges
future
perspectives
proposed
with
hope
achieving
ongoing
this
emerging
field.
