Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: March 10, 2024
Abstract
Covalent
organic
frameworks
(COFs)
attract
significant
attention
due
to
their
ordered,
crystalline,
porous,
metal‐free,
and
predictable
structures.
These
unique
characteristics
offer
great
opportunities
for
the
diffusion
transmission
of
photogenerated
charges
during
photocatalysis.
Currently,
a
considerable
number
COFs
are
used
as
metal‐free
semiconductor
photocatalysts.
This
review
aims
understand
relationships
between
structure
photocatalysis
performance
provides
in‐depth
insight
into
synthetic
strategy
improve
performance.
Subsequently,
focuses
on
structural
motif
in
sustainable
photocatalytic
hydrogen
evolution,
carbon
dioxide
reduction,
peroxide
generation,
compound
transformations.
Last,
conjunction
with
progress
achieved
challenges
yet
be
overcome,
candid
discussion
is
undertaken
regarding
field
COF
photocatalysis,
accompanied
by
presentation
potential
research
avenues
future
directions.
seeks
provide
readers
comprehensive
understanding
pivotal
role
robust
guidance
innovative
utilization
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 28, 2023
Constructing
photocatalytically
active
and
stable
covalent
organic
frameworks
containing
both
oxidative
reductive
reaction
centers
remain
a
challenge.
In
this
study,
benzotrithiophene-based
with
spatially
separated
redox
are
rationally
designed
for
the
photocatalytic
production
of
hydrogen
peroxide
from
water
oxygen
without
sacrificial
agents.
The
triazine-containing
framework
demonstrates
high
selectivity
H2O2
photogeneration,
yield
rate
2111
μM
h-1
(21.11
μmol
1407
g-1
h-1)
solar-to-chemical
conversion
efficiency
0.296%.
Codirectional
charge
transfer
large
energetic
differences
between
linkages
linkers
verified
in
double
donor-acceptor
structures
periodic
frameworks.
sites
mainly
concentrated
on
electron-acceptor
fragments
near
imine
bond,
which
regulate
electron
distribution
adjacent
carbon
atoms
to
optimally
reduce
Gibbs
free
energy
O2*
OOH*
intermediates
during
formation
H2O2.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Sept. 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.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Oct. 1, 2022
Abstract
Covalent
organic
frameworks
(COFs)
have
constituted
an
emerging
class
of
photocatalysts
showing
enormous
potential
for
visible
photocatalytic
H
2
evolution
from
water.
However,
suffering
sluggish
reaction
kinetics,
COFs
often
cooperate
with
precious
metal
co-catalysts
essential
proton-reducing
capability.
Here,
we
synthesize
a
chiral
β-ketoenamine-linked
COF
coordinated
10.51
wt%
atomically
dispersed
Cu(II)
as
electron
transfer
mediator.
The
enantioselective
combination
the
COF-Cu(II)
skeleton
L-/D-cysteine
sacrificial
donors
remarkably
strengthens
hole
extraction
and
in
turn,
photoinduced
electrons
accumulate
rapidly
via
Cu
ions.
Also,
parallelly
stacking
sequence
provides
energetically
favorable
arrangement
H-adsorbed
sites.
Thus,
without
metal,
rate
reaches
high
14.72
mmol
h
−1
g
enantiomeric
mixtures.
This
study
opens
up
strategy
optimizing
kinetics
promises
exciting
photocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(49)
Published: Oct. 14, 2022
Construction
of
catalytic
covalent
organic
frameworks
(COFs)
for
oxygen
reduction
reaction
(ORR)
and
evolution
(OER)
is
significant
but
rarely
demonstrated.
In
this
work,
we
have
first
constructed
bifunctional
COFs
towards
ORR
OER
by
integrating
diarylamine
derivatives
into
the
Co-porphyrin
based
frameworks.
Both
new
(CoTAPP-PATA-COF
CoTAPP-BDTA-COF)
good
ordered
structures,
high
surface
areas,
robust
chemical
stability.
The
units,
as
a
typical
electron
donor
redox-active
cores,
promote
intramolecular
transport
along
improve
electrochemically
active
areas.
Thus,
showed
higher
activities
than
that
COF
without
units.
CoTAPP-PATA-COF
had
halfwave
potential
0.80
V
ORR,
delieved
an
overpotential
420
mV
in
0.1
M
KOH.
theoretical
calculation
revealed
introducing
unites
improved
electrocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(31)
Published: May 31, 2023
Covalent
organic
frameworks
(COFs),
possessing
pre-designable
structures
and
tailorable
functionalities,
are
promising
candidates
for
photocatalysis.
Nevertheless,
the
most
studied
imine-linked
COFs
(Im-COFs)
usually
suffer
from
unsatisfactory
stability
photocatalytic
performance.
To
meet
this
challenge,
a
series
of
highly
stable
enaminone-linked
(En-COFs)
have
been
synthesized
afford
much
improved
visible-light-driven
hydrogen
production
activities,
ranging
44
to
1078
times
that
isoreticular
Im-COFs,
with
only
difference
being
linkages
(enaminone
vs.
imine)
in
their
structures.
The
enhanced
light-harvesting
ability,
facilitated
exciton
dissociation
chemical
account
superior
activity.
Furthermore,
quinoline-linked
(Qu-COFs)
further
obtained
via
post-modification
Im-COFs.
Compared
activities
Qu-COFs
significantly
after
modification,
but
still
below
those
corresponding
En-COFs
(3-107
times).
facile
synthesis,
excellent
activity,
high
demonstrate
platform
