Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
Abstract
Cyano‐functionalized
sp
2
‐carbon‐conjugated
covalent
organic
frameworks
(CN‐COFs)
have
been
considered
as
promising
candidates
for
artificial
photosynthesis
of
hydrogen
peroxide
(H
O
).
Nevertheless,
the
performance
CN‐COFs
is
inherently
limited
by
constrained
oxygen
capture
capacity,
insufficient
charge
separation,
and
rapid
carrier
recombination.
Herein,
study
rationally
reports
a
strategy
integrating
amidoxime
groups
(AO)
into
COF
through
one‐step
cyano
hydrolysis
process
to
increase
photocatalytic
H
production.
Combined
simulations
characterizations
reveal
that
introducing
AO
enhances
hydrophilicity,
stabilizes
adsorbed
Oxygen
(O
)
via
bonding,
accelerates
separation
transfer,
well
lowers
energy
barrier
reduction
reaction
pathway,
thus
achieving
an
unmatched
production
rate
6024
µmol
h
−1
g
.
Importantly,
solar‐to‐chemical
conversion
(SCC)
efficiency
PTTN‐AO
reaches
0.61%,
significantly
surpassing
natural
plants
(≈0.1%)
most
COF‐based
photocatalysts.
The
current
findings
are
encouraging
molecular
design
polymers
green
efficient
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(40)
Опубликована: Июль 18, 2024
Abstract
The
integration
of
electron
donor
(D)
and
acceptor
(A)
units
into
covalent
organic
frameworks
(COFs)
has
received
increasing
interest
due
to
its
potential
for
efficient
photocatalytic
hydrogen
(H
2
)
evolution
from
water.
Nevertheless,
the
advancement
D–A
COFs
is
still
constrained
by
limited
investigations
on
engineering,
which
enables
highly
effective
charge
transfer
pathways
in
deliver
photoexcited
electrons
a
preferential
orientation
enhance
performance.
Herein,
two
systems
with
D–A–A
configurations
based
molecular
engineering
strategy
are
proposed
construct
three
distinct
COFs.
Specifically,
TAPPy‐DBTDP‐COF
merging
one
pyrene‐based
benzothiadiazole
acceptors
realized
an
average
H
rate
12.7
mmol
h
−1
g
under
visible
light,
among
highest
ever
reported
typical
D–A‐type
COF
systems.
combination
experimental
theoretical
analysis
signifies
crucial
role
dual‐acceptor
arrangement
promoting
exciton
dissociation
carrier
migration.
These
findings
underscore
significant
structural
design,
conducive
separation
holes
resulting
superior
activities.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Май 6, 2024
Abstract
Despite
the
pivotal
role
of
molecular
oxygen
(O
2
)
activation
in
artificial
photosynthesis,
efficiency
is
often
restricted
by
sluggish
exciton
dissociation
and
charge
transfer
kinetics
within
polymer
photocatalysts.
Herein,
we
propose
two
tetrathiafulvalene
(TTF)‐based
imine‐linked
covalent
organic
frameworks
(COFs)
with
tailored
donor‐acceptor
(D–A)
structures,
TTF‐PDI‐COF
TTF‐TFPP‐COF,
to
promote
O
activation.
Because
enhanced
electron
push‐pull
interactions
that
facilitated
separation
behavior,
exhibited
superior
photocatalytic
activity
electron‐induced
reactions
over
TTF‐TFPP‐COF
under
visible
light
irradiation,
including
photosynthesis
(
E
)‐3‐amino‐2‐thiocyano‐
α
,
β
‐unsaturated
compounds
H
.
These
findings
highlight
significant
potential
rational
design
COFs
D–A
configurations
as
suitable
candidates
for
advanced
applications.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 3584 - 3594
Опубликована: Фев. 13, 2025
Photocatalytic
hydrogen
peroxide
(H2O2)
production
via
the
oxygen
reduction
reaction
(ORR)
provides
a
promising
and
energy-saving
alternative
to
traditional
energy-intensive
anthraquinone
process.
Nevertheless,
how
decrease
energy
barrier
of
two-electron
(2e–)
ORR
process
photosynthesize
H2O2
efficiently
is
still
challenging.
Herein,
three
hydroxyl-functionalized
donor–acceptor
covalent
organic
frameworks
(COFs)
are
synthesized
for
photocatalytic
under
visible-light
irradiation
(420
≤
λ
780
nm).
It
observed
that
dihydroxyl
functionalization
(2,5-DhaTph
2,3-DhaTph)
facilitates
transportation
photogenerated
carriers
between
acceptor
donor
units
accelerates
kinetics
rate-limiting
step
when
comparing
with
monohydroxyl
(2-DhaTph).
Further,
2,5-DhaTph
para-position
hydroxyl
shows
higher
photosynthesis
efficiency
than
2,3-DhaTph
(ortho-positioned
hydroxyl),
probably
due
greater
exposure
catalytically
active
sites.
This
supported
by
better
structural
symmetry
2,5-DhaTph,
which
contributes
crystallinity
specific
surface
areas.
Electron
paramagnetic
resonance
(EPR)
spectra
theoretical
calculations
show
produces
*OOH
intermediates
reduced
barrier,
resulting
in
high
rate
2103.1
μmol
h–1
g–1.
Regulating
amount
substituents
their
location
on
COFs
an
effective
strategy
boost
carrier
transfer
reduce
O2-to-H2O2
conversion.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 24, 2025
Abstract
Photosynthesizing
H
2
O
from
real
seawater
is
a
promising
and
green
avenue
but
suffers
salt‐deactivated
effects
with
limitations
on
stability
photocatalytic
activity.
Herein,
by
the
Pictet–Spengler
reaction,
two
fully
conjugated
thieno[3,2‐c]pyridine‐linked
covalent
organic
frameworks
(named
TBA‐COF
TCA‐COF)
are
synthesized
for
photoproduction
first
time.
Without
sacrificial
agents
in
,
TCA‐COF
exhibit
impressive
generation
rates
of
8878
6023
µmol
g
−1
h
solar‐to‐chemical
conversion
efficiency
0.62%
0.42%,
respectively,
superior
to
their
Schiff
base
analogs.
Further
experimental
theoretical
investigations
reveal
that,
compared
imine‐linkage
counterparts,
one‐pot
cyclized
TCA‐COF,
reaction
improves
charge
carrier
separation
efficiency,
alters
photoreduction
center
triazine
benzene
parts
pyridine
units,
modulates
energy
band
structures
drive
2e
−
oxygen
reduction
water
oxidation
thereby
enhances
photosynthetic
Notably,
seawater‐produced
flow
reactors
packed
can
be
directly
utilized
E.
coli
sterilization.
The
present
study
highlights
construction
robust
COFs
thieno[3,2‐c]pyridine
linkage
via
sustainable
producing
seawater.
Abstract
Since
2020,
covalent
organic
frameworks
(COFs)
are
emerging
as
robust
catalysts
for
the
photosynthesis
of
hydrogen
peroxide
(H
2
O
),
benefiting
from
their
distinct
advantages.
However,
current
efficiency
H
production
and
solar‐to‐chemical
energy
conversion
(SCC)
remain
suboptimal
due
to
various
constraints
in
reaction
mechanism.
Therefore,
there
is
an
imperative
propose
improvement
strategies
accelerate
development
this
system.
This
comprehensive
review
delineates
recent
advances,
challenges,
utilizing
COFs
photocatalytic
production.
It
explores
fundamentals
challenges
(e.g.,
oxygen
(O
)
mass
transfer
rate,
adsorption
capacity,
response
sunlight,
electron‐hole
separation
efficiency,
charge
selectivity,
desorption)
associated
with
process,
well
advantages,
applications,
classification,
preparation
purpose.
Various
enhance
performance
highlighted.
The
aims
stimulate
further
advancements
discusses
potential
prospects,
application
areas
field.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 9, 2024
Abstract
The
global
energy
crisis
and
environmental
concerns
are
driving
research
into
renewable
sustainable
conversion
storage
technologies.
Solar
energy,
as
an
ideal
resource,
has
significant
potential
to
contribute
the
goal
of
net‐zero
carbon
emissions
if
effectively
harnessed
converted
a
reliable
storable
form
energy.
Photocatalysts
have
convert
sunlight
chemical
carriers.
In
this
respect,
covalent
organic
frameworks
(COFs)
shown
great
promise
due
their
tunable
structure
on
different
length
scales,
high
surface
areas,
beneficial
optical
properties
such
broad
visible
light
absorption.
This
review
offers
comprehensive
overview
key
developments
in
COF‐based
photocatalysts
for
various
applications,
including
water
splitting,
hydrogen
peroxide
generation,
transformations,
dioxide
nitrogen
reduction.
underlying
mechanisms,
essential
principles
material
design,
structure‐function
relationships
COFs
photocatalytic
applications
discussed.
challenges
faced
by
also
summarized
strategies
enhance
performance
explained,
improving
crystallinity,
regulating
molecular
structures,
tailoring
linkages,
incorporating
cocatalysts.
Finally,
critical
proposed
utilization
photocatalytically
generated
chemicals
value‐added
products.
