Advanced Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 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 Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 16, 2024
Abstract
Covalent
organic
frameworks
(COFs)
with
stable
crystalline
porous
structures
and
flexible
assembly
properties
contribute
to
the
direct
photocatalytic
synthesis
of
H
2
O
meet
growing
global
demand.
To
address
challenges
insufficient
redox
capacity
photogenerated
carrier
recombination
COFs,
S‐scheme
heterojunction
is
constructed
from
COFs
quantum
dots
(QDs)
improve
production
.
Herein,
0D
ZnCdS
QDs
(ZCS)
uniformly
anchor
on
surface
a
2D
conjugated
tetrathiafulvalene‐based
COF
(TT‐COF),
affording
TT‐COF/ZCS.
Formation
effectively
prevents
agglomeration
ZCS,
modulates
energy
band
structure
TT‐COF,
enhances
migration
carriers
ability.
As
total
consequence,
optimized
(TZ‐40)
able
afford
in
yield
up
5171
µmol
g
−1
h
under
visible
light
irradiation
,
much
higher
than
those
for
2520
2647
The
present
result
demonstrates
great
potential
COFs/QDs‐based
heterojunctions
applications
including
production.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 27, 2024
Abstract
Photocatalysis
leverages
solar
energy
to
overcome
the
thermodynamic
barrier,
enabling
efficient
chemical
reactions
under
mild
conditions.
It
can
greatly
reduce
reliance
on
traditional
sources
and
has
attracted
significant
research
interest.
Reticular
materials,
including
metal‐organic
frameworks
(MOFs)
covalent
organic
(COFs),
represent
a
class
of
crystalline
materials
constructed
from
molecular
building
blocks
linked
by
coordination
bonds,
respectively.
function
as
heterogeneous
catalysts,
combining
well‐defined
structures
high
tailorability
akin
homogeneous
catalysts.
In
this
review,
regulation
light
absorption,
charge
separation,
surface
in
photocatalytic
process
through
precise
molecular‐level
design
based
features
reticular
is
elaborated.
Notably,
for
MOFsmicroenvironment
modulation
around
catalytic
sites
affects
performance
delved,
with
emphasis
their
unique
dynamic
flexible
microenvironments.
For
COFs,
inherent
excitonic
effects
due
fully
nature
discussed
highlight
strategies
regulate
charge‐
and/or
energy‐transfer‐mediated
photocatalysis.
Finally,
current
challenges
future
directions
field,
aiming
provide
comprehensive
understanding
how
be
optimized
enhanced
photocatalysis
discussed.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Abstract
Modulating
the
molecular
structure
to
achieve
full
reaction
including
oxygen
reduction
and
water
oxidation
is
a
promising
strategy
for
efficient
photosynthesis
of
hydrogen
peroxide
(H
2
O
)
but
remains
challenge.
Herein,
triphenylamine
naphthalimide‐based
conjugated
porous
polymers
are
synthesized
with
photo
oxidation‐reduction
structures,
then
sulfonate
(─SO
3
H)
quaternary
ammonium
groups
introduced
via
post‐modification
produce
two
photocatalysts
named
NI‐TPA‐NI‐SO
H
NI‐TPA‐NI‐N,
respectively.
Introducing
charged
functional
has
improved
hydrophilicity
(O
adsorption,
beyond
that,
─SO
further
stabilizes
adsorbed
bonding
as
well
accelerates
photogenerated
carrier
separation
electron/proton
transport
that
enables
.
Therefore,
motivated
by
charge
separation,
stabilized
boosted
proton‐coupled
electron
transfer,
exhibits
highest
light‐driven
production
rate
among
three
photocatalysts,
reaching
3.40
mmol
g
−1
h
,
which
4.9‐fold
NI‐TPA‐NI.
Remarkably,
in
presence
ethylenediaminetetraacetic
acid
disodium
salt,
its
significantly
enhances
14.5
superior
most
reported
organic
best
knowledge.
Small,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 27, 2024
Abstract
Constitutional‐isomerized
covalent
organic
frameworks
(COFs),
constructed
by
swapping
monomers
around
imine
bonds,
have
attracted
attention
for
their
distinct
optoelectronic
properties,
which
significantly
impact
photocatalytic
performance.
However,
limited
research
has
delved
into
the
inherent
relationship
between
isomerization
and
enhancement
of
H
2
O
photosynthesis.
Herein,
a
pair
isomeric
COFs
linked
bonds
(PB‐PT‐COF
PT‐PB‐COF)
is
synthesized,
it
proved
that
exhibit
different
rate‐determining
steps
in
generation
process
,
resulting
twofold
increase
efficiency.
Specifically,
PT‐PB‐COF
demonstrates
effective
adsorption
activation
molecular
oxygen
(O
+
e
−
→
•O
),
leading
to
significant
improvement
In
contrast,
PB‐PT‐COF
exhibits
robust
interaction
with
O,
enabling
direct
oxidation
(H
h
).
This
study
provides
thorough
understanding
intrinsic
mechanism
underlying
constitutional‐isomerized
generation,
offering
insights
further
optimizing
building
units.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Polycyclic
aromatic
hydrocarbons
(PAHs)
hold
the
predominant
role
either
as
individual
molecules
or
building
blocks
in
field
of
organic
semiconductors
nanocarbons.
Connecting
PAHs
via
sp
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(74), P. 10046 - 10063
Published: Jan. 1, 2024
This
review
focuses
on
the
role
of
different
COFs
as
solid-state
electrolytes,
aiming
to
guide
development
electrolyte
materials
and
battery
technology.
