Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 24, 2025
Electrochemiluminescence
(ECL)
is
a
light-emitting
process
in
which
the
stability
of
electrochemically
generated
radicals
has
crucial
impact
on
efficiency
and
durability
excited
state
generation.
Therefore,
deciphering
relationship
between
radical
ECL
performance
highly
appealing.
In
this
work,
three
sp2
carbon-conjugated
covalent
organic
framework
(COF)
reticular
nanoemitters
compositing
same
pyrene
luminophores
but
different
acrylonitrile
linkers
are
designed
with
progressive
electron
affinities,
named
as
CN-COF-1,
2,
3.
By
precisely
modulating
affinity
CN-COFs,
volcano
discovered
78
folds
enhancement
intensity.
Density
functional
theoretical
calculations
indicate
that
CN-COF-2
exhibits
moderate
stabilization
capacity
well
efficient
transport
cores,
facilitating
Significantly,
appropriate
not
only
achieves
self-enhanced
cathodic
also
promotes
The
rational
regulation
paves
way
for
developing
decoding
fundamentals.
Deciphering
electrochemiluminescence
important
since
an
Here,
authors
describe
shaped
via
acrylonitrile-linked
frameworks.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Март 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
ACS Materials Letters,
Год журнала:
2024,
Номер
6(5), С. 2007 - 2049
Опубликована: Апрель 17, 2024
Hydrogen
peroxide
(H2O2),
a
valuable
chemical,
is
widely
used
as
powerful
oxidizing
agent
in
chemical
synthesis,
pharmaceuticals,
medical
disinfection,
and
environmental
treatment
industries.
Currently,
over
95%
of
H2O2
produced
industrially
using
the
anthraquinone
process,
which
associated
with
its
high
energy
consumption
hazardous
byproducts.
Therefore,
photochemical
synthesis
from
water
oxygen
covalent
organic
framework
based
photocatalysts
have
attracted
considerable
attention.
This
review
aims
to
outline
recent
achievements,
challenges
future
prospects
COFs
heterogeneous
for
sustainable
generation.
We
summarize
chronological
development
COFs,
different
mechanisms
involved,
detailed
experiments
quantification
methods
photocatalytic
The
puts
forward
an
outlook,
highlighting
advantages
limitations
anticipate
that
this
will
provide
insight
into
current
progress
inspire
next-generation
production.
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.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(29)
Опубликована: Март 14, 2024
Abstract
Porous
organic
polymers
have
an
outstanding
performance
in
the
field
of
photocatalysis
with
advantage
diverse
structure
composition
and
purposeful
molecular
design.
However,
inherent
high
impedance
poor
electrical
conductivity
semiconductors
still
restrict
charge
transfer
efficiency
thus
discount
photocatalytic
performance.
Herein,
study
reports
a
highly
conductive
covalent
triazine
framework
(CTF)
loading
carbon
quantum
dots
(CQDs)
into
porous
as
electron
transport
medium.
The
addition
CQDs
(0.5
wt%)
can
enhance
electronic
CTF
by
tenfold.
In
addition,
as‐prepared
CQD‐CTFs
express
much‐promoted
separation
efficiency.
Furthermore,
embedded
improve
oxidization
capacity
increase
affinity
H
+
due
to
more
negative
zeta
potential.
enhanced
oxidizing
ability
increased
are
positive
for
water
oxidation
reaction
(WOR)
oxygen
reduction
(ORR)
process
hydrogen
peroxide
(H
2
O
)
generation,
respectively.
optimized
CQD‐CTF
exhibits
generation
rate
up
1036
µmol
g
−1
h
pure
without
any
sacrificial
agent
under
visible
light,
which
is
4.6
times
than
pristine
CTF.
This
work
provides
new
idea
efficient
production
semiconductors.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 8, 2025
The
conversion
of
solar
energy
into
chemical
or
high-value
chemicals
has
attracted
considerable
research
interest
in
the
context
global
crisis.
Hydrogen
peroxide
(H2O2)
is
a
versatile
and
powerful
oxidizing
agent
widely
used
synthesis
medical
disinfection.
H2O2
also
serves
as
clean
source
fuel
cells,
generating
electricity
with
zero-carbon
emissions.
Recently,
sustainable
production
from
water
oxygen
using
covalent
organic
frameworks
(COFs)
photocatalysts
attention;
however,
systematic
studies
highlighting
role
linkages
determining
photocatalytic
performance
are
scarce.
Under
these
circumstances,
herein,
we
demonstrate
that
varying
imine
hydrazone
within
framework
significantly
influences
production.
COFs
high-density
linkages,
providing
optimal
docking
sites
for
oxygen,
enhance
generation
activity
(1588
μmol
g−1
h−1
pure
air),
leading
to
highly
efficient
solar-to-chemical
conversion.
This
work
systematically
investigates
effect
linkage
density
on
enhancement
hydrogen
generation,
aim
achieving
high-performance
photocatalysis.
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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 17, 2025
The
generation
of
radicals
through
photo-Fenton-like
reactions
demonstrates
significant
potential
for
remediating
emerging
organic
contaminants
(EOCs)
in
complex
aqueous
environments.
However,
the
excitonic
effect,
induced
by
Coulomb
interactions
between
photoexcited
electrons
and
holes,
reduces
carrier
utilization
efficiency
these
systems.
In
this
study,
we
develop
Cu
single-atom-loaded
covalent
frameworks
(CuSA/COFs)
as
models
to
modulate
effects.
Temperature-dependent
photoluminescence
ultrafast
transient
absorption
spectra
reveal
that
incorporating
acenaphthene
units
into
linker
(CuSA/Ace-COF)
significantly
exciton
binding
energy
(Eb).
This
modification
not
only
enhances
peroxymonosulfate
adsorption
at
active
sites
but
also
facilitates
rapid
electron
transfer
promotes
selective
hydroxyl
radical
generation.
Compared
CuSA/Obq-COF
(Eb
=
25.6
meV),
CuSA/Ace-COF
12.2
meV)
shows
a
39.5-fold
increase
pseudo-first-order
rate
constant
sulfamethoxazole
degradation
(0.434
min-1).
work
provides
insights
modulating
behavior
single-atom
catalysts
via
engineering
EOCs
degradation.