ACS Applied Materials & Interfaces,
Journal Year:
2024,
Volume and Issue:
17(2), P. 3503 - 3513
Published: Dec. 30, 2024
Visible-light-driven
photocatalytic
uranium
extraction
based
covalent
organic
frameworks
(COFs)
are
green
and
sustainable,
but
their
performance
is
severely
restricted
by
a
strong
exciton
effect.
Herein,
inspired
the
physiology
of
cardiac
pacing,
novel
fluorine-based
COF
(PyF-DaS-COF)
with
biomimetic
electronic
pump
has
been
fabricated
used
for
uranium.
Both
experimental
theoretical
calculations
confirm
that
strongly
electronegative
fluorine
plays
crucial
role
in
dissociation
charge
transfer.
The
enhanced
electron
push–pull
effect
increases
intrinsic
separation
driving
force
separation.
Furthermore,
substitution
thermodynamically
favors
generation
*OOH
intermediate
reduction
reaction.
As
result,
PyF-DaS-COF
achieves
record
k
value
(T
=
293
K)
0.082
min–1
an
capacity
991.5
mg
g–1.
Importantly,
removal
rate
over
99%
real
uranium-containing
wastewater.
current
work
provides
unique
insights
into
designing
effective
COFs
controlling
radioactive
contamination.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 17654 - 17663
Published: Nov. 15, 2024
The
photosynthesis
of
hydrogen
peroxide
(H2O2)
from
pure
water
and
oxygen
using
metal-free
photocatalysts
offers
a
renewable
approach
to
convert
solar
energy
storable
chemical
energy.
However,
the
efficiency
H2O2
is
often
hindered
by
rapid
recombination
photogenerated
charge
carriers.
Herein,
we
present
an
elegantly
designed
covalent
triazine
framework
(CTF)
photocatalyst,
denoted
as
Ace-asy-CTF,
with
stepwise
electron
transfer
pathway
for
highly
efficient
H2O2.
Notably,
Ace-asy-CTF
possesses
localized
excited-state
distribution
that
created
weakly
conjugated
acetenyl
units
in
asymmetric
frameworks,
revealed
transient
spectroscopies
further
supported
theoretical
calculations.
Meanwhile,
introduced
also
serve
active
sites
reduction
reaction
(ORR).
simultaneously
enhanced
two-step
2e–
ORR
result
excellent
yield
2594
μmol
g–1
h–1,
directly
produced
without
requiring
any
sacrificial
reagents.
This
work
paves
way
development
next-generation
catalysts,
providing
feasible
benchmark
stable
Advanced Energy Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 3, 2025
Abstract
The
artificial
photosynthesis
of
hydrogen
peroxide
(H
2
O
)
using
semiconductor
photocatalysts
is
gaining
attention
as
an
eco‐friendly
and
energy‐efficient
method.
Covalent
organic
frameworks
(COFs)
show
great
promise
in
enhancing
photocatalytic
H
production
due
to
their
tunable
structures
functional
diversity.
However,
the
efficiency
generation
close
photoelectric
properties
COFs
microenvironment
active
sites.
Herein,
synthesis
pyridyl‐imine‐functionalized
(PyIm‐COFs)
featuring
donor–acceptor
(D–A)
moieties
improve
reported.
By
employing
benzothiadiazole
(BT)
units
with
varied
fluorine
substitutions,
electronic
environment
sites,
optimizing
selective
two‐electron
(2e
−
oxygen
reduction
reaction
(ORR),
tuned.
Among
synthesized
COFs,
PyIm‐BT_F
exhibits
highest
activity,
achieving
a
rate
5342
µmol
g
−1
h
.
importance
D–A
rational
design
COF‐based
photocatalysts,
providing
novel
strategy
for
sustainable
through
optimized
site
environments,
underscored.
Small,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 9, 2024
Abstract
Covalent
organic
frameworks
(COFs)
have
emerged
as
one
of
the
most
studied
photocatalysts
owing
to
their
adjustable
structure
and
bandgaps.
However,
there
is
limited
research
on
regulating
light‐harvesting
capabilities
acceptor
building
blocks
in
donor–acceptor
(D–A)
isomer
COFs
with
different
bond
orientations.
This
investigation
crucial
for
elucidating
structure‐property‐performance
relationship
COF
photocatalysts.
Herein,
a
series
D–A
isostructural
are
synthesized
imine
orientations
using
benzothiadiazole
its
derivatives‐based
units.
Extended
light
absorption
achieved
groups
that
strong
electron‐withdrawing
capacities,
although
this
resulted
decreased
hydrogen
generation
efficiency.
Photocatalytic
experiments
indicated
dialdehyde
benzothiadiazole‐based
COFs,
HIAM‐0015,
exhibit
highest
rate
(17.99
mmol
g
−1
h
),
which
15
times
higher
than
isomer.
The
excellent
photocatalytic
performance
HIAM‐0015
can
be
attributed
fast
charge
separation
migration.
work
provides
insights
into
rational
design
synthesis
achieve
efficient
activity.
Applied Organometallic Chemistry,
Journal Year:
2025,
Volume and Issue:
39(2)
Published: Jan. 9, 2025
ABSTRACT
A
D‐A
1
‐A
2
type
covalent
triazine
framework
(CTF)
was
prepared
for
the
photocatalytic
hydrogen
evolution
(HER).
In
resulting
CTF‐CZ‐Bpy
2+
,
9‐ethyl‐9
H
‐carbazole
(CZ)
group
is
used
as
donor,
ring
first
acceptor,
and
cyclic
diquat
(Bpy
)
moiety
second
acceptor.
Both
experimental
theoretical
results
show
that
structure
significantly
enhances
efficiency
of
photogenerated
charge
separation
transfer.
As
a
result,
demonstrated
outstanding
HER
activity
with
yield
rate
31.1
mmol
g
−1
h
which
7.8
times
higher
than
nonfunctionalized
CTF‐CZ‐Bpy.
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
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 21, 2025
Comprehensive
Summary
Compared
to
the
conventional
trial‐and‐error
approach,
computational
prediction
is
becoming
an
increasingly
prominent
approach
in
discovery
of
covalent
organic
frameworks
(COFs)
with
specific
applications,
yet
it
has
been
rarely
demonstrated.
Herein,
we
employed
density
functional
theory
(DFT)
pre‐screen
electronic
and
optical
properties
thiophene‐based
donor‐acceptor
(D‐A)
pairs
simplified
from
their
corresponding
COF
structures.
Theoretical
calculation
illustrates
BMTB‐BTTC
highest
number
thiophene
units
expected
exhibit
best
photocatalytic
performance
for
hydrogen
production.
According
prediction,
four
COFs
have
prepared
activities
experimentally
validated.
Interestingly,
BMTB‐BTTC‐COF
shows
production
rate
12.37
mmol·g
–1
·h
among
COFs.
Combining
experimental
results,
proven
that
activity
can
be
fine‐tuned
by
modulating
units.
Our
study
provides
a
new
strategy
rational
design
regulation
D‐A
enhance
through
prediction.
