Applied Organometallic Chemistry,
Journal Year:
2024,
Volume and Issue:
38(9)
Published: July 16, 2024
In
order
to
specifically
demonstrate
the
improvement
of
photocatalytic
activity
attributed
donor‐acceptor
(D‐A)
structure
rather
than
other
contributing
factors,
two
highly
comparable
COFs
incorporating
porphyrin
and
thiophene
species
are
synthesized
in
this
work.
The
first
COF,
named
BTDA‐Por,
is
composed
(Por)
as
donor
unit
2,2′‐bithiophene
(BTDA)
acceptor
moiety.
second
referred
TT‐Por,
constructed
using
Por
thieno[3,2‐b]thiophene
(TT)
units
while
lacking
a
D‐A
structure.
These
serve
effective
models
for
investigating
role
structures
improving
activity.
Photoelectronic
property
studies
density
function
theory
calculations
indicate
that
configuration
can
significantly
enhance
efficiency
charge
carrier
generation,
separation,
migration.
Consequently,
type
BTDA‐Por
exhibits
superior
performance
photochemical
reactions
such
oxidative
homocoupling
aromatic
amine
reversible
complexation‐mediated
radical
polymerization
when
compared
non‐D‐A
TT‐Por.
Advanced Functional Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 4, 2025
Abstract
Covalent
organic
frameworks
(COFs)
are
promising
for
photocatalytic
H₂O₂
generation.
However,
imine‐linked
COFs
often
suffer
from
poor
charge
separation
and
low
performance.
Therefore,
constructing
sp
2
carbon‐linked
with
extended
π‐conjugation
is
very
significant
in
boosting
the
properties,
but
their
synthesis
challenging
due
to
reversibility
of
C═C
bond.
Here,
two
vinylene‐linked
COFs:
BBT‐ACN
COF‐1
COF‐2
designed.
To
investigate
effects
different
structures
on
exciton
binding
energy
(
E
b
),
designed
possesses
a
Donor–Acceptor
(D–A)
structure
electron‐deficient
benzobisthiazole
(BBT)
as
acceptor
benzotrithiophene
donor,
while
latter
holds
π‐A
pyrene
π‐unit
BBT
acceptor.
Both
show
production
activity
two‐step
2e
−
oxygen
reduction
reaction
(ORR).
As
anticipated,
D–A
structured
exhibits
lower
value,
its
H
O
rate
pure
water
air
reaches
up
2.50
mmol
g⁻¹
h⁻¹,
≈3
times
higher
than
that
(0.91
h⁻¹).
This
study
reveals
fully
‐carbon‐linked
beneficial
production,
which
provides
an
effective
approach
designing
high‐performance
photocatalysts.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(49)
Published: Aug. 14, 2023
Abstract
Benefiting
from
the
excellent
structural
tunability,
robust
framework,
ultrahigh
porosity,
and
rich
active
sites,
covalent
organic
frameworks
(COFs)
are
widely
recognized
as
promising
photocatalysts
in
chemical
conversions,
emerged
hydrogen
peroxide
(H
2
O
)
photosynthesis
2020.
H
,
serving
an
environmental‐friendly
oxidant
a
liquid
fuel,
has
attracted
increasing
researchers
to
explore
its
potential.
Over
past
few
years,
numerous
COFs‐based
developed
with
encouraging
achievements
production,
whereas
no
comprehensive
review
articles
exist
summarize
this
specific
significant
area.
Herein
we
provide
systematic
overview
of
advances
challenges
COFs
photocatalytic
production.
We
first
introduce
priorities
photosynthesis.
Then,
various
strategies
improve
efficiency
discussed.
The
perspective
outlook
for
future
emerging
field
finally
offered.
This
timely
will
pave
way
development
highly
efficient
practical
production
value‐added
chemicals
not
limited
.
Nanoscale,
Journal Year:
2024,
Volume and Issue:
16(34), P. 16015 - 16025
Published: Jan. 1, 2024
We
computationally
screened
metal-single-atom
catalysts
(M-SAC)
on
carbon
nitride
for
selective
CO
2
reduction.
NiCN
significantly
lowered
the
rate-determining
potential
conversion
to
formic
acid
via
*OCHO
key
intermediate.
Covalent
organic
frameworks
(COFs),
with
well-designed
structure
and
molecular
functionality
materials,
showed
great
promising
as
metal-free
catalysts
for
heterogeneous
photocatalysis.
Nevertheless,
the
influence
of
pore
COFs
on
photocatalytic
performances
is
always
neglected
in
ever
reports.
Herein,
by
rational
designation
topology
diagrams,
two-dimensional
porphyrin-based
(ETBA-por
COF
ETBC-por
COF)
different
sizes
were
synthesized
first
time.
Both
as-synthesized
exhibited
outstanding
crystallinity,
rich
micropores
high
surface
area.
Moreover,
also
have
similar
photoelectrochemical
efficaciously
production
superoxide
radical
anions
under
visible
irradiation.
To
test
effect
performances,
two
typical
characteristic
reactions
organics
transformation,
including
selective
aerobic
oxidation
sulfides
oxidative
amine
coupling
evaluated.
Interestingly,
although
both
good
recyclability
stability,
ETBA-por
smaller
size
has
higher
conversion
(94
%)
sulfoxides
selectivity
(>99
%),
while
things
reversed
imines
(99
%
substrate
96
yield
that
larger
size).
Mechanisms
activity
revealed
combing
experiments
simulation,
which
infers
suitable
molecules
accesses
critical
to
ensure
photocatalysis
performances.
This
study
confirmed
importance
efficient
transformation
organics.
