Advanced Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 19, 2025
Abstract
The
photocatalytic
synthesis
of
hydrogen
peroxide
(H
2
O
)
at
room
temperature
has
garnered
significant
attention
as
an
environmentally
friendly
alternative
to
traditional
anthraquinone
oxidation
processes.
However,
the
low
exciton
dissociation
efficiency
often
hinders
performance.
In
this
study,
it
is
demonstrated
that
tuning
substitution
sites
electron
donors
in
Donor‐Acceptor
(D‐A)
conjugated
polymers
can
significantly
enhance
by
reducing
activation
energy,
which
facilitates
spontaneous
separation
excitons
temperature.
For
comparison,
materials
with
energies
≈89
meV
exhibit
a
production
rate
2692
µmol·g
−1
·h
.
contrast,
main
material
developed
work,
O‐PTAQ,
demonstrates
substantially
lower
energy
22
meV,
resulting
4989
under
ambient
conditions,
outperforming
most
reported
organic
semiconductors.
This
enhancement
attributed
increased
delocalization
donors,
lowers
promote
efficient
separation.
findings
highlight
critical
role
molecular‐level
structural
enhancing
dissociation,
providing
promising
strategy
for
development
high‐efficiency
photocatalysts
sustainable
H
production.
Photocatalytic
hydrogen
peroxide
(H2O2)
production
using
conjugated
polymers
as
photocatalysts
is
a
green
and
sustainable
approach
to
synthesizing
H2O2.
Nevertheless,
the
efficiency
still
hindered
by
inefficient
charge
separation
transfer
dynamics.
Herein,
series
of
coplanar
2D
ladder
with
different
substituents
were
reported
metal-free
for
artificial
photosynthesis
Detailed
experimental
theoretical
investigations
reveal
that
skeleton
strong
electron-withdrawing
could
profoundly
facilitate
transfer.
Possessing
these
notable
merits,
cyano-substituted
polymer
(PAE-CN)
exhibits
remarkable
photocatalytic
performance
on
H2O2
evolution.
This
study
contributes
development
effective
tailored
potential
applications
in
photosynthesis.
Small,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 16, 2025
Abstract
Graphite
phase
carbon
nitride
(CN)
emerges
as
a
promising
catalyst
for
sunlight‐driven
H
2
O
synthesis
owing
to
its
merits
of
stable
physicochemical
properties,
distinctive
electronic
structure,
adjustable
bandgap,
etc.,
yet
poor
charge
behavior,
especially
high
carrier
recombination
and
low
migration
rate,
limit
photocatalytic
activity.
Herein,
molecularly
tunable
donor‐acceptor
(D‐A)
integrated
CN
is
fabricated
via
cytosine
doping
combined
with
molten
salt‐assisted
calcination.
The
utilized
achieves
the
highest
H₂O₂
yield
8.07
mmol
g
−1
h
,
which
exceeds
initial
by
factor
40.4,
surpassing
numerous
reported
CN‐based
photocatalysts.
Series
characterizations/tests
(e.g.,
transient
absorption,
steady‐state
SPV
spectra,
KPFM)
theoretical
calculations
HOMO/LUMO,
adsorption
energy)
confirm
that
incorporation
K
+
‐C≡N
pyrimidine
ring
disrupts
symmetry
establishes
D‐A
significantly
augmenting
separation
photogenerated
charges.
capture
experiment
rotating
disk
electrode
test
affirm
two‐step
single
electron
oxygen
reduction
pathway
occurs
in
process
synthesis.
This
work
offers
novel
approaches
profound
revelations
development
Donor-acceptor
(D-A)-type
conjugated
microporous
polymers
(CMPs)
are
considered
promising
photocatalytic
materials
due
to
their
easily
tunable
structures
and
optical
properties.
However,
the
rational
combination
of
D
A
units
design
D-A-type
CMPs
with
efficient
electron-hole
separation
transfer
dynamics
remains
an
ongoing
challenge.
Herein,
we
employed
Density
Functional
Theory
(DFT)
calculations
evaluate
16
potential
D-A
pair
combinations
respective
dynamics.
These
consisted
M-salens
(M
=
Zn,
Cu,
Co,
Ni)
as
bromine-containing
monomers
four
alkyne-based
monomers:
2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine
(TEPT),
4,4″-diethyl-5'-(4-ethynylphenyl)-1,
1':3',1″-terphenyl
(TEPB),
tris(4-ethynylphenyl)
amine
(TEPA),
3,7-diethyl-10-(4-ethynylphenyl)-10H-phenothiazine
(TEPP).
Eight
were
obtained
via
DFT
calculation,
ranking
follows:
Zn-salen-TEPA
>
Zn-salen-TEPP
Zn-salen-TEPT
Cu-salen-TEPP
Cu-salen-TEPA
Cu-salen-TEPT
Ni-salen-TEPT
Co-salen-TEPT.
Based
on
these
results,
three
pairs
exhibiting
highest
selected
for
synthesis
corresponding
subsequent
photoelectric
characterization.
Experimental
enhancements
aligned
closely
predictions.
Notably,
aerobic
oxidative
amidation
diverse
aldehydes
amines
catalyzed
by
under
blue
LED
irradiation
achieved
a
yield
up
97%,
which
surpassed
performance
most
reported
works.
This
work
offers
novel
perspectives
endowed
highly
activity.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(10), P. 2190 - 2190
Published: May 16, 2025
The
strategic
design
of
donor–acceptor
(D-A)
conjugated
porous
polymers
has
emerged
as
a
pivotal
methodology
for
advancing
efficient
photocatalytic
hydrogen
evolution.
However,
conventional
D-A
polymeric
architectures
face
inherent
limitations:
excessively
strong
acceptor
units
may
lower
the
LUMO
energy
level,
compromising
proton
(H+)
reduction
capability,
while
weak
interactions
result
in
inadequate
light-harvesting
capacity
and
insufficient
photogenerated
electrons,
ultimately
diminishing
activity.
To
address
these
challenges,
we
developed
new
D1-A-D2
polymer
(CPP)
system.
incorporation
secondary
donor
benzothiophene
(DBBTh)
unit
enabled
precise
bandgap
engineering
CPPs.
Experimental
results
demonstrate
that
DBBTh
integration
significantly
enhances
both
light
absorption
efficiency
ability.
Under
visible-light
irradiation
(λ
>
420
nm),
Py-BKh1
photocatalyst
achieved
evolution
rate
(HER)
10.2
mmol
h−1
g−1
with
an
apparent
quantum
yield
(AQY)
9.5%
at
500
nm.
This
work
provides
groundbreaking
paradigm
designing
high-performance
organic
photocatalysts.
