Abstract
Conjugated
porous
polymers
(CPPs)
have
emerged
as
promising
candidates
for
photocatalytic
H
2
production
(PHP)
in
recent
years
due
to
their
structural
diversity,
tunable
electronic
properties,
and
high
specific
surface
area.
Herein,
three
CPPs
are
synthesized
by
the
Suzuki
coupling
reaction
O
splitting
produce
.
Through
molecular
tuning
strategies,
π‐conjugation
degree
of
is
adjusted,
significantly
impacting
charge
separation
transfer
efficiency
photocatalysts
well
light‐harvesting
ability.
The
optimal
photocatalyst,
namely
PyDF,
shows
a
evolution
rate
12.8
mmol
g
−1
h
with
large
number
continuous
visible
bubbles,
which
up
five
times
higher
than
its
counterparts.
Advanced
characterization
techniques,
including
photo‐irradiated
Kelvin
probe
force
microscopy
(KPFM)
femtosecond
transient
absorption
(fs‐TA)
spectroscopy,
together
theoretical
calculations,
reveal
that
PyDF
smaller
dihedral
angle
has
much‐improved
degree,
resulting
efficiency.
This
work
provides
new
perspective
application
PHP
emphasizes
importance
modulation
degree.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
Abstract
Poly
(triazine
imide)
(PTI),
a
crystalline
allotrope
of
polymeric
carbon
nitride,
holds
great
promise
for
photocatalytic
overall
water
splitting
(OWS).
However,
previous
results
reveal
that
both
H
2
and
O
evolution
cocatalysts
prefer
to
deposit
on
the
prismatic
facets,
which
in
undesired
backward
reaction
current
unsatisfied
quantum
efficiency
OWS
reaction.
Herein,
situ
decoration
with
heptazine
based
nitride
(HCN)
at
interface
PTI
is
successfully
employed
construct
S‐scheme
hetero‐phase
junctions.
The
built‐in
electric
field
HCN
endows
directed
carrier
separation,
thereby
enabling
separation
redox
sites,
as
validated
by
theoretical
experimental
results.
Accordingly,
as‐synthesized
PTI/HCN
spatially
separated
charge
carriers
restrained
achieves
solar‐to‐hydrogen
energy
conversion
0.35%
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 8, 2024
Abstract
Two‐dimensional
(2D)
polymeric
semiconductors
are
a
class
of
promising
photocatalysts;
however,
it
remains
challenging
to
facilitate
their
interlayer
charge
transfer
for
suppressed
in‐plane
recombination
and
thus
improved
quantum
efficiency.
Although
some
strategies,
such
as
π–π
stacking
van
der
Waals
interaction,
have
been
developed
so
far,
directed
still
cannot
be
achieved.
Herein,
we
report
strategy
forming
asymmetric
Zn−N
3
units
that
can
bridge
nitrogen
(N)‐doped
carbon
layers
with
nitride
nanosheets
(C
N
4
−Zn−N(C))
address
this
challenge.
The
symmetry‐breaking
moiety,
which
has
an
local
distribution,
enables
interfacial
between
the
C
photocatalyst
N‐doped
co‐catalyst.
As
evidenced
by
femtosecond
transient
absorption
spectroscopy,
separation
significantly
enhanced
bonding
bridges.
result,
designed
−Zn−N(C)
catalyst
exhibits
dramatically
H
2
O
photosynthesis
activity,
outperforming
most
reported
‐based
catalysts.
This
work
highlights
importance
tailoring
chemical
channels
in
photocatalysts
at
molecular
level
achieve
effective
spatial
separation.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
Abstract
The
photosynthesis
of
hydrogen
peroxide
(H
2
O
)
via
the
selective
two‐electron
oxygen
reduction
reaction
(ORR)
is
emerging
as
a
promising
method
for
producing
this
important
chemical.
However,
reliance
on
sacrificial
agents
has
limited
practical
application
many
photocatalysts.
Herein,
nitrogen‐doped
graphene
quantum
dots
(NGQDs)
are
loaded
onto
surface
Mn
x
Cd
1‐
S
solid
solution
nanowires
to
enable
overall
H
in
pure
water
under
an
air
atmosphere.
optimized
0.2
0.8
S/NGQDs
(M
NG5)
composite
achieves
high
yield
6885
µmol
g
−1
h
,
which
10.4
times
and
4.5
higher
than
that
CdS
(661
(1522
),
respectively.
NGQDs
act
co‐catalysts,
enhancing
conductivity
system.
strong
electronegativity
polarity
incorporated
nitrogen
functional
groups
edges
enhance
ability
carbon
atoms
activate
into
·O
−
.
mechanism
investigated
using
situ
Fourier
transform
infrared
spectroscopy,
intermediate
trapping
experiments,
theoretical
calculations.
This
work
offers
new
insights
design
non‐noble
metal
co‐catalyst‐modified
photocatalysts
sacrificial‐agent‐free
production.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
Photocatalytic
nitroarene
reduction
provides
a
promising
strategy
for
the
sustainable
production
of
aniline.
The
construction
S-scheme
heterostructures
with
clear
interfacial
charge
transfer
mechanism
is
considered
as
an
effective
to
improve
photocatalytic
performance
photocatalysts.
assembly
MOF-on-MOF
might
be
used
construct
heterojunctions
due
rich
structures,
transport
channels,
and
fast
mass
MOFs.
Herein,
2D
Pd-PPF-1
was
coated
on
3D
Pd-PCN-222
through
presurface
modification
strategy,
prepared
Pd-PPF-1/Pd-PCN-222
heterojunction
displayed
morphology
nanoflower
winding
around
rod.
As
hydrogenation,
as-obtained
catalyst
exhibited
much
higher
than
Pd-PPF-1,
Pd-PCN-222,
or
physical
mixture
Pd-PCN-222.
high
catalytic
attributed
formation
heterojunction,
which
not
only
retained
redox
capability
parent
MOFs
but
also
separated
photogenerated
carriers.
This
work
presents
constructive
route
designing
2D-on-3D
MOF
controllable
ability.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 15, 2024
Abstract
Understanding
charge
carrier
transfer
at
heterojunction
interfaces
is
critical
for
advancing
solar
energy
conversion
technologies.
This
study
utilizes
continuous
wave
(CW),
pulse,
and
time‐resolved
(TR)
electron
paramagnetic
resonance
(EPR)
spectroscopy
to
explore
the
radical
species
formed
TAPA
(tris(4−aminophenyl)amine)‐PDA
(Terephthaldicarboxaldehyde)/ZnIn
2
S
4
(TP/ZIS)
interface.
CW
pulse
EPR
identify
stable
defects
localized
near
interface,
accessible
water
molecules.
Time‐resolved
reveals
a
photoinduced
from
TP
ZIS,
leading
generation
of
spin‐correlated
pairs
under
light
irradiation,
signifying
efficient
separation
spatial
within
S‐scheme
heterojunction.
mechanism,
confirmed
through
in
situ
X–ray
photoelectron
femtosecond
transient
absorption
spectroscopy,
suppresses
undesirable
recombination,
extending
lifetimes.
These
findings
provide
novel
insights
into
transport
direction
carriers
offering
valuable
guidance
designing
highly
organic–inorganic
photocatalysts
applications.
