Small,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 22, 2025
Abstract
Photocatalytic
acceptorless
dehydrogenation
(PAD)
of
amines
represents
an
innovative
method
for
the
production
hydrogen
(H
2
)
and
imines.
Nonetheless,
efficiency
this
reaction
is
often
compromised
by
formation
undesirable
by‐products,
such
as
dibenzylamine
resulting
from
imine
hydrogenation
1,2‐diphenyl
ethylenediamine
due
to
C─C
coupling.
In
study,
a
novel
hollow
core/shell
photocatalyst,
MoS
‐ZnIn
S
4
/CeO
(M‐ZIS/C),
designed
developed
with
spatially
separated
redox
active
sites
mitigate
these
challenges.
The
optimized
M
3%
‐ZIS/C
45%
catalyst
demonstrates
remarkable
performance,
achieving
27.5‐fold
increase
in
rate
H
18.7‐fold
yield
N‐benzylidenebenzylamine
(N‐BBA)
during
benzylamine
PAD
compared
pure
ZnIn
.
Notably,
selectivity
N‐BBA
improved
significantly
15.6
97.4%
upon
modification
Isotopic
tracing
experiments
further
confirmed
that
generated
amines,
trace
amounts
water
acting
proton‐transfer
mediator
accelerate
kinetics.
Additionally,
situ
infrared
spectroscopy
revealed
pathway
N─H
bond
cleavage
generate
aldehyde
intermediates,
which
subsequently
undergo
condensation
products.
This
approach
significant
advancement
energy‐chemical
coupled
photocatalytic
systems
improving
versatility
synthesis.
Advanced Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 23, 2025
Abstract
Exciton
effects
caused
by
the
inherent
dielectric
confinement
in
2D
material
carbon
nitride
(CN)
severely
limit
transfer
of
photogenerated
carriers
and
selective
generation
free
radicals.
Herein,
a
homo‐hetero
double
junction
coupling
strategy
is
reported
to
address
these
challenges.
Ternary
homojunction
(HCCN)
functionalized
with
cyano
cyanamide
groups
constructed
built‐in
electric
field
that
efficiently
separates
electron–hole
into
different
structural
units,
thereby
reducing
reverse
charge
recombination
weakening
exciton
effects.
The
introduction
α‐Fe
2
O
3
(FO)
subsequently
constructs
catalyst
FO/HCCN
127
times
stronger
than
HCCN,
which
promotes
directional
migration
after
dissociation
achieves
≈100%
·O
−
from
.
These
results
suggest
99.6%
removal
tetracycline
within
20
min,
degradation
rate
12
46
higher
FO/CN
respectively.
In
addition,
system
shows
excellent
stability
cyclability
real‐life
light
experiments
trace
organic
contaminant
removal.
This
opens
up
new
avenues
precisely
controlling
Advanced Functional Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 16, 2025
Abstract
Heterojunction
engineering
into
quantum
dot
(QD)
assemblies
has
emerged
as
an
effective
approach
to
optimize
photocatalytic
systems
through
enhanced
charge
separation
and
extended
light‐harvesting
capabilities.
Nevertheless,
fabricating
QD
heterojunctions
with
robust
interfacial
coupling
remains
challenging
due
stringent
morphological
lattice
matching
constraints.
Here,
a
class
of
atomically
fused
ZnCdSe–CdS
aerogels
tailored
heterointerfaces
is
reported
for
superior
solar‐driven
CO
2
reduction.
The
high
compatibility
between
ZnCdSe
CdS
enables
seamless
heterojunction
formation
strong
electronic
coupling,
while
strategic
Cd
doping
in
ZnSe
extends
optical
absorption
maximize
solar
utilization.
optimized
exhibit
exceptional
photoreduction
activity,
achieving
CH
4
production
rate
240
µmol
g⁻
1
h⁻
87%
selectivity
apparent
yield
(AQY)
1.2%
under
visible
light.
Combined
spectroscopic
characterization
density
functional
theory
(DFT)
simulations
elucidate
that
suppressed
carrier
recombination
at
the
engineered
interface
serves
key
mechanistic
determinant
performance.
This
work
establishes
universal
platform
designing
interfacial‐engineered
aerogels,
advancing
their
applicability
high‐efficiency
fuel
generation
systems.
