ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 15, 2025
Metal
halide
perovskite
nanocrystals
(NCs),
known
for
their
strong
visible-light
absorption
and
tunable
optoelectronic
properties,
show
significant
promise
photocatalytic
applications.
However,
efficiency
is
often
hindered
by
rapid
charge
recombination
insufficient
exciton
dissociation,
limiting
effective
catalysis.
Excited-state
interactions
at
the
NC
interface
are
critical
in
determining
performance,
underscoring
need
strategies
that
enhance
separation
minimize
recombination.
To
address
these
challenges,
we
developed
a
composite
material
combining
cesium
lead
bromide
(CsPbBr3)
with
ferrocene
carboxylic
acid
(FcA),
hole-extracting
moiety.
This
integration
enhances
dissociation
through
energy
level
alignment
suppression,
resulting
3-fold
increase
oxidation
yield
of
benzylamine
to
N-benzylidenebenzylamine
(35
±
5%
versus
12
2%
pristine
CsPbBr3).
Additionally,
thionyl
(SOBr2)
surface
modification
strips
off
ligands
introduces
ions
onto
CsPbBr3
NCs,
further
improving
transfer
substrate
accessibility,
27
within
3
h.
While
SOBr2
treatment
initial
catalytic
its
acidic
nature
may
reversible
reactions
side
products
over
extended
reaction
times.
study
highlights
impact
molecular
engineering
on
optimizing
interfacial
dynamics,
providing
pathway
toward
robust,
high-efficiency
photocatalysts
sustainable
chemical
transformations.
ACS Applied Nano Materials,
Год журнала:
2024,
Номер
7(14), С. 16913 - 16921
Опубликована: Июль 16, 2024
Metal
halide
perovskite
nanocrystals
(NCs)
possess
immense
potential
in
photocatalysis.
However,
deciphering
the
intricate
surface
chemistry
that
governs
these
catalytic
processes
remains
a
challenge.
This
study
investigates
C–X
bond
activation
with
CsPbBr3
NCs,
focusing
on
elucidating
role
of
dynamic
molecular
domains
dictating
activity.
By
manipulating
interactions
through
ligand
dynamics,
we
identify
vacancies
as
critical
sites
for
activation.
A
systematic
exploration
different
types
reveals
varying
kinetics
exchange,
oleyl
amine-capped
NCs
demonstrating
highest
reactivity.
Temperature-dependent
photoluminescence
measurements
corroborate
findings,
highlighting
influence
dynamics
interactions.
Additionally,
postsynthetic
treatments,
such
lead
oleate
modification,
which
leads
to
an
increase
density
active
(halide
vacancies),
significantly
enhance
performance.
Conversely,
SOBr2
treatment,
repairs
bromide
vacancies,
results
almost
completely
suppressed
So,
by
engineering
environments,
demonstrate
significant
improvement
performance
metal
offering
valuable
insights
future
development.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 11, 2025
Abstract
Over
the
past
decade,
lead
halide
perovskite
(LHP)
nanocrystals
(NCs)
have
attracted
significant
attention
due
to
their
tunable
optoelectronic
properties
for
next‐generation
printed
photonic
and
electronic
devices.
High‐energy
photons
in
presence
of
haloalkanes
provide
a
scalable
sustainable
pathway
precise
bandgap
engineering
LHP
NCs
via
photo‐induced
anion
exchange
reaction
(PIAER)
facilitated
by
situ
generated
anions.
However,
mechanisms
driving
remain
not
fully
understood.
This
study
elucidates
underlying
PIAER
through
an
advanced
microfluidic
platform.
Additionally,
first
instance
PIAER,
transforming
CsPbBr
3
into
high‐performing
CsPbI
NCs,
with
assistance
thiol‐based
additive
is
reported.
Utilizing
intensified
photo‐flow
microreactor
accelerates
rate
3.5‐fold,
reducing
material
consumption
100‐fold
compared
conventional
batch
processes.
It
demonstrated
that
act
as
photocatalysts,
oxidative
bond
cleavage
dichloromethane
promoting
photodissociation
1‐iodopropane
using
high‐energy
photons.
Furthermore,
it
plays
dual
role:
surface
passivation,
which
enhances
photoluminescence
quantum
yield,
facilitates
PIAER.
These
findings
pave
way
tailored
design
perovskite‐based
materials.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
Lead
halide
perovskite
quantum
dots
(LHP
QDs)
CsPbX3
generate
immense
interest
as
narrow-band
emitters
for
displays,
lasers,
and
light
sources.
All
QD
applications
rely
on
suited
engineering
of
surface
capping
ligands.
The
first
generation
LHP
QDs
employed
oleic
acid/oleyl
amine
have
found
only
a
limited
use
in
photoredox
catalysis.
These
catalysts
been
reported
to
be
unstable
decompose
over
the
course
reaction,
thus
reducing
turnover
numbers
(TONs)
limiting
their
synthetic
ability.
Herein,
impact
eight
distinct
ligands
monodisperse
CsPbBr3
is
reported,
affording
thorough
comprehension
performance
photocatalytic
C–H
brominations.
efforts
yielded
operating
at
extremely
low
catalyst
loadings
(<100
ppb)
with
TONs
9,000,000
per
QD.
We
emphasize
that
optimal
catalytic
requires
increased
accessibility
without
compromising
structural
colloidal
integrity.
Control
experiments
indicated
well-known
such
Ir(ppy)3,
Ru(bpy)3Cl2,
or
4CzlPN
are
ineffective
same
reaction.
Mechanistic
studies
reveal
C–Br
bond
reduction
CH2Br2
rate-limiting
step
likely
facilitated
through
interaction
surface.
This
work
outlines
holistic
approach
toward
design
practically
useful
photocatalysts
out
comprising
structurally
soft
cores
dynamically
bound
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 13, 2025
Dual
functionalization
in
organic
synthesis
represents
a
powerful
strategy
aimed
at
achieving
multiple
transformations
within
single
reaction
cycle,
thereby
streamlining
synthetic
processes,
enhancing
efficiency,
and
imparting
economic
paths
for
complex
molecules.
Here,
we
report
heterogeneous
perovskite
nanocrystal
(NC)
photocatalytic
system
that
can
simultaneously
drive
two
photoredox
cycles
reaction.
The
dual
process
incorporates
distinct
functional
groups
(N-heterocycles
bromines)
into
N-arylamines
under
the
influence
of
catalyst
(CsPbBr3
NCs),
allowing
concurrent
formation
architectures
3-bromo-N-arylindoles.
Mechanistically,
long-lived
charge
separation
carrier
accumulation
NC
surface
enable
to
these
simultaneously.
approach
exploits
light-induced
holes
an
amine
oxidation
one
cycle
(I)
cooperatively
utilizes
dibromomethane
(CH2Br2),
solvent-grade
mild
reagent
site-selective
bromination,
achieve
other
(II).
We
find
chiral
induces
enantioselective
axial
C–N
bond
formation,
but
is
inactive
C–C
arylindoles.
Merging
rare;
thus,
photocatalysis
not
only
aligns
with
principles
green
chemistry
also
holds
immense
potential
rapid
economical
design
A
graphitic
carbon
nitride/lead-free
double
perovskite
heterojunction
(g-C3N4/Cs2AgBiCl6)
has
been
adopted
as
a
heterogeneous
photocatalyst
under
visible
light
irradiation.
The
employed
material
enabled
the
atom
transfer
radical
addition-type
carbohalogenation
of
multiple
C-C
bonds,
including
(internal)
alkenes
and
alkynes,
with
alkyl
halides.
protocol
showed
remarkable
functional
group
tolerance,
compatible
late-stage
functionalization
natural
pharmaceutical
derivatives,
could
be
easily
scaled
up,
delivering
>1
g
desired
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Сен. 4, 2024
Allylic
C-H
amination
has
emerged
as
a
powerful
tool
to
construct
allylamines,
common
motifs
in
molecular
therapeutics.
Such
reaction
implies
an
oxidative
path
for
activation
but
furnishes
reductive
amines,
inferring
mild
oxidants'
inactivity
oxidation
strong
detriment
products.
Herein
we
report
heterogeneous
catalytic
approach
that
manipulates
halogen-vacancies
of
perovskite
photocatalyst
and
exploits
halogenated-solvents
(i.e.
CH
