Abstract
Thiolate‐protected
Au
nanoclusters
(NCs)
have
developed
as
a
promising
class
of
model
catalysts
to
achieve
fundamental
understanding
metal
nanocatalysis.
Whereas,
the
packing
mode
peripheral
ligand
on
core
is
changeful
in
reaction
medium
and
show
elusive
impact
catalytic
activity.
In
this
work,
using
glutathione
(GSH)
protected
NCs
(Au@GSH
NCs)
with
aggregation‐induced‐emission
(AIE)
characteristics
catalyst
for
hydrogenation
4‐nitrophenol
(4‐NP),
photoluminescence
(PL)
intensity
correlated
activity
Au@GSH
was
successfully
mediated
by
addition
Ag
+
preparation
or
poor
solvent
medium,
showing
relationship
“as
one
falls,
another
rises.”
intense
PL
implied
dense
ligand,
which
hampered
accessibility
active
site
thus
exhibited
slowest
kinetics
reduction
4‐NP
vice
versa.
Based
methodology,
case
study
effect
salt
additives
carried
out,
different
mechanisms
are
distinguished
change
intensity,
combination
diagnostic
deuterium
isotope
experiments,
it
has
been
demonstrated
that
proton
from
water
involved
transfer
process
rate‐determining
step,
contribution
ionic
hydrogen
bonding
network
determines
their
kinetics.
The
correlation
between
could
provide
an
efficient
way
design
highly
NC
give
new
insight
understand
unique
optoelectronic
properties
mechanism.
Advanced Energy Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 5, 2025
Abstract
Electrocatalytic
CO
2
reduction
(CO
RR)
is
rapidly
emerging
as
a
promising
sustainable
strategy
for
transforming
into
valuable
fuels
and
chemical
feedstocks,
crucial
step
toward
carbon‐neutral
society.
The
efficiency,
selectivity,
stability
of
RR
are
heavily
influenced
by
the
chosen
catalyst
operating
conditions
used.
Despite
substantial
advances
in
development
catalysts,
there
scarcity
comprehensive
reviews
focusing
on
influence
different
environments
performance.
This
review
offers
detailed
examination
internal
external
environmental
control
strategies
designed
to
enhance
efficiency.
fundamental
reaction
mechanisms
through
situ
operational
techniques,
paired
with
theoretical
analyses,
discussed
while
also
identifying
key
challenges
future
research
directions
technology.
By
delivering
overview
current
state
field,
this
highlights
critical
role
control,
mechanistic
insights,
practical
considerations
needed
successful
commercialization
Chemical Society Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
Ligand-protected
metal
nanoclusters
are
an
emerging
class
of
nanomaterials
at
the
interface
atomic
and
plasmonic
regimes
with
unique
photophysical
electrochemical
properties,
leading
to
diverse
applications.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
Abstract
Atomically
precise
copper(I)
nanoclusters
with
stable
active
sites
are
highly
sought‐after
catalysts
for
the
electrocatalytic
CO₂
reduction
reaction
(CO₂RR),
providing
an
exceptional
platform
to
elucidate
structure–activity
relationships.
However,
rational
synthesis
of
robust
copper
as
effective
electrocatalysts
and
understanding
relationship
between
a
more
realistic
site
its
performance
remain
significant
challenge
due
their
inherent
instability.
Here,
novel
dipropyne‐modified
NHC
ligand
is
elaborately
devised
two
atomically
nanoclusters,
[Cu
17
H
6
(NHC
)
4
(dppm)
]
3+
(
Cu17a
Ph
Cu17b
),
both
exhibiting
distinct
unique
square
orthobicupola
Cu
core
J
28
,
Johnson
solid).
The
σ‐
π‐bonding
ligands
imparts
ultrahigh
stability
while
coordination
pattern
μ
7
‐
η
σ
1
:
π
2
facilitates
exposure
neighboring
atoms,
generating
accessible
catalytic
sites.
Electrocatalytic
CO
experiments
show
that
achieves
highest
Faradaic
efficiency
ethylene
production
among
reported
nanoclusters.
tandem
mechanism
RR
elucidated
through
combination
theoretical
calculations
attenuated
total
reflection‐surface‐enhanced
IR
absorption
spectroscopy
(ATR‐SEIRAS).
This
work
not
only
introduces
synthesizing
but
also
offers
critical
insights
into
molecular
design
principles
catalysts.
Current
advances
in
synthesizing
and
characterizing
atomically
precise
monodisperse
metal
clusters
(AMCs)
at
the
subnanometer
scale
have
opened
up
new
possibilities
quantum
materials
research.
Their
quantizied
“molecule‐like”
electronic
structure
showcases
unique
stability,
physical
chemical
properties
differentiate
them
from
larger
nanoparticles.
When
integrated
into
inorganic
that
interact
with
environment
sunlight,
AMCs
serve
to
enhance
their
(photo)catalytic
activity
optoelectronic
properties.
tiny
size
makes
isolated
gas
phase
amenable
atom‐scale
modeling
using
either
density
functional
theory
(DFT)
or
methods
a
high
level
of
ab
initio
theory,
even
addressing
nonadiabatic
(e.g.,
Jahn–Teller)
effects.
Surface‐supported
can
be
routinely
modeled
DFT,
enabling
long
real‐time
molecular
dynamics
simulations.
optical
also
addressed
time‐dependent
DFT
reduced
matrix
(RDM)
theory.
These
theoretical–computational
efforts
aim
achieve
predictability
molecular‐level
understanding
stability
as
function
composition,
size,
structural
fluxionality
different
thermodynamical
conditions
(temperature
pressure).
In
this
perspective,
potential
DFT‐based
is
illustrated
through
recent
studies
unsupported
surface‐supported
AMCs.
Future
directions
research
are
discussed,
including
applications
methodological
enhancements
beyond
state‐of‐the‐art.
EcoEnergy,
Год журнала:
2024,
Номер
2(3), С. 400 - 418
Опубликована: Июль 10, 2024
Abstract
Understanding
the
intricate
relationship
between
structure
and
properties
is
paramount
in
distinguishing
nanocluster
(NC)
materials
from
their
counterparts.
Despite
progress
synthesizing
new
NCs,
sluggish
exploration
of
potential
applications
persists
due
to
difficulty
stabilizing
these
materials.
However,
recent
investigations
have
unveiled
remarkable
efficacy
as
catalysts
electrochemical
CO
2
reduction
reactions,
surpassing
traditional
This
discovery,
addressing
urgent
global
concerns,
has
quickly
drawn
significant
attention
this
field,
leading
its
rapid
expansion.
Hence,
there
an
need
outline
research
landscape
pinpoint
effective
strategies,
marking
a
advancement.
In
context,
our
endeavor
dedicated
offering
researchers
thorough
understanding
recently
synthesized
NC
We
aim
elucidate
distinct
structural
architectures
associated
essential
for
catalyst
design.
envision
that
systematic
review
will
serve
guiding
beacon
future
endeavors
burgeoning
field.
RSC Advances,
Год журнала:
2025,
Номер
15(7), С. 5007 - 5010
Опубликована: Янв. 1, 2025
Direct
addition
of
N-heterocyclic
carbene
silver
or
gold
complexes
to
CTAC
coated
nanorods
yields
chemisorbed
ligands
via
a
facile,
one-step
procedure.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
nearly
perfect
icosahedral
Ir@Au
12
superatom
was
formed
using
a
diphosphine
ligand
with
benzo[
b
]phosphindole
rings.
The
exhibited
bright
photoluminescence
due
to
the
symmetric
structure
rigidified
core.
