Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Structural
isomers
of
atomically
precise
metal
nanoclusters
are
highly
sought
after
for
investigating
structure-property
relationships
in
nanostructured
materials.
However,
they
extremely
rare,
particularly
those
alloys,
primarily
due
to
the
challenges
their
synthesis
and
structural
characterization.
Herein,
first
time,
a
pair
bimetallic
isomeric
AgCu
has
been
controllably
synthesized
structurally
characterized.
These
two
share
an
identical
molecular
formula,
Ag
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(17)
Published: Feb. 26, 2024
Atomically
precise
metal
nanoclusters
(NCs)
with
unique
optical
properties
and
abundant
catalytic
sites
are
promising
in
photocatalysis.
However,
their
light-induced
instability
the
difficulty
of
utilizing
photogenerated
carriers
for
photocatalysis
pose
significant
challenges.
Here,
MAg
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(50), P. 27407 - 27414
Published: Dec. 6, 2023
Unraveling
the
atomistic
synergistic
effects
of
nanoalloys
on
electrocatalytic
CO2
reduction
reaction
(eCO2RR),
especially
in
presence
copper,
is
paramount
importance.
However,
this
endeavor
encounters
significant
challenges
due
to
lack
crystallographically
determined
atomic-level
structure
appropriate
monometallic
and
bimetallic
analogues.
Herein,
we
report
a
one-pot
synthesis
characterization
AuCu
nanoalloy
cluster
catalyst,
[Au15Cu4(DPPM)6Cl4(C≡CR)1]2+
(denoted
as
Au15Cu4).
Single-crystal
X-ray
diffraction
analysis
reveals
that
Au15Cu4
comprises
two
interpenetrating
incomplete,
centered
icosahedra
(Au9Cu2
Au8Cu3)
protected
by
six
DPPM,
four
halide,
one
alkynyl
ligand.
The
its
closest
monometal
structural
analogue,
[Au18(DPPM)6Br4]2+
Au18),
model
systems,
enable
elucidation
Au
Cu
eCO2RR.
results
reveal
an
excellent
eCO2RR
catalyst
gas
diffusion
electrode-based
membrane
electrode
assembly
(MEA)
cell,
exhibiting
high
CO
Faradaic
efficiency
(FECO)
>90%,
substantially
higher
than
undoped
Au18
(FECO:
60%
at
−3.75
V).
exhibits
industrial-level
partial
current
density
up
−413
mA/cm2
V
with
CO2-fed
MEA,
which
2-fold
Au18.
functional
theory
(DFT)
calculations
demonstrate
are
induced
doping,
where
exposed
pair
dual
sites
was
suggested
for
launching
process.
Besides,
DFT
simulations
these
special
synergistically
coordinate
moderate
shift
d-state,
thus
enhancing
overall
catalytic
performance.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 30, 2025
We
report
the
synthesis
of
[Ag17(o1-CBT)12]3-
abbreviated
as
Ag17,
a
stable
8e⁻
anionic
cluster
with
unique
Ag@Ag12@Ag4
core-shell
structure,
where
o1-CBT
is
ortho-carborane-1-thiol.
By
substituting
Ag
atoms
Au
and/or
Cu
at
specific
sites
we
created
isostructural
clusters
[AuAg16(o1-CBT)12]3-
(AuAg16),
[Ag13Cu4(o1-CBT)12]3-
(Ag13Cu4)
and
[AuAg12Cu4(o1-CBT)12]3-
(AuAg12Cu4).
These
substitutions
make
systematic
modulation
their
structural
electronic
properties.
show
that
preferentially
occupies
core,
while
localizes
in
tetrahedral
shell,
influencing
stability
diversity
clusters.
The
band
gap
expands
systematically
(2.09
eV
for
Ag17
to
2.28
AuAg12Cu4),
altering
optical
absorption
emission.
Ultrafast
measurements
reveal
longer
excited-state
lifetimes
Cu-containing
clusters,
highlighting
effect
heteroatom
incorporation.
results
demonstrate
tunable
platform
designing
nanoclusters
tailored
properties,
implications
optoelectronics
catalysis.
Tuning
structure
composition
atomically
precise
metal
leads
property
changes
which,
however,
are
still
poorly
understood.
Here,
authors
synthesize
precisely
substituted
analogues
study
luminescence
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(4)
Published: Dec. 11, 2023
Abstract
Recently,
CO
2
hydrogenation
had
a
new
breakthrough
resulting
from
the
design
of
catalysts
to
effectively
activate
linear
with
symmetry‐breaking
sites.
However,
understanding
relationship
between
sites
and
catalytic
activity
at
atomic
level
is
still
great
challenge.
In
this
study,
set
gold‐copper
alloy
Au
13
Cu
x
(x=0–4)
nanoclusters
were
used
as
research
objects
show
symmetry‐controlled
breaking
structure
on
surface
help
manipulability
atoms.
Among
them,
3
nanocluster
displays
highest
degree
its
crystal
compared
other
in
family.
Where
three
copper
atoms
occupying
icosahedral
kernel
unevenly
one
atom
coordinately
unsaturated
(CuS
motif
relative
CuS
motif).
As
expected,
has
an
excellent
,
which
current
density
high
70
mA
cm
−2
(−0.97
V)
maximum
FE
reaches
99
%
−0.58
V.
Through
combination
structures
theoretical
calculations,
revealed
be
indeed
closely
related
asymmetric
structure.
Polyoxometalates,
Journal Year:
2023,
Volume and Issue:
2(4), P. 9140031 - 9140031
Published: Aug. 2, 2023
Hydrogen
evolution
reaction
(HER)
is
a
vital
step
for
water
electrolysis
toward
H2
production,
but
the
conventional
nanocatalysts
lack
uniform
size,
composition,
structure,
and
chemical
coordination
environment
hence
making
it
extremely
challenging
to
establish
unambiguous
structure-performance
relationship.
Owing
ultrasmall
definitive
well-defined
at
atomic
level,
atomically
precise
Au
nanoclusters
can
serve
as
model
catalysts
improve
knowledge
gap
between
structure
catalytic
properties.
This
review
first
explains
significance
fundamental
mechanism
of
HER,
highlights
unique
advantages
employing
catalysts.
Subsequently,
recent
progress
including
promote
catalyze
Au-alloy
HER
discussed,
with
focus
on
elaborating
With
some
explicit
examples,
key
factors
that
affect
performance
not
limited
electronic
interaction,
interfacial
effect,
size
charge
state,
ligand
metal
core
single
atom
doping,
geometric
configuration
effect
are
analyzed.
Finally,
current
critical
challenges
future
perspectives
discussed.
We
hope
this
shed
light
designing
efficient
stable
coinage
nanocluster-based
catalyst
electrochemical
production
beyond.
Nanoscale Horizons,
Journal Year:
2024,
Volume and Issue:
9(8), P. 1262 - 1278
Published: Jan. 1, 2024
This
review
summarizes
the
recent
progress
in
atomically
precise
metal
nanoclusters
various
photocatalytic
applications
and
highlights
strategy
for
constructing
nanocluster-based
heterostructures
to
improve
stability
catalytic
activity.
