Journal of Materials Chemistry A,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
F-doping
forms
an
oxygen
molecule
potential
well,
altering
the
energy
distribution
function
of
oxygen.
Thus,
this
effect
induces
a
localized
enrichment
zone
for
oxygen,
leading
to
enhanced
O
2
adsorption.
Valence
tuning
of
transition
metal
oxides
is
an
effective
approach
to
design
high-performance
catalysts,
particularly
for
the
oxygen
evolution
reaction
(OER)
that
underpins
solar/electric
water
splitting
and
metal-air
batteries.
Recently,
high-valence
(HVOs)
are
reported
show
superior
OER
performance,
in
association
with
fundamental
dynamics
charge
transfer
intermediates.
Particularly
considered
adsorbate
mechanism
(AEM)
lattice
oxygen-mediated
(LOM).
High-valence
states
enhance
performance
mainly
by
optimizing
e
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
146(1), С. 1174 - 1184
Опубликована: Дек. 28, 2023
Controlling
multimetallic
ensembles
at
the
atomic
level
is
significantly
challenging,
particularly
for
high-entropy
alloys
with
more
than
five
elements.
Herein,
we
report
an
innovative
ultrasmall
(∼2
nm)
PtFeCoNiCuZn
intermetallic
(PFCNCZ-HEI)
a
well-ordered
structure
synthesized
by
using
space-confined
strategy.
By
exploiting
these
combined
metals,
PFCNCZ-HEI
nanoparticles
achieve
ultrahigh
mass
activity
of
2.403
A
mgPt–1
0.90
V
vs
reversible
hydrogen
electrode
oxygen
reduction
reaction,
which
up
to
19-fold
higher
that
state-of-the-art
commercial
Pt/C.
proton
exchange
membrane
fuel
cell
assembled
as
cathode
(0.03
mgPt
cm–2)
exhibits
power
density
1.4
W
cm–2
and
high
mass-normalized
rated
45
mgPt–1.
Furthermore,
theoretical
calculations
reveal
outer
electrons
non-noble-metal
atoms
on
surface
nanoparticle
are
modulated
show
characteristics
multiple
active
centers.
This
work
offers
promising
catalyst
design
direction
developing
highly
ordered
HEI
electrocatalysis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6644 - 6649
Опубликована: Апрель 16, 2024
The
steric
effects
on
the
oxygen
reduction
reaction
(ORR)
have
been
rarely
studied
because
O2
is
small
in
size
and
ORR
catalysts
with
only
difference
hindrance
are
difficult
to
be
designed
synthesized.
Herein,
we
report
homogeneous
catalyzed
by
four
Co
porphyrin
atropisomers
tetrahydrofuran
decamethylferrocene
HClO4
at
298
K.
All
active
selective
for
2H+/2e–
an
activity
order
αααα
>
αααβ
ααββ
αβαβ.
Kinetic
studies
revealed
that
same
mechanism
proton-coupled
binding
as
rate-determining
step.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Фев. 23, 2024
Abstract
Oxygen
reduction
reaction
(ORR)
is
the
bottleneck
of
metal‐air
batteries
and
fuel
cells.
Strain
regulation
can
change
geometry
adjust
surface
charge
distribution
catalysts,
which
a
powerful
strategy
to
optimize
ORR
activity.
The
introduction
controlled
strain
material
still
difficult
achieve.
Herein,
we
present
temperature‐pressure‐induced
achieve
lattice
for
metal
coordination
polymers.
Through
systematic
study
effect
on
performance,
relationship
between
geometric
electronic
effects
further
understood
confirmed.
strained
Co‐DABDT
(DABDT=2,5‐diaminobenzene‐1,4‐dithiol)
with
2
%
compression
exhibits
superior
half‐wave
potential
0.81
V.
Theoretical
analysis
reveals
that
changes
spin‐charge
densities
around
S
atoms
Co‐DABDT,
then
regulates
hydrogen
bond
interaction
intermediates
promote
catalytic
process.
This
work
helps
understand
mechanism
from
atomic
level.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(28)
Опубликована: Апрель 25, 2024
Abstract
Aqueous
soluble
and
stable
Cu(I)
molecular
catalysts
featuring
a
catenane
ligand
composed
of
two
dicationic,
mutually
repelling
but
mechanically
interlocked
macrocycles
are
reported.
The
interlocking
not
only
fine‐tunes
the
coordination
sphere
kinetically
stabilizes
against
air
oxidation
disproportionation,
also
buries
hydrophobic
portions
ligands
prevents
their
dissociation
which
necessary
for
good
water
solubility
sustained
activity.
These
complexes
can
catalyze
oxidative
C−C
coupling
indoles
tetrahydroisoquinolines
in
water,
using
H
2
O
as
green
oxidant
with
substrate
scope.
successful
use
exploiting
aqueous
catalysis
thus
highlights
many
unexplored
potential
mechanical
bond
design
element
exploring
transition
metal
under
challenging
conditions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 13, 2024
Although
catenated
cages
have
been
widely
constructed
due
to
their
unique
and
elegant
topological
structures,
cyclic
catenanes
formed
by
the
connection
of
multiple
catenane
units
rarely
reported.
Herein,
based
on
orthogonal
metal-coordination-driven
self-assembly,
we
prepare
a
series
heterometallic
[2]catenanes
bis[2]catenanes,
whose
structures
are
clearly
evidenced
single-crystal
X-ray
analysis.
Owing
positively
charged
nature,
as
well
potential
synergistic
effect
Cu(I)
Pt(II)
metal
ions,
bis[2]catenanes
display
broad-spectrum
antibacterial
activity.
This
work
not
only
provides
an
efficient
strategy
for
construction
but
also
explores
applications
superior
agents,
which
will
promote
advanced
supramolecular
biomedical
applications.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 14, 2023
We
report
herein
the
first
nonheme
CuFe
oxygen
reduction
catalyst
([CuII
(bpbp)(μ-OAc)2
FeIII
]2+
,
CuFe-OAc),
which
serves
as
a
functional
model
of
cytochrome
c
oxidase
and
can
catalyze
to
water
with
turnover
frequency
2.4×103
s-1
selectivity
96.0
%
in
presence
Et3
NH+
.
This
performance
significantly
outcompetes
its
homobimetallic
analogues
(2.7
CuCu-OAc
%H2
O2
98.9
%,
inactive
FeFe-OAc)
under
same
conditions.
Structure-activity
relationship
studies,
combination
density
theory
calculation,
show
that
center
efficiently
mediates
O-O
bond
cleavage
via
CuII
(μ-η1
:
η2
-O2
)FeIII
peroxo
intermediate
ligand
possesses
distinctive
coordinating
electronic
character.
Our
work
sheds
light
on
nature
Cu/Fe
heterobimetallic
cooperation
catalysis
demonstrates
potential
this
synergistic
effect
design
catalysts.