Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 9, 2024
Abstract
Establishing
a
targeted
switch
for
CO
2
conversion
under
electric
drive
is
essential
achieving
carbon‐balance
by
enabling
selective
chemicals.
However,
engineering
the
topological
assembly
of
active
sites
to
precisely
regulate
competing
pathways
various
intermediates
has
been
plagued
unclear
structure‐function
relationships.
To
tailor
CO/formate
pathways,
herein
we
established
robust
nonlinear
with
tunable
Co
x
integrated
into
Pd
metallene,
which
involves
1
/Pd
single‐atom
alloy
(favoring
CO)
and
diatomic
formate).
Transitioning
from
atomic
bimetallenes
resulted
in
nonlinear,
high‐contrast
flip
selectivity,
surpassing
94
%
formate
productions
both
H‐cell
flow
cell.
Furthermore,
superior
selectivity
current
efficiency
(>80
%)
(>88
were
consistently
maintained
at
−150
mA
cm
−2
over
continuous
200
h.
Theoretical
simulations
situ
spectroscopy
analyses
unveiled
that
appropriate
adjacent
metal
site
combinations
(Pd−Pd,
Pd−Co
Co−Co)
lead
d
z
band
center
shift
preferred
adsorption
configurations
intermediates,
dictating
C
pathways.
Our
finding
reveals
desired
stability
within
system,
providing
new
perspective
fine‐tuning
energy
processes
through
specific
assembly.
ACS Energy Letters,
Год журнала:
2024,
Номер
9(9), С. 4414 - 4440
Опубликована: Авг. 17, 2024
Electrochemical
reactions,
including
water
splitting,
oxygen
reduction,
hydrogen
oxidation,
carbon
dioxide
nitrogen
oxide
etc.,
are
critical
for
sustainable
energy
conversion
and
storage.
Achieving
high
efficiency
in
these
reactions
requires
catalysts
with
superior
activity,
selectivity,
stability,
often
realized
through
nanostructured
metal
catalysts.
However,
practical
challenges
such
as
low
selectivity
catalytic
degradation
persist.
In
situ
operando
characterization
techniques
offer
real-time
insights
into
catalyst
behavior
under
reaction
conditions,
enabling
a
deeper
understanding
of
structure–performance
relationships
and,
therefore,
guiding
the
design
optimization
electro-catalysts.
This
review
discusses
common
situ/operando
techniques,
highlights
their
applications
model
catalysts,
single-atom
single-crystal
further
explores
combinational
analysis
to
study
complex
nanocatalysts.
Finally,
we
provide
suggestions
perspectives
on
development
advance
field
electrochemical
catalysis.
Proceedings of the National Academy of Sciences,
Год журнала:
2025,
Номер
122(10)
Опубликована: Март 5, 2025
Although
bismuth
catalysts
enable
accelerated
electrochemical
CO2-to-formate
conversion,
the
intrinsic
active
sites
and
forming
mechanisms
under
operating
conditions
remain
elusive.
Herein,
we
prepared
Bi2O2NCN,
Bi2O3,
Bi2O2S
as
precatalysts.
Among
them,
Bi2O2NCN-derived
catalyst
possesses
optimum
performance
of
CO2-to-formate,
exhibiting
an
upsurge
Faradaic
efficiency
to
98.3%
at
-0.6
V
vs.
reversible
hydrogen
electrodes.
In-situ
infrared
impedance
spectra
trace
interpret
superior
performance.
Multimodal
structural
analyses
utilizing
quasi-in-situ
X-ray
diffraction,
in-situ
absorption
near
edge
structure
Raman
provide
powerful
support
monitoring
catalysts'
transforms
metallic
Bi,
identifying
formation
influenced
by
chalcogenide
ions-guided:
Carbodiimide
promotes
form
dominant
Bi(003)
facet
exposure,
which
distinguishes
from
sulfide-
oxide-preferred
Bi(012)
facets
exposure.
Concurrently,
theoretical
insights
garnered
multiscale/multilevel
computational
harmoniously
corroborate
experimental
findings.
These
findings
show
pivotal
role
in
tailoring
electrocatalysts
for
selective
CO2
reduction
formate,
illuminating
significance
controlling
chemistry
designing
toward
high-efficiency
renewable
energy
conversion.
Abstract
The
thickness
and
composition
of
the
solid
electrolyte
interphase
(SEI)
on
lithium
(Li)
metal
are
critical
factors
influencing
dendrite
growth.
This
study
introduces
a
novel
selection
strategy
based
electrochemical
corrosion
principles.
By
employing
LiCl
LiNO
3
simultaneously,
itself
has
high
donor
number,
low
desolvation
energy,
Li⁺
transference
number
conductivity,
moderate
stability
window.
In
addition,
it
dynamically
reduces
SEI
reactivates
dead
Li,
forming
≈100
nm
enriched
with
LiF
Li
2
O
anode,
which
ensures
stable
cycling
symmetric
cells
for
2000
h
at
current
density
5
mA
cm⁻
.
Consequently,
using
LiFePO
4
(LFP)
as
cathode
‐LiCl‐added
exhibit
excellent
performance
1600
cycles
680
g⁻
1
Even
thin
(5
µm)|LFP
cell
retains
95%
capacity
after
70
170
universality
feasibility
this
design
also
validated
in
diverse
battery
chemistries
such
anode‐free
Cu|LFP,
Li|LiNi
0.8
Mn
0.1
Co
(NMC811),
Li|S
cells,
well
pouch
high‐loading
LFP
NMC811
cathodes,
showcasing
promising
batteries.
Abstract
2D
layered
black
phosphorus
(BP),
also
known
as
phosphorene,
has
attracted
significant
attention
for
its
potential
applications
in
transistors,
catalysis,
biomedicine,
energy
conversion,
and
storage.
However,
addressing
the
reactivity
of
BP
with
oxygen
water,
thus
achieving
an
effective
passivation
deprotection
remains
a
key
challenge.
Here,
we
demonstrate
protective
strategy
based
on
covalent
functionalization
chelation
to
passivate
surface.
This
approach
involves
modification
tannic
acid
(TA)
reduce
lone
electron
pairs
BP,
followed
by
Fe
III
ions
TA
yield
shielding
layer,
thereby
providing
dual
protection.
protection
confers
exceptional
stability
allowing
it
remain
stable
over
five
months
under
ambient
conditions.
Furthermore,
can
be
deprotected
treatment
weak
acids
ultrasonic
conditions,
restoring
utilizing
broader
fields.
Thermoelectric
materials
are
particularly
relevant
to
the
current
energy
infrastructure
and
demands
of
21st
century,
converting
waste
heat
into
usable
electricity.
The
solution
intercalation
zerovalent
copper
Sb2Te3
nanoplates,
a
well-established
thermoelectric
material,
is
reported.
intercalant
homogeneously
distributed
throughout
confirmed
by
scanning
transmission
electron
microscopy
coupled
with
energy-dispersive
X-ray
spectroscopy.
composition
was
shown
be
6
at.
%
photoelectron
Copper
ordering
within
van
der
Waals
gaps
nanoplates
selected
area
diffraction.
Fabrication
property
measurements
single-crystal
Cu-Sb2Te3
nanoplate
devices
show
effective
modulation
electrical
conductivity
Seebeck
coefficient
Cu
intercalation.
spectroscopic
studies
in
valence-band
region
reveal
additional
electronic
states
from
that
appear
near
Fermi
energy,
postulated
act
as
acceptors,
leading
transport
properties.
Black
phosphorus
quantum
dots
(BPQDs)
have
shown
promising
applications
in
biosensors
and
energy
storage
devices.
However,
the
electrochemiluminescence
(ECL)
properties
of
pristine
BPQDs
an
organic
system
rarely
been
reported.
In
this
paper,
N,N′-dimethylformamide
passivated
with
a
small
size
2.3
nm
were
obtained
by
ultrasonication-assisted
liquid
exfoliation
process,
their
ECL
studied.
A
reversible
reduction
peak
was
recorded
differential
pulse
voltammetry,
while
no
apparent
oxidation
observed.
signal
not
seen
annihilation
route.
Persulfate
proved
to
be
effective
coreactant
yellow
emission
observed
which
greatly
red-shifted
comparison
that
photoluminescence.
is
believed
generated
from
both
surface
states
electron
promotion
over
band
gap.
Abstract
Black
phosphorus
(BP)
holds
significant
potential
for
various
applications,
but
its
widespread
use
requires
the
development
of
efficient
and
cost‐effective
preparation
methods.
Sn‐P‐I
clathrates
are
identified
as
catalysts
BP
growth;
however,
intact
structure
leads
to
prolonged
times,
rapid
deactivation,
an
unclear
catalytic
mechanism.
In
this
study,
a
Te‐doping
strategy
is
proposed
simultaneously
improve
activity
stability
catalysts.
Te
doping
induces
formation
Sn─Te
bonds,
creates
intrinsic
anti‐healing
vacancies,
while
also
mitigates
iodine
loss
due
lower
electronegativity
compared
P.
This
changes
deactivation
mechanism
Sn‐I‐P
from
saturation
in
Te‐doped
Sn‐I‐P.
To
further
catalyst
reusability,
iodination
treatment
introduced
reactivate
Te‐Sn‐P‐I
The
optimized
reduced
reaction
time
synthesis
15
h
just
45
min,
achieving
yield
96.7%.
reactivation
process
restores
100%
performance.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 9, 2024
Abstract
Establishing
a
targeted
switch
for
CO
2
conversion
under
electric
drive
is
essential
achieving
carbon‐balance
by
enabling
selective
chemicals.
However,
engineering
the
topological
assembly
of
active
sites
to
precisely
regulate
competing
pathways
various
intermediates
has
been
plagued
unclear
structure‐function
relationships.
To
tailor
CO/formate
pathways,
herein
we
established
robust
nonlinear
with
tunable
Co
x
integrated
into
Pd
metallene,
which
involves
1
/Pd
single‐atom
alloy
(favoring
CO)
and
diatomic
formate).
Transitioning
from
atomic
bimetallenes
resulted
in
nonlinear,
high‐contrast
flip
selectivity,
surpassing
94
%
formate
productions
both
H‐cell
flow
cell.
Furthermore,
superior
selectivity
current
efficiency
(>80
%)
(>88
were
consistently
maintained
at
−150
mA
cm
−2
over
continuous
200
h.
Theoretical
simulations
situ
spectroscopy
analyses
unveiled
that
appropriate
adjacent
metal
site
combinations
(Pd−Pd,
Pd−Co
Co−Co)
lead
d
z
band
center
shift
preferred
adsorption
configurations
intermediates,
dictating
C
pathways.
Our
finding
reveals
desired
stability
within
system,
providing
new
perspective
fine‐tuning
energy
processes
through
specific
assembly.
