ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
16(43), С. 58648 - 58656
Опубликована: Окт. 16, 2024
The
electrochemical
nitrogen
reduction
reaction
(eNRR)
under
ambient
conditions
is
a
promising
method
to
generate
ammonia
(NH3),
crucial
precursor
for
fertilizers
and
chemicals,
without
carbon
emissions.
Single-atom
alloy
catalysts
(SAACs)
have
reinvigorated
catalytic
processes
due
their
high
activity,
selectivity,
efficient
use
of
active
atoms.
Here,
we
employed
density
functional
theory
(DFT)
calculations
integrated
with
machine
learning
(ML)
investigate
dodecahedral
nanocluster-based
SAACs
analyzing
structure–activity
relationships
in
eNRR.
Over
300
were
screened
all
the
transition
metals
as
dopants
develop
an
ML
model
predicting
stability
performance.
Facet
sites
identified
optimal
doping
positions,
particularly
late
group
showing
superior
activity.
Utilizing
DFT+ML,
8
highly
suitable
Interestingly,
number
valence
d-electrons
proved
screening
eNRR
These
exhibited
low
activity
hydrogen
evolution
reaction,
further
enhancing
suitability
This
successful
ML-driven
approach
accelerates
catalyst
design
discovery,
holding
significant
practical
implications.
ACS Energy Letters,
Год журнала:
2024,
Номер
9(8), С. 3790 - 3795
Опубликована: Июль 11, 2024
Recently,
the
lithium-mediated
nitrogen
reduction
reaction
(Li-NRR)
has
emerged
as
a
promising
approach
for
electrochemical
ammonia
synthesis,
facilitating
more
localized
production.
However,
systematic
investigation
of
lithium
salts
in
this
process,
especially
when
coupled
with
hydrogen
oxidation
(HOR)
at
anode
side
continuous-flow
reactor,
remains
largely
underexplored.
This
study
systematically
investigates
effects
various
on
Li-NRR
selectivity
and
efficiency
reactor
HOR
anode.
Among
evaluated
salts,
tetrafluoroborate
(LiBF4)
demonstrated
highest
NH3
61%
under
ambient
conditions.
Conversely,
bis(trifluoromethanesulfonyl)imide
(LiTFSI)
showed
significantly
lower
Faradaic
(FE)
18%,
due
to
its
decomposition
subsequent
sulfur
poisoning
catalysts.
These
findings
highlight
importance
selecting
appropriate
establishing
critical
design
principles
efficient
stable
electrolytes
advancing
sustainable
synthesis.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 21, 2024
Abstract
The
lithium‐mediated
nitrogen
reduction
reaction
(Li‐NRR)
is
a
promising
green
alternative
to
the
Haber–Bosch
process
for
ammonia
synthesis.
solid
electrolyte
interphase
(SEI)
crucial
high
efficiency
and
stability,
as
it
regulates
reactant
diffusion
suppresses
side
reactions.
SEI
properties
are
greatly
influenced
by
Li
+
ion
solvation
structure,
which
controllable
through
engineering.
Although
anion‐derived
enhances
selectivity
has
typically
been
engineered
using
high‐concentration
electrolytes
(HCEs),
face
mass
transfer,
viscosity,
cost
issues.
In
this
study,
localized
(LHCE)
in
Li‐NRR
first
introduced,
enabling
formation
of
low‐concentration
(LCE)
enhancing
Li–anion
coordination
an
antisolvent.
Among
various
antisolvents,
1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl
ether
(TTE)
achieves
highest
Faradaic
(73.6
±
2.5%),
more
than
double
that
LCE
(34.3
2.8%)
exceeding
HCE
(56.0
2.8%).
Systematic
calculations
experimental
analyses
show
LHCE
exhibits
anion‐rich
structures
forms
thin,
inorganic
SEI.
Moreover,
advantages
low
viscosity
N
2
solubility,
facilitate
transport.
This
study
suggests
application
effective
engineering
strategy
enhance
efficiency.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 2, 2025
Electrified
interfaces
are
critical
to
the
performance
of
energy
systems
and
often
demonstrate
substantial
complexity
under
operating
conditions.
A
nanoscale
understanding
interfacial
microenvironment,
i.e.,
solid-electrolyte
interphase
(SEI),
in
lithium-mediated
nitrogen
reduction
(Li-N2R)
is
key
for
realizing
efficient
ammonia
(NH3)
production.
Herein,
we
used
time-resolved
neutron
reflectometry
(NR)
observe
SEI
formation
Li-N2R
We
found
that
LiBF4-based
electrolyte
provided
a
substantially
more
well-defined
layer
than
previous
NR
interrogations
LiClO4,
highlighting
underlying
chemistry
dictates
design
enabling
new
NR-based
studies.
Using
situ
NR,
LiBF4-derived
conditions
comprises
thick,
diffuse
outer
thin,
compact
inner
at
low
current
cycling
(<2
mA/cm2),
revealing
structure
which
ex
studies
have
not
been
able
probe.
Increased
sustained
led
merging
layers
into
single-layer
SEI.
isotope
contrast
methods
with
d6-EtOH
d8-THF
drive
tracking
growth
cycling,
proton
donor
modifies
layer,
solvent
layer.
Li
dendritic
was
observed
absence
donor.
Neutron
absorption
also
indicated
presence
boron
SEI,
underscoring
value
neutron-based
interrogation.
Our
results
inform
Li-based
reaction
microenvironments,
these
can
be
applied
broadly
technologies.
