Nano Letters,
Год журнала:
2023,
Номер
23(16), С. 7733 - 7742
Опубликована: Июнь 28, 2023
Electrochemical
reduction
of
nitrate
to
ammonia
(NH3)
converts
an
environmental
pollutant
a
critical
nutrient.
However,
current
electrochemical
operations
based
on
monometallic
and
bimetallic
catalysts
are
limited
in
NH3
selectivity
catalyst
stability,
especially
acidic
environments.
Meanwhile,
with
dispersed
active
sites
generally
exhibit
higher
atomic
utilization
distinct
activity.
Herein,
we
report
multielement
alloy
nanoparticle
Ru
(Ru-MEA)
other
synergistic
components
(Cu,
Pd,
Pt).
Density
functional
theory
elucidated
the
synergy
effect
Ru-MEA
than
Ru,
where
better
reactivity
(NH3
partial
density
-50.8
mA
cm-2)
high
faradaic
efficiency
(93.5%)
is
achieved
industrially
relevant
wastewater.
In
addition,
showed
good
stability
(e.g.,
19.0%
decay
FENH3
three
hours).
This
work
provides
potential
systematic
efficient
discovery
process
that
integrates
data-guided
design
novel
synthesis
for
range
applications.
Ammonia
(NH3
)
is
an
indispensable
feedstock
for
fertilizer
production
and
one
of
the
most
ideal
green
hydrogen
rich
fuel.
Electrochemical
nitrate
(NO3-
reduction
reaction
RR)
being
explored
as
a
promising
strategy
to
synthesize
industrial-scale
NH3
,
which
has
nonetheless
involved
complex
multi-reaction
process.
This
work
presents
Pd-doped
Co3
O4
nanoarray
on
titanium
mesh
(Pd-Co3
/TM)
electrode
highly
efficient
selective
electrocatalytic
NO3-
RR
at
low
onset
potential.
The
well-designed
Pd-Co3
/TM
delivers
large
yield
745.6
µmol
h-1
cm-2
extremely
high
Faradaic
efficiency
(FE)
98.7%
-0.3
V
with
strong
stability.
These
calculations
further
indicate
that
doping
Pd
improves
adsorption
characteristic
optimizes
free
energies
intermediates,
thereby
facilitating
kinetics
reaction.
Furthermore,
assembling
this
catalyst
in
Zn-NO3-
battery
realizes
power
density
3.9
mW
excellent
FE
98.8%
.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(50)
Опубликована: Авг. 17, 2023
Abstract
Electrochemically
converting
waste
nitrate
(NO
3
−
)
into
ammonia
(NH
is
a
green
route
for
both
wastewater
treatment
and
high‐value‐added
generation.
However,
the
NO
‐to‐NH
reaction
involves
multistep
electron
transfer
complex
intermediates,
making
it
grand
challenge
to
drive
efficient
electroreduction
with
high
NH
selectivity.
Herein,
an
in‐operando
electrochemically
synthesized
Cu
2
O/NiO
heterostructure
electrocatalyst
proven
electrosynthesis.
In
situ
Raman
spectroscopy
reveals
that
obtained
O/NiO,
induced
by
electrochemistry‐driven
phase
conversion,
real
active
phase.
This
electronically
coupled
can
modulate
interfacial
charge
distribution,
dramatically
lower
overpotential
in
rate‐determining
step
thus
requiring
energy
input
proceed
The
orbital
hybridization
calculations
further
identify
O
beneficial
adsorption,
NiO
could
promote
desorption
of
,
forming
excellent
tandem
electrocatalyst.
Such
system
leads
Faradaic
efficiency
95.6%,
super‐high
selectivity
88.5%
at
−0.2
V
versus
RHE,
surpassing
most
electrosynthesis
catalysts
ultralow
voltage.
Nano Letters,
Год журнала:
2023,
Номер
23(16), С. 7733 - 7742
Опубликована: Июнь 28, 2023
Electrochemical
reduction
of
nitrate
to
ammonia
(NH3)
converts
an
environmental
pollutant
a
critical
nutrient.
However,
current
electrochemical
operations
based
on
monometallic
and
bimetallic
catalysts
are
limited
in
NH3
selectivity
catalyst
stability,
especially
acidic
environments.
Meanwhile,
with
dispersed
active
sites
generally
exhibit
higher
atomic
utilization
distinct
activity.
Herein,
we
report
multielement
alloy
nanoparticle
Ru
(Ru-MEA)
other
synergistic
components
(Cu,
Pd,
Pt).
Density
functional
theory
elucidated
the
synergy
effect
Ru-MEA
than
Ru,
where
better
reactivity
(NH3
partial
density
-50.8
mA
cm-2)
high
faradaic
efficiency
(93.5%)
is
achieved
industrially
relevant
wastewater.
In
addition,
showed
good
stability
(e.g.,
19.0%
decay
FENH3
three
hours).
This
work
provides
potential
systematic
efficient
discovery
process
that
integrates
data-guided
design
novel
synthesis
for
range
applications.
