Electrocatalytic
reduction
of
waste
nitrate
(NO3
-)
in
water
represents
a
sustainable
and
economic
route
for
selective
electrosynthesis
recycled
ammonia
(NH3),
but
their
performance
still
falls
behind
the
needed.
Herein,
bimetallic
rhodium-copper
nanocavities
(RhCu
NCs),
featuring
open
mesoscopic
structure
well-alloyed
composition
at
atomic
level,
are
demonstrated
as
high-performance
electrocatalyst
efficient
nitrate-to-ammonia
--to-NH3)
electrocatalysis
neutral
condition.
In
comparison
to
other
counterpart
electrocatalysts,
best
RhCu
NCs
deliver
superior
NO3
--to-NH3
very
positive
potential
-0.10
V
versus
RHE
with
Faradaic
efficiency
97.5%,
yield
rate
8.1
mg
h-1
mg-1,
energy
39%,
cycling
stability
reaching
15
cycles.
The
combination
kinetic
analysis,
situ
Raman
spectroscopy,
density
functional
theory
calculation
reveals
that
active
hydrogen
radicals
can
be
kinetically
formed
selectively
consumed
by
nitrogen
intermediates
promote
[2e
+
6e]
tandem
pathway
-
NH3
electrosynthesis.
work
thus
provides
some
insights
into
designing
electrocatalysts
multi-electron
products
from
various
electrocatalytic
reactions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 29, 2024
Abstract
Electrochemical
nitrate
reduction
reaction
(NO
3
RR)
is
a
promising
approach
to
achieve
remediation
of
nitrate‐polluted
wastewater
and
sustainable
production
ammonia.
However,
it
still
restricted
by
the
low
activity,
selectivity
Faraday
efficiency
for
ammonia
synthesis.
Herein,
we
propose
an
effective
strategy
modulate
electrolyte
microenvironment
in
electrical
double
layer
(EDL)
mediating
alkali
metal
cations
enhance
NO
RR
performance.
Taking
bulk
Cu
as
model
catalyst,
experimental
study
reveals
that
−
‐to‐NH
performance
different
electrolytes
follows
trend
Li
+
<Cs
<Na
<K
.
Theoretical
studies
illustrate
proton
transport
rate
activity
rate‐determining
step
2
)
increase
order
The
cation
effects
are
also
general
two
typical
nanostructured
catalysts
including
copper/cuprous
oxide
nickel
phosphides,
achieving
near‐100
%
Faradaic
over
99
conversion
NH
Furthermore,
demonstrate
can
be
converted
high‐purity
4
Cl
catalyst
K
‐containing
electrolyte.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(36)
Опубликована: Апрель 5, 2024
Abstract
Facilitating
equilibrium
in
the
nitrogen
cycle,
electrochemical
nitrate
reduction
(NitRR)
to
ammonia
stands
as
a
carbon‐free
method
for
synthesis.
Copper‐based
catalysts,
renowned
NitRR,
face
hurdle
supplying
sufficient
hydrogen
radicals
(*H)
efficient
hydrogenation
of
NitRR
intermediates.
Addressing
this,
NiMoO
4
is
leveraged
an
excellent
*H
donor,
synergistically
coupling
it
with
copper‐based
catalyst.
The
work
introduces
high‐performance
/CuO
nanowire
(NW)/Copper
foam
(CF)
catalyst
achieving
remarkable
Faraday
efficiency
(FE)
98.8%
and
yield
0.8221
mmol
cm
−2
h
−1
.
Operating
at
−0.2
V
versus
reversible
electrode
(vs
RHE)
H‐type
electrolytic
cell,
demonstrates
exceptional
stability
over
20
h.
Additionally,
air
stripping
process
enables
collection
NH
Cl
products,
offering
practical
avenue
converting
waste
nitrates
into
valuable
products.
In‐depth
situ
electrochemistry
density‐functional
theory
(DFT)
calculations
affirm
transformation
CuO
Cu/Cu
2
O
during
electrocatalytic
process.
catalyzes
conversion
nitrite,
while
,
serving
facilitates
deoxidation
other
N
intermediates
on
surface,
effectively
driving
ammonia.
Energy & Environmental Science,
Год журнала:
2024,
Номер
17(14), С. 5183 - 5190
Опубликована: Янв. 1, 2024
A
novel
Ru–Cu
9
Bi/CNT
multi-site
alloy
is
synthesised
for
electrocatalytic
C–N
coupling
to
generate
urea
across
a
broad
range
of
NO
3
−
concentrations.
By
improving
the
coverage
key
intermediate
*NHO,
ensure
subsequent
electrosynthesis
urea.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Abstract
Nitrate
electroreduction
is
promising
for
achieving
effluent
waste‐water
treatment
and
ammonia
production
with
respect
to
the
global
nitrogen
balance.
However,
due
impeded
hydrogenation
process,
high
overpotentials
need
be
surmounted
during
nitrate
electroreduction,
causing
intensive
energy
consumption.
Herein,
a
hydroxide
regulation
strategy
developed
optimize
interfacial
H
2
O
behavior
accelerating
conversion
of
at
ultralow
overpotentials.
The
well‐designed
Ru─Ni(OH)
electrocatalyst
shows
remarkable
efficiency
44.6%
+0.1
V
versus
RHE
nearly
100%
Faradaic
NH
3
synthesis
0
RHE.
In
situ
characterizations
theoretical
calculations
indicate
that
Ni(OH)
can
regulate
structure
promoted
dissociation
process
contribute
spontaneous
hydrogen
spillover
boosting
NO
−
Ru
sites.
Furthermore,
assembled
rechargeable
Zn‐NO
/ethanol
battery
system
exhibits
an
outstanding
long‐term
cycling
stability
charge–discharge
tests
high‐value‐added
ammonium
acetate,
showing
great
potential
simultaneously
removal,
conversion,
chemical
synthesis.
This
work
not
only
provide
guidance
in
extensive
reactions
but
also
inspire
design
novel
hybrid
flow
multiple
functions.
Advanced Energy Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 13, 2025
Abstract
Electrochemical
nitrate
(NO
3
−
)
reduction
to
ammonia
(NH
presents
a
promising
route
for
both
wastewater
treatment
and
generation
but
still
suffers
from
sluggish
catalytic
activity,
insufficient
mass
transfer,
the
reliance
on
high‐concentration
supporting
electrolytes.
This
work
reports
an
innovative
efficient
electrosynthesis
reactor
by
integrating
self‐assembled
iron‐doped
Ni
2
P
(Fe‐Ni
P/NF)
nanoflower
cathode
with
solid‐electrolyte
(SE).
The
SE
design
eliminates
need
electrolytes,
providing
highly
ion‐conducting
pathway
enabling
direct
production
of
NH
NO
.
Through
tailoring
electronic
surface
characteristics
Fe‐Ni
P/NF,
this
achieves
complete
reduction,
96.7%
selectivity,
81.8%
faradaic
efficiency
concentration
100
m
at
current
density
mA
−2
Density
functional
theory
(DFT)
calculations
reveal
that
phosphating
Fe
doping
synergistically
enhance
adsorption
increase
availability
active
hydrogen,
thus
favoring
low
energy
barrier
0.695
eV.
Additionally,
superhydrophilicity
P/NF
catalyst
promotes
transfer
facilitating
electrolyte
access
ensuring
rapid
gas
bubble
release.
study
provides
sustainable
scalable
method
converting
‐laden
into
valuable
products.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(48)
Опубликована: Авг. 16, 2024
Abstract
The
nitrate
electroreduction
reaction
(NO
3
RR)
offers
an
eco‐friendly
alternative
to
the
Haber–Bosch
technology
for
ammonia
(NH
)
synthesis.
However,
complex
process
and
diverse
products
make
efficient
NH
synthesis
challenging.
Therefore,
rational
design
preparation
of
highly
electrocatalysts
are
crucial
NO
RR.
Herein,
ultrathin
copper‐nickel
oxide
(Cu‐NiO)
nanosheets
(Cu‐NiO
UTNSs)
synthesized
via
cyanogel‐NaBH
4
hydrolysis‐reduction
method,
which
applied
cathodic
RR
‐assisted
with
anodic
sulfur
ion
(S
2−
oxidation
(SOR)
in
electrolyzer.
nanosheet
structure,
interaction
between
NiO
Cu,
formation
oxygen
vacancy
contribute
generating
rich
active
sites,
regulating
electronic
improving
substance
adsorption.
Thus,
Cu‐NiO
UTNSs
exhibit
excellent
electrocatalytic
performance
SOR.
As
a
bifunctional
UTNSs||Cu‐NiO
electrolyzer,
it
can
reach
10
mA
cm
−1
at
only
0.1
V
−
‐to‐NH
conversion
cathode
S
‐to‐S
8
anode.
This
work
provides
promising
approach
producing
value‐added
chemicals
low
electrolysis
voltage
strategy
pollutant
treatment.
