The
electroreductive
conversion
of
waste
nitrate
(NO₃⁻)
to
high-value
ammonia
(NH₃)
offers
an
alternative
the
energy-intensive
Haber-Bosch
process.
However,
this
reaction
involves
multistep
electron-coupled
proton
transfer,
posing
kinetic
challenges
for
NH₃
generation.
Herein,
a-CuCoOx-based
tandem
electrocatalyst
nitrate-to-ammonia
is
presented.
In
1
M
KOH
with
50
mM
NO₃⁻,
amorphous
catalyst
achieves
a
Faradaic
efficiency
(FE)
95.61%
and
yield
rate
4.01
mg
h⁻¹
cm⁻2
at
-0.3
V
versus
RHE,
outperforming
its
crystalline
counterpart
(FE:
80.21%;
rate:
0.91
cm⁻2).
Integrated
into
Zn-NO₃⁻
battery,
a-CuCoOx
exhibits
peak
power
density
7.21
mW
robust
stability.
Systematic
electrochemical
analyses
revealed
that
structure
Cu-Co
synergy
enhance
active
hydrogen
(H*)
generation
accelerate
nitrite-to-ammonia
conversion.
This
study
provides
insights
designing
advanced
electrocatalysts
sustainable
energy
catalysis.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 5, 2025
Abstract
Aqueous
Zn‐ion
batteries
are
promising
for
large‐scale
energy
storage
due
to
low
cost
and
high
safety.
However,
aqueous
electrolyte
induces
severe
side
reactions
at
Zn
anode,
especially
hydrogen
evolution
reaction
(HER).
Herein,
it
is
first
revealed
that
the
freshly
nucleated‐Zn
(FN‐Zn)
atoms
during
plating
process
show
higher
reactivity
stronger
adsorption
of
proton
than
metallic
anode
by
X‐ray
absorption
near
edge
structure
(XANES)
corresponding
extended
fine
(EXAFS),
density
functional
theory
simulations,
promoting
decomposition
H
2
O.
Then,
a
universal
effective
capping
effect
strategy
proposed
alleviate
HER
electrostatically
shielding
FN‐Zn
activity.
Specifically,
sodium
benzenesulfonate
(SBS)
selected
as
typical
example
screening
comparing
series
additives,
in
which
sulfonate
group
with
coordination
can
be
preferentially
capped
on
reduce
its
reactivity.
Consequently,
symmetrical
cell
SBS
not
only
generates
negligible
amounts
situ
electrochemical‐gas
chromatography
but
also
up
2550
h
1
mA
cm
−2
.
More
importantly,
HER‐free
verified
coin
full
cells
exhibiting
capacity
retention
of≈87.1%
after
1000
cycles
large‐area
(4
×
6
)
pouch
desired
performance.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
Abstract
Electrochemical
nitrate
reduction
reaction
(NO
3
−
RR)
has
emerged
as
an
alternative
strategy
for
wastewater
treatment
and
ammonia
production
in
neutral
low‐concentration
nitrate.
However,
the
electrocatalyst
faces
challenge
of
limited
NO
distribution
deficient
active
hydrogen
(H
ads
)
on
catalyst
surface
resulting
from
low
concentration
difficulty
water
splitting
under
conditions.
Here,
a
Cu‐Co
dual
sites
tandem
synergistic
catalysis
mechanism
been
proposed
by
doping
Cu
into
CoP
to
facilitate
adsorption
conversion
accelerate
leading
significantly
high
RR
performance.
The
designed
Cu‐CoP
exhibits
yield
7.65
mg
h
−1
cm
−2
Faraday
efficiency
85.1%
at
−1.0
V
(10
m
M
),
which
is
highest
reported
data.
In
situ
characterization
theoretical
calculations
confirm
effect,
site
favors
activation
form
2
,
concurrently
modulates
electronic
structure
Co
with
optimized
H
enhanced
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 10, 2025
Abstract
Electrochemically
promoted
nitrate
reduction
reaction
(NITRR)
holds
great
potential
for
the
“green”
synthesis
of
ammonia
(NH
3
).
However,
NITRR
in
neutral
media,
though
close
to
practical
scenario,
is
often
limited
by
an
insufficient
supply
active
hydrogen
(*H)
due
sluggish
water
cleavage.
In
this
work,
it
demonstrated
that
a
bimetallic
alloy
FeIr
can
optimize
trade‐off
between
and
*H
formation
media.
As
result,
exhibits
excellent
catalytic
performance
toward
with
Faradaic
efficiency
NH
up
97.3%
high
yield
rate
11.67
mg
h
−1
cm
−2
at
low
working
−0.6
V
(versus
reversible
electrode
(RHE)),
surpassing
monometallic
catalysts
as
well
majority
Fe‐based
state‐of‐the‐art.
It
also
found
displays
remarkable
electron
rearrangement
hetero‐atoms
their
significant
orbital
hybridization,
which
benefits
not
only
but
process.
Moreover,
coupling
FeIr‐based
methanol
oxidation
(MOR)
results
sustainable
productions
formate
combined
FE
nearly
200%
cell‐voltage
2
V.
This
work
thus
demonstrates
promising
strategy
designing
efficient
NITRR.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
The
orientation
of
β-CuPc
favours
the
overlap
central
Cu
with
N
parallel
molecules,
which
is
reason
behind
high
electrical
conductivity
and
selectivity
in
NH
3
production
via
nitrate
reduction,
impossible
other
polymorphs.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
Electrochemical
nitrate
reduction
reaction
(eNO3-RR)
to
ammonia
(NH3)
holds
great
promise
for
the
green
treatment
of
NO3-
and
ambient
NH3
synthesis.
Although
Fe-based
electrocatalysts
have
emerged
as
promising
alternatives,
their
excellent
eNO3-RR-to-NH3
activity
is
usually
limited
harsh
alkaline
electrolytes
or
alloying
noble
metals
with
Fe
in
sustainable
neutral
electrolytes.
Herein,
we
demonstrate
an
unusual
self-triggering
localized
alkalinity
Co4Fe6
electrocatalyst
efficient
media,
which
breaks
down
conventional
pH-dependent
kinetics
restrictions
shows
a
98.6%
Faradaic
efficiency
(FE)
99.9%
selectivity
at
-0.69
V
vs
RHE.
The
synergetic
Co-Fe
dual
sites
were
demonstrated
enable
optimal
free
energies
species
balance
water
dissociation
protonation
adsorbed
NO2-.
Notably,
can
attain
high
current
density
100
mA
cm-2
FE
surpassing
96%
long-term
stability
over
500
h
membrane
electrode
assembly
(MEA)
electrolyzer.
This
work
provides
insight
into
tailoring
self-reinforced
local-alkalinity
on
alloy
thus
avoids
practical
upcycling
technology.
