Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 6, 2024
Abstract
Electrochemical
nitrate
reduction
reaction
(NO
3
RR)
is
emerging
as
a
promising
strategy
for
removal
and
ammonia
(NH
)
production
using
renewable
electricity.
Although
great
progresses
have
been
achieved,
the
crystal
phase
effect
of
electrocatalysts
on
NO
RR
remains
rarely
explored.
Here,
epitaxial
growth
unconventional
2H
Cu
hexagonal
close‐packed
(
hcp
IrNi
template,
resulting
in
formation
three
IrNiCu@Cu
nanostructures,
reported.
IrNiCu@Cu‐20
shows
superior
catalytic
performance,
with
NH
Faradaic
efficiency
(FE)
86%
at
−0.1
(vs
reversible
hydrogen
electrode
[RHE])
yield
rate
687.3
mmol
g
−1
h
,
far
better
than
common
face‐centered
cubic
Cu.
In
sharp
contrast,
IrNiCu@Cu‐30
IrNiCu@Cu‐50
covered
by
shell
display
high
selectivity
toward
nitrite
2
−
),
FE
above
60%
0.1
RHE).
Theoretical
calculations
demonstrated
that
has
optimal
electronic
structures
due
to
highest
d‐band
center
strongest
trend
lowest
energy
barriers.
The
electroactivity
originates
from
abundant
low
coordination
sites
surface,
which
guarantees
fast
electron
transfer
accelerate
intermediate
conversions.
This
work
provides
feasible
tactic
regulate
product
distribution
engineering
electrocatalysts.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
36(17)
Published: June 9, 2023
Natural
nitrogen
cycle
has
been
severely
disrupted
by
anthropogenic
activities.
The
overuse
of
N-containing
fertilizers
induces
the
increase
nitrate
level
in
surface
and
ground
waters,
substantial
emission
oxides
causes
heavy
air
pollution.
Nitrogen
gas,
as
main
component
air,
used
for
mass
ammonia
production
over
a
century,
providing
enough
nutrition
agriculture
to
support
world
population
increase.
In
last
decade,
researchers
have
made
great
efforts
develop
processes
under
ambient
conditions
combat
intensive
energy
consumption
high
carbon
associated
with
Haber-Bosch
process.
Among
different
techniques,
electrochemical
reduction
reaction
(NO
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(19), P. 12976 - 12983
Published: April 3, 2024
Electrocatalytic
reduction
of
nitrate
to
ammonia
(NRA)
has
emerged
as
an
alternative
strategy
for
sewage
treatment
and
generation.
Despite
excellent
performances
having
been
achieved
over
cobalt-based
electrocatalysts,
the
reaction
mechanism
well
veritable
active
species
across
a
wide
potential
range
are
still
full
controversy.
Here,
we
adopt
CoP,
Co,
Co3O4
model
materials
solve
these
issues.
CoP
evolves
into
core@shell
structured
CoP@Co
before
NRA.
For
Co
catalysts,
three-step
relay
is
carried
out
superficial
dynamical
Coδ+
under
low
overpotential,
while
continuous
hydrogenation
from
unveiled
high
overpotential.
In
comparison,
stable
steadily
catalyze
range.
As
result,
exhibit
much
higher
NRA
activity
than
especially
Moreover,
performance
although
they
experience
same
mechanism.
A
series
characterizations
clarify
reason
enhancement
highlighting
that
core
donates
abundant
electrons
species,
leading
generation
more
hydrogen
nitrogen-containing
intermediates.
Advanced Energy Materials,
Journal Year:
2024,
Volume and Issue:
14(28)
Published: March 3, 2024
Abstract
Electrochemically
reducing
nitrate
(NO
3
−
),
a
common
water
pollutant,
to
valuable
ammonia
(NH
)
offers
green,
sustainable,
and
decentralized
route
for
synthesis.
Electrochemical
reduction
reaction
RR)
involves
two
crucial
steps:
deoxygenation
followed
by
nitrite
hydrogenation;
in
particular,
the
hydrogenation
is
rate‐determining
step
(RDS)
NO
RR.
In
this
work,
an
atomically
dispersed
cobalt‐phosphorus
(Co─P)
catalytic
pair
(CP)
with
strong
electronic
coupling
reported.
The
Co
site
Co─P
CP
effectively
activates
,
while
P
facilitates
dissociation
release
H
+
synergistically
enhancing
thermodynamic
kinetic
performance
of
electrochemical
ammonia.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(38)
Published: Aug. 8, 2023
One-dimensional
fiber
architecture
serves
as
an
excellent
catalyst
support.
The
orderly
arrangement
of
active
materials
on
such
a
substrate
can
enhance
catalytic
performance
by
exposing
more
sites
and
facilitating
mass
diffusion;
however,
this
remains
challenge.
We
developed
interfacial
assembly
strategy
for
the
distribution
metal
nanocrystals
different
substrates
to
optimize
their
electrocatalytic
performance.
Using
electrochemical
nitrate
reduction
reaction
(NO3-
RR)
representative
reaction,
iron-based
nanofibers
(Fe/NFs)
structure
achieved
removal
capacity
2317
mg
N/g
Fe
N2
selectivity
up
97.2
%.
This
could
promote
rational
design
synthesis
fiber-based
electrocatalysts.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(35)
Published: May 4, 2024
Abstract
Directly
electrochemical
conversion
of
nitrate
(NO
3
−
)
is
an
efficient
and
environmentally
friendly
technology
for
ammonia
(NH
production
but
challenged
by
highly
selective
electrocatalysts.
High‐entropy
alloys
(HEAs)
with
unique
properties
are
attractive
materials
in
catalysis,
particularly
multi‐step
reactions.
Herein,
we
first
reported
the
application
HEA
(FeCoNiAlTi)
electrocatalytic
NO
reduction
to
NH
(NRA).
The
bulk
active
NRA
limited
unsatisfied
yield
0.36
mg
h
−1
cm
−2
Faradaic
efficiency
(FE)
82.66
%.
Through
effective
phase
engineering
strategy,
uniform
intermetallic
nanoparticles
introduced
on
increase
surface
area
charge
transfer
efficiency.
resulting
nanostructured
(n‐HEA)
delivers
enhanced
performance
terms
(0.52
FE
(95.23
%).
Further
experimental
theoretical
investigations
reveal
that
multi‐active
sites
(Fe,
Co,
Ni)
dominated
electrocatalysis
over
n‐HEA.
Notably,
typical
Co
exhibit
lowest
energy
barrier
*NH
2
as
rate‐determining
step.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: April 8, 2024
Abstract
Electrocatalytic
nitrate
reduction
reaction
(NO
3
RR)
driven
by
renewable
energy
is
a
promising
technology
for
the
removal
of
nitrate‐containing
wastewater.
However,
sluggish
kinetics
resulted
from
complex
proton‐coupled
electron
transfer
and
various
intermediates
remain
key
barriers
large‐scale
application
NO
RR.
Herein,
tactic
reported
to
raise
rate
RR
increase
selectivity
N
2
using
bimetal
catalyst:
Co
inclined
act
on
steps
needed
in
process,
rate‐determining
step
(RDS:
*NO
,
asterisk
means
intermediates)
subsequent
*N
hydrogenation
as
well
Fe
exhibits
efficient
activity
selectivity‐
determining
(SDS:
then
)
via
relay
catalysis
mechanism.
A
efficiency
78.5%
an
ultra‐long
cycle
stability
60
cycles
(12
h
per
cycle)
are
achieved
FeCo
alloy
confined
with
nitrogen‐doped
porous
carbon
nanofibers
(FeCo‐NPCNFs).
DFT
calculations
unveil
that
introduction
active
site
not
only
regulates
d‐band
center
alloy,
optimizes
adsorption
intermediates,
but
also
has
strong
capacity
supply
hydrogen
species.
Clearly,
this
study
elucidates
effects
bimetallic
performance
electrocatalytic
offers
avenues
designing
Fe‐based
catalysts
realize
nitrogen‐neutral
cycle.
