Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 10044 - 10051
Published: April 1, 2024
The
electrochemical
NO
reduction
reaction
(NORR)
is
a
promising
approach
for
both
nitrogen
cycle
regulation
and
ammonia
synthesis.
Due
to
the
relatively
low
concentration
of
source
poor
solubility
in
solution,
mass
transfer
limitation
serious
but
easily
overlooked
issue.
In
this
work,
porous
carbon-supported
ultrafine
Cu
clusters
grown
on
nanowire
arrays
(defined
as
Cu@Cu/C
NWAs)
are
prepared
low-concentration
NORR.
A
high
Faradaic
efficiency
(93.0%)
yield
rate
(1180.5
μg
h–1
cm–2)
realized
NWAs
at
−0.1
V
vs
reversible
hydrogen
electrode
(RHE),
which
far
superior
those
other
reported
performances
under
similar
conditions.
construction
carbon
support
can
effectively
decrease
diffusion
kinetics
promote
coverage
subsequent
highly
effective
conversion.
Moreover,
favorable
metal–support
interaction
between
enhances
adsorption
decreases
barrier
*HNO
formation
comparison
with
that
pure
NWAs.
Overall,
whole
NORR
be
fully
strengthened
concentrations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(13)
Published: Feb. 2, 2023
The
aqueous
electrocatalytic
reduction
of
NO3-
into
NH3
(NitrRR)
presents
a
sustainable
route
applicable
to
production
and
potentially
energy
storage.
However,
the
NitrRR
involves
directly
eight-electron
transfer
process
generally
required
large
overpotential
(<-0.2
V
versus
reversible
hydrogen
electrode
(vs.
RHE))
reach
optimal
efficiency.
Here,
inspired
by
biological
nitrate
respiration,
was
separated
two
stages
along
[2+6]-electron
pathway
alleviate
kinetic
barrier.
system
employed
Cu
nanowire
catalyst
produces
NO2-
with
current
efficiencies
91.5
%
100
%,
respectively
at
lower
overpotentials
(>+0.1
vs.
RHE).
high
efficiency
for
such
further
explored
in
zinc-nitrate
battery.
This
battery
could
be
specified
output
voltage
0.70
V,
an
average
density
566.7
Wh
L-1
10
mA
cm-2
power
14.1
mW
,
which
is
well
beyond
all
previously
reported
similar
concepts.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: July 22, 2023
The
electrochemical
conversion
of
nitrate
pollutants
into
value-added
ammonia
is
a
feasible
way
to
achieve
artificial
nitrogen
cycle.
However,
the
development
electrocatalytic
nitrate-to-ammonia
reduction
reaction
(NO3-
RR)
has
been
hampered
by
high
overpotential
and
low
Faradaic
efficiency.
Here
we
develop
an
iron
single-atom
catalyst
coordinated
with
phosphorus
on
hollow
carbon
polyhedron
(denoted
as
Fe-N/P-C)
NO3-
RR
electrocatalyst.
Owing
tuning
effect
atoms
breaking
local
charge
symmetry
single-Fe-atom
catalyst,
it
facilitates
adsorption
ions
enrichment
some
key
intermediates
during
process.
Fe-N/P-C
exhibits
90.3
%
efficiency
yield
rate
17980
μg
h-1
mgcat-1
,
greatly
outperforming
reported
Fe-based
catalysts.
Furthermore,
operando
SR-FTIR
spectroscopy
measurements
reveal
pathway
based
observed
under
different
applied
potentials
durations.
Density
functional
theory
calculations
demonstrate
that
optimized
free
energy
ascribed
asymmetric
atomic
interface
configuration,
which
achieves
optimal
electron
density
distribution.
This
work
demonstrates
critical
role
atomic-level
precision
modulation
heteroatom
doping
for
RR,
providing
effective
strategy
improving
catalytic
performance
single
atom
catalysts
in
reactions.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
33(29)
Published: April 23, 2023
Abstract
Ammonia
is
not
only
an
important
feedstock
for
chemical
industry
but
also
a
carbon‐free
energy
carrier
and
safe
storage
media
hydrogen.
Due
to
the
advantages
compared
Haber–Bosch
process,
electrochemical
NO
3
−
‐to‐NH
conversion
via
nitrate
reduction
reaction
(NO
RR)
received
attention.
Recently,
“green
hydrogen”
generated
from
water
electrolysis
shows
promise
become
future
limited
by
safety
of
transportation.
This
review
proposes
can
store
renewable
electric
into
NH
,
which
potential
solution
solving
puzzle
Moreover,
theoretical
insights
RR
electrocatalyst
design
are
discussed.
Finally,
challenges
opportunities
in
this
field
elucidated.
provides
novel
perspective
accelerates
development
effective
electrocatalysts
conversion.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(16), P. 10846 - 10854
Published: Aug. 2, 2023
Electrocatalytic
nitrate
reduction
reaction
(NO3–RR)
opens
opportunities
for
ammonia
production.
The
sluggish
kinetics
of
this
multielectron
and
multiproton
process
has
been
regarded
as
the
key
issue.
Herein,
we
report
a
Cu1Co5
alloy
electrocatalytic
NO3–RR
to
NH3.
It
achieves
high
current
density
(453
mA
cm–2)
Faradaic
efficiency
(96.2%)
NH3
production
at
0.075
V
vs
RHE,
with
half-cell
energy
44.9%,
higher
than
those
Cu,
Co,
other
Co-based
alloys,
is
among
highest
value
reported.
We
found
that
interaction
between
Cu
Co
reorganizes
their
electronic
structure
in
alloys.
NO3–
adsorption
switches
spontaneous
process,
*NO
→
*N
*NH
*NH2
processes
are
promoted.
Importantly,
water
dissociation
concerted
transformation
N-species
proven
be
rate-determining,
which
facilitated
on
sites
essential
enhanced
NO3–RR.
This
inspires
us
strategy
designing
more
efficient
catalysts
under
alkaline
condition
by
promoting
H2O
process.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(12), P. 6899 - 6904
Published: March 14, 2023
Electrocatalytic
nitric
oxide
(NO)
reduction
not
only
provides
an
extremely
promising
strategy
for
ambient
NH3
generation
but
also
alleviates
the
artificially
disrupted
N-cycle
balance.
However,
exploring
efficient
electrocatalysts
to
enhance
NO
electroreduction
performance
remains
a
significant
challenge.
Herein,
hexagonal-close-packed
Co
nanosheet
(hcp-Co)
is
prepared
and
exhibits
high
yield
of
439.50
μmol
cm-2
h-1
Faraday
efficiency
72.58%,
outperforming
face-centered
cubic
phase
(fcc-Co)
most
reported
electrocatalysts.
Through
combination
density
functional
theory
calculations
temperature-programmed
desorption
experiments,
superior
catalytic
reaction
(NORR)
activity
on
hcp-Co
can
be
attributed
unique
electron
structures
proton
shuttle
effect.
A
proof-of-concept
device
Zn-NO
batteries
using
as
cathode
assembled
shows
power
4.66
mW
cm-2,
which
in
literature
so
far.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
35(24)
Published: Feb. 17, 2023
Ammonia
is
an
indispensable
commodity
in
the
agricultural
and
pharmaceutical
industries.
Direct
nitrate-to-ammonia
electroreduction
a
decentralized
route
yet
challenged
by
competing
side
reactions.
Most
catalysts
are
metal-based,
metal-free
with
high
conversion
activity
rarely
reported.
Herein,
it
shown
that
amorphous
graphene
synthesized
laser
induction
comprising
strained
disordered
pentagons,
hexagons,
heptagons
can
electrocatalyze
eight-electron
reduction
of
NO3-
to
NH3
Faradaic
efficiency
≈100%
ammonia
production
rate
2859
µg
cm-2
h-1
at
-0.93
V
versus
reversible
hydrogen
electrode.
X-ray
pair-distribution
function
analysis
electron
microscopy
reveal
unique
molecular
features
facilitate
reduction.
In
situ
Fourier
transform
infrared
spectroscopy
theoretical
calculations
establish
critical
role
these
stabilizing
reaction
intermediates
via
structural
relaxation.
The
enhanced
catalytic
enables
implementation
flow
electrolysis
for
on-demand
synthesis
release
>70%
selectivity,
resulting
significantly
increased
yields
survival
rates
when
applied
plant
cultivation.
results
this
study
show
significant
promise
remediating
nitrate-polluted
water
completing
NOx
cycle.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(11), P. 7529 - 7537
Published: May 19, 2023
Developing
effective
electrocatalysts
for
nitrate
reduction
to
ammonia
is
paramount
synthesis
while
addressing
the
water
pollutant
issue.
Identifying
active
structure
and
its
correlation
with
catalytic
behavior
during
reaction
process
essential
challenging
rational
design
of
advanced
electrocatalysts.
Herein,
starting
from
Cu2O
particles
controllable
crystal
facets,
electrochemically
reconstituted
Cu/Cu2O
was
fabricated
as
a
suitable
system,
relationship
between
chemical
state
copper
product
selectivity
in
studied.
At
−0.9
V
versus
reversible
hydrogen
electrode,
oxide-derived
Cu0
(OD-Cu)
cube
achieved
high
Faradaic
efficiency
93.9%
productivity
up
219.8
μmol
h–1
cm–2,
surpassing
those
most
Cu-based
catalysts.
In
situ
Raman
analysis,
well-designed
pulsed
electrolysis
experiments,
theoretical
calculations
showed
that
preferentially
produced
on
OD-Cu
at
potentials
presence
interface
favored
nitrite
formation
low
potentials.
The
originated
enhanced
adsorption
lower
barrier
potential-determining
step
(*NH3
→
NH3).
This
work
presents
an
strategy
boost
electrocatalysis
offers
insight
into
real
phase
corresponding
Energy & Environmental Science,
Journal Year:
2022,
Volume and Issue:
16(1), P. 201 - 209
Published: Nov. 23, 2022
A
novel
2D
nickel
porphyrin-based
covalent
organic
framework
is
fabricated
as
an
efficient
nitrate
reduction
electrocatalyst
that
shows
a
great
selectivity
of
∼90%
under
mild
overpotential
with
remarkable
production
rate
and
turnover
frequency.
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.