Coordination Chemistry Reviews,
Год журнала:
2024,
Номер
518, С. 216061 - 216061
Опубликована: Июль 8, 2024
The
pervasive
contamination
of
industrial,
domestic,
and
agricultural
wastewater
with
nitrate
poses
profound
ecological
public
health
risks.
Traditional
methods
for
remediating
nitrate-laden
water
face
formidable
challenges
due
to
its
high
solubility
stability.
However,
a
promising
solution
emerges
in
the
form
electrochemical
reduction
(eNO3RR),
offering
both
efficient
removal
valuable
ammonia
generation
sustainable
manner.
This
review
explores
burgeoning
field
eNO3RR,
focusing
on
recent
advancements
utilizing
porous
crystalline
framework
materials
−
metal–organic
frameworks
(MOFs)
covalent-organic
(COFs)
as
novel
class
electrocatalysts.
These
innovative
exhibit
unique
properties
such
adjustable
porosity,
diverse
structures,
tunable
pore
sizes,
well-defined
active
sites,
making
them
ideal
candidates
enhancing
efficiency
selectivity
under
ambient
conditions.
By
dissecting
structure–activity
relationship
inherent
MOF/COF-based
electrocatalysts,
this
aims
provide
comprehensive
understanding
their
role
driving
conversion
NO3−
NH3.
Moreover,
it
identifies
current
proposes
future
prospects
leveraging
these
advanced
pollutants,
glimpse
into
greener
more
effective
approach
remediation
resource
recovery.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(28)
Опубликована: Март 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,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
Electrocatalytic
reduction
of
nitrate
to
ammonia
provides
a
green
alternate
the
Haber-Bosch
method,
yet
it
suffers
from
sluggish
kinetics
and
low
yield
rate.
The
follows
tandem
reaction
nitrite
subsequent
hydrogenation
generate
ammonia,
Faraday
efficiency
(FE)
is
limited
by
competitive
hydrogen
evolution
reaction.
Herein,
we
design
heterostructure
catalyst
remedy
above
issues,
which
consists
Ni
nanosphere
core
Ni(OH)
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 Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 11, 2024
Abstract
Electrochemical
nitrate
reduction
reaction
(NO
3
RR)
is
a
promising
approach
to
realize
ammonia
generation
and
wastewater
treatment.
However,
the
transformation
from
NO
−
NH
involves
multiple
proton‐coupled
electron
transfer
processes
by‐products
2
,
H
etc.),
making
high
selectivity
challenge.
Herein,
two‐phase
nanoflower
P‐Cu/Co(OH)
electrocatalyst
consisting
of
P‐Cu
clusters
P‐Co(OH)
nanosheets
designed
match
two‐step
tandem
process
)
more
compatible,
avoiding
excessive
accumulation
optimizing
whole
reaction.
Focusing
on
initial
2e
process,
inhibited
*
desorption
Cu
sites
in
gives
rise
appropriate
released
electrolyte.
Subsequently,
exhibits
superior
capacity
for
trapping
transforming
desorbed
during
latter
6e
due
thermodynamic
advantage
contributions
active
hydrogen.
In
1
m
KOH
+
0.1
leads
yield
rate
42.63
mg
h
cm
Faradaic
efficiency
97.04%
at
−0.4
V
versus
reversible
hydrogen
electrode.
Such
well‐matched
achieves
remarkable
synthesis
performance
perspective
catalytic
reaction,
offering
novel
guideline
design
RR
electrocatalysts.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Янв. 31, 2024
Abstract
Tandem
nitrate
electroreduction
reaction
(NO
3
−
RR)
is
a
promising
method
for
green
ammonia
(NH
)
synthesis.
However,
the
mismatched
kinetics
processes
between
NO
‐to‐NO
2
and
‐to‐NH
results
in
poor
selectivity
NH
excess
evolution
electrolyte
solution.
Herein,
Ni
2+
substitution
strategy
developing
oxide
heterostructure
Co/Fe
layered
double
oxides
(LDOs)
was
designed
employed
as
tandem
electrocataltysts
RR.
(Co
0.83
0.16
Fe
exhibited
high
yield
rate
of
50.4
mg
⋅
cm
−2
h
−1
with
Faradaic
efficiency
97.8
%
at
−0.42
V
vs.
reversible
hydrogen
electrode
(RHE)
pulsed
electrolysis
test.
By
combining
situ
/
operando
characterization
technologies
theoretical
calculations,
we
observed
strong
over
Fe,
playing
dual
role
RR
by
i)
modifying
electronic
behavior
Co,
ii)
serving
complementary
site
active
(*H)
supply.
Therefore,
adsorption
capacity
*NO
its
subsequent
hydrogenation
on
Co
sites
became
more
thermodynamically
feasible.
This
study
shows
that
promotes
provides
insights
into
design
electrocatalysts
evolution.
