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.
ACS Nano,
Год журнала:
2022,
Номер
16(10), С. 15512 - 15527
Опубликована: Окт. 14, 2022
Artificial
nitrogen
conversion
reactions,
such
as
the
production
of
ammonia
via
dinitrogen
or
nitrate
reduction
and
synthesis
organonitrogen
compounds
C–N
coupling,
play
a
pivotal
role
in
modern
life.
As
alternatives
to
traditional
industrial
processes
that
are
energy-
carbon-emission-intensive,
electrocatalytic
reactions
under
mild
conditions
have
attracted
significant
research
interests.
However,
electrosynthesis
process
still
suffers
from
low
product
yield
Faradaic
efficiency,
which
highlight
importance
developing
efficient
catalysts.
In
contrast
transition-metal-based
catalysts
been
widely
studied,
p-block-element-based
recently
shown
promising
performance
because
their
intriguing
physiochemical
properties
intrinsically
poor
hydrogen
adsorption
ability.
this
Perspective,
we
summarize
latest
breakthroughs
development
electrocatalysts
toward
applications,
including
N2
urea
using
nitrogen-containing
feedstocks
carbon
dioxide.
The
catalyst
design
strategies
underlying
reaction
mechanisms
discussed.
Finally,
major
challenges
opportunities
future
directions
also
proposed.
Industrial
ammonia
production
mainly
relies
on
the
conventional
Haber–Bosch
process
accompanied
by
high
energy
consumption
and
plentiful
carbon
dioxide
emissions,
which
triggered
recent
interest
to
explore
more
energy‐efficient
environmentally
benign
alternatives.
Very
recently,
electrochemical
nitrite
reduction
in
an
aqueous
medium
promises
new
opportunities
for
advanced,
energy‐efficient,
sustainable
at
ambient
conditions.
The
formation
rate
Faradic
efficiency
are
strongly
associated
with
adopted
electrocatalysts;
therefore,
striving
high‐efficient
electrocatalysts
is
key
via
reaction.
Herein,
a
critical
overview
of
advances
reaction
presented,
highlighting
latest
innovative
heterogenous
including
noble
metal
catalysts,
transition‐metal‐based
their
compounds.
Meanwhile,
possible
pathway
electroreduction
ammonia,
detection,
catalytic
activity
descriptor
briefly
summarized.
Finally,
perspective
research
challenges
that
convert
outlined,
increasing
contributions
route
realizing
neutral
footprint.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(8)
Опубликована: Янв. 5, 2024
Abstract
Electrocatalytic
reduction
of
nitrate
(NO
3
RR)
to
synthesize
ammonia
(NH
)
provides
a
competitive
manner
for
carbon
neutrality
and
decentralized
NH
synthesis.
Atomically
precise
nanoclusters,
as
an
advantageous
platform
investigating
the
NO
RR
mechanisms
actual
active
sites,
remain
largely
underexplored
due
poor
stability.
Herein,
we
report
4
9
[Ag
(mba)
]
nanoclusters
(Ag
NCs)
loaded
on
Ti
C
2
MXene
/MXene)
highly
efficient
performance
towards
ambient
synthesis
with
improved
stability
in
neutral
medium.
The
composite
structure
Ag
NCs
enables
tandem
catalysis
process
reduction,
significantly
increasing
selectivity
FE
.
Besides,
compared
individual
NCs,
/MXene
has
better
current
density
performed
no
decay
after
108
hours
reaction.
This
work
strategy
improving
catalytic
activity
atomically
metal
expanding
mechanism
research
application
NCs.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(35)
Опубликована: Май 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.
Proceedings of the National Academy of Sciences,
Год журнала:
2023,
Номер
120(50)
Опубликована: Дек. 8, 2023
Zinc-nitrate
batteries
can
integrate
energy
supply,
ammonia
electrosynthesis,
and
sewage
disposal
into
one
electrochemical
device.
However,
current
zinc-nitrate
still
severely
suffer
from
the
limited
density
poor
rechargeability.
Here,
we
report
synthesis
of
tetraphenylporphyrin
(tpp)-modified
heterophase
(amorphous/crystalline)
rhodium-copper
alloy
metallenes
(RhCu
M-tpp).
Using
RhCu
M-tpp
as
a
bifunctional
catalyst
for
nitrate
reduction
reaction
(NO
ACS Catalysis,
Год журнала:
2024,
Номер
14(21), С. 16205 - 16213
Опубликована: Окт. 18, 2024
The
electrochemical
reduction
of
nitrate
ions
to
valuable
ammonia
enables
the
recovery
pollutants
from
industrial
wastewater,
thereby
synchronously
balancing
nitrogen
cycle
and
achieving
NH3
production.
However,
currently
reported
electrocatalysts
still
suffer
low
yield
rate,
Faradaic
inefficiency,
partial
current
density.
Herein,
a
strategy
based
on
regulation
d-band
center
by
Ru
doping
is
presented
boost
Theoretical
calculations
unravel
that
dopant
in
Ni
metal–organic
framework
shifts
neighboring
sites
upward,
optimizing
adsorption
strength
N-intermediates,
resulting
greatly
enhanced
reaction
performance.
synthesized
Ru-doped
rod
array
electrode
delivers
rate
1.31
mmol
h–1
cm–2
efficiency
91.5%
at
−0.6
V
versus
reversible
hydrogen
electrode,
as
well
good
cycling
stability.
In
view
multielectron
transfer
electrocatalytic
activity,
Zn-NO3–
battery
assembled
this
Zn
anode,
which
high
open-circuit
voltage
1.421
maximum
output
power
density
4.99
mW
cm–2,
demonstrating
potential
application
value.
Energy & Environmental Science,
Год журнала:
2023,
Номер
16(4), С. 1590 - 1596
Опубликована: Янв. 1, 2023
Herein,
we
demonstrate
cobaloximes
as
a
bioinspired
molecular
platform
for
exclusive
ammonia
synthesis
via
electrocatalytic
NO
2
−
reduction
(eNO
RR),
which
attained
98.5%
faradaic
efficiency
(FE)
under
close-to-neutral
conditions.
Inorganic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(5), С. 1431 - 1435
Опубликована: Янв. 1, 2023
An
Ag
nanoparticle-decorated
TiO
2
nanoribbon
array
on
a
titanium
plate
performs
efficiently
in
electrocatalytic
NO
−
reduction
to
NH
3
,
achieving
large
yield
of
8743.1
μg
h
−1
cm
−2
with
high
faradaic
efficiency
96.4%.
