Small Methods,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 14, 2024
Abstract
Ammonia
is
an
important
raw
material
for
agricultural
production,
playing
a
key
role
in
global
food
production.
However,
conventional
ammonia
synthesis
resulted
extensive
greenhouse
gas
emissions
and
huge
energy
consumption.
Recently,
researchers
have
proposed
electrocatalytic
reverse
artificial
nitrogen
cycle
(eRANC)
routes
to
circumvent
these
issues,
which
can
be
driven
by
electrocatalysis
sustainable
electricity.
Here,
theoretical
computational
perspective
on
the
challenges
opportunities
with
comparison
experimental
results:
electrochemical
reduction
of
nitrate
(eNO
3
RR)
nitrite
2
RR),
nitric
oxide
(eNORR)
combined
oxidative
fixation
are
presented.
By
comparison,
N
→NO→NH
route
as
most
promising
case
NO
solubility
solved
well
reactor
design.
Its
high
efficiency
production
demonstrated.
Instead,
eNO
RR
another
choice
because
it
non‐toxic
solid‐liquid
interface
usually
efficient
reactions,
while
its
low
selectivity
at
overpotentials
issue.
These
fundamentals
highlight
potential
factors
eRANC
As
primary
air
pollutants
from
fossil
fuel
combustion,
the
excess
emission
of
nitric
oxides
(NOx)
results
in
a
series
atmospheric
environmental
issues.
Although
selective
catalytic
reduction
technology
has
been
confirmed
to
be
effective
for
NOx
removal,
green
purification
and
value-added
conversion
under
ambient
conditions
are
still
facing
great
challenges,
especially
nitrogen
resource
recovery.
To
address
that,
photo-/electrocatalysis
offers
sustainable
routes
efficient
upcycling
temperature
pressure,
which
received
considerable
attention
scientific
communities.
In
this
review,
recent
advances
critically
summarized.
The
target
products
reaction
mechanisms
systems,
together
with
responsible
active
sites,
discussed,
respectively.
Then,
realistic
practicability
is
proposed,
including
strict
performance
evaluation
criteria
application
by
photo-/electrocatalysis.
Finally,
current
challenges
future
opportunities
proposed
terms
catalyst
design,
enhancement,
mechanism
understanding,
practical
conditions,
product
separation
techniques.
Journal of Materials Chemistry A,
Journal Year:
2024,
Volume and Issue:
12(35), P. 23612 - 23621
Published: Jan. 1, 2024
Designing
flexible
single-atom
catalysts
with
tunable
centers
and
coordination
environments
is
crucial
for
highly
active
selective
electrochemical
catalysis.
New Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
FeY-Cr(Zr)-BPor
COF
catalysts
not
only
maintain
the
advantages
of
bimetallic
but
also
utilize
role
B
atoms
to
fully
activate
NO
and
CO
2
,
thereby
exhibiting
good
catalytic
activity
with
a
very
low
limiting
potential
(−0.20
V).
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 2, 2025
Single-atom
Fe-N-C
catalysts
have
attracted
significant
attention
in
the
NOx
reduction
reaction
(NOxRR).
However,
origin
of
their
selectivity
NOxRR
remains
unclear,
impeding
further
advancements
application.
Herein,
we
investigate
potential-driven
competitive
mechanism
for
NH3
and
NH2OH
production
over
single-atom
pyridinic-FeN4
pyrrolic-FeN4
sites
using
constant-potential
density
functional
theory
calculations.
The
is
linked
to
switching
Fe
3d
orbitals
as
they
interact
with
intermediates.
between
determined
by
applied
potentials.
predominantly
generates
at
higher
potentials
(-0.6
-1.2
V,
vs
SHE),
while
favored
lower
(0.6
-0.6
V).
shows
a
similar
potential-dependent
product
distribution,
crossover
potential
-1.0
V.
selectivity-determining
intermediates
(SDIs)
are
*NH2OH
*NH2
+
*OH.
governed
interacting
SDIs,
from
dumbbell-shaped
3dz2
four-leaf
clover-like
3dxz,
3dyz,
3dx2-y2,
which
plays
crucial
role
controlling
distribution
based
on
These
findings
offer
new
insights
into
NOxRR.
Research Square (Research Square),
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
Abstract
The
electrocatalytic
synthesis
of
cyclohexanone
oxime
from
NO
and
with
high
Faradaic
efficiency
at
ampere-level
current
density
is
highly
desirable
but
challenging.
Here,
theoretical
calculations
reveal
that
coverage
on
the
Ag
catalyst
plays
a
critical
role
in
electrosynthesis.
We
then
adjust
local
concentration
experimentally
by
tuning
reaction
rate.
find
low
benefits
NH3
formation,
whereas
delivers
N-2
(N2O
N2)
products.
A
mechanistic
study
indicates
increasing
coverage,
active
sites
transfer
bridge
step
to
hollow
terrace
sites,
which
results
weaker
adsorption
O*
species,
leading
stable
existence
NH2OH*
intermediate
rather
than
decomposing
form
NH₃.
However,
N‒N
coupling
also
easily
occurs
coverage.
This
understanding
further
inspires
us
develop
doping
strategy
break
equivalent
surface
can
inhibit
NO–NO
thus
realize
density.
Ru-doped
developed,
realizing
86%
1.0
cm−
2,
far
exceeding
reported
performance.
The Journal of Physical Chemistry Letters,
Journal Year:
2025,
Volume and Issue:
unknown, P. 3447 - 3453
Published: March 28, 2025
Although
noble
metals
Ag
and
Au
have
similar
chemical
reactivities,
their
catalytic
selectivity
for
NO
electroreduction
is
significantly
different.
Namely,
hydroxylamine
often
considerably
produced
on
while
not
observed
the
electrode.
In
this
study,
first-principles
calculations
electric
field
controlling
constant
potential
(EFC-CP)
method
are
adopted
to
unveil
underlying
reasons.
We
first
reveal
a
distinct
NO*
adsorption
configuration,
vertical
inclined
Au,
leading
different
reduction
pathways
NOH*
HNO*,
respectively.
Via
complete
electrochemical
barrier
detailed
kinetic
analysis,
we
find
difference
between
mainly
induced
by
strength
of
NH2OH*.
On
Ag,
obtained
NH2OH*
prefers
desorb
produce
hydroxylamine,
bonded
strongly
favors
further
ammonia.
The
study
advances
our
understanding
factors
regulating
product
selectivity,
providing
crucial
insights
designing
catalysts
toward
production.
The Journal of Chemical Physics,
Journal Year:
2025,
Volume and Issue:
162(13)
Published: April 1, 2025
Electrocatalysis
is
one
of
the
key
technologies
for
developing
sustainable
and
fossil
resource
free
routes
to
produce
fuels
chemicals.
The
limiting
potential
(UL),
defined
by
reaction
energy
most
difficult
electrochemical
step
in
a
given
pathway,
an
effective
descriptor
establishing
activity
trend
set
electrocatalysts,
allowing
high
throughput
screening
new
catalysts.
However,
network
electrocatalytic
processes
rather
complex,
especially
reactions
with
necessary
thermochemical
steps,
e.g.,
synthesis
valuable
C–N
bond-containing
Thermochemical
steps
cannot
be
significantly
enhanced
electrode
potentials,
where
kinetics
non-negligible
issue
at
even
overpotentials.
This
makes
it
challenge
using
accurately
describe
trends
steps.
To
this
end,
we
propose
scheme
determine
improved
descriptor.
We
suggest
refining
complex
first.
In
particular,
suggested
decouple
electro-
exclude
unfavorable
pathways
excessively
barrier.
Then,
global
comparison
among
other
can
made,
optimal
pathway
(the
as
ΔGrRPD-limiting).
addition,
studies
on
are
also
understand
exception
best
catalysts
provide
direction
experimental
optimization.
great
compromise
between
practical
efficiency
accuracy
toward
rational
design
electrocatalysts.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Low-dimensional
materials
(LDMs),
including
0D,
1D,
and
2D
nanostructures
their
heterostructures,
are
reviewed
for
applications
in
photocatalytic,
electrocatalytic,
photoelectrocatalytic
synthesis
of
value-added
ammonia.
