Angewandte Chemie,
Год журнала:
2024,
Номер
136(44)
Опубликована: Июль 12, 2024
Abstract
Renewable
electricity
driven
electrosynthesis
of
cyclohexanone
oxime
(C
6
H
11
NO)
from
10
O)
and
nitrogen
oxide
(NO
x
)
is
a
promising
alternative
to
traditional
environment‐unfriendly
industrial
technologies
for
green
synthesis
C
NO.
Precisely
controlling
the
reaction
pathway
O/NO
‐involved
electrochemical
reductive
coupling
crucial
selectively
producing
NO,
which
yet
still
challenging.
Herein,
we
report
porous
high‐entropy
alloy
PdCuAgBiIn
metallene
(HEA‐PdCuAgBiInene)
boost
NO
O
nitrite,
achieving
high
Faradaic
efficiency
(47.6
%)
almost
100
%
yield
under
ambient
conditions.
In
situ
Fourier
transform
infrared
spectroscopy
theoretical
calculations
demonstrate
that
unconventional
orbital
hybridization
between
d‐block
metals
p‐block
could
regulate
local
electronic
structure
active
sites
induce
electron
localization
electron‐rich
Pd
sites,
tunes
hydrogen
supply,
facilitates
generation
enrichment
key
intermediates
NH
2
OH*
O*,
efficiently
promotes
their
C−N
produce
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(15), С. 10934 - 10942
Опубликована: Апрель 6, 2024
Hydroxylamine
(HA,
NH2OH)
is
a
critical
feedstock
in
the
production
of
various
chemicals
and
materials,
its
efficient
sustainable
synthesis
great
importance.
Electroreduction
nitrate
on
Cu-based
catalysts
has
emerged
as
promising
approach
for
green
ammonia
(NH3)
production,
but
electrosynthesis
HA
remains
challenging
due
to
overreduction
NH3.
Herein,
we
report
first
work
ketone-mediated
using
water.
A
metal–organic-framework-derived
Cu
catalyst
was
developed
catalyze
reaction.
Cyclopentanone
(CP)
used
capture
situ
form
CP
oxime
(CP-O)
with
C═N
bonds,
which
prone
hydrolysis.
could
be
released
easily
after
electrolysis,
regenerated.
It
demonstrated
that
CP-O
formed
an
excellent
Faradaic
efficiency
47.8%,
corresponding
formation
rate
34.9
mg
h–1
cm–2,
remarkable
carbon
selectivity
>99.9%.
The
hydrolysis
release
regeneration
also
optimized,
resulting
96.1
mmol
L–1
stabilized
solution,
significantly
higher
than
direct
reduction.
Detailed
characterizations,
control
experiments,
theoretical
calculations
revealed
surface
reconstruction
reaction
mechanism,
showed
coexistence
Cu0
Cu+
facilitated
protonation
reduction
*NO2
*NH2OH
desorption,
leading
enhancement
production.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(38)
Опубликована: Июнь 21, 2024
Electrochemical
reduction
reactions,
as
cathodic
processes
in
many
energy-related
devices,
significantly
impact
the
overall
efficiency
determined
mainly
by
performance
of
electrocatalysts.
Metal-organic
frameworks
(MOFs)
derived
carbon-supported
metal
materials
have
become
one
star
electrocatalysts
due
to
their
tunable
structure
and
composition
through
ligand
design
screening.
However,
for
different
electroreduction
required
active
species
vary
phase
component,
electronic
state,
catalytic
center
configuration,
hence
requiring
effective
customization.
From
this
perspective,
review
comprehensively
analyzes
structural
principles,
loading
strategies,
practical
performance,
complex
mechanisms,
thereby
providing
insights
guidance
future
rational
such
catalysts.
Chemical Engineering Journal,
Год журнала:
2024,
Номер
494, С. 153111 - 153111
Опубликована: Июнь 14, 2024
This
review
article
comprehensively
explores
the
significant
advancements
in
electrodialysis
(ED)
technology
within
field
of
chemical
engineering,
presenting
a
holistic
overview
that
spans
fundamental
principles,
membrane
materials
and
fabrication
techniques,
operational
parameters,
wide
array
applications.
Unlike
previous
studies
often
narrow
their
focus
to
specific
aspects
ED,
this
work
synthesizes
global
advances,
bridging
gaps
between
diverse
research
themes
offer
coherent
understanding
current
trends
future
directions.
membrane-based
separation
process
driven
by
electric
potential,
is
pivotal
for
its
applications
water
purification,
desalination,
resource
recovery,
beyond.
delves
into
evolution
ion-exchange
membranes,
highlighting
innovations
materials,
alongside
advances
techniques
enhance
selectivity
efficiency.
It
also
scrutinizes
impact
parameters
on
performance
ED
systems,
addressing
challenges
like
ion
leakage,
fouling,
balance
conductivity.
Process
intensification
system
optimization
strategies
are
discussed,
revealing
how
recent
developments
contribute
energy
efficiency,
scalability,
sustainability.
The
further
extends
emerging
sectors
ranging
from
environmental
management
hydrometallurgy
industries,
underscored
case
demonstrate
practical
implementations.
Conclusively,
underlines
multidisciplinary
approach
required
advancement
technologies,
suggesting
avenues
prioritize
impact,
economic
feasibility,
technological
innovation.
Through
perspective,
it
aims
catalyze
exploration
application
some
most
pressing
challenges.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(26)
Опубликована: Апрель 10, 2024
Oxime
ethers
are
attractive
compounds
in
medicinal
scaffolds
due
to
the
biological
and
pharmaceutical
properties,
however,
crucial
widespread
step
of
industrial
oxime
formation
using
explosive
hydroxylamine
(NH
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 10, 2025
The
synergistic
Cu0-Cu+
sites
is
regarded
as
the
active
species
towards
NH3
synthesis
from
nitrate
electrochemical
reduction
reaction
(NO3-RR)
process.
However,
mechanistic
understanding
and
roles
of
Cu0
Cu+
remain
exclusive.
big
obstacle
that
it
challenging
to
effectively
regulate
interfacial
motifs
sites.
In
this
paper,
we
describe
tunable
construction
structure
by
modulating
size-effect
Cu2O
nanocube
electrocatalysts
NO3-RR
performance.
We
elucidate
formation
mechanism
correlating
macroscopic
particle
size
with
microscopic
coordinated
properties,
identify
effect
on
NO3-RR.
Based
rational
design
electrocatalyst,
develop
an
efficient
paired-electrolysis
system
simultaneously
achieve
production
2,5-furandicarboxylic
acid
at
industrially
relevant
current
densities
(2
A
cm−2),
while
maintaining
high
Faradaic
efficiencies,
yield
rates,
long-term
operational
stability
in
a
100
cm2
electrolyzers,
indicating
promising
practical
applications.
It
understand
for
reaction.
Here,
authors
report
electrocatalysts.
The
electrochemical
NO
reduction
reaction
(NORR)
toward
NH3
synthesis
not
only
helps
address
issues
of
air
pollution
but
also
holds
significant
energy
and
economic
value,
making
it
an
innovative
method
with
broad
application
prospects.
However,
designing
NORR
electrocatalysts
that
are
both
highly
active
selective
remains
a
formidable
challenge.
Herein,
we
study
the
main-group
p-block
metal
(M
=
Al,
Ga,
In)-doped
C3N
monolayers
as
promising
single-atom
catalysts
(SACs)
for
through
spin-polarized
first-principles
calculations.
Our
results
show
Al@VCC,
Al@VCN,
Ga@VCC,
Ga@VCN
systems
stable
exhibit
metallic
characteristics,
ensuring
effective
charge
transfer
during
process.
Moreover,
nitric
oxide
(NO)
can
be
strongly
chemisorbed
activated
on
all
four
candidates
adsorption
free
energies
ranging
from
−0.83
to
−1.59
eV
then
spontaneously
converted
into
without
need
any
applied
voltage.
More
importantly,
possesses
well-suppressed
ability
formation
H2/N2O/N2
byproducts,
indicating
excellent
selectivity.
These
findings
offer
electrocatalyst
NO-to-NH3
conversion
highlight
great
potential
metals
SACs
reactions.
