Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(44)
Published: July 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,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10934 - 10942
Published: April 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,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 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,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
The
electrocatalytic
utilization
of
oxidized
nitrogen
waste
for
C-N
coupling
chemistry
is
an
exciting
research
area
with
great
potential
to
be
adopted
as
a
sustainable
method
generation
organonitrogen
molecules.
most
widely
used
reaction
reductive
amination.
In
this
work,
we
develop
alternative
electrochemical
amination
that
can
proceed
in
neutral
aqueous
electrolyte
nitrite
the
nitrogenous
reactant
and
via
oxime
intermediate.
We
selection
criterion
reduction
electrocatalysts
suited
electrosynthesis
and,
doing
so,
find
Pd
highly
efficient
catalyst
reaction,
reaching
Faradaic
efficiency
82%
at
-0.21
V
vs
reversible
hydrogen
electrode.
aliphatic
or
aromatic
structure
carbonyl
impacts
efficacy
catalyst,
substrates
leading
suppressed
formation
detrimental
alcohol.
developed
Pb/PbO
electrocatalyst
selectively
performs
electrolyte.
With
acetone
model
substrate,
demonstrate
one-pot,
two-step
conversion
isopropyl
amine
85%
yield
50%
global
efficiency.
ACS Nano,
Journal Year:
2024,
Volume and Issue:
18(35), P. 23894 - 23911
Published: Aug. 20, 2024
The
C-N
coupling
reaction
demonstrates
broad
application
in
the
fabrication
of
a
wide
range
high
value-added
organonitrogen
molecules
including
fertilizers
(e.g.,
urea),
chemical
feedstocks
amines,
amides),
and
biomolecules
amino
acids).
electrocatalytic
pathways
from
waste
resources
like
CO
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(2), P. 2206 - 2215
Published: Jan. 7, 2025
The
performance
of
nanomaterials
is
significantly
determined
by
the
interfacial
microenvironment,
in
which
a
surfactant
plays
an
essential
role
as
adsorbent,
but
its
involvement
reaction
often
overlooked.
Here,
it
was
discovered
that
citrate
and
ascorbic
acid,
two
primarily
used
surfactants
for
colloidal
gold
nanoparticles
(Au
NPs),
can
spontaneously
undergo
catalytic
with
trace-level
nitrogenous
residue
under
ambient
environment
to
form
oxime,
subsequently
cleaved
generate
CN-
or
compound
containing
-CN
group.
Such
shows
wide
universality
both
reactants,
including
various
carbonaceous
sources,
metal
catalysts,
Au,
Ag,
Fe,
Cu,
Ni,
Pt,
Pd
NPs.
Furthermore,
removal
this
reaction,
adsorbed
CO
diverse
adsorption
configurations
observed
via
surface-enhanced
Raman
spectroscopy
conditions
without
applied
potential.
Our
work
highlights
non-negligible
significance
microenvironments
provides
crucial
insights
into
fundamental
understanding
chemical
reactions.
