Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(46)
Published: Aug. 8, 2024
Abstract
Coupling
in
situ
generated
intermediates
with
other
substrates/intermediates
is
a
viable
approach
for
diversifying
product
outcomes
of
catalytic
reactions
involving
two
or
multiple
reactants.
Cyclohexanone
oxime
key
precursor
caprolactam
synthesis
(the
monomer
Nylon‐6),
yet
its
current
production
uses
unsustainable
carbon
sources,
noble
metal
catalysts,
and
harsh
conditions.
Herein,
we
report
the
first
work
to
synthesize
cyclohexanone
through
electroreduction
phenol
hydroxylamine.
The
Faradaic
efficiency
reached
69.1
%
over
Cu
catalyst,
accompanied
by
corresponding
formation
rate
82.0
g
h
−1
cat
.
In
addition,
conversion
was
up
97.5
%.
characterizations,
control
experiments,
theoretical
calculations
suggested
importance
balanced
activation
water,
phenol,
hydroxylamine
substrates
on
optimal
metallic
catalyst
achieving
high‐performance
synthesis.
Besides,
tandem
route
upgrading
lignin
has
been
successfully
developed
integration
thermal
catalysis,
electrocatalysis,
Beckmann
rearrangement,
which
achieved
0.40
from
4.0
raw
material.
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.
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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 17, 2024
The
pursuit
of
sustainable
practices
through
the
chemical
recycling
polyamide
wastes
holds
significant
potential,
particularly
in
enabling
recovery
a
range
nitrogen-containing
compounds.
Herein,
we
report
novel
strategy
to
upcycle
tertiary
amines
with
assistance
H
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.
