Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
Abstract
Oximes
are
important
intermediates
for
various
chemicals
synthesis
such
as
pharmaceuticals,
among
which
one
vital
precursor
producing
neurological
disease,
antimicrobial
and
anticancer
agents
is
piperidone
oxime
(PDO).
Compared
with
conventional
thermocatalytic
method,
it's
more
attractive
to
synthesize
PDO
via
green
electrocatalytic
technology
especially
utilizing
waste
nitrogen
oxides
gas
source.
However,
there
great
challenges
in
catalyst
design
high‐efficiency
electrosynthetic
due
the
low
electron
transport
rate
multiple
competing
reactions.
Herein,
we
propose
an
interfacial
coordination
strategy
based
on
metal–organic
frameworks
(MOF)
electrocatalyst
first
time
promote
electrosynthesis,
by
building
Zn−O
bridges
between
graphite
felt
(GF)
zeolitic
imidazolate
framework
(ZIF‐7/CGF).
Specially,
ZIF‐7/CGF
delivers
a
Faraday
efficiency
(FE)
of
75.9
%
yield
up
73.1
1‐methyl‐4‐piperidone
oxime,
far
superior
without
(a
FE
10.7
10.3
%).
In‐depth
mechanism
study
shows
that
introducing
can
transfer
induce
Zn
sites
transforming
into
distorted
tetrahedron
(Zn‐N
3
O)
mode,
benefits
adsorption
conversion.
The
developed
presents
wide
universalities
towards
oximes
electrosynthesis
adapts
other
MOF
materials
(ZIF‐8,
ZIF‐4).
This
work
provides
new
insights
organic
upgrading
cycle
through
rational
surficial
coordinated
electrocatalysts.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(28)
Опубликована: Март 29, 2024
Abstract
The
effectuation
of
pH‐universal
electrocatalysis
is
highly
attractive
but
still
challenging
for
the
hydrogen
evolution
reaction
(HER).
It
appeals
not
only
facilitated
electron
transport
also
kinetical
proton
mass
transfer.
In
this
study,
a
via‐hole
Ru/MoO
2
confined
heterostructure
profiled
as
metal‐support
platform
electron/mass
transfer‐boosted
HER
studies.
indicated
that
as‐formed
Ru─O─Mo
bridge
can
modulate
electronic
at
interface,
and
adsorption
transfer
are
kinetically
derived
by
intensified
metallic
Ru─Ru
bond.
Resultantly,
stably
attains
Pt‐beyond
activity
with
an
ultralow
overpotential
9.2
mV
10
mA
cm
−2
in
1
m
KOH,
achieves
competitive
stability
acidic/neutral
electrolytes.
Both
experimental
computational
results
reveal
accelerated
kinetics
attributable
to
intensive
through
interfacial
Ru→MoO
spillover
effect.
This
work
opens
up
opportunities
rationalize
advanced
electrocatalysts
effect
bond
engineering.
Advanced Materials,
Год журнала:
2024,
Номер
36(18)
Опубликована: Янв. 25, 2024
The
artificial
disturbance
in
the
nitrogen
cycle
has
necessitated
an
urgent
need
for
nitric
oxide
(NO)
removal.
Electrochemical
technologies
NO
conversion
have
gained
increasing
attention
recent
years.
This
comprehensive
review
presents
advancements
selective
electrocatalytic
of
to
high
value-added
chemicals,
with
specific
emphasis
on
catalyst
design,
electrolyte
composition,
mass
diffusion,
and
adsorption
energies
key
intermediate
species.
Furthermore,
explores
synergistic
electrochemical
co-electrolysis
carbon
source
molecules,
enabling
synthesis
a
range
valuable
chemicals
C─N
bonds.
It
also
provides
in-depth
insights
into
intricate
reaction
pathways
underlying
mechanisms,
offering
perspectives
challenges
prospects
electrolysis.
By
advancing
comprehension
fostering
awareness
balance,
this
contributes
development
efficient
sustainable
systems
from
NO.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3287 - 3297
Опубликована: Фев. 15, 2024
Cyclohexanone
oxime
is
an
important
precursor
for
Nylon-6
and
typically
synthesized
via
the
nucleophilic
addition–elimination
of
hydroxylamine
with
cyclohexanone.
Current
technologies
production
are,
however,
not
environment-friendly
due
to
requirement
harsh
reaction
conditions.
Here,
we
report
electrochemical
method
one-pot
synthesis
cyclohexanone
under
ambient
conditions
aqueous
nitrate
as
nitrogen
source.
A
series
Zn–Cu
alloy
catalysts
are
developed
drive
reduction
nitrate,
where
intermediate
formed
in
electroreduction
process
can
undergo
a
chemical
present
electrolyte
produce
corresponding
oxime.
The
best
performance
achieved
on
Zn93Cu7
electrocatalyst
97%
yield
27%
Faradaic
efficiency
at
100
mA/cm2.
By
analyzing
catalytic
activities/selectivities
different
alloys
conducting
in-depth
mechanistic
studies
situ
Raman
spectroscopy
theoretical
calculations,
demonstrate
that
adsorption
species
plays
central
role
performance.
Overall,
this
work
provides
attractive
strategy
build
C–N
bond
organic
through
reduction,
while
highlighting
importance
controlling
surface
product
selectivity
electrosynthesis.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(28)
Опубликована: Фев. 21, 2024
Abstract
Electrocatalytic
C−N
couplings
are
promising
alternatives
to
construct
bonds
and
synthesize
vital
chemicals,
including
amine,
amide,
amino
acid,
oxime,
imine,
nitrile,
under
ambient
conditions.
In
recent
years,
the
electrocatalytic
coupling
has
attracted
a
wide
range
of
research
interest
achieved
considerable
developments.
Here,
is
systematically
reviewed
aiming
at
reductive
cathode
oxidative
anode.
cathodic
part,
reaction
systems,
corresponding
design
principles
electrocatalysts
for
different
mechanism
studies
from
experimental
theoretical
aspects,
application‐oriented
devices
summarized.
Anodic
offers
potential
approach
replace
conventional
energy‐demand
synthesis
protocols,
an
indispensable
part
green
controllable
construction
unsaturated
C
=
N
C≡N
bonds.
According
principle
that
electron
transfer
crucial
point
in
anodic
coupling,
reactions
sorted
out
based
on
direct
indirect
paths,
respectively.
Finally,
challenges
outlooks
this
field
proposed.
appealing
topic
electrochemistry
possesses
infinite
possibilities
future.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Янв. 16, 2024
Abstract
Chemical
manufacturing
utilizing
renewable
sources
and
energy
emerges
as
a
promising
path
towards
sustainability
carbon
neutrality.
The
electrocatalytic
reactions
involving
nitrogen
oxides
(NO
x
)
offered
potential
strategy
for
synthesizing
various
nitrogenous
chemicals.
However,
it
is
currently
hindered
by
low
selectivity/efficiency
limited
reaction
pathways,
mainly
due
to
the
difficulties
in
controllable
generation
utilization
of
intermediates.
In
this
minireview,
focusing
on
intermediates
NO
‐involved
reactions,
we
discuss
newly
developed
methodologies
studying
controlling
generation,
conversion,
intermediates,
which
enable
recent
developments
that
yield
products,
including
ammonia
(NH
3
),
organonitrogen
molecules,
compounds
exhibiting
unconventional
oxidation
states.
Furthermore,
also
make
an
outlook
highlight
future
directions
emerging
field
reactions.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 20, 2024
Abstract
The
growth
and
sustainable
development
of
humanity
is
heavily
dependent
upon
molecular
nitrogen
(N
2
)
fixation.
Herein
we
discover
ambient
catalyst-free
disproportionation
N
by
water
plasma
which
occurs
via
the
distinctive
HONH-HNOH
+•
intermediate
to
yield
economically
valuable
nitroxyl
(HNO)
hydroxylamine
(NH
OH)
products.
Calculations
suggest
that
reaction
prompted
coordination
electronically
excited
with
dimer
radical
cation,
(H
O)
,
in
its
two-center-three-electron
configuration.
products
are
collected
a
76-needle
array
discharge
reactor
product
yields
1.14
μg
cm
–2
h
–1
for
NH
OH
0.37
HNO.
Potential
applications
these
compounds
demonstrated
make
ammonia
(for
OH),
as
well
chemically
react
convert
cysteine,
serve
neuroprotective
agent
HNO).
conversion
into
HNO
could
offer
great
profitability
reduction
polluting
emissions,
thus
giving
an
entirely
look
perspectives
problem
green
Deleted Journal,
Год журнала:
2024,
Номер
1(2), С. 181 - 206
Опубликована: Авг. 4, 2024
Abstract
Metal–organic
frameworks
(MOFs)
have
emerged
as
promising
materials
in
the
realm
of
electrocatalysis
due
to
their
high
surface
area,
tunable
porosity,
and
versatile
chemical
functionality.
However,
practical
application
has
been
hampered
by
inherent
limitations
such
low
electrical
conductivity
a
limited
number
active
metal
sites.
Researchers
addressed
these
challenges
through
various
strategies,
including
enhancing
incorporating
conductive
nanoparticles,
modifying
structure
composition
MOFs
replacing
nodes
functionalizing
linkers,
preparing
catalysts
thermal
processes
decarburization
conversion
into
oxides,
phosphides
(MPs),
sulfides
(MSs).
This
review
provided
comprehensive
summary
strategies
that
were
employed
enhance
electroactivity
for
improved
electrocatalytic
performance
recent
years.
It
also
explored
future
directions
potential
innovations
design
synthesis
MOF‐based
electrocatalysts,
offering
valuable
insights
advancing
sustainable
energy
technologies.
