Science,
Год журнала:
2023,
Номер
380(6640), С. 81 - 87
Опубликована: Апрель 6, 2023
The
Kolbe
reaction
forms
carbon-carbon
bonds
through
electrochemical
decarboxylative
coupling.
Despite
more
than
a
century
of
study,
the
has
seen
limited
applications
owing
to
extremely
poor
chemoselectivity
and
reliance
on
precious
metal
electrodes.
In
this
work,
we
present
simple
solution
long-standing
challenge:
Switching
potential
waveform
from
classical
direct
current
rapid
alternating
polarity
renders
various
functional
groups
compatible
enables
sustainable
carbon-based
electrodes
(amorphous
carbon).
This
breakthrough
enabled
access
valuable
molecules
that
range
useful
unnatural
amino
acids
promising
polymer
building
blocks
readily
available
carboxylic
acids,
including
biomass-derived
acids.
Preliminary
mechanistic
studies
implicate
role
in
modulating
local
pH
around
crucial
acetone
as
an
unconventional
solvent
for
reaction.
Science,
Год журнала:
2024,
Номер
385(6705), С. 216 - 223
Опубликована: Июль 11, 2024
Direct
current
(DC)
electrosynthesis,
which
has
undergone
optimization
over
the
past
century,
plays
a
pivotal
role
in
variety
of
industrial
processes.
Alternating
(AC)
characterized
by
polarity
reversal
and
periodic
fluctuations,
may
be
advantageous
for
multiple
chemical
reactions,
but
apparatus,
principles,
application
scenarios
remain
underdeveloped.
In
this
work,
we
introduce
protocol
programmed
AC
(pAC)
electrosynthesis
that
systematically
adjusts
currents,
frequencies,
duty
ratios.
The
representative
pAC
waveforms
facilitates
copper-catalyzed
carbon-hydrogen
bond
cleavage
cross-coupling
difunctionalization
reactions
exhibit
suboptimal
performance
under
DC
oxidation
conditions.
Moreover,
observing
catalyst
dynamic
variation
diverse
waveform
applications
provides
mechanistic
insight.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(50)
Опубликована: Авг. 22, 2023
Abstract
Organic
electrosynthesis
has
consistently
aroused
significant
interest
within
both
academic
and
industrial
spheres.
Despite
the
considerable
progress
achieved
in
this
field,
majority
of
electrochemical
transformations
have
been
conducted
through
utilization
direct‐current
(DC)
electricity.
In
contrast,
application
alternating
current
(AC),
characterized
by
its
polarity‐alternating
nature,
remains
infancy
sphere
organic
synthesis,
primarily
due
to
absence
a
comprehensive
theoretical
framework.
This
minireview
offers
an
overview
recent
advancements
AC‐driven
seeks
elucidate
differences
between
DC
AC
electrolytic
methodologies
probing
into
their
underlying
physical
principles.
These
encompass
ability
preclude
deposition
metal
catalysts,
precision
modulating
oxidation
reduction
intensities,
mitigation
mass
transfer
processes.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(18)
Опубликована: Янв. 3, 2023
Alternating
current
(AC)
electrolysis
is
receiving
increased
interest
as
a
versatile
tool
for
mild
and
selective
electrochemical
transformations.
This
work
demonstrates
that
AC
can
enable
the
concept
of
stirring-free
reactor
where
periodic
switch
electrode
polarity,
inherent
to
AC,
provides
uniform
across
whole
volume
reactor.
Such
design
implies
straightforward
approach
scaling
up
electrosynthesis.
was
demonstrated
on
range
transformations
performed
in
three
different
RVC-packed
reactors
50-mmol
scale.
Redox-neutral,
oxidative,
reductive
processes
were
successfully
implemented
using
suggested
applicable
frequency
ranges
further
investigated
types
reactions.
The
advantages
AC-enabled
-
such
absence
stirring
maximized
surface
area
electrodes
provide
possibility
its
universal
application
both
small-scale
screening
experimentation
large-scale
preparative
electrosynthesis
without
significant
optimization
needed
between.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15619 - 15626
Опубликована: Май 23, 2024
Electrochemical
steps
are
increasingly
attractive
for
green
chemistry.
Understanding
reactions
at
the
electrode–solution
interface,
governed
by
kinetics
and
mass
transport,
is
crucial.
Traditional
insights
into
these
mechanisms
limited,
but
our
study
bridges
this
gap
through
an
integrated
approach
combining
voltammetry,
electrochemical
impedance
spectroscopy,
electrospray
ionization
spectrometry.
This
technique
offers
real-time
monitoring
of
chemical
processes
tracking
changes
in
intermediates
products
during
reactions.
Applied
to
reduction
oxygen
catalyzed
iron(II)
tetraphenyl
porphyrin
complex,
it
successfully
reveals
various
reaction
degradation
pathways
under
different
kinetic
regimes.
Our
findings
illuminate
complex
electrocatalytic
propose
new
ways
studying
alternating
current
voltage-pulse
electrosynthesis.
advancement
enhances
capacity
optimize
more
sustainable
processes.
