Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
Water
microdroplets
have
been
demonstrated
to
exhibit
extraordinary
chemical
behaviors,
including
the
abilities
accelerate
reactions
by
several
orders
of
magnitude
and
trigger
that
cannot
occur
in
bulk
water.
One
most
striking
examples
is
spontaneous
generation
hydroxyl
radical
from
hydroxide
ions.
Alcohols
alkoxide
ions,
being
structurally
similar
water
might
behavior
on
microdroplets.
Here,
we
report
radicals
alcohols
(RCH
2
OH)
aqueous
through
quantum
calculations,
mechanical/molecular
mechanical
(QM/MM)
molecular
dynamics
(MD)
simulations,
ab
initio
MD
mass
spectrometry.
Our
results
show
an
electric
field
(EF)
order
10
−1
V/Å
partial
solvation
at
air‐water
interface
jointly
promote
dissociation
RCH
OH
into
O
−
H
3
+
QM/MM
simulations
indicate
can
be
ionized
produce
O⋅
microdroplet
surface.
Furthermore,
EF
collaboratively
catalyze
isomerization
a
more
stable
tautomer,
R⋅CHOH.
This
study
highlights
mechanisms
underlying
widespread
surface
provides
insights
importance
fundamental
alcohol
chemistry
atmosphere.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(43), С. 29267 - 29271
Опубликована: Окт. 18, 2024
Microdroplet
chemistry
is
now
well-known
to
be
able
remarkably
accelerate
otherwise
slow
reactions
and
trigger
impossible
reactions.
The
uniqueness
of
the
microdroplet
attributable
either
air–water
interface
or
solid–liquid
interface,
depending
on
medium
that
in
contact
with.
To
date,
importance
might
have
been
confirmed,
but
contribution
from
seems
elusive
due
lack
method
for
generating
contactless
microdroplets.
In
this
study,
we
used
a
droplet
atomization
with
acoustic
levitation.
Upon
manipulation
field,
levitated
parent
can
further
atomized
into
progeny
With
method,
only
was
present,
large
variety
were
successfully
tested.
We
anticipate
study
an
advance
toward
understanding
interfacial
processes
chemistry.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(46), С. 31585 - 31596
Опубликована: Ноя. 12, 2024
Often,
chemical
reactions
are
markedly
accelerated
in
microdroplets
compared
with
the
corresponding
bulk
phase.
While
identifying
precise
causative
factors
remains
challenging,
interfacial
electric
field
(IEF)
and
partial
solvation
two
widely
proposed
factors,
accounting
for
acceleration
or
turning
on
of
many
microdroplets.
In
sharp
contrast,
this
combined
computational
experimental
study
demonstrates
that
these
critical
have
a
negligible
effect
promoting
model
Diels-Alder
(DA)
reaction
between
cyclopentadiene
acrylonitrile
water
Instead,
DA
appears
to
be
driven
by
confinement
concentration
increase
caused
evaporation.
Quantum
calculations
ab
initio
molecular
dynamics
simulations
coupled
enhanced
sampling
techniques
predict
air-water
interface
exhibits
higher
free-energy
barrier
than
bulk,
while
external
fields
marginally
reduce
barrier.
Remarkably,
catalytic
capability
IEF
at
microdroplet
surface
is
largely
hampered
its
fluctuating
character.
Mass
spectrometric
assessment
corroborates
findings,
suggesting
not
facilitated
as
increasing
spray
potential
suppresses
products
substrate
oxidation.
preference
microdroplets,
same
tends
occur
mainly
within
core
acetonitrile
microdroplet,
necessarily
factor
accelerating
Moreover,
experiments
indicate
rapid
evaporation
subsequent
reagent
enrichment
accessible
confined
volume
observed
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 22, 2025
Microdroplet
chemistry
has
attracted
much
attention
owing
to
its
ability
accelerate
otherwise
slow
reactions
and
trigger
thermodynamically
forbidden
reactions.
The
cause
of
this
unique
behavior
is
the
intrinsic
properties
droplets,
such
as
spontaneously
generated
electric
field
on
droplet
surface.
However,
some
have
argued
that
generation
methods
provided
energy
reactions,
different
interfaces
droplets
contact
also
played
important
roles;
therefore,
it
activation
or
environment,
not
properties,
responsible
for
observed
chemistry.
In
study,
we
used
adiabatic
expansion
dry
ice
in
water
generate
homogeneous,
contactless,
supercooled,
unactivated
microdroplets.
A
large
variety
were
successfully
tested.
We
opine
activation,
are
microdroplet
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Water
microdroplets
have
been
demonstrated
to
exhibit
extraordinary
chemical
behaviors,
including
the
abilities
accelerate
reactions
by
several
orders
of
magnitude
and
trigger
that
cannot
occur
in
bulk
water.
One
most
striking
examples
is
spontaneous
generation
hydroxyl
radical
from
hydroxide
ions.
Alcohols
alkoxide
ions,
being
structurally
similar
water
might
behavior
on
microdroplets.
Here,
we
report
radicals
alcohols
(RCH
The Journal of Physical Chemistry B,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 24, 2024
This
study
investigates
the
catalytic
effects
of
external
electric
fields
(EEFs)
on
two
reactions
in
solution:
Menshutkin
reaction
and
Chapman
rearrangement.
Utilizing
a
scanning
tunneling
microscope-based
break-junction
(STM-BJ)
setup
monitoring
rates
through
high-performance
liquid
chromatography
connected
to
UV
detector
(HPLC-UV)
ultraperformance
coupled
with
quadrupole
time-of-flight
mass
spectrometry
(UPLC-q-ToF-MS),
we
observed
no
rate
enhancement
for
either
under
ambient
conditions.
Density
functional
theory
(DFT)
calculations
indicate
that
field-induced
changes
reactant
orientation
minimization
activation
energy
are
crucial
factors
determining
efficacy
EEF-driven
catalysis.
Our
findings
suggest
current
experimental
setups
field
strengths
insufficient
catalyze
these
reactions,
underscoring
importance
criteria
assessing
candidates.
JACS Au,
Год журнала:
2024,
Номер
4(11), С. 4141 - 4147
Опубликована: Ноя. 1, 2024
Water
has
made
Earth
a
habitable
planet
by
electrifying
the
troposphere.
For
example,
lightning
caused
electrification
and
discharge
of
cloudwater
microdroplets
is
closely
related
to
atmospheric
chemistry.
Recent
work
revealed
that
high
electric
field
exists
at
interface
water
microdroplets,
which
∼3
orders
magnitude
higher
than
accounts
for
lightning.
A
surge
exotic
redox
reactions
were
recently
found
over
can
be
contributed
such
an
interfacial
field.
However,
role
net
charge
in
microdroplet
chemistry
should
not
ignored.
In
this
Perspective,
we
show
how
driven
electron
transfer
pathways
process
microdroplets.
Understanding
harnessing
origin
evolution
charged
are
likely
lead
paradigm
shift
electrochemistry,
may
play
overlooked
geological
environmental
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
Two-phase
reactions
involving
microdroplets
have
gained
significant
attention
in
recent
years
due
to
their
unique
ability
catalyze
and
accelerate
that
typically
do
not
occur
under
standard
conditions
by
leveraging
chemical
physical
effects
at
the
micrometer-scale
interface.
In
this
work
we
innovatively
developed
a
scaled-up
microdroplet
reactor
for
efficient
resource
utilization
of
CO2.
The
reaction
liquid
is
sprayed
form
mist
(d32
<
20
μm),
facilitating
complete
contact
with
gaseous
We
explored
spray
properties
parameters
on
continuous
production
organic
carbonates
from
Remarkably,
enhanced
efficiency
least
10-fold
compared
conventional
high-pressure
setups.
Additionally,
used
computational
fluid
dynamics
(CFD)
simulations
optimize
process
parameters,
systematically
studying
scaling
up
device.
Here,
present
insights
into
reactors
CO2
conversion
applications,
supported
robust
data.
The Journal of Physical Chemistry Letters,
Год журнала:
2025,
Номер
unknown, С. 2957 - 2964
Опубликована: Март 14, 2025
The
reactive
uptake
of
bromine
nitrate
(BrONO2)
into
aqueous
aerosols
is
a
pivotal
process
in
atmospheric
chemistry.
BrONO2
forms
halogen
bonds
with
adjacent
water
molecules,
disrupting
hydrogen-bond
networks
and
potentially
triggering
unique
chemical
behaviors.
However,
the
role
interfacial
reactions
remains
an
open
question.
Herein,
we
employ
comprehensive
approach
combining
quantum
chemistry
calculations,
classical
molecular
dynamics,
ab
initio
dynamics
(AIMD)
simulations,
advanced
enhanced
sampling
methods
to
investigate
solvation
hydrolysis
at
air-water
interface.
Our
simulations
reveal
that
can
stably
exist
interface,
providing
favorable
conditions
for
its
hydrolysis.
interplay
between
bonding
facilitates
spontaneous
formation
H2OBrONO2
which
subsequently
reacts
produce
HOBr
HNO3.
Free
energy
calculations
indicate
this
reaction
both
kinetically
thermodynamically
interface
barrier
approximately
3.0
kcal/mol
300
K.
insights
from
simulation
study
will
help
guide
future
experiments
explore
how
clouds
affect
