The Journal of Physical Chemistry C,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 29, 2024
The
specific
binding
of
solution
components
to
a
catalytic
surface
and
the
interfacial
electric
field
are
critical
electrocatalysis,
but
two
factors
entangled.
Distinguishing
whether
adsorbate
is
governed
by
through-bond
charge
transfer
that
modulated
or
through-space
electrostatic
effects
essential
for
rational
catalyst
design.
Here,
we
probed
thiocyanate
(SCN–)
Au
Pd
as
function
applied
potential
(ϕapp)
using
surface-enhanced
infrared
absorption
spectroscopy
(SEIRAS).
IR
data
showed
distinct
shifts
CN
stretching
wavenumbers
(ν̃CN)
with
ϕapp
S-
versus
N-bound
SCN–
on
Pd.
These
ν̃CN
result
different
extents
(Stark)
chemical
effects.
presence
modes
metal
surfaces
provided
separate
probes,
which
enabled
estimating
contributions
overall
slopes
quantitatively.
Competitive
adsorption
experiments
halides
(Cl–,
Br–,
I–)
support
our
conclusions.
While
effect
S-bound
more
pronounced
than
Au,
similar.
Our
also
suggest
similar
change
Au.
This
work
offers
method
differentiate
key
contributors
chemistry
in
an
external
provides
important
groundwork
development
future
electrocatalysts.
Nature Energy,
Год журнала:
2024,
Номер
9(5), С. 548 - 558
Опубликована: Март 14, 2024
Abstract
Ion
(de)solvation
at
solid–electrolyte
interfaces
is
pivotal
for
energy
and
chemical
conversion
technology,
such
as
(electro)catalysis,
batteries
bipolar
membranes.
For
example,
during
the
electrocatalytic
hydrogen
evolution
reaction
in
alkaline
media,
water
needs
to
be
dissociated
hydroxide
ions
solvated—a
process
that
not
well
understood.
Here
we
study
dissociation
ion
solvation
kinetics
isolation
polymeric
membrane
electrolyte–metal
interfaces.
We
discover
bias-dependent
relationships
between
activation
entropy
enthalpy,
which
link
a
dispersion
of
interfacial
capacitance.
Furthermore,
our
results
indicate
OH
−
kinetically
slower
than
H
+
display
characteristics
are
independent
catalyst
structure.
attribute
this
universal
amount
excess
charge
needed
induce
electric
fields
alter
water.
Of
fundamental
interest,
these
critical
enable
knowledge-driven
electrocatalyst
design.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13438 - 13444
Опубликована: Апрель 30, 2024
The
Baeyer–Villiger
oxidation
of
ketones
is
a
crucial
oxygen
atom
transfer
(OAT)
process
used
for
ester
production.
Traditionally,
accomplished
by
thermally
oxidizing
the
OAT
from
stoichiometric
peroxides,
which
are
often
difficult
to
handle.
Electrochemical
methods
hold
promise
breaking
limitation
using
water
as
source.
Nevertheless,
existing
demonstrations
electrochemical
face
challenges
low
selectivity.
We
report
in
this
study
strategy
overcome
challenge.
By
employing
well-known
catalyst,
Fe2O3,
we
achieved
nearly
perfect
selectivity
cyclohexanone.
Mechanistic
studies
suggest
that
it
essential
produce
surface
hydroperoxo
intermediates
(M-OOH,
where
M
represents
metal
center)
promote
nucleophilic
attack
on
ketone
substrates.
confining
reactions
catalyst
surfaces,
competing
(e.g.,
dehydrogenation,
carboxylic
acid
cation
rearrangements,
and
hydroxylation)
greatly
limited,
thereby
offering
high
surface-initiated
nature
reaction
confirmed
kinetic
spectroelectrochemical
characterizations.
This
discovery
adds
toolbox
organic
synthesis.
Advanced Materials,
Год журнала:
2024,
Номер
36(32)
Опубликована: Июнь 11, 2024
Abstract
The
precise
manipulation
of
the
microstructure
(pore
size,
free
volume
distribution,
and
connectivity
free‐volume
elements),
thickness,
mechanical
characteristics
membranes
holds
paramount
significance
in
facilitating
effective
utilization
self‐standing
membranes.
In
this
contribution,
synthesis
two
innovative
ester‐linked
covalent–organic
framework
(COF)
is
first
reported,
which
are
generated
through
selection
plant‐derived
ellagic
acid
quercetin
phenolic
monomers
conjunction
with
terephthaloyl
chloride
as
a
building
block.
optimization
these
COF
systematically
achieved
application
three
different
interfacial
electric
field
systems:
neutrality,
positive
electricity,
negative
electricity.
It
observed
that
positively
charged
system
facilitates
record
increase
rate
membrane
formation,
resulting
denser
uniform
pore
size
enhanced
flexibility.
addition,
correlation
identified
wherein
an
alkyl
chain
length
surfactants
leads
to
more
decrease
molecular
weight
cutoff
membrane.
exhibits
unprecedented
combination
high
water
permeance,
superior
sieving
capability,
robust
strength,
chemical
robustness
for
promising
membrane‐based
separation
science
technology.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 10, 2025
Abstract
A
feasible
Fe–N–C
catalysts
(Fe/Fe
SA
@GNC)
with
multiple
Fe
species
and
well‐graphitized
carbon
layers
is
prepared
to
boost
the
carbamate
decomposition
kinetics
for
energy‐saving
CO
2
capture
amine
solvent.
precursor
carbothermic
reaction
creates
graphitic
doped
pyridinic‐N,
which
significantly
enhances
activity
of
coordinated
sites.
Furthermore,
enclosed
nanoparticles
originate
from
excess
firmed
atomically
dispersed
sites
in
layers.
The
as‐prepared
exhibit
superior
under
relatively
mild
conditions.
maximum
desorption
rate
soar
5.4
mmol
min
−1
,
marking
440%
increment
compared
catalyst‐free
reaction.
Notably,
Fe/Fe
@GNC
delivered
exceptional
stability
durability
after
20
cycles
alkaline
organic
solutions,
single‐atom
without
NPs.
Bench‐scale
testing
continuous
absorption
presented
a
19.5%
increase
efficiency
40.7%
decrease
heat
duty
only
0.1
wt.%
dosage
@GNC.
role
demonstrated
process
proton
transfer
C−N
breaking
during
solvent
regeneration
(CO
desorption).
Thus,
catalytic
offered
an
appealing
technology
solution
high
challenge
associated
chemisorption
using
amine‐based
Abstract
Endowing
conventional
materials
with
specific
functions
that
are
hardly
available
is
invariably
of
significant
importance
but
greatly
challenging.
TiO
2
proven
to
be
highly
active
for
the
photocatalytic
hydrogen
evolution
while
intrinsically
inert
electrocatalytic
reaction
(HER)
due
its
poor
electrical
conductivity
and
unfavorable
adsorption/desorption
behavior.
Herein,
first
activation
HER
demonstrated
by
synergistically
modulating
positions
d‐band
center
triggering
spillover
through
dual
doping‐induced
partial
phase
transition.
The
N,
F
co‐doping‐induced
transition
from
anatase
rutile
in
(AR‐TiO
|(N,F))
exhibits
extraordinary
performance
overpotentials
74,
80,
142
mV
at
a
current
density
10
mA
cm
–2
1.0
M
KOH,
0.5
H
SO
4
,
phosphate‐buffered
saline
electrolytes,
respectively,
which
substantially
better
than
pure
even
superior
benchmark
Pt/C
catalysts.
These
findings
may
open
new
avenue
development
low‐cost
alternative
noble
metal
catalysts
production.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
The
hydrogen
evolution
reaction
(HER)
is
one
of
the
most
prominent
electrocatalytic
reactions
green
energy
transition.
However,
kinetics
across
materials
and
electrolyte
pH
impact
coverage
at
high
current
densities
remain
poorly
understood.
Here,
we
study
HER
over
a
large
set
nanoparticle
catalysts
in
industrially
relevant
acidic
alkaline
membrane
electrode
assemblies
that
are
only
operated
with
pure
water
humidified
gases.
We
discover
distinct
kinetic
fingerprints
between
iron
triad
(Fe,
Ni,
Co),
coinage
(Au,
Cu,
Ag),
platinum
group
metals
(Ir,
Pt,
Pd,
Rh).
Importantly,
applied
bias
changes
not
activation
(EA)
but
also
pre-exponential
factor
(A).
interpret
these
as
entropic
interfacial
solvent
differ
acid
base
on
surface
due
to
changing
coverage.
Finally,
observe
anions
can
induce
Butler–Volmer
behavior
for
acid.
Our
results
provide
new
foundation
understand
and,
more
broadly,
highlight
pressing
need
update
common
understanding
basic
concepts
field
electrocatalysis.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 6, 2025
Electrocatalysis
is
one
of
the
principal
pathways
for
transition
to
sustainable
chemistry,
promising
greater
energy
efficiency
and
reduced
emissions.
As
field
has
grown,
our
theoretical
understanding
matured.
The
influence
applied
potential
on
reactivity
developed
from
first-order
predictions
based
Nernst
equation
implicit
inclusion
second-order
effects
including
interaction
reacting
species
with
interfacial
electric
field.
In
this
review,
we
explore
these
non-Nernstian
in
electrocatalysis,
aiming
both
understand
exploit
them
through
theory
computation.
We
summarize
critical
distinction
between
Nernstian
outline
strategies
address
latter
studies.
Subsequently,
examine
specific
energetic
contributions
capacitive
faradaic
processes
separately.
also
underscore
importance
considering
catalyst
screening
mechanistic
analysis.
Finally,
provide
suggestions
how
experimentally
unravel
effects,
offering
insights
into
practical
approaches
advancing
Journal of Chemical Theory and Computation,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 17, 2025
Electric-field
(EF)-mediated
chemistry
has
recently
garnered
increasing
attention
partly
owing
to
its
capability
catalyze
a
broad
range
of
chemical
reactions.
How
the
EF
affects
kinetics
and
thermodynamics
target
reactions
is
critical
question.
Herein,
both
density
functional
theory
(DFT)
MP2
calculations
suggest
that
change
activation
energy
ΔΔE‡
reaction
ΔΔErxn
under
an
display
linear
relationship
(LER)
=
mΔΔErxn.
This
been
tested
against
several
such
as
SN2
proton
transfer
reactions,
including
neutral
charged
systems
endothermic
exothermic
processes.
The
coefficient
m
approximates
ratio
dipole
moment
change,
i.e.,
Δμ‡/Δμrxn,
studied
LER
holds
well
at
strengths
up
≈1
V/nm
but
deviates
from
DFT-calculated
results
larger
EFs.
Such
deviations
are
mainly
caused
by
molecular
geometry
changes
EF.
Systems
with
polarizability
experience
greater
EF,
thus
leading
deviations.
In
addition,
we
propose
barrier
can
be
predicted
-Δμ‡F
-
0.5Δα‡F2,
while
it
approximated
for
small
strengths.
proposed
field-dependent
estimation
promise
applicability
in
EF-mediated
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 22, 2025
Decentralized
water
treatment
technologies,
designed
to
align
with
the
specific
characteristics
of
source
and
requirements
user,
are
gaining
prominence
due
their
cost
energy-saving
advantages
over
traditional
centralized
systems.
The
application
chemical
via
heterogeneous
advanced
oxidation
processes
using
peroxide
(O-O)
represents
a
potentially
attractive
option.
These
serve
initiate
redox
at
solid-water
interface.
Nevertheless,
mechanism
exemplified
by
typical
Fenton-like
persulfate-based
oxidation,
in
which
electron
transfer
dominates,
is
almost
universally
accepted.
Here,
we
present
experimental
results
that
challenge
this
view.
At
solid-liquid
interface,
it
demonstrated
protons
thermodynamically
coupled
electrons.
In
situ
quantitative
titration
provides
direct
evidence
coupling
ratio
transferred
electrons
1:1.
Comprehensive
thermodynamic
analyses
further
demonstrate
net
proton-coupled
occurs,
both
entering
cycle.
findings
will
inform
future
developments
O-O
activation
enabling
more
efficient
activity
tight