Catalysis Reviews,
Год журнала:
2024,
Номер
unknown, С. 1 - 66
Опубликована: Июнь 6, 2024
The
surface
chemistry
of
metal
oxides
and
their
catalytic
roles
in
activating
transforming
oxygenate
hydrocarbon
feedstocks
is
rich.
This
review
provides
an
update
on
mechanisms
such
reactions,
as
well
modern
promising
concepts
for
selective
conversions
oxide
catalysts,
including
those
occurring
molecularly
confining
reaction
environments.
Case
examples
built
upon
electronic
structure
modeling
transition
states
are
emphasized,
contemporary
ideas
to
enable
low
free
energies
activation.
covered
broad,
includes
Lewis
acid–base
chemistry,
Brønsted
oxygen
vacancy-based
redox
chemistry.
reactions
include
C-H
activation
alkanes,
C–C
coupling
aldehydes,
carboxylic
acids
(ketonization),
dehydration
alcohols
over
confined
sites,
bond
formation
between
aldehydes
sites.
For
each
type,
molecular-level
knowledge
elementary
steps
critically
reviewed.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
The
sluggish
anodic
oxygen
evolution
reaction
(OER)
in
proton
exchange
membrane
(PEM)
electrolysis
necessitates
applied
bias
to
facilitate
electron
transfer
as
well
bond
cleavage
and
formation.
Traditional
electrocatalysis
focuses
on
analyzing
the
effects
of
transfer,
while
role
charge
accumulation
induced
by
overpotential
has
not
been
thoroughly
investigated.
To
explore
influence
mechanism
bias-driven
accumulation,
capacitive
Mn
is
incorporated
into
IrO
ACS Catalysis,
Год журнала:
2023,
Номер
13(22), С. 14699 - 14715
Опубликована: Окт. 31, 2023
Recent
studies
have
focused
on
the
promotion
of
methanol
synthesis
by
CeO2
and
inhibition
reverse
water
gas
shift
reaction
(r-WGSR)
TiO2
support
from
perspective
nature
active
sites
morphology.
Nevertheless,
rational
design
catalysts
needs
to
account
additionally
for
mechanism,
a
topic
that
has
not
yet
been
addressed
CuCeOx/TiO2.
Herein,
CO
formation
pathways
over
this
catalytic
system
were
unraveled.
Kinetic,
isotopic,
spectroscopic
techniques
combined
obtain
mechanistic
insights
both
reactions.
Particularly,
H2/D2
kinetic
isotopic
effect
(KIE),
hourly
space
velocity
(GHSV)
effect,
cofeeding
products,
operando-diffuse
reflectance
infrared
Fourier
transform
spectroscopy
(operando-DRIFTS)
under
steady-state,
transient,
exchange
conditions,
12CO2/13CO2
steady-state
isotopic-transient
analysis-DRIFT/mass
spectrometry
(SSITKA-DRIFTS/MS)
performed.
The
results
unequivocally
ruled
out
an
r-WGSR
+
hydrogenation
pathway
and,
furthermore,
demonstrated
species
is
formed
through
stepwise
formates
Cu–Ce
interfacial
sites.
Moreover,
it
was
concluded
occurs
assisted
hydrogen
site
different
involved
in
synthesis.
Likewise,
relevance
surface-detected
carbonate
discarded.
From
these
insights,
formal
model
derived,
which
accurately
fitted
experimental
data
correctly
predicted
properties
behavior
CuCeOx/TiO2
with
concentrations.
This
study
highlights
importance
combining
analyses
labeling
order
elucidate
mechanisms
interface
between
metal
metal-oxide
plays
relevant
role.
