Abstract
Transition
metal‐doped
ceria
(M−CeO
2
)
catalysts
(M=Fe,
Co,
Ni
and
Cu)
with
multiple
loadings
were
experimentally
investigated
for
reverse
water
gas
shift
(RWGS)
reaction.
Density
functional
theory
(DFT)
calculations
performed
to
benchmark
the
properties
that
impact
catalytic
activity
of
CO
reduction.
Temperature‐programmed
desorption
(TPD)
was
conducted
study
binding
strength
on
doped
CeO
surfaces;
trend
energy
along
increasing
metal
loading
agrees
DFT
calculations.
Notably,
dissociative
adsorption
oxygen
vacancy
(OV)
formation
are
key
descriptors
obtained
from
both
experiments,
which
can
be
used
evaluate
performance.
Results
show
effectiveness
transition
doping
in
enhancing
reducibility
surfaces,
Fe
showing
particularly
promising
results,
i.
e.,
conversion
higher
than
56
%
at
600
°C
100
selectivity
CO.
Cu
exhibits
but
low
conversion,
while
Co
showed
notable
ability
methanation,
high
loadings.
This
finds
an
effective
based
RWGS
catalyst
corresponds
OV
sites
have
energies
surface
reduction,
moderate
strong
interaction
promote
C−O
bond
scission.
Catalysts,
Год журнала:
2022,
Номер
12(10), С. 1101 - 1101
Опубликована: Сен. 23, 2022
The
catalytic
conversion
of
CO2
to
CO
by
the
reverse
water
gas
shift
(RWGS)
reaction
followed
well-established
synthesis
technologies
could
be
a
practical
technique
convert
valuable
chemicals
and
fuels
in
industrial
settings.
For
catalyst
developers,
prevention
side
reactions
like
methanation,
low-temperature
activity,
selectivity
enhancements
for
RWGS
are
crucial
concerns.
Cerium
oxide
(ceria,
CeO2)
has
received
considerable
attention
recent
years
due
its
exceptional
physical
chemical
properties.
This
study
reviews
use
ceria-supported
active
metal
catalysts
along
with
discussing
some
basic
fundamental
features
ceria.
mechanism,
kinetics
on
supported
catalysts,
as
well
importance
oxygen
vacancies
also
explored.
Besides,
advances
CeO2
design
strategies
increasing
activity
towards
systematically
identified,
summarized,
assessed
understand
impacts
physicochemical
parameters
performance
such
morphologies,
nanosize
effects,
compositions,
promotional
abilities,
metal-support
interactions
(MSI)
role
selected
procedures
forming
distinct
structural
morphologies.
brief
review
may
help
future
optimization.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 17, 2023
Abstract
CO
2
hydrogenation
to
methane
is
gaining
increasing
interest
as
one
of
the
most
promising
ways
store
intermittent
renewable
energy
in
form
chemical
fuels.
Ni
particles
supported
on
CeO
represent
a
highly
efficient,
stable
and
inexpensive
catalyst
for
this
reaction.
Herein,
Ni‐doped
nanoparticles
were
tested
methanation
showing
an
extremely
high
mass‐specific
activity
CH
4
selectivity.
Operando
characterization
reveals
that
performance
tightly
associated
with
ionic
Νi
Ce
3+
surface
sites,
while
formation
metallic
does
not
seem
considerably
promote
Theoretical
calculations
confirmed
stability
interstitial
sites
ceria
surfaces
highlighted
role
Ce‐O
frustrated
Lewis
pair
(FLP),
Ni‐O
classical
(CLP)
Ni‐Ce
activation
H
molecules.
To
large
extent,
theoretical
predictions
validated
by
situ
spectroscopy
under
:
gaseous
environments.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3158 - 3168
Опубликована: Фев. 14, 2024
Strong
metal–support
interactions
(SMSIs),
characterized
by
the
encapsulation
of
metal
nanoparticles
support
oxide,
have
a
significant
impact
on
various
heterogeneous
catalytic
reactions.
In
this
study,
we
present
our
investigations
tuning
performance
CO2
hydrogenation
through
regulating
SMSI
in
Ni/Sm2O3
catalyst.
Our
results
demonstrate
that
complete
Ni
with
amorphous
Sm2O3,
achieved
H2
reduction,
leads
to
nearly
full
selectivity
CO.
contrast,
controlled
situ
thermal
postannealing
an
H2/CO2/N2
mixture,
encapsulated
Sm2O3
layer
can
be
partially
removed
and
crystallized,
as
revealed
atomic-resolution
transmission
electron
microscopy
analyses,
which
enhanced
activity
toward
CH4.
addition,
prolonged
durations
completely
remove
overlayer,
causing
decline
methanation
activity.
These
findings
underscore
critical
role
effect
offer
valuable
insights
for
produce
targeted
value-added
chemicals.
Advanced Materials,
Год журнала:
2024,
Номер
36(21)
Опубликована: Фев. 14, 2024
Abstract
High
entropy
alloys
and
metallic
glasses,
as
two
typical
metastable
nanomaterials,
have
attracted
tremendous
interest
in
energy
conversion
catalysis
due
to
their
high
reactivity
nonequilibrium
states.
Herein,
a
novel
nanomaterial,
layered
glass
(HEMG),
higher
state
than
low‐entropy
its
crystalline
counterpart
both
the
disordered
elemental
structural
arrangements,
is
synthesized.
Specifically,
MnNiZrRuCe
HEMG
exhibits
highly
enhanced
photothermal
catalytic
activity
long‐term
stability.
An
unprecedented
CO
2
methanation
rate
of
489
mmol
g
−1
h
at
330
°C
achieved,
which
is,
authors’
knowledge,
highest
flow
reactors.
The
remarkable
originates
from
abundant
free
volume
internal
HEMG,
lead
extraordinary
heterolytic
H
dissociation
capacity.
high‐entropy
effect
also
ensures
excellent
stability
for
up
450
h.
This
work
not
only
provides
new
perspective
on
mechanism
but
sheds
light
great
potential
future
carbon‐negative
industry.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 14149 - 14156
Опубликована: Май 8, 2024
The
technology
of
liquid
organic
hydrogen
carriers
presents
great
promise
for
large-scale
storage.
Nevertheless,
the
activation
inert
C(sp3)–H
bonds
in
hydrocarbon
poses
formidable
challenges,
resulting
a
sluggish
dehydrogenation
process
and
necessitating
high
operating
temperatures.
Here,
we
break
shackles
C–H
bond
under
visible
light
irradiation
by
fabricating
subnanometer
Pt
clusters
on
defective
Ce–Zr
solid
solutions.
We
achieved
an
unprecedented
production
rate
2601
mmol
gcat.–1
h–1
(turnover
frequency
>50,000
molH2
molPt–1
h–1)
from
cyclohexane,
surpassing
most
advanced
thermo-
photocatalysts.
By
optimizing
temperature-dominated
transfer
process,
achievable
harnessing
hitherto
wasted
infrared
sunlight,
astonishing
56%
apparent
quantum
efficiency
5.2%
solar-to-hydrogen
are
attained
at
353
K.
Our
research
stands
as
one
effective
photocatalytic
processes
to
date,
holding
profound
practical
significance
utilization
solar
energy
exploitation
alkanes.
