ACS Sustainable Chemistry & Engineering,
Год журнала:
2023,
Номер
11(14), С. 5537 - 5546
Опубликована: Март 24, 2023
Light-driven
methane
conversion
to
methanol
with
high
selectivity
is
considered
a
challenging
and
promising
reaction
for
sustainable
development.
Herein,
Cu/CeO2
catalysts
were
prepared
photocatalytic
CO2
as
soft
oxidant.
Methanol
was
the
sole
liquid
product
of
96.2%
yield
88.9
μmol
g–1
h–1
2Cu/CeO2
catalyst.
Investigation
structure–performance
relationship
indicated
that
oxygen
vacancies
facilitated
trapping
photogenerated
electrons
avoided
carrier
recombination.
In
addition,
oxidant,
can
also
capture
be
reduced
CO
further
accelerate
formation
CH3OH.
A
catalytic
mechanism
study
demonstrated
hydroxyl
oxidized
by
holes
•CH3
•OH,
respectively,
thus,
generated
through
combination
•OH.
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.
Abstract
In
heterogeneous
catalysis,
heterolytic
H
2
activation
for
(selective)
hydrogenation
and
hydroprocessing
reactions
involves
the
dissociation
of
adsorbed
molecules
into
proton
(H
δ+
)
hydride
δ−
on
catalyst
surface.
This
approach
offers
several
advantages,
including
high
selectivity
polar
bond
(s),
a
low
energy
barrier
dissociation,
capacity
reaction‐favorable
adsorption,
reduced
poisoning.
requires
construction
frustrated
Lewis
pairs
surface,
satisfying
specific
criteria,
such
as
having
an
abundant
quantity
with
steric
hindrance
maintaining
certain
distance
3–5
Å
between
pairs.
review
highlights
intrinsic
properties
based
state‐of‐the‐art
reports.
The
main
components
necessary
this
include
supports
strong
basic
sites
and/or
oxygen
vacancies,
metals
single
atom.
For
purpose,
designed
catalytic
materials
aim
to
strengthen
acidity
basicity,
improve
polarization
pairs,
enrich
maximize
interfacial
area
metal
species
base,
enhance
metal–support
interaction.
Therefore,
catalysts
retaining
characteristics
will
be
significantly
effective
in
various
reactions.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(43), С. 17961 - 17971
Опубликована: Окт. 19, 2023
The
employment
of
stoichiometric
alcohols
and
amines
for
imine
synthesis
under
mild
green
reaction
conditions
is
still
a
challenge
in
the
field.
In
this
work,
based
on
our
research
foundation
thermocatalytic
imines
over
ceria,
CdS/CeO2
heterojunction
photocatalyst
was
constructed
successfully
realized
atom-economic
visible
light
without
additives
at
room
temperature.
Mechanistic
experiments
corresponding
characterizations
indicated
that
can
improve
separation
efficiency
photogenerated
carriers,
which
be
further
enhanced
by
Ce4+/Ce3+
redox
pair
rapidly
combining
e-.
situ-reduced
Ce3+
better
activate
O2
to
form
Ce-O-O·,
which,
together
with
h+,
efficiently
accelerates
alcohol
oxidation,
rate-determined
step
via
oxidative
coupling
amine.
addition,
exhibited
fairly
decent
reusability
substrate
universality.
This
work
solves
problems
using
base
excess
amine
or
reported
photocatalytic
systems
provides
new
insight
designing
CeO2-based
oxidation
catalysts.
Discovered
almost
130
years
ago
by
P.
Sabatier,
CO
2
hydrogenation
to
methane
(CO
methanation)
is
presently
attracting
attention
as
one
of
the
most
promising
methods
for
storing
intermittent
renewable
energy
in
form
chemical
fuels.
Ni
particles
supported
CeO
constitute
a
very
effective,
reliable,
and
reasonably
priced
catalyst
methanation.
Recently
new
type
methanation
catalyst,
consisting
cerium
oxide
(ceria)
nanoparticles
doped
with
nickel
(NiCeO
x
)
specific
square‐planar
configuration
an
extremely
high‐Ni
mass‐specific
activity
100%
CH
4
selectivity,
was
reported.
Here,
50%
enhancement
conversion
NiCeO
carefully
adjusting
calcination
temperature
demonstrated.
Notably,
thermal
aging
at
600
°C
enhances
performance
partially
exsolving
surface,
while
higher
temperatures
(750
°C)
lead
larger
particles,
increased
production,
surface
carbon
deposition.
Several
situ
operando
characterization
are
employed
correlate
activation
deactivation
its
nanoscale
characteristics.
Apart
from
their
clear
implications
design
next‐generation
Ni‐based
catalysts,
these
findings
significantly
enhance
understanding
complex
interplay
nature
various
sites
involved
hydrogenation.
