Advanced Energy Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
Abstract
Directly
converting
methane
to
methanol
with
solar
light
and
eco‐friendly
oxidants
is
challenging
due
single‐step
conversion
process
where
the
designed
active
sites
commonly
cleave
C─H
bonds
in
both
methanol.
Herein,
a
novel
method
proposed
break
activity‐selectivity
trade‐off
through
interface
engineering.
Taking
BiOI/BN
as
proof‐of‐concept
model,
it's
discovered
that
engineered
provides
distinct
for
activation
overoxidation
products
photoreduction.
Based
on
situ
infrared
spectroscopy,
ultrafast
laser
theoretical
calculations,
it
unlocked
induces
passivation
of
original
trap
states
BiOI
component,
greatly
hindering
trap‐mediated
recombination
photo‐induced
carriers
(≈39.7
ps).
Benefiting
from
it,
long‐lived
electrons
could
directly
participate
radicals
generation,
ensuring
effective
activation.
Subsequently,
carbon
intermediates
protons
are
captured
by
BN
component
rapidly
accumulated
surface.
This
enables
injection
into
bonding
orbitals
methanol,
accelerating
occurrence
re‐bonding
process.
Ultrafast
charge
transfer
at
interfaces
results
high
rate
15.5%
under
atmospheric
pressure
maintains
selectivity
86.4%
24
h
long‐time
reaction
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
Light-driven
direct
conversion
of
methane
to
formic
acid
is
a
promising
approach
convert
value-added
chemicals
and
promote
sustainability.
However,
this
process
remains
challenging
due
the
complex
requirements
for
multiple
protons
electrons.
Herein,
we
report
design
WO3-based
photocatalysts
modified
with
Pt
active
sites
address
challenge.
We
demonstrate
that
modulating
dimensional
effect
on
WO3
support
key
enhancing
catalytic
performance
selective
CH4-to-HCOOH
conversion.
The
nanoparticles
exhibit
superior
rate,
selectivity
durability
in
production
HCOOH
compared
Pt-free
sample
decorated
single
atoms.
optimal
PtNPs-WO3
catalyst
achieves
rate
17.7
mmol
g–1,
84%
stability
maintained
up
48
h.
Mechanistic
studies
show
protonation
O2
hydroxyl
radicals
limiting
step
yield.
can
facilitate
electron
transfer
dissociation,
generating
via
proton-coupled
process.
This
provides
sufficient
lower
formation
barrier
•OH
radicals,
thereby
promoting
activation
CH4.
In
addition,
regulate
adsorption
oxygenated
hydrocarbon
intermediates,
increasing
reaction.
work
advances
our
understanding
effective
regulation
reaction
pathways.
ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
17(9), С. 14119 - 14128
Опубликована: Фев. 24, 2025
Photocatalytic
oxidative
dehydrogenation
of
ethane
offers
a
promising
approach
for
producing
ethylene
under
mild
conditions.
However,
achieving
high
yields
and
selectivity
is
challenging
due
to
the
C-H
bond
activation
barrier
in
tendency
overoxidation
CO2.
In
this
study,
we
demonstrate
that
TiO2
with
highly
dispersed
AuPd
nanoparticles
serves
as
an
efficient
selective
photocatalyst
O2
flow
reactor.
The
optimized
Au0.33Pd0.67/TiO2
achieves
up
20.3
mmol
g-1
h-1
91.5%
selectivity,
resulting
5.9%
apparent
quantum
efficiency
at
365
nm.
Detailed
characterizations
reveal
Au0.33Pd0.67
cocatalyst
plays
crucial
role
facilitating
photocarrier
separation
regulating
formation
active
oxygen
species.
effectively
activates
lattice
TiO2,
which
localized
oxidant
promote
dissociation
through
photoassisted
Mars-van
Krevelen
mechanism.
Additionally,
facilitates
dioxygen
reduction
ensures
rapid
replenishment
lattice,
thereby
yield
formation.
This
work
provides
valuable
insights
designing
composite
photocatalysts
dehydrogenation.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 22, 2025
The
direct
photocatalytic
oxidation
of
methane
to
value-added
chemicals
has
garnered
considerable
interest
in
recent
years.
However,
achieving
high
productivity
while
maintaining
selectivity
at
an
appreciable
conversion
rate
remains
a
formidable
challenge.
Here,
we
present
photochemically-triggered
and
photothermally-enhanced
oxidative
coupling
multi-carbon
C2+
alkanes
over
Au
CeO2
nanoparticle-decorated
ZnO
photocatalyst,
which
exhibits
record-breaking
production
17,260
μmol
g−1
h−1
with
~90%
under
wide-spectrum
light
irradiation
without
secondary
source
heating.
Comprehensive
characterizations
computational
studies
reveal
that
CH4
activation
is
photochemical
reaction
initiated
by
ultraviolet
light-excited
ZnO,
the
introduction
substantially
enhances
O2
due
cooperative
interaction
between
CeO2.
Concurrently,
nanoparticles
capture
visible
near-infrared
generate
localized
heating,
greatly
promotes
subsequent
desorption
produced
methyl
radical
for
C–C
prior
undergoing
further
undesired
overoxidation.
Achieving
both
activity
photooxidation
hydrocarbons
challenging.
This
work
shows
integrating
photothermal
effects
both,
enabling
efficient
alkanes.
Catalysis Science & Technology,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
study
presents
an
effective
synergistic
mechanism
between
plasma
and
light
in
gold-modified
TiO
2
materials
for
the
direct
conversion
of
methane
into
value-added
C
2+
hydrocarbons.
The Journal of Physical Chemistry Letters,
Год журнала:
2025,
Номер
16(6), С. 1424 - 1431
Опубликована: Янв. 31, 2025
Dual-metal
site
catalysts
(DMSCs)
supported
on
nitrogen-doped
graphene
have
shown
great
potential
in
heterogeneous
catalysis
due
to
their
unique
properties
and
enhanced
efficiency.
However,
the
precise
control
stabilization
of
metal
dimers,
particularly
oxygen
activation
reactions,
present
significant
challenges
practical
applications.
In
this
study,
we
integrate
high-throughput
density
functional
theory
calculations
with
machine
learning
techniques
predict
optimize
catalytic
DMSCs.
Transfer
is
employed
enhance
model's
generalization
capability,
successfully
predicting
performance
across
new
combinations.
Additionally,
application
SISSO
method
enables
derivation
interpretable
symbolic
regression
models,
revealing
critical
correlations
between
electronic
structure
features
This
approach
not
only
advances
understanding
dual-metal
but
also
provides
a
novel
framework
for
systematic
design
optimization
highly
efficient
catalysts,
broad
applicability
science.
ABSTRACT
Methane,
recognized
as
a
promising
substitute
for
conventional
fossil
fuels
due
to
its
abundant
availability,
low
cost,
and
high
energy
density,
can
be
converted
into
value‐added
products,
providing
sustainable
energy–carbon
utilization
approach.
However,
inert
molecules
require
significant
C–H
bond
activation.
Photocatalytic
conversion
offers
an
effective
mild‐condition
solution,
reducing
thermocatalysis
demands
enhancing
activation
efficiency
selective
chemical
production.
This
review
systematically
arranges
photocatalytic
mechanisms,
categorizes
discusses
challenges,
prospects,
solutions
methane
photocatalysis
development.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 17, 2025
Abstract
In
this
work,
a
CdTe@TiO
2
single
atoms
(SAs)
catalysts
is
successfully
synthesized,
realizing
unique
portion
of
nonbonding
oxygen‐coordinated
configuration
Cd─O─Te
dimers
coupling.
Astonishingly,
the
5th
(0.027
min
−1
)
shows
progressively
augmenting
phenomenon,
accompanied
with
2.73
times
higher
than
that
fresh
(0.010
on
photocatalytic
rate
constant
gaseous
toluene
conversion.
The
incrementally
enhanced
activity
attributed
to
atomically
dispersed
Cd/Te
SAs
sites
generation
during
photoreduction
process,
and
further
leading
optimized
electron
interactions
between
Cd,
Te
atoms,
TiO
NTs
causing
positive
shift
in
d‐band
center
closer
Fermi
level.
Density
Functional
Theory
(DFT)
calculations
reveal
increasing
phenomenon
can
mutually
elevate
electronic
density
around
generate
substantial
local
electric
field
at
interface.
essence,
free
energy
barriers
benzene
intermediates
ring‐opening
as
rate‐determining
step
appeared
significantly
diminish
tendency
from
1.10
0.96
eV,
line
ICOHP
calculation
Cd/Te─O
bonds
TS
promoted
−2.43
−3.49
eV.
This
work
unearths
mechanism
for
ascendant
states
synergies
dual‐metal
sites,
providing
versatile
strategy
tailor
solar
