ACS Catalysis,
Год журнала:
2024,
Номер
14(13), С. 10214 - 10222
Опубликована: Июнь 21, 2024
Various
decarbonylation
reactions
via
oxidative
addition
of
carbonyl
compounds
to
metal
catalysts
can
be
applied
late-stage
modification
and
have
been
actively
studied
date;
however,
several
inherent
problems
derived
from
the
are
difficult
solve,
such
as
toxic
CO
production,
deactivation
by
adsorption,
intolerance
some
functional
groups,
or
air-sensitivity
catalysts.
In
this
context,
formal
decarbonylation,
which
eliminates
other
without
involving
addition,
is
attractive
but
hardly
reported,
especially
using
heterogeneous
Herein,
diaryl
1,2-diketones
afford
monoketones
CeO2
a
reusable
catalyst
O2
in
air
terminal
oxidant
was
developed,
generating
CO2
only
byproduct.
The
results
revealed
that
reaction
enabled
synergistic
catalytic
effect
Lewis
acid–base
pairs
redox
properties
CeO2.
Abstract
Frustrated
Lewis
pairs
(FLPs)
present
new
opportunities
for
the
development
of
highly
active
spinel
materials
activation
stable
molecules.
Herein,
a
Ni
and
Co‐based
with
abundant
FLPs
sites
(NiCo
2
O
4
‐F)
is
synthesized
through
morphologic
defect
engineering
used
efficient
catalytic
ozonation
CH
3
SH
elimination.
Characterization
results
reveal
that
NiCo
‐F
nanoflower
structure
exposes
more
surface
oxygen
vacancies
(Ov),
inducing
local
charge
redistribution
forming
regions.
Ov
acts
as
basic
sites,
while
unsaturated
coordinated
atoms
(Ni
uc
)
act
acidic
spatially
≈4.08
Å.
The
Ov···Ni
function
“electron
shuttles”
in
reaction,
facilitating
specific
adsorption
reactants
via
dual
acidic–basic
reaction
thereby
activating
to
generate
·O
−
1
species
achieve
deep
oxidation
SH.
resulting
catalyst
exhibits
an
outstanding
removal
efficiency
94.4%,
achieving
high
mass
activity
(5.6
ppm
mg
−1
),
which
70
times
greater
than
commercial
MnO
(0.08
).
This
work
presents
promising
approach
developing
sophisticated
ozone
catalysts
by
controllable
construction
acid–base
on
surface,
enhancing
understanding
role
molecular
activation.
Energies,
Год журнала:
2024,
Номер
17(4), С. 839 - 839
Опубликована: Фев. 9, 2024
The
direct
synthesis
of
dimethyl
carbonate
(DMC)
from
methanol
and
CO2
presents
an
attractive
route
to
turn
abundant
into
value-added
chemicals.
However,
insufficient
DMC
yields
arise
due
the
inert
nature
limitations
reaction
equilibrium.
Oxygen
vacancies
are
known
facilitate
activation
improve
catalytic
performance.
In
this
work,
we
have
demonstrated
that
tuning
oxygen
in
catalysts
implementing
situ
water
removal
can
enable
highly
efficient
production
CO2.
CexZryO2
nanorods
with
were
synthesized
via
a
hydrothermal
method.
liquid-phase
synthesis,
Ce10Zr1O2
exhibited
1.7-
1.4-times
higher
yield
compared
CeO2
nanoparticles
undoped
nanorods,
respectively.
Zr
doping
yielded
CeZr
solid
solution
increased
vacancies,
promoting
adsorption
activation.
addition,
adding
2-cyanopyridine
as
organic
dehydrating
agent
achieved
outstanding
87%
conversion
>99%
selectivity
by
shifting
equilibrium
desired
product.
Moreover,
mixing
hydrophobic
fumed
SiO2
gas-phase
led
doubling
yield.
This
significant
increase
was
attributed
faster
diffusion
molecules
away
catalyst
surface,
facilitated
SiO2.
study
illustrates
effective
dual
strategy
enhancing
boost
also
be
applied
other
reactions
impacted
accumulation.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(34), С. 16011 - 16017
Опубликована: Авг. 15, 2024
A
porous
metal–organic
framework
(MOF)-based
frustrated
Lewis
pairs
(FLPs)
were
prepared
via
a
ligand
replacement
strategy
to
generate
organic
linker
defects
in
zirconium-based
MOF
(MOF-808),
thereby
exposing
Zr
sites
as
acid.
Due
the
rigid
features
of
skeleton,
unsaturated
metal
cluster
and
adjacent
lattice
oxygen
(Lewis
bases)
are
sterically
hindered
positions,
which
formed
FLP
with
efficient
H2
activation
ability.
This
heterogeneous
catalyst
[MOF-808-OH
(15%)]
exhibits
high
performance
styrene
hydrogenation
ethylbenzene
99%
yield.
The
structural
stability
reusability
enabled
maintain
an
over
98%
activity
after
five
cycles.
work
provides
defect
modulation
prepare
MOF-based
solid
catalysts.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 26, 2025
Abstract
Optimizing
the
binding
sites
of
substrates
for
small
molecules
activation
plays
a
crucial
role
in
enzyme‐like
catalysts
design.
Herein,
frustrated
Lewis
pairs
(FLPs)
are
successfully
constructed
through
boron
(B)
doping
into
CoO
x
(CoBO
)
with
abundant
oxygen
vacancies
(O
v
).
The
O
optimizes
valence
active
sites,
creates
coordinatively
unsaturated
state,
and
elongates
distance
pairs.
electron‐deficient
acid
(LA)
(Co)
facilitate
adsorption
dissociation
2
,
electron‐rich
base
(LB)
(O)
draw
positively
charged
TMB
closer
to
Co
shorten
reaction
distance,
which
synergistically
improve
oxidase
(OXD)‐like
activity.
Besides,
increase
electron
density
induced
by
FLPs
promotes
electrons
transfer,
intermediates
stabilization,
decreases
energy
barrier
rate‐determining
step
.
Significantly,
proof‐of‐concept
application
colorimetric
biosensing
platform,
as‐developed
CoBO
demonstrate
highly
sensitive
selective
detection
capacity
dopamine
(DA)
targets.
This
work
verifies
possibility
activating
catalysis.
