ACS Catalysis,
Год журнала:
2023,
Номер
13(20), С. 13756 - 13767
Опубликована: Окт. 11, 2023
The
inferior
stability
of
noble
metal-based
thermocatalysts
for
effective
catalytic
hydrogenation
reaction
severely
restricts
the
production
value-added
fine
chemicals
under
a
strong
acid
environment.
Herein,
shield
effect
strategy
is
proposed
to
establish
ultrafine
metal
NPs
with
oxidation
layers
encapsulated
in
S-
and
N-doped
graphene
robust
coupling-efficient
acid-catalyzed
Bamberger
rearrangement
nitrobenzene
p-aminophenol.
unconventional
structure
based
on
comprises
an
oxide
layer
dislocation
tensile
strain,
enabling
sluggish
dissociation
H2
H*,
coupled
local
electron-enriched
S,N-doped
shell,
restraining
ultrafast
rate
form
aniline
enhancing
catalyst.
In
addition,
experimental
characterization
density
functional
theory
simulation
further
manifest
that
oxidizing
nitric
reconstitutes
charge
rendering
it
highly
specific
phenylhydroxylamine
obtain
p-aminophenol
high
selectivity.
this
work
showcases
universal
practicable
method
pinpoint
modulation
inherent
performance
attainable
nanoparticles
programmable
shell
microenvironment
toward
catalysis
Abstract
Single‐atom
catalysts
(SACs)
are
widely
employed
in
Fenton‐like
catalysis,
yet
guidelines
for
their
high‐performance
design
remain
elusive.
The
Sabatier
principle
provides
guidance
the
ideal
catalyst
with
highest
activity.
Herein,
study
meticulously
engineered
a
series
of
SACs
featuring
broad
distribution
d‐band
center
through
single‐atom
coordination
engineering,
facilitating
comprehensive
exploration
relationship
catalysis.
A
volcanic
correlation
between
centers
and
catalytic
activity
is
identified.
Theoretical
experimental
results
show
that
moderate
peroxymonosulfate
adsorption
energy
can
lead
to
lowest
reaction
barriers
rate‐determining
step
generating
singlet
oxygen,
thus
enhancing
efficiency
toward
optimum.
As
proof
concept,
Fe‐N
2
O
/C
demonstrates
degradation
rate
constant
1.89
min
−1
,
surpassing
4
by
3.2
times
Fe‐O
272
times.
Moreover,
shows
exceptional
tolerance
various
environmental
challenges,
providing
opportunities
achieving
nearly
eco‐friendly
pollutant
degradation.
findings
reveal
how
use
guide
advanced
efficient
removal.
Advanced Materials,
Год журнала:
2024,
Номер
36(35)
Опубликована: Июль 14, 2024
Precise
control
over
the
size,
species,
and
breakthrough
of
activity-selectivity
trade-off
are
great
challenges
for
sub-nano
non-noble
metal
catalysts.
Here,
first
time,
a
"multiheteroatom
induced
SMSI
+
in
situ
P
activation"
strategy
that
enables
high
stability
effective
construction
sub-2
nm
sites
optimizing
selective
hydrogenation
performance
is
developed.
It
synthesized
smallest
phosphide
clusters
(<2
nm)
including
from
unary
to
ternary
systems,
accompanied
by
unprecedented
thermal
stability.
In
proof-of-concept
demonstration,
further
modulation
size
species
results
creation
site
platform,
directionally
achieving
single
atom
(Ni
ACS Catalysis,
Год журнала:
2023,
Номер
13(20), С. 13756 - 13767
Опубликована: Окт. 11, 2023
The
inferior
stability
of
noble
metal-based
thermocatalysts
for
effective
catalytic
hydrogenation
reaction
severely
restricts
the
production
value-added
fine
chemicals
under
a
strong
acid
environment.
Herein,
shield
effect
strategy
is
proposed
to
establish
ultrafine
metal
NPs
with
oxidation
layers
encapsulated
in
S-
and
N-doped
graphene
robust
coupling-efficient
acid-catalyzed
Bamberger
rearrangement
nitrobenzene
p-aminophenol.
unconventional
structure
based
on
comprises
an
oxide
layer
dislocation
tensile
strain,
enabling
sluggish
dissociation
H2
H*,
coupled
local
electron-enriched
S,N-doped
shell,
restraining
ultrafast
rate
form
aniline
enhancing
catalyst.
In
addition,
experimental
characterization
density
functional
theory
simulation
further
manifest
that
oxidizing
nitric
reconstitutes
charge
rendering
it
highly
specific
phenylhydroxylamine
obtain
p-aminophenol
high
selectivity.
this
work
showcases
universal
practicable
method
pinpoint
modulation
inherent
performance
attainable
nanoparticles
programmable
shell
microenvironment
toward
catalysis
