Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 3396 - 3404
Опубликована: Янв. 24, 2024
Covalent
organic
frameworks
(COFs),
with
the
features
of
flexible
structure
regulation
and
easy
introduction
functional
groups,
have
aroused
broad
interest
in
field
photocatalysis.
However,
due
to
low
light
absorption
intensity,
photoelectron
conversion
efficiency,
lack
suitable
active
sites,
it
remains
a
great
challenge
achieve
efficient
photocatalytic
aerobic
oxidation
reactions.
Herein,
based
on
reticular
chemistry,
we
rationally
designed
series
three-motif
molecular
junction
type
COFs,
which
formed
dual
photosensitizer
coupled
redox
junctions
containing
multifunctional
COF
photocatalysts.
Significantly,
strong
adsorption
ability
units
integrated
reduction
features,
PY-BT
exhibited
highest
activity
for
oxidation.
Especially,
achieved
benzylamine
efficiency
99.9%
2.5
h,
is
much
higher
than
that
two-motif
only
one
or
unit
lacking
COFs.
The
mechanism
selective
was
studied
through
comprehensive
experiments
density
theory
calculations.
results
showed
photoinduced
electron
transfer
occurred
from
PY
then
triphenylamine
BT.
Furthermore,
thermodynamics
energy
lower
others,
confirmed
synergistic
effect
This
work
provided
new
strategy
design
COFs
also
represented
insight
into
catalytic
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Май 25, 2022
Methane
(CH4)
oxidation
to
high
value
chemicals
under
mild
conditions
through
photocatalysis
is
a
sustainable
and
appealing
pathway,
nevertheless
confronting
the
critical
issues
regarding
both
conversion
selectivity.
Herein,
visible
irradiation
(420
nm),
synergy
of
palladium
(Pd)
atom
cocatalyst
oxygen
vacancies
(OVs)
on
In2O3
nanorods
enables
superior
photocatalytic
CH4
activation
by
O2.
The
optimized
catalyst
reaches
ca.
100
μmol
h-1
C1
oxygenates,
with
selectivity
primary
products
(CH3OH
CH3OOH)
up
82.5%.
Mechanism
investigation
elucidates
that
such
induced
dedicated
function
Pd
single
atoms
boosting
hole
electron
transfer,
respectively.
O2
proven
be
only
source
for
CH3OH
production,
while
H2O
acts
as
promoter
efficient
·OH
production
facilitates
product
desorption
indicated
DFT
modeling.
This
work
thus
provides
new
understandings
simultaneous
regulation
activity
cocatalysts
vacancies.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
144(2), С. 740 - 750
Опубликована: Дек. 20, 2021
Direct
and
efficient
oxidation
of
methane
to
methanol
the
related
liquid
oxygenates
provides
a
promising
pathway
for
sustainable
chemical
industry,
while
still
remaining
an
ongoing
challenge
owing
dilemma
between
activation
overoxidation.
Here,
ZnO
with
highly
dispersed
dual
Au
Cu
species
as
cocatalysts
enables
selective
photocatalytic
conversion
one-carbon
(C1)
using
O2
oxidant
operated
at
ambient
temperature.
The
optimized
AuCu-ZnO
photocatalyst
achieves
up
11225
μmol·g-1·h-1
primary
products
(CH3OH
CH3OOH)
HCHO
nearly
100%
selectivity,
resulting
in
14.1%
apparent
quantum
yield
365
nm,
much
higher
than
previous
best
photocatalysts
reported
oxygenates.
In
situ
EPR
XPS
disclose
that
serve
photoinduced
electron
mediators
promote
•OOH,
simultaneously
is
hole
acceptor
enhance
H2O
•OH,
thus
synergistically
promoting
charge
separation
transformation.
This
work
highlights
significances
co-modification
suitable
on
simultaneous
regulation
activity
selectivity.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(15), С. 4878 - 4932
Опубликована: Янв. 1, 2023
Recently,
the
missing
link
between
homogeneous
and
heterogeneous
catalysis
has
been
found
it
was
named
single-atom
(SAC).
However,
SAC
field
still
faces
important
challenges,
one
of
which
is
controlling
bonding/coordination
single
atoms
support
in
order
to
compensate
for
increase
surface
energy
when
particle
size
reduced
due
atomic
dispersion.
Excellent
candidates
meet
this
requirement
are
carbon
nitride
(CN)-based
materials.
Metal
can
be
firmly
trapped
nitrogen-rich
coordination
sites
CN
materials,
makes
them
a
unique
class
hosts
preparing
catalysts
(SACs).
As
most
promising
two-dimensional
supports
stabilize
isolated
metal
atoms,
materials
have
increasingly
employed
SACs.
Herein,
we
will
cover
recent
advances
single-atoms
supported
by
In
review,
characterization
techniques
challenges
faced
topic
discussed,
commonly
synthetic
methods
delineated
different
Finally,
catalytic
performance
SACs
based
on
nitrides
reviewed
with
special
focus
their
photocatalytic
applications.
particular,
prove
as
non-innocent
support.
The
relationship
two-way,
where
change
electronic
properties
support,
while
features
matrix
tune
activity
reactions.
highlight
frontiers
field,
including
analytical
method
development,
truly
controlled
methods,
allowing
fine
control
loading
multi-element
synthesis,
how
understanding
two-way
exchange
behind
push
next
level.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(21)
Опубликована: Март 3, 2022
Regulating
the
distribution
of
reactive
oxygen
species
generated
from
H2
O2
activation
is
prerequisite
to
ensuring
efficient
and
safe
use
in
chemistry
life
science
fields.
Herein,
we
demonstrate
that
constructing
a
dual
Cu-Fe
site
through
self-assembly
single-atomic-layered
Cu5
nanoclusters
onto
FeS2
surface
achieves
selective
with
high
efficiency.
Unlike
its
unitary
Cu
or
Fe
counterpart,
sites
residing
at
perimeter
zone
/FeS2
interface
facilitate
adsorption
barrierless
decomposition
into
⋅OH
via
forming
bridging
Cu-O-O-Fe
complex.
The
robust
situ
formation
governed
by
this
atomic-layered
catalyst
enables
effective
oxidation
several
refractory
toxic
pollutants
across
broad
pH
range,
including
alachlor,
sulfadimidine,
p-nitrobenzoic
acid,
p-chlorophenol,
p-chloronitrobenzene.
This
work
highlights
concept
building
catalytic
manipulating
on
molecular
level
towards
environmental
control
beyond.
Chemical Reviews,
Год журнала:
2023,
Номер
123(8), С. 4443 - 4509
Опубликована: Апрель 17, 2023
Energy
from
renewable
resources
is
central
to
environmental
sustainability.
Among
the
renewables,
sunlight-driven
fuel
synthesis
a
sustainable
and
economical
approach
produce
vectors
such
as
hydrogen
through
water
splitting.
The
photocatalytic
splitting
limited
by
oxidation
half-reaction,
which
kinetically
energetically
demanding
entails
designer
photocatalysts.
Such
challenges
can
be
addressed
employing
alternative
half-reactions.
Photoreforming
drive
breakdown
of
waste
plastics
biomass
into
valuable
organic
products
for
production
H2.
We
provide
an
overview
photoreforming
its
underlying
mechanisms
that
convert
polymers
H2
fuels
fine
chemicals.
This
paramount
importance
two
complementary
perspectives:
(i)
green
energy
harvesting
(ii)
sustainability
decomposing
valuables.
Competitive
results
generation
without
hazards
are
being
generated.
process,
mechanisms,
critical
assessment
field
scarce.
address
points
focusing
on
concept
up-to-date
knowledge
with
key
milestones
achieved,
uncovering
concepts
in
photoreforming,
(iii)
design
photocatalysts
pathways
use
different
polymer
wastes
substrates.
Advanced Functional Materials,
Год журнала:
2022,
Номер
32(52)
Опубликована: Окт. 17, 2022
Abstract
This
study
proposes
a
strategy
based
on
heterovalent
ion
doping
that
gives
rise
to
synergistic
piezo‐phototronic
effect
with
significantly
improved
catalytic
activity
and
leads
selective
enhancement
for
specific
pollutants.
Owing
the
enhanced
light
absorption,
hydrogen
evolution
rates
are
as
high
3704
3178
µmolg
−1
h
in
0.01Li‐doped
BaTiO
3
0.02La‐doped
nanosheets,
respectively,
under
simultaneous
irradiation
by
ultrasound
light,
factor
of
4.6
3.9
times
higher
than
pure
.
The
performance
also
far
exceeds
single
piezocatalysis,
photocatalysis,
or
sum
two
Li/La‐doped
nanosheets
due
effects
piezoelectric
field
promoting
photo‐induced
separation
electron‐hole
pairs.
Further,
carefully
selecting
donor
acceptor
doping,
significant
catalyst
pollutants
is
obtained
controlling
band
structure.
Compared
,
possesses
anionic
dyes
such
Methyl
blue
Malachite
Green,
reaching
0.067
1.379
min
while
exhibits
better
cationic
Rhodamine
B
Orange,
degradation
up
0.274
0.029
respectively.
offers
path
design
efficient
piezocatalysts
applications.