ACS Nano,
Год журнала:
2024,
Номер
18(13), С. 9670 - 9677
Опубликована: Март 22, 2024
Employing
water
as
a
hydrogen
source
to
participate
in
the
atom
transfer
(HAT)
process
is
low-cost
and
carbon-free
demonstrating
great
economic
environmental
potential
catalysis.
However,
low
efficiency
of
abstraction
from
leads
slow
kinetics
HAT
for
most
hydrogenative
reactions.
Here,
we
prepared
ultrathin
Bi4O5Cl2
nanosheets
where
surface
can
be
situ
reconstructed
via
hydroxylation
under
light
illumination
facilitate
atoms
pure
efficient
nitrogen
fixation.
Consequently,
isotope
labeling
Fourier-transform
infrared
spectroscopy
(FT-IR)
involving
H2O
D2O
has
clearly
revealed
that
hydroxyl
groups
tend
adsorbed
on
chloride
vacancy
sites
form
hydroxylated
surfaces,
photocatalyst
enables
partial
dehydrogenation
into
H2O2,
allowing
utilization
H
N2
hydrogenation
steps.
This
work
elucidates
in-depth
reaction
mechanism
extraction
molecules
light-generated
promote
photocatalytic
fixation,
ultimately
enabling
inspiration
providing
crucial
rules
design
important
functional
materials
efficiently
deliver
active
chemical
synthesis.
ACS Catalysis,
Год журнала:
2022,
Номер
12(16), С. 10004 - 10017
Опубликована: Авг. 2, 2022
Semiconductor-based
photocatalysis
is
an
ideal
method
for
air
purification
by
eliminating
nitrogen
oxide
(NO).
However,
sluggish
carrier
separation,
photocatalysts
deactivation
and
incomplete
oxidation
are
significant
bottlenecks
photocatalytic
treatment
of
indoor
pollutant
NO.
Herein,
ZnO
with
assorted
structures
fabricated
undergoes
further
modification
deliberate
surface
defect
constructions.
Utilized
flux
agents
during
the
synthesis
provide
a
more
feasible
reducing
atmosphere,
under
which
spontaneous
generations
vacancies
become
easier,
gradient
concentrations
precisely
controlled.
Photocatalyst
characterizations
affirm
successful
creation
defects,
evaluated
solar-light-driven
NO
(ppb
level)
removal
investigations.
Results
showed
that
rich
in
oxygen
(VO-rich
ZnO)
exhibited
5.43
1.63
times
enhanced
fewer
toxic
product
NO2
formations
than
its
counterparts
pristine
VO-poor
ZnO,
respectively.
Importantly,
higher
VO
on
unusual
nonpolar
facets,
VO-rich
does
not
only
display
conversion,
but
also
shows
unselective
process
producing
NO3–.
The
plausible
reaction
mechanisms
promoted
conversions
investigated
based
VO,
well-positioned
band
structures,
separations.
facilitate
molecular
activation,
leading
to
strong
oxidant
superoxide
radicals
(·O2–),
contributing
improved
efficiency.
Adsorption
small
molecules
(O2,
H2O
NO)
defective
was
density
functional
theory
(DFT)
calculations,
validated
adsorption/activation
O2,
contributed
conversions.
Advanced Materials,
Год журнала:
2022,
Номер
34(37)
Опубликована: Июль 21, 2022
A
universal
atomic
layer
confined
doping
strategy
is
developed
to
prepare
Bi24
O31
Br10
materials
incorporating
isolated
Cu
atoms.
The
local
polarization
can
be
created
along
the
CuOBi
interface,
which
enables
better
electron
delocalization
for
effective
N2
activation.
optimized
Cu-Bi24
layers
show
5.3×
and
88.2×
improved
photocatalytic
nitrogen
fixation
activity
than
bulk
,
respectively,
with
NH3
generation
rate
reaching
291.1
µmol
g-1
h-1
in
pure
water.
polarized
Cu-Bi
site
pairs
increase
non-covalent
interaction
between
catalyst's
surface
molecules,
then
further
weaken
covalent
bond
order
NN.
As
a
result,
hydrogenation
pathways
altered
from
associative
distal
pathway
alternating
.
This
provides
an
accessible
designing
metal
or
tuning
order.
ACS Catalysis,
Год журнала:
2022,
Номер
12(22), С. 14015 - 14025
Опубликована: Окт. 31, 2022
Identifying
the
dynamic
structural
changes
of
active
sites
in
a
catalytic
reaction
under
realistic
working
conditions
is
great
challenge.
In
this
work,
we
demonstrate
that
situ
electron
paramagnetic
resonance
(EPR)
technology
an
important
technique
for
electronic-level
recognition
evolution
over
defective
BiOCl
catalyst
during
gas–solid
photocatalytic
reaction.
The
formation
and
recovery
photoexcited
oxygen
vacancies
(PE-OVs)
with
or
without
UV
light
irradiation
are
experimentally
verified,
these
can
be
defined
as
photoswitchable
OVs.
OVs
could
function
genuine
to
activate
O2
molecules
via
directional
single-electron
transfer
from
px
pz
Bi
6p
π2py*
molecules.
FT-IR
spectra
elucidate
PE-OVs
were
available
promote
conversion
intermediates
final
product.
Thus,
identified
photocatalysis
reactions,
challenging
common
view
static
sites.
This
work
provides
innovative
concept
defects
real
catalysis
reactions.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5779 - 5787
Опубликована: Апрель 1, 2024
Photocatalytic
dinitrogen
(N2)
fixation
is
regarded
as
an
achievable
technology
for
ammonia
(NH3)
production.
However,
the
poor
separation
efficiency
of
photoinduced
carriers
and
ineffective
N2
activation
remain
grand
obstacles
to
high-performance
NH3
photosynthesis.
Designing
advanced
heterostructured
systems
accelerate
charge
activate
molecule
a
feasible
strategy
optimize
photocatalytic
activity.
Herein,
direct
Z-scheme
configuration
established
between
BiOBr
Bi4O5Br2
through
facile
one-step
solvothermal
reaction.
This
enables
effective
spatial
electron–hole
pairs
preserves
robust
redox
ability
carriers,
concurrently
promoting
N≡N
bond
diminishing
energy
barrier
rate-determining
step.
The
formation
BiOBr/Bi4O5Br2
heterojunctions
mostly
attributed
similarities
in
their
lattice
structures
crystal
growth
conditions.
As
result,
heterojunction
exhibits
high
yield
66.87
μmol
g–1
h–1
without
using
sacrificing
reagents,
surpassing
that
pristine
by
approximately
3.3
5.6
times,
respectively.
study
provides
approach
construct
implementing
under
mild
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(24)
Опубликована: Фев. 19, 2024
Abstract
Photocatalytic
nitrogen
reduction
represents
a
viable
technology
for
green
ammonia
synthesis
under
mild
conditions.
However,
the
performance
of
photocatalysts
is
typically
limited
by
high
charge
carrier
recombination
and
low
adsorption
activation
molecules.
Herein,
Bi/Bi
2
Sn
O
7
(Bi/BSO)
heterojunction
nanocomposites
are
prepared
via
one‐step
hydrothermal
method,
where
NaOH
etching
oxygen
vacancies
in
Bi─O
bonds
Bi
(BSO)
exploited
situ
formation
metallic
hence
Schottky
junctions
with
semiconducting
BSO.
This
leads
to
separation
rate
photogenerated
carriers.
Consequently,
compared
pure‐phase
BSO,
Bi/BSO
heterostructures
exhibit
markedly
enhanced
production,
reaching
an
optimum
284.5
µmol
g
−1
h
,
rectifying
contact
between
BSO
facilitates
directional
electron
transfer,
leading
enrichment
electrons
at
active
sites
Bi.
First‐principles
calculations
confirm
alteration
guided
flow
surface
vacancies.
Results
from
this
study
offer
effective
paradigm
structural
engineering
manipulating
photocatalytic
activity
bismuth‐based
pyrochlore
materials
toward
fixation
ammonia.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(24)
Опубликована: Апрель 17, 2023
Seawater
is
one
of
the
most
important
CO2
sequestration
media
for
delivering
value-added
chemicals/fuels
and
active
chlorine;
however,
this
scenario
plagued
by
sluggish
reaction
rates
poor
product
selectivity.
Herein,
we
first
report
synthesis
nitrogen-doped
BiOCl
atomic
layers
to
directly
split
carbon-sequestrated
natural
seawater
(Yellow
Sea,
China)
into
stoichiometric
CO
(92.8
μmol
h-1
)
HClO
(83.2
under
visible
light
with
selectivities
greater
than
90
%.
Photoelectrons
enriched
on
exposed
BiOCl{001}
facet
kinetically
facilitate
-to-CO
reduction
via
surface-doped
nitrogen
bearing
Lewis
basicity.
Photoholes,
mainly
located
lateral
facets
van
der
Waals
gaps,
promote
selective
oxidation
Cl-
HClO.
Sequestrated
also
maintains
pH
at
around
4.2
prevent
alkaline
earth
cations
from
precipitating.
The
produced
can
effectively
kill
typical
bacteria
in
ballast
water
ocean-going
cargo
ships,
offering
a
green
safe
way
onsite
sterilization.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(29)
Опубликована: Март 31, 2023
Abstract
Piezocatalytic
pure
water
splitting
for
H
2
evolution
carries
the
virtues
of
efficacious
utilization
mechanical
energy,
easy
operation,
and
high
value‐added
products,
while
lacking
desirable
piezoelectrics
chemical
energy
production.
Here,
two
polar
layered
bismuth‐rich
oxyhalides
Bi
4
O
5
X
(XBr,
I)
thin
nanosheets
(≈4
nm)
are
first
exploited
as
efficient
piezocatalysts
to
be
capable
dissociating
water.
The
unique
asymmetrical
structures
composed
interleaved
[Bi
]
2+
layer
double
−
ions
slabs
along
[1
0
1_]
orientation
cause
large
intrinsic
dipole
moment,
excellent
piezoelectricity
deformation.
Without
any
cocatalyst
sacrificial
agent,
Br
I
display
remarkable
piezocatalytic
production
rate
1149.0
764.5
µmol
g
−1
h
,
respectively,
standing
among
best
piezocatalysts,
accompanied
by
hydroxyl
radicals
(·OH)
oxidative
products.
smaller
radius
higher
electronegativity
than
a
more
strongly
crystal
structure
in
contributing
activity
compared
.
This
study
broadens
scope
piezoelectric
materials
applied
sustainable
catalysis
efficiently
converting
illustrates
importance
configuration
composition
fabricating
systems.