Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: Aug. 11, 2023
Abstract
Highly
selective
photoreduction
of
CO
2
to
valuable
hydrocarbons
is
great
importance
achieving
a
carbon‐neutral
society.
Precisely
manipulating
the
formation
Metal
1
⋅⋅⋅C=O⋅⋅⋅Metal
(M
⋅⋅⋅C=O⋅⋅⋅M
)
intermediate
on
photocatalyst
interface
most
critical
step
for
regulating
selectivity,
while
still
significant
challenge.
Herein,
inspired
by
polar
electronic
structure
feature
molecule,
we
propose
strategy
whereby
Lewis
acid‐base
dual
sites
confined
in
bimetallic
catalyst
surface
are
conducive
forming
M
precisely,
which
can
promote
selectivity
hydrocarbon
formation.
Employing
Ag
Cu
O
3
nanowires
with
abundant
Cu⋅⋅⋅Ag
preferred
exposed
{110}
as
model
catalyst,
100
%
toward
into
CH
4
has
been
achieved.
Subsequent
surface‐quenching
experiments
and
density
functional
theory
(DFT)
calculations
verify
that
do
play
vital
role
considered
be
prone
convert
hydrocarbons.
This
study
reports
highly
photocatalyst,
was
designed
basis
newly
proposed
precise
regulation
reaction
intermediates.
Our
findings
will
stimulate
further
research
dual‐site
design
reduction
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: June 30, 2023
Photoconversion
of
CO2
and
H2
O
into
ethanol
is
an
ideal
strategy
to
achieve
carbon
neutrality.
However,
the
production
with
high
activity
selectivity
challenging
owing
less
efficient
reduction
half-reaction
involving
multi-step
proton-coupled
electron
transfer
(PCET),
a
slow
C-C
coupling
process,
sluggish
water
oxidation
half-reaction.
Herein,
two-dimensional/two-dimensional
(2D/2D)
S-scheme
heterojunction
consisting
black
phosphorus
Bi2
WO6
(BP/BWO)
was
constructed
for
photocatalytic
benzylamine
(BA)
oxidation.
The
as-prepared
BP/BWO
catalyst
exhibits
superior
performance
toward
reduction,
yield
61.3
μmol
g-1
h-1
(selectivity
91
%).In
situ
spectroscopic
studies
theoretical
calculations
reveal
that
can
effectively
promote
photogenerated
carrier
separation
via
Bi-O-P
bridge
accelerate
PCET
process.
Meanwhile,
electron-rich
BP
acts
as
active
site
plays
vital
role
in
process
coupling.
In
addition,
substitution
BA
further
enhance
C2
H5
OH.
This
work
opens
new
horizon
exploring
novel
heterogeneous
photocatalysts
photoconversion
OH
based
on
cooperative
photoredox
systems.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(48)
Published: Oct. 6, 2023
Atomically
precise
Cu
clusters
are
highly
desirable
as
catalysts
for
CO2
reduction
reaction
(CO2
RR),
and
they
provide
an
appropriate
model
platform
elaborating
their
structure-activity
relationship.
However,
efficient
overall
photocatalytic
RR
with
H2
O
using
assembled
Cu-cluster
aggregates
single
component
photocatalyst
has
not
been
reported.
Herein,
we
report
a
stable
crystalline
Cu-S-N
cluster
local
protonated
N-H
groups
(denoted
Cu6
-NH).
The
catalyst
exhibits
suitable
redox
potentials,
high
structural
stability,
active
catalytic
species,
narrow
band
gap,
which
account
its
outstanding
performance
under
visible
light,
≈100
%
selectivity
CO
evolution.
Remarkably,
systematic
isostructural
control
experiments,
in
situ
infrared
spectroscopy,
density
functional
theory
calculations
revealed
that
the
pyrimidine
N
atoms
-NH
act
proton
relay
station,
providing
during
RR.
This
efficiently
lowers
energy
barrier
formation
of
*COOH
intermediate,
is
rate-limiting
step,
enhancing
performance.
work
lays
foundation
development
atomically
metal-cluster-based
photocatalysts.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 5, 2024
Abstract
Photothermal
CO
2
conversion
to
ethanol
offers
a
sustainable
solution
for
achieving
net-zero
carbon
management.
However,
serious
carrier
recombination
and
high
C-C
coupling
energy
barrier
cause
poor
performance
in
generation.
Here,
we
report
Cu/Cu
Se-Cu
O
heterojunction-nanosheet
array,
showcasing
good
yield
under
visible–near-infrared
light
without
external
heating.
The
Z-scheme
Cu
heterostructure
provides
spatially
separated
sites
reduction
water
oxidation
with
boosted
transport
efficiency.
microreactors
induced
by
Se
nanosheets
improve
the
local
concentration
of
intermediates
(CH
3
*
CO*),
thereby
promoting
process.
effect
elevates
system’s
temperature
around
200
°
C.
Through
synergizing
electron
heat
flows,
achieve
an
generation
rate
149.45
µmol
g
−1
h
,
selectivity
48.75%
apparent
quantum
0.286%.
Our
work
can
serve
as
inspiration
developing
photothermal
catalysts
into
multi-carbon
chemicals
using
solar
energy.
Advanced Materials,
Journal Year:
2022,
Volume and Issue:
35(5)
Published: Dec. 5, 2022
Obtaining
multi-carbon
products
via
CO2
photoreduction
is
a
major
catalytic
challenge
involving
multielectron-mediated
CC
bond
formation.
Complex
design
of
multicomponent
interfaces
that
are
exploited
to
achieve
this
chemical
transformation,
often
leads
untraceable
deleterious
changes
in
the
interfacial
environment
affecting
conversion
efficiency
and
product
selectivity.
Alternatively,
robust
metal
centers
having
asymmetric
charge
distribution
can
effectuate
coupling
reaction
through
stabilization
intermediates,
for
desired
However,
generating
inherent
single
component
catalyst
difficult
material
challenge.
Here,
novel
photocatalyst,
Bi19
S27
Cl3
,
presented
which
selectively
converts
C2
product,
ethanol,
high
yield
under
visible
light
irradiation.
Structural
analysis
transmission
electron
microscopy,
X-ray
diffraction,
photoelectron
spectroscopy,
absorption
spectroscopy
reveals
presence
polarized
bismuth
.
The
intrinsic
electric
field
induced
by
renders
better
separation
photogenerated
electron-hole
pair.
Furthermore,
adsorption
CO*
intermediate
accelerate
rate
determining
step
formation
OCCOH
intermediate.
Formation
these
intermediates
experimentally
mapped
situ
Fourier-transform
infrared
further
confirmed
theoretical
calculation.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(9)
Published: Dec. 20, 2022
We
present
surface
reconstruction-induced
C-C
coupling
whereby
CO2
is
converted
into
ethylene.
The
wurtzite
phase
of
CuGaS2.
undergoes
in
situ
reconstruction,
leading
to
the
formation
a
thin
CuO
layer
over
pristine
catalyst,
which
facilitates
selective
conversion
ethylene
(C2
H4
).
Upon
illumination,
catalyst
efficiently
converts
C2
with
75.1
%
selectivity
(92.7
terms
Relectron
)
and
20.6
μmol
g-1
h-1
evolution
rate.
Subsequent
spectroscopic
microscopic
studies
supported
by
theoretical
analysis
revealed
operando-generated
Cu2+
,
assistance
existing
Cu+
functioning
as
an
anchor
for
generated
*CO
thereby
facilitating
coupling.
This
study
demonstrates
strain-induced
reconstruction
heterojunction
formation,
finetunes
oxidation
state
Cu
modulates
reduction
reaction
pathway
