Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(41)
Published: Aug. 26, 2023
Abstract
Solar‐driven
CO
2
reduction
integrated
with
C−C/C−X
bond‐forming
organic
synthesis
represents
a
substantially
untapped
opportunity
to
simultaneously
tackle
carbon
neutrality
and
create
an
atom‐/redox‐economical
chemical
synthesis.
Herein,
we
demonstrate
the
first
cooperative
photoredox
catalysis
of
efficient
tunable
syngas,
paired
direct
alkylation/arylation
unactivated
allylic
sp
3
C−H
bonds
for
accessing
C−C
products,
over
SiO
‐supported
single
Ni
atoms‐decorated
CdS
quantum
dots
(QDs).
Our
protocol
not
only
bypasses
additional
oxidant/reductant
pre‐functionalization
substrates,
affording
broad
products
moderate
excellent
yields,
but
also
produces
syngas
CO/H
ratios
(1
:
2–5
1).
Such
win‐win
coupling
highlights
high
atom‐,
step‐
redox‐economy,
good
durability,
illuminating
tantalizing
possibility
renewable
sunlight‐driven
feedstocks
manufacturing
industry.
Journal of Materials Chemistry A,
Journal Year:
2023,
Volume and Issue:
11(8), P. 4013 - 4019
Published: Jan. 1, 2023
Cu
2
S/ZnIn
S
4
and
Ru
composites
are
constructed
to
achieve
highly
selective
divergent
synthesis
of
imines
secondary
amines
via
the
tunable
visible
light-driven
amine
dehydrogenation
coupling
reaction.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(47)
Published: Aug. 13, 2024
Abstract
Photo‐driven
cross‐coupling
of
o
‐arylenediamines
and
alcohols
has
emerged
as
an
alternative
for
the
synthesis
bio‐active
benzimidazoles.
However,
tackling
key
problem
related
to
efficient
adsorption
activation
both
coupling
partners
over
photocatalysts
towards
activity
enhancement
remains
a
challenge.
Here,
we
demonstrate
interface
synergy
strategy
by
exposed
oxygen
vacancies
(V
O
)
Pd
Lewis
acid
sites
benzimidazole
hydrogen
(H
2
coproduction
Pd‐loaded
TiO
nanospheres
with
highest
photoredox
compared
previous
works
so
far.
The
results
show
that
introduction
V
optimizes
energy
band
structure
supplies
coordinatively
unsaturated
adsorbing
activating
ethanol
molecules,
affording
acetaldehyde
active
intermediates.
acts
site,
enhancing
alkaline
amine
molecules
via
acid‐base
pair
interactions
driving
condensation
process.
Furthermore,
synergistically
promote
interfacial
charge
transfer
separation.
This
work
offers
new
insightful
guidance
rational
design
semiconductor‐based
at
molecular
level
high‐performance
renewable
fuels
value‐added
feedstocks.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4581 - 4592
Published: March 12, 2024
The
integration
of
solar-driven
H2
evolution
with
the
selective
conversion
biomass-derived
alcohols
into
value-added
chemicals
has
gained
significant
attention
for
full
use
electrons
and
holes.
We
develop
a
dual-functional
photocatalyst
highly
oxidation
Cα–H
bond
benzyl
alcohol
to
C–C
coupled
products
(hydrobenzoin
deoxybenzoin),
in
cooperation
evolution,
using
point-to-face
interface
engineering
by
decorating
CdS
quantum
dots
on
Zn2In2S5
nanosheets
(CdS
QDs/Zn2In2S5
NS).
NS
exhibit
high
rate
13
mmol
g–1
h–1
formation
10.8
96.3%
selectivity.
Benzyl
achieves
91%
an
89%
yield
gram-scale.
introduction
enhances
interfacial
contact,
facilitating
efficient
spatial
separation
photogenerated
electron–hole
pairs
providing
active
sites
evolution.
In
situ
characterization
DFT
calculation
reveal
that
carbon-centered
radical
•CH(OH)C6H5,
generated
abstracting
alcohol,
is
reactive
intermediate
photocatalytic
process.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
15(1), P. 129 - 138
Published: Dec. 16, 2024
Semiconductor-based
photocatalysis
has
evolved
over
the
past
decade
into
a
prevalent
approach
for
alcohol
oxidation
to
afford
corresponding
carbonyl
compounds
or
C–C/C–O
coupled
products.
Nonetheless,
photocatalytic
oxidative
lactonization
of
diols
lactones
still
significantly
lags
behind,
even
though
represent
class
ring
moieties
with
excellent
biological
activities.
In
this
work,
we
present
high-performance
visible-light-mediated
and
H2
Ti3C2Tx
MXene-supported
CdS
quantum
dots
(QDs)
Ni
decoration
(Ni/CdS/Ti3C2Tx).
acts
as
two-dimensional
platform
immobilizing
promote
separation
migration
charge
carriers,
while
concomitantly
Cd2+
confinement
effect
retards
hole-induced
photocorrosion
CdS.
The
unique
modifications
atomically
dispersed
species
are
either
incorporated
clusters
in
accelerate
evolution,
anchored
single
atom
on
efficient
adsorption
cyclization
diols.
optimized
Ni/CdS/Ti3C2Tx
exhibits
remarkably
enhanced
activity
lactone
synthesis,
which
is
80.4
times
higher
than
that
blank
CdS,
along
selectivity
high
durability.
This
work
brings
conceptual
idea
overcome
well-known
intrinsic
drawback
photoinduced
decomposition
semiconductor-based
photocatalysts
offers
generic
robust
strategy
utilizing
cocatalyst
active
sites
photoredox
synthesis
evolution.
ACS Materials Letters,
Journal Year:
2024,
Volume and Issue:
7(1), P. 359 - 367
Published: Dec. 24, 2024
Solar-driven
CO2
reduction
combined
with
plastic
waste
valorization
presents
a
versatile
approach
to
simultaneously
reset
misaligned
hydrocarbon
resources
and
achieve
carbon-neutral
cycle.
Herein,
we
demonstrate
co-upcycling
heterogeneous
photoredox
catalysis
for
efficient
tunable
syngas,
integrated
polyethylene
terephthalate
(PET)
conversion
accessing
acetate,
over
the
spherical
band-gap-engineered
ZnxCd1–xS
catalyst.
The
key
steering
syngas
H2/CO
rate
is
modulate
conduction
band
bottom
potentials
of
photocatalysts
by
altering
Zn/Cd
ratio,
which
results
in
production
wide
range.
Moreover,
controlled
variations
molar
ratio
regulate
electron–hole
separation
capability,
thereby
endowing
Zn0.8Cd0.2S
optimum
acetate
rates.
underlying
mechanistic
origin
such
redox
reaction
involving
CO2-assisted
PET
has
been
systematically
investigated.
This
win-win
cooperative
offers
tantalizing
possibility
into
value-added
feedstocks.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(34)
Published: June 11, 2024
Abstract
Light‐driven
photoredox
catalysis
presents
a
promising
approach
for
the
activation
and
conversion
of
methane
(CH
4
)
into
high
value‐added
chemicals
under
ambient
conditions.
However,
C−H
bond
dissociation
energy
CH
absence
well‐defined
sites
on
catalysts
significantly
limit
highly
efficient
toward
multicarbon
(C
2+
hydrocarbons,
particularly
ethylene
2
H
).
Herein,
we
demonstrate
bimetallic
design
Ag
nanoparticles
(NPs)
Pd
single
atoms
(SAs)
ZnO
cascade
C
with
highest
production
rate
compared
previous
works.
Mechanistic
studies
reveal
that
synergistic
effect
NPs
SAs,
upon
effecting
key
bond‐breaking
‐forming
events,
lowers
overall
barrier
process
both
resulting
6
,
constituting
truly
catalytic
system
to
facilitate
generation.
This
work
offers
novel
perspective
advancement
photocatalytic
directional
hydrocarbons
through
subtle
catalyst
strategy.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Jan. 16, 2024
Abstract
Activation
of
ubiquitous
C(sp
3
)−H
bonds
is
extremely
attractive
but
remains
a
great
challenge.
Heterogeneous
photocatalysis
offers
promising
and
sustainable
approach
for
activation
has
been
fast
developing
in
the
past
decade.
This
Minireview
focuses
on
mechanism
strategies
heterogeneous
photocatalytic
activation.
After
introducing
mechanistic
insights,
including
precise
design
active
sites,
regulation
reactive
radical
species,
improving
charge
separation
reactor
innovations
are
discussed.
In
addition,
recent
advances
hydrocarbons,
alcohols,
ethers,
amines
amides
by
summarized.
Lastly,
challenges
opportunities
outlined
to
encourage
more
efforts
development
this
exciting
field.
